JP2000045183A - Deodorant agent for fiber treatment and deodorant fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous deodorant agent for fibers and a deodorant fibers using the same. SOLUTION: This deodorant agent for fiber treatment contains (A) a (meth) acrylamide copolymer and/or its derivative containing only an anion group having >=1.2×107 molecular weight measured by an intrinsic viscosity method, or containing the anion group and a cation group, (B) hyaluronic acid and/or its salt and (C) a water-soluble and/or water-dispersible polyepoxy compound as essential components. In this case, the molecular weight of the polyepoxy compound is >=103, and an ionomer having a structure obtained by reacting a polyester with a polyisocyanate and neutralizing unreacted hydroxyl groups of the resultant polyurethane with an alkali metal to make the product water-soluble and/or water-dispersible is contained in the deodorant agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to a method of adhering, absorbing, sorbing, and adsorbing molecules or aerosols having odors such as malodor, perfume, cigarette smoke, and incense sticks (hereinafter collectively referred to as adsorption). In addition, the present invention provides a fiber treatment deodorant which can significantly reduce the odor intensity of odor by remarkably reducing or delaying the re-evaporation of odor, and a deodorant fiber obtained thereby. The material of deodorant fiber is one of natural and synthetic fiