JP2014129635A - Adsorbing material for age-related body odor and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber material exhibiting a high removing effect for aging odor, particularly a high removing effect for unsaturated aldehydes such as nonenal and octenal, and maintaining the effect, and to provide a method for producing the same.SOLUTION: There is provided a fiber assembly for countermeasure for aging odor. The fiber assembly comprises a fiber composed of a polymeric base material into which a side chain having an amino group as well as a linear alkyl group or an alkanol group having 4 to 20 carbon atoms is introduced . Since the side chain is covalently bonded to the base material by the radiation graft polymerization method, the side chain do not fall out. In addition, the functional group introduced into the side chain is designed for effectively adsorbing an unsaturated aldehyde or an organic acid odor which are representative components of the aging odor, thereby maintaining the initial effect for a long period of time.

Description

Detailed Description of the Invention

  The present invention relates to a fiber that removes nonenal or octenal odor, which are main components of an aging odor, and a method for producing the same. Moreover, it is related with the age-related odor removal technique using the material. In recent years, disgust with odors, which has not been a problem in the past, has increased with the improvement of quality of life and the desire for cleanliness. In particular, aging odors are a problem for young people in recent years. Therefore, the expectation for an effective aging odor removal material appearance is great.

  The main components of aging odor are said to be ammonia, acetic acid, isovaleric acid, and unsaturated aldehydes such as nonenal and octenal. Ammonia can be easily removed with acidic functional groups such as carboxyl groups and sulfonic acid groups. In addition, organic acids such as acetic acid and isovaleric acid can be removed relatively easily with a basic functional group such as a quaternary ammonium group or a tertiary amine or lower amine.

  However, nonenal, which is a representative example of an unsaturated aldehyde, has a double bond and an aldehyde group as shown in the chemical structure of FIG. 1, and is difficult to remove by an acidic functional group or a basic functional group alone.

  In order to remove nonenal, a kneaded or sprayed component mainly composed of diethanolamine is used (Japanese Patent Laid-Open No. 2001-97838). However, this method is not sustainable because diethanolamine has a low molecular weight and the interaction with the substrate to be supported is small, so that the method drops off from the substrate.

  In addition, a material in which a solution obtained by mixing a methacrylic acid graft-polymerized cotton, an emulsion of an alkylpolyamine derivative, and an amino-modified dimethylpolysiloxane is attached to a woven fabric or knitted fabric has been proposed (Japanese Patent Laid-Open No. 2012-140731). This method is also a method of attaching a chemical that reacts with Nonenal to a woven fabric or a knitted fabric, and there is a problem in the sustainability of the effect due to dropping off.

JP 2001-97838 A JP2012-140731

  It is an object of the present invention to provide a fiber material that has a high effect of removing aging odors and has a sustained effect, and a method for producing the same. In particular, it is an object to provide a fiber material having a high effect of removing unsaturated aldehydes such as nonenal and octenal and a method for producing the same.

  The present inventors have developed a material capable of removing malodors such as ammonia and organic acids and harmful metals in water by using a radiation graft polymerization method. In the process of research and development, the present inventors have found a material that can be removed very effectively against unsaturated aldehydes such as nonenal which is particularly difficult to remove among aging odors.

The present invention has the following configuration.
(1) A fiber assembly for anti-aging odors comprising a fiber having an amino group and an alkyl group or alkanol group having 2 to 20 carbon atoms in the side chain (2) The side chain is formed on an organic polymer fiber by a radiation graft polymerization method. (1) The fiber assembly for anti-aging odor described in (1) (3) The organic polymer fiber is made of a synthetic polymer or a natural polymer, and the shape thereof is a single fiber, a woven fabric that is the assembly A fiber assembly for anti-aging odors according to (1) or (2), comprising a nonwoven fabric, a non-woven fabric, a twisted yarn, and a cut product thereof. (4) After irradiating the organic polymer fiber with radiation, one of the following radiation graft polymerization methods A method for producing an anti-aging odor fiber by introducing an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group according to 1. Monomers having amino groups and alkyl groups having 2 to 20 carbon atoms or alkanol groups are individually graft-polymerized, or monomers having amino groups and alkyl groups having 2 to 20 carbon atoms or alkanol groups are graft-polymerized in a mixed solution. 2. After graft polymerization of a monomer capable of introducing an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group, an amino group and an alkyl group or alkanol group are introduced. (5) Regenerating gamma rays or electron beams from natural cellulose After irradiating the substrate with a fiber material selected from cellulose, polyolefin, polyamide, polyester, polyurethane, and polyacrylonitrile, glycidyl monomer is graft polymerized, and then alkyl having 2 to 20 carbon atoms. (1) to (1) to (6) A method for producing a fiber for aging odors that introduces a group or an alkanol group (6) 5) Fiber assembly for anti-aging odor described in (7) (6) The cation exchange group described in (6) is introduced using a radiation graft polymerization method. Is (6) odor countermeasure fiber assembly according (8) (1) to (7) the method used to use odor countermeasure fiber aggregate according to the odor removal

  Since amino groups, particularly primary and secondary amines, react with aldehyde groups, they are often used to remove aldehyde odors. However, as shown in FIG. 1, Nonenal has a hydrophobic carbon chain with 9 carbon atoms. Therefore, the removal of Nonenal odor expected only for the reaction of a hydrophilic functional group such as an amino group and an aldehyde group is not possible. Not effective.

  In this invention, the functional group which has an amino group and a C2-C20 alkyl group or alkanol group is introduce | transduced into a side chain. Thereby, the interaction of both the interaction of an amino group and an aldehyde group and the hydrophobic interaction of an alkyl can be made to function for the removal of a nonenal odor.

  In particular, graft side chains obtained by radiation graft polymerization have a long chain length of several tens of thousands or more (several hundreds or more as ethylene units) in terms of molecular weight. As the graft is translated as “grafting”, one end of the polymer chain is bonded to the main chain and the other end is a free end, so that odorous components such as a nonenal odor are easily diffused and fixed between the graft chains. It is suitable as a functionalization means of the invention.

  Here, as the amino group, any of primary amine to tertiary amine or quaternary ammonium group can be used. Tertiary amines and quaternary ammonium groups are strongly basic and more hydrophilic. In that case, organic acids which are other components of aging odor such as acetic acid and isovaleric acid can be effectively used.

  As a drug having an amino group, dimethylamine, diethylamine, triethylamine and the like can be used in addition to linear alkylamines such as ethylamine, butylamine, pentylamine, dodecylamine and octadecylamine. Also, amines having a plurality of amino groups such as ethylenediamine and hexamethylenediamine can be used. Piperazine, 1,4 diazabicyclo [2.2.2] octane and the like can also be used. Furthermore, amines such as diethylenetriamine, triethylenetritetramine, and polyethyleneimine can be used.

  Among these, when the number of carbon atoms is larger than 20, the hydrophobicity increases, so that the graft chains attract each other and the space necessary for the adsorption cannot be maintained, so that the adsorption performance cannot be sufficiently exhibited. In addition, when the number of carbon atoms is 1, the hydrophobic portion is small, so that the hydrophobic interaction is small, and the amine odor is strong, which is a problem in the working environment.

  Alkanolamines can be used in the same manner as in the case of amines. Monoethanolamine and diethanolamine can be preferably used. Since it has a hydroxyl group, the hydrophilicity increases, but the boiling point is very high, and the problem of amine odor is reduced. The type of amine can be determined according to the place where the aging odor is generated, the purpose and the production method.

  The radiation graft polymerization method is a method of irradiating a substrate with ionizing radiation such as γ-rays or electron beams and utilizing a radical generated on the surface of the substrate or inside the substrate (hereinafter referred to as “monomer”). Is a method of growing a graft chain from a substrate. Although the length of the graft side chain depends on the graft ratio, it usually ranges from several to several hundreds of ethylene units. Therefore, it is convenient for the aging odor component to diffusely adsorb between the graft side chains.

  In particular, when a fixed charge such as an amino group is present in the graft chain, the fixed charges repel each other electrostatically, so that the graft chain extends and the graft chains repel each other. For this reason, a wide space is formed between the graft chains. Therefore, the component of an aging odor becomes easy to spread | diffuse.

  Examples of the base fiber of the present invention include synthetic fibers, cellulose fibers such as cotton, animal fibers, mineral fibers, regenerated fibers, or mixed fibers thereof. Synthetic fibers include polyester, polyamide, acrylic, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyvinyl alcohol, fluorine, and the like. Cellulosic fibers include natural cellulose fibers such as cotton and hemp, viscose rayon, copper ammonia rayon, regenerated cellulose fibers such as polynosic, purified cellulose fibers such as tencel, and semi-synthetic fibers such as acetate and diacetate. It is. Mineral fibers include asbestos and basalt fibers. Animal fibers include animal hair fibers such as wool, silk and the like. The recycled fiber includes chitin / chitosan fiber, collagen fiber and the like. It is also possible to use blends of these fiber materials.

  Since the radiation graft polymerization method is a means for developing a material capable of introducing a function while maintaining the shape of an existing polymer, it can be applied to any shape. Organic polymer fibers, which have a fast aging odor adsorption rate and are easy to use in clothing and living environment, are suitable for the use of the present invention, the shape of which is a single fiber, a woven fabric that is an aggregate, a nonwoven fabric, Those selected from twisted yarns and their cut products can be suitably used.

  As the ionizing radiation used in the radiation graft polymerization method, alpha rays, beta rays, gamma rays, electron rays, ultraviolet rays, and the like can be used. Industrially available gamma rays and electron rays are suitable for the present invention.

  There are a pre-irradiation graft polymerization method and a simultaneous irradiation graft polymerization method depending on the timing at which the substrate is irradiated with radiation. The former performs graft polymerization by irradiating a substrate with radiation and then contacting with a monomer. In the latter, irradiation is performed in a state where the substrate and the monomer are present simultaneously. Either method can be adopted.

  In addition, a liquid phase graft polymerization method in which the graft polymerization is performed in a monomer liquid, a gas phase graft polymerization method in which the monomer is vaporized, an impregnation gas phase grafting in which an amount of the monomer to be grafted is added and then reacted in an inert gas. Any graft polymerization method such as a polymerization method can be used.

The following can be used as the graft polymerization monomer.
A combination of a monomer having an amino group and a monomer having an alkyl group having 2 to 20 carbon atoms, or a monomer having an amino group and a monomer having an alkanol group having 2 to 20 carbon atoms, individually or mixed, is graft polymerized. Thereby, an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group can be polymerized at a predetermined blending ratio.
(1) After graft polymerization of a monomer capable of introducing an amino group and an alkyl group having 2 to 20 carbon atoms or an amino group and an alkanol group having 2 to 20 carbon atoms, the amino group and the alkyl group having 2 to 20 carbon atoms Alternatively, an alkanol group having 2 to 20 carbon atoms is introduced.

  (1) In the case of a combination of a monomer having an amino group and a monomer having an alkyl group having 2 to 20 carbon atoms, there is a problem of the reactivity, workability, and availability of the monomer, so that a simultaneous irradiation method is adopted. is necessary.

  In the method (2), examples of the monomer capable of introducing an amine having an alkyl group having 2 to 20 carbon atoms or an alkanol group include glycidyl methacrylate and glycidyl acrylate having an epoxy group. A monomer such as chloromethylstyrene having a halogenated alkyl group can also be used. After graft polymerization of these monomers, the reaction to be brought into contact with an alkylamine such as ethylamine, propylamine, butylamine, pentylamine, dodecylamine having 12 carbon atoms, or octadecylamine having 20 carbon atoms easily proceeds. Further, alkanolamines such as ethanolamine, propanolamine and butanolamine can be easily reacted.

  Particularly preferably, a synthetic or natural polymer fiber is irradiated with gamma rays or electron beams, and then a glycidyl monomer represented by glycidyl methacrylate is graft-polymerized, and then an alkyl group having 2 to 20 carbon atoms, particularly preferably It is aminated with an amine having an alkyl group having about 10 to 20 carbon atoms. When the number of carbon atoms is 10 or less, bad odor is strong and workability is poor. When the number of carbon atoms is 20 or more, the melting point is high and it is difficult to handle because it is solid at room temperature. In the case of alkanolamine, since the hydrogen bond of a hydroxyl group works, it can be suitably used because it has about 2 carbon atoms and has little odor.

  In addition to unsaturated aldehydes such as Nonenal, the main components of aging odors include organic acids typified by isovaleric acid, formic acid and acetic acid, and basic gas components typified by ammonia.

  Organic acids are adsorbed with basic functional groups such as amino groups. The amino group introduced to remove nonenals can be used for organic acid adsorption. In particular, it is easy to introduce an amino group into a side chain composed of a monomer such as glycidyl methacrylate having an epoxy group. For example, an alkylamine such as dodecylamine having 12 carbon atoms can be easily introduced. In this way, a pendant in which the alkyl group is directed outward through the amino group on the graft side chain is formed.

  Here, the amine reacts with the epoxy group to become a higher amine and become basic. For example, a secondary amine is formed that reacts with a primary amine. When a secondary amine is reacted, a tertiary amine is formed. In addition, since the amine portion is positively charged, adjacent side chains repel each other and the interval between the graft chains is widened. An aging odor component diffuses and a space effective for reaction adsorption is formed. If there is no amine and the alkyl chains are adjacent to each other, the alkyl chains are adsorbed by hydrophobic interaction, the graft chain becomes a contraction system, and the diffusion of aging odor components is not sufficient, and the deodorizing effect is Get smaller.

  The amino group effectively adsorbs organic acids as aging odor components. Since the space between the graft chains is widened by charge repulsion, the organic acid easily penetrates and is adsorbed. Unlike materials that are coated on the surface of the substrate, not only the adsorption speed and adsorption capacity are increased, but the substrate, side chains, and pendant parts are firmly fixed by covalent bonds. There is no such thing as dropping out.

  In order to adsorb and remove the basic gas typified by ammonia, which is another component of the aging odor, the fiber for aging odor countermeasures described in (1) to (5) and a fiber having a cation exchange group were used in combination. Fiber assemblies are particularly useful. The cation exchange group is preferably introduced using a radiation graft polymerization method.

  Ammonia is adsorbed by acidic functional groups. Carboxyl groups, sulfonic acid groups, and phosphoric acid groups are effective. A fiber obtained by graft polymerization of a monomer having an acidic functional group typified by acrylic acid can be suitably used.

  Since glycidyl methacrylate is a convenient monomer, the acidic functional group can be easily introduced. For example, when a glycidyl methacrylate graft product is immersed in a phosphoric acid solution and heated for a predetermined time, a cation exchanger having a phosphate group introduced therein can be obtained. Further, when immersed in 10-15% sodium sulfite and 10-20% isopropanol aqueous solution and heated for a predetermined time, a sulfonic acid group is introduced and a strongly acidic cation exchanger is formed. By selecting a fiber as the substrate, a cation exchange fiber can be produced.

  The cation exchange fiber thus produced has a cation exchange group in the graft side chain and is negatively charged. Although the sign of the amino group is opposite to that of the amino group described above, a basic gas such as ammonia is efficiently adsorbed because the space between the graft chains spreads due to charge repulsion. However, it does not necessarily have to have a graft side chain.

  The combination of a fiber having an alkylamine group or an alkanolamine group and a cation exchange fiber can effectively remove the unsaturated aldehyde nonenal, organic acid, and ammonia, which are the main components of an aging odor.

  In the fiber assembly for preventing aging odors of the present invention, functional groups such as amino groups and alkyl groups for removing aging odors are introduced into the fiber base by covalent bonding to side chains. Therefore, since it is not washed away by washing or the like, it can be applied to bedding, clothes, towels, handkerchiefs, etc. that perform washing regularly.

  Moreover, since the substrate shape is a fiber and the graft side chain has a functional group, the adsorption rate is high. It can also be used as a component of filters for air and air purifiers and air conditioners.

  Furthermore, since the base material is fibrous, building materials such as wall materials for homes, interiors such as curtains, carpets and sofas, sanitary products such as diapers, seat seats in vehicle compartments such as automobiles, filters for automobile air conditioners, and stationary Applicable to deodorizing products of molds.

  A method of applying the above-described fiber assembly for preventing aging odor to remove the aging odor is also included in the scope of the present invention.

Production of Nonenal Odor Removal Fiber (1)
A nylon fiber having a diameter of about 35 μm was irradiated with 40 kGy of gamma rays. Next, it was immersed in a monomer solution of glycidyl methacrylate / methanol (= 1/9) previously deoxygenated by nitrogen bubbling and reacted at 45 ° C. for 6 hours. After completion of the reaction, the fiber was immersed in a dimethylformamide solution, and further immersed in methanol for washing. By measuring the weight after drying, a weight increase rate of 128% and an immediate graft rate of 128% were obtained. Next, it was immersed in a 10% isopropanol solution of dodecylamine and reacted at 70 ° C. for 6 hours. The fiber was washed with methanol, and then the dry weight was measured. From the weight increase rate, a nonenal odor removing material into which 1.5 mmol / g of dodecylamine was introduced was obtained.

Nonenal odor removal test 10 L Tedra bag was charged with 2 g of the fiber produced in (1) and sealed with policy la. Next, the headspace part of the ampoule containing Nonenal was collected with a microsyringe and injected into a Tedra bag. The change over time in the concentration of nonenal in the tedlar bag was measured using a gas detector tube. The initial concentration of 0.6 ppm was not detected after 5 minutes and 0.1 ppm, and after 15 minutes, the effect of removing the nonenal odor was high.

Acetic acid odor removal test Using the nonenal odor removing fiber described in Example 1, an acetic acid odor removal test was conducted. The test method was the same as the nonenal odor removal test, that is, 2 g of fiber and acetic acid gas were injected into a 10 L tedra bag, and the change in acetic acid concentration with time was measured with a gas detector tube. The initial concentration of 4.1 ppm was not detected after 5 minutes and 0.4 ppm, and after 15 minutes, the effect of removing acetic acid odor was high.

Production of Nonenal Odor Removal Fiber (2)
The glycidyl methacrylate-grafted fiber produced in Example 1 was immersed in an 80-degree C solution of octadecylamine and reacted for 12 hours to produce an octadecylamine-introduced fiber. From this weight increase rate of the fiber, a nonenal odor removing material into which 1.6 mmol / g of octadecylamine was introduced was obtained.

Nonenal Odor Removal Test A nonenal odor removal test was conducted in the same manner as in Example 1. As a result, the initial concentration of 0.6 ppm was not detected after 5 minutes and 0.2 ppm, and after 15 minutes, the effect of removing the nonenal odor was high.

Acetic acid odor removal test An acetic acid odor removal test was conducted in the same manner as in Example 1. As a result, the initial concentration of 3.8 ppm was not detected after 5 minutes and 0.5 ppm, and after 15 minutes, the acetic acid odor removal effect was high.

  From the above results, it can be seen that the fibers of Examples 1 and 2 are materials that can simultaneously remove unsaturated aldehydes such as Nonenal and organic acid odors such as acetic acid.

Production of Ammonia Odor Removing Fiber The glycidyl methacrylate graft product produced in Example 1 was immersed in an aqueous solution of sodium sulfite / isopropyl alcohol / water = 10/10/80 (weight ratio), reacted at 80 ° C. for 10 hours, and sulfonic acid A group was introduced. This fiber was a strongly acidic cation exchange fiber having a neutral salt decomposition capacity of 1.7 meq / g.

Ammonia odor removal test Ammonia odor removal test was conducted in the same manner as in Example 1. As a result, an initial concentration of 5 ppm was not detected after 1 minute after 5 minutes and after 15 minutes, and the ammonia odor removal effect was high.

  The fibers produced in Example 1 and Example 3 were mixed at a weight ratio of 1/1 to produce a cotton-like fiber lump. Using this mixed fiber, the aldehyde and acetic acid odor removal tests described in Example 1 and the ammonia odor removal test described in Example 3 were conducted in the same manner. None of the concentrations after 30 minutes were detected.

  From Example 4, the shape and amount of various fibers can be changed according to the use conditions such as household items such as bedding and underwear, dwelling materials such as curtains and wallpaper, and vehicles.

Detailed Description of the Invention

  The present invention relates to a fiber that removes nonenal or octenal odor, which are main components of an aging odor, and a method for producing the same. Moreover, it is related with the age-related odor removal technique using the material. In recent years, disgust with odors, which has not been a problem in the past, has increased with the improvement of quality of life and the desire for cleanliness. In particular, aging odors are a problem for young people in recent years. Therefore, the expectation for an effective aging odor removal material appearance is great.

  The main components of aging odor are said to be ammonia, acetic acid, isovaleric acid, and unsaturated aldehydes such as nonenal and octenal. Ammonia can be easily removed with acidic functional groups such as carboxyl groups and sulfonic acid groups. In addition, organic acids such as acetic acid and isovaleric acid can be removed relatively easily with a basic functional group such as a quaternary ammonium group or a tertiary amine or lower amine.

  However, nonenal, which is a representative example of an unsaturated aldehyde, has a double bond and an aldehyde group as shown in the chemical structure of FIG. 1, and is difficult to remove by an acidic functional group or a basic functional group alone.

  In order to remove nonenal, a kneaded or sprayed component mainly composed of diethanolamine is used (Japanese Patent Laid-Open No. 2001-97838). However, this method is not sustainable because diethanolamine has a low molecular weight and the interaction with the substrate to be supported is small, so that the method drops off from the substrate.

  In addition, a material in which a solution obtained by mixing a methacrylic acid graft-polymerized cotton, an emulsion of an alkylpolyamine derivative, and an amino-modified dimethylpolysiloxane is attached to a woven fabric or knitted fabric has been proposed (Japanese Patent Laid-Open No. 2012-140731). This method is also a method of attaching a chemical that reacts with Nonenal to a woven fabric or a knitted fabric, and there is a problem in the sustainability of the effect due to dropping off.

JP 2001-97838 A JP2012-140731

  It is an object of the present invention to provide a fiber material that has a high effect of removing aging odors and has a sustained effect, and a method for producing the same. In particular, it is an object to provide a fiber material having a high effect of removing unsaturated aldehydes such as nonenal and octenal and a method for producing the same.

  The present inventors have developed a material capable of removing malodors such as ammonia and organic acids and harmful metals in water by using a radiation graft polymerization method. In the process of research and development, the present inventors have found a material that can be removed very effectively against unsaturated aldehydes such as nonenal which is particularly difficult to remove among aging odors.

The present invention has the following configuration.
(1) Fiber assembly for anti-aging odor containing fibers having an amino group and an alkyl group or alkanol group having 2 to 20 carbon atoms in the side chain (2) The side chain is formed on the organic polymer fiber by a radiation graft polymerization method. (1) The fiber assembly for anti-aging odor described in (1) (3) The organic polymer fiber is made of a synthetic polymer or a natural polymer, and the shape thereof is a single fiber, a woven fabric that is the assembly (1) or the fiber assembly for anti-aging odors according to (2), comprising a nonwoven fabric, a twisted yarn, and a cut product thereof. (4) After irradiating the organic polymer fiber with radiation, one of the following radiation graft polymerization methods The manufacturing method of the fiber for anti-aging smell which introduce | transduces an amino group and a C2-C20 alkyl group, or an alkanol group by 1. A monomer having an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group is individually graft-polymerized, or a monomer having an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group is graft-polymerized with a mixed solution 2 . After graft polymerization of a monomer capable of introducing an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group, the amino group and the alkyl group or alkanol group are introduced. (5) Regenerating gamma rays or electron beams from natural cellulose After irradiating the base material with a fiber material selected from cellulose, polyolefin, polyamide, polyester, polyurethane and polyacrylonitrile, glycidyl monomer is graft polymerized, and then an alkyl having 2 to 20 carbon atoms. (6) (1)-(5) which used together the fiber for age-proof odor countermeasures of (1)-(5), and the fiber which has a cation exchange group ) Fiber assembly for preventing aging odors described in (7) The cation exchange group described in (6) is introduced using a radiation graft polymerization method. That (6) odor countermeasure fiber assembly according (8) (1) to (7) Using the use of odor countermeasure fiber aggregate according to the odor removal

  Since amino groups, particularly primary and secondary amines, react with aldehyde groups, they are often used to remove aldehyde odors. However, as shown in FIG. 1, Nonenal has a hydrophobic carbon chain with 9 carbon atoms. Therefore, the removal of Nonenal odor expected only for the reaction of a hydrophilic functional group such as an amino group and an aldehyde group is not possible. Not effective.

  In this invention, the functional group which has an amino group and a C2-C20 alkyl group or alkanol group is introduce | transduced into a side chain. Thereby, the interaction of both the interaction of an amino group and an aldehyde group and the hydrophobic interaction of an alkyl can be made to function for the removal of a nonenal odor.

  In particular, graft side chains obtained by radiation graft polymerization have a long chain length of several tens of thousands or more (several hundreds or more as ethylene units) in terms of molecular weight. As the graft is translated as “grafting”, one end of the polymer chain is bonded to the main chain and the other end is a free end, so that odorous components such as a nonenal odor are easily diffused and fixed between the graft chains. It is suitable as a functionalization means of the invention.

  Here, as the amino group, any of primary amine to tertiary amine or quaternary ammonium group can be used. Tertiary amines and quaternary ammonium groups are strongly basic and more hydrophilic. In that case, organic acids which are other components of aging odor such as acetic acid and isovaleric acid can be effectively used.

  As a drug having an amino group, dimethylamine, diethylamine, triethylamine and the like can be used in addition to linear alkylamines such as ethylamine, butylamine, pentylamine, dodecylamine and octadecylamine. Also, amines having a plurality of amino groups such as ethylenediamine and hexamethylenediamine can be used. Piperazine, 1,4 diazabicyclo [2.2.2] octane and the like can also be used. Furthermore, amines such as diethylenetriamine, triethylenetritetramine, and polyethyleneimine can be used.

  Among these, when the number of carbon atoms is larger than 20, the hydrophobicity increases, so that the graft chains attract each other and the space necessary for the adsorption cannot be maintained, so that the adsorption performance cannot be sufficiently exhibited. In addition, when the number of carbon atoms is 1, the hydrophobic portion is small, so that the hydrophobic interaction is small, and the amine odor is strong, which is a problem in the working environment.

  Alkanolamines can be used in the same manner as in the case of amines. Monoethanolamine and diethanolamine can be preferably used. Since it has a hydroxyl group, the hydrophilicity increases, but the boiling point is very high, and the problem of amine odor is reduced. The type of amine can be determined according to the place where the aging odor is generated, the purpose and the production method.

  The radiation graft polymerization method is a method of irradiating a substrate with ionizing radiation such as γ-rays or electron beams and utilizing a radical generated on the surface of the substrate or inside the substrate (hereinafter referred to as “monomer”). Is a method of growing a graft chain from a substrate. Although the length of the graft side chain depends on the graft ratio, it usually ranges from several to several hundreds of ethylene units. Therefore, it is convenient for the aging odor component to diffusely adsorb between the graft side chains.

  In particular, when a fixed charge such as an amino group is present in the graft chain, the fixed charges repel each other electrostatically, so that the graft chain extends and the graft chains repel each other. For this reason, a wide space is formed between the graft chains. Therefore, the component of an aging odor becomes easy to spread | diffuse.

  Examples of the base fiber of the present invention include synthetic fibers, cellulose fibers such as cotton, animal fibers, mineral fibers, regenerated fibers, or mixed fibers thereof. Synthetic fibers include polyester, polyamide, acrylic, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyvinyl alcohol, fluorine, and the like. Cellulosic fibers include natural cellulose fibers such as cotton and hemp, viscose rayon, copper ammonia rayon, regenerated cellulose fibers such as polynosic, purified cellulose fibers such as tencel, and semi-synthetic fibers such as acetate and diacetate. It is. Mineral fibers include asbestos and basalt fibers. Animal fibers include animal hair fibers such as wool, silk and the like. The recycled fiber includes chitin / chitosan fiber, collagen fiber and the like. It is also possible to use blends of these fiber materials.

  Since the radiation graft polymerization method is a means for developing a material capable of introducing a function while maintaining the shape of an existing polymer, it can be applied to any shape. Organic polymer fibers, which have a fast aging odor adsorption rate and are easy to use in clothing and living environment, are suitable for the use of the present invention, the shape of which is a single fiber, a woven fabric that is an aggregate, a nonwoven fabric, Those selected from twisted yarns and their cut products can be suitably used.

  As the ionizing radiation used in the radiation graft polymerization method, alpha rays, beta rays, gamma rays, electron rays, ultraviolet rays, and the like can be used. Industrially available gamma rays and electron rays are suitable for the present invention.

  There are a pre-irradiation graft polymerization method and a simultaneous irradiation graft polymerization method depending on the timing at which the substrate is irradiated with radiation. The former performs graft polymerization by irradiating a substrate with radiation and then contacting with a monomer. In the latter, irradiation is performed in a state where the substrate and the monomer are present simultaneously. Either method can be adopted.

  In addition, a liquid phase graft polymerization method in which the graft polymerization is performed in a monomer liquid, a gas phase graft polymerization method in which the monomer is vaporized, an impregnation gas phase grafting in which an amount of the monomer to be grafted is added and then reacted in an inert gas. Any graft polymerization method such as a polymerization method can be used.

The following can be used as the graft polymerization monomer.
A combination of a monomer having an amino group and a monomer having an alkyl group having 2 to 20 carbon atoms, or a monomer having an amino group and a monomer having an alkanol group having 2 to 20 carbon atoms, individually or mixed, is graft polymerized. Thereby, an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group can be polymerized at a predetermined blending ratio.
(1) After graft polymerization of a monomer capable of introducing an amino group and an alkyl group having 2 to 20 carbon atoms or an amino group and an alkanol group having 2 to 20 carbon atoms, the amino group and an alkyl group having 2 to 20 carbon atoms or Introducing an alkanol group having 2 to 20 carbon atoms

  (1) In the case of a combination of a monomer having an amino group and a monomer having an alkyl group having 2 to 20 carbon atoms, there is a problem of the reactivity, workability, and availability of the monomer, so that a simultaneous irradiation method is adopted. is necessary.

  In the method (2), examples of the monomer capable of introducing an amine having an alkyl group having 2 to 20 carbon atoms or an alkanol group include glycidyl methacrylate and glycidyl acrylate having an epoxy group. A monomer such as chloromethylstyrene having a halogenated alkyl group can also be used. After graft polymerization of these monomers, the reaction to be brought into contact with an alkylamine such as ethylamine, propylamine, butylamine, pentylamine, dodecylamine having 12 carbon atoms, or octadecylamine having 20 carbon atoms easily proceeds. Further, alkanolamines such as ethanolamine, propanolamine and butanolamine can be easily reacted.

  Particularly preferably, a synthetic or natural polymer fiber is irradiated with gamma rays or electron beams, and then a glycidyl monomer represented by glycidyl methacrylate is graft-polymerized, and then an alkyl group having 2 to 20 carbon atoms, particularly preferably It is aminated with an amine having an alkyl group having about 10 to 20 carbon atoms. When the number of carbon atoms is 10 or less, bad odor is strong and workability is poor. When the number of carbon atoms is 20 or more, the melting point is high and it is difficult to handle because it is solid at room temperature. In the case of alkanolamine, since the hydrogen bond of a hydroxyl group works, it can be suitably used because it has about 2 carbon atoms and has little odor.

  In addition to unsaturated aldehydes such as Nonenal, the main components of aging odors include organic acids typified by isovaleric acid, formic acid and acetic acid, and basic gas components typified by ammonia.

  Organic acids are adsorbed with basic functional groups such as amino groups. The amino group introduced to remove nonenals can be used for organic acid adsorption. In particular, it is easy to introduce an amino group into a side chain composed of a monomer such as glycidyl methacrylate having an epoxy group. For example, an alkylamine such as dodecylamine having 12 carbon atoms can be easily introduced. In this way, a pendant in which the alkyl group is directed outward through the amino group on the graft side chain is formed.

  Here, the amine reacts with the epoxy group to become a higher amine and become basic. For example, a secondary amine is formed that reacts with a primary amine. When a secondary amine is reacted, a tertiary amine is formed. In addition, since the amine portion is positively charged, adjacent side chains repel each other and the interval between the graft chains is widened. An aging odor component diffuses and a space effective for reaction adsorption is formed. If there is no amine and the alkyl chains are adjacent to each other, the alkyl chains are adsorbed by hydrophobic interaction, the graft chain becomes a contraction system, and the diffusion of aging odor components is not sufficient, and the deodorizing effect is Get smaller.

  The amino group effectively adsorbs organic acids as aging odor components. Since the space between the graft chains is widened by charge repulsion, the organic acid easily penetrates and is adsorbed. Unlike materials that are coated on the surface of the substrate, not only the adsorption speed and adsorption capacity are increased, but the substrate, side chains, and pendant parts are firmly fixed by covalent bonds. There is no such thing as dropping out.

  In order to adsorb and remove the basic gas typified by ammonia, which is another component of the aging odor, the fiber for aging odor countermeasures described in (1) to (5) and a fiber having a cation exchange group were used in combination. Fiber assemblies are particularly useful. The cation exchange group is preferably introduced using a radiation graft polymerization method.

  Ammonia is adsorbed by acidic functional groups. Carboxyl groups, sulfonic acid groups, and phosphoric acid groups are effective. A fiber obtained by graft polymerization of a monomer having an acidic functional group typified by acrylic acid can be suitably used.

  Since glycidyl methacrylate is a convenient monomer, the acidic functional group can be easily introduced. For example, when a glycidyl methacrylate graft product is immersed in a phosphoric acid solution and heated for a predetermined time, a cation exchanger having a phosphate group introduced therein can be obtained. Further, when immersed in 10-15% sodium sulfite and 10-20% isopropanol aqueous solution and heated for a predetermined time, a sulfonic acid group is introduced and a strongly acidic cation exchanger is formed. By selecting a fiber as the substrate, a cation exchange fiber can be produced.

  The cation exchange fiber thus produced has a cation exchange group in the graft side chain and is negatively charged. Although the sign of the amino group is opposite to that of the amino group described above, a basic gas such as ammonia is efficiently adsorbed because the space between the graft chains spreads due to charge repulsion. However, it does not necessarily have to have a graft side chain.

  The combination of a fiber having an alkylamine group or an alkanolamine group and a cation exchange fiber can effectively remove the unsaturated aldehyde nonenal, organic acid, and ammonia, which are the main components of an aging odor.

  An application method in which the fiber assembly for preventing aging odor described above is applied for removing aging odor is also included in the scope of the present invention.

  It is possible to introduce a graft chain composed of a functional monomer into a substrate using a radiation graft polymerization method. Therefore, it is possible to control and introduce functional groups necessary for removal with respect to an aging odor which is a complex complex odor such as ammonia, organic acid odor and aldehyde odor.

  In addition, since the function can be introduced into various shapes of substrates such as fibers, it has become possible to apply and expand to industrial fields such as general household goods, sanitary goods, air cleaning filters, and vehicles. The function introduced by the radiation graft polymerization method is covalently bonded to the base material, so that it can be used repeatedly after washing.

Nonenal chemical structure

  Hereinafter, embodiments of the present invention will be described based on examples.

Production of Nonenal Odor Removal Fiber (1)
A nylon fiber having a diameter of about 35 μm was irradiated with 40 kGy of gamma rays. Next, it was immersed in a monomer solution of glycidyl methacrylate / methanol (= 1/9) previously deoxygenated by nitrogen bubbling and reacted at 45 ° C. for 6 hours. After completion of the reaction, the fiber was immersed in a dimethylformamide solution, and further immersed in methanol for washing. By measuring the weight after drying, a weight increase rate of 128% and an immediate graft rate of 128% were obtained. Next, it was immersed in a 10% isopropanol solution of dodecylamine and reacted at 70 ° C. for 6 hours. The fiber was washed with methanol, and then the dry weight was measured. From the weight increase rate, a nonenal odor removing material into which 1.5 mmol / g of dodecylamine was introduced was obtained.

Nonenal odor removal test 2 g of the fiber produced in (1) was placed in a 10 L tedra bag and encapsulated with policy la. Next, the headspace part of the ampoule containing Nonenal was collected with a microsyringe and injected into a Tedra bag. The change over time in the concentration of nonenal in the tedlar bag was measured using a gas detector tube. The initial concentration of 0.6 ppm was not detected after 5 minutes and 0.1 ppm, and after 15 minutes, the effect of removing the nonenal odor was high.

Acetic acid odor removal test Using the nonenal odor removing fiber described in Example 1, an acetic acid odor removal test was conducted. The test method was the same as the nonenal odor removal test, that is, 2 g of fiber and acetic acid gas were injected into a 10 L tedra bag, and the change in acetic acid concentration with time was measured with a gas detector tube. The initial concentration of 4.1 ppm was not detected after 5 minutes and 0.4 ppm, and after 15 minutes, the effect of removing acetic acid odor was high.

Production of Nonenal Odor Removal Fiber (2)
The glycidyl methacrylate-grafted fiber produced in Example 1 was immersed in an 80-degree C solution of octadecylamine and reacted for 12 hours to produce an octadecylamine-introduced fiber. From this weight increase rate of the fiber, a nonenal odor removing material into which 1.6 mmol / g of octadecylamine was introduced was obtained.

Nonenal Odor Removal Test A nonenal odor removal test was conducted in the same manner as in Example 1. As a result, the initial concentration of 0.6 ppm was not detected after 5 minutes and 0.2 ppm, and after 15 minutes, the effect of removing the nonenal odor was high.

Acetic acid odor removal test An acetic acid odor removal test was conducted in the same manner as in Example 1. As a result, the initial concentration of 3.8 ppm was not detected after 5 minutes and 0.5 ppm, and after 15 minutes, the acetic acid odor removal effect was high.

  From the above results, it can be seen that the fibers of Examples 1 and 2 are materials that can simultaneously remove unsaturated aldehydes such as Nonenal and organic acid odors such as acetic acid.

Production of Ammonia Odor Removing Fiber The glycidyl methacrylate graft product produced in Example 1 was immersed in an aqueous solution of sodium sulfite / isopropyl alcohol / water = 10/10/80 (weight ratio), reacted at 80 ° C. for 10 hours, and sulfonic acid A group was introduced. This fiber was a strongly acidic cation exchange fiber having a neutral salt decomposition capacity of 1.7 meq / g.

Ammonia odor removal test An ammonia odor removal test was conducted in the same manner as in Example 1. As a result, an initial concentration of 5 ppm was not detected after 1 minute after 5 minutes and after 15 minutes, and the ammonia odor removal effect was high.

  The fibers produced in Example 1 and Example 3 were mixed at a weight ratio of 1/1 to produce a cotton-like fiber lump. Using this mixed fiber, the aldehyde and acetic acid odor removal tests described in Example 1 and the ammonia odor removal test described in Example 3 were conducted in the same manner. None of the concentrations after 30 minutes were detected.

  From Example 4, the shape and amount of various fibers can be changed according to the use conditions such as household items such as bedding and underwear, dwelling materials such as curtains and wallpaper, and vehicles.

  In the fiber assembly for preventing aging odors of the present invention, functional groups such as amino groups and alkyl groups for removing aging odors are introduced into the fiber base by covalent bonding to side chains. Therefore, since it is not washed away by washing or the like, it can be applied to bedding, clothes, towels, handkerchiefs, etc. that perform washing regularly.

  Moreover, since the substrate shape is a fiber and the graft side chain has a functional group, the adsorption rate is high. It can also be used as a component of filters for air and air purifiers and air conditioners.

  Furthermore, since the base material is fibrous, building materials such as wall materials for homes, interiors such as curtains, carpets and sofas, sanitary products such as diapers, seat seats in vehicle compartments such as automobiles, filters for automobile air conditioners, and stationary Applicable to deodorizing products of molds.

Claims (8)

  Fiber assembly for anti-aging odors, comprising fibers having amino groups and linear alkyl groups having 4 to 20 carbon atoms or alkanol groups in the side chain   2. The fiber assembly for anti-aging odor according to claim 1, wherein the side chain is introduced into an organic polymer fiber by a radiation graft polymerization method.   The countermeasure against aging odor according to claim 1 or 2, wherein the organic polymer fiber is composed of a synthetic polymer or a natural polymer, and the shape thereof is a single fiber, a woven fabric, a nonwoven fabric, a twisted yarn, or a cut product thereof. Fiber assembly After irradiating the organic polymer fiber with radiation, one of the following radiation graft polymerization methods is used. Individually graft-polymerize monomers having amino groups and alkyl groups or alkanol groups having 2 to 20 carbon atoms, or graft-polymerize monomers having amino groups and alkyl groups or alkanol groups having 2 to 20 carbon atoms in a mixed solution. 2. After graft polymerization of a monomer capable of introducing an amino group and an alkyl group having 2 to 20 carbon atoms or an alkanol group, the amino group to which the amino group and alkyl group or alkanol group are introduced and a linear chain having 4 to 20 carbon atoms Method for producing fiber for preventing aging odor by introducing alkyl group or alkanol group   After irradiating the base material with a fiber material selected from natural cellulose, regenerated cellulose, polyolefin, polyamide, polyester, polyurethane and polyacrylonitrile with gamma rays or electron rays, graft polymerization of glycidyl monomers is performed. Next, a method for producing a fiber for preventing aging odors by introducing a linear alkyl group having 4 to 20 carbon atoms or an alkanol group   The fiber assembly for anti-aging odor according to claims 1 to 5, wherein the fiber for anti-aging odor according to claim 1 and a fiber having a cation exchange group are used in combination.   The fiber assembly for anti-aging odor according to claim 6, wherein the cation exchange group according to claim 6 is introduced using a radiation graft polymerization method.   The usage method which uses the fiber assembly for age-related odor countermeasures of Claims 1-7 for age-related odor removal

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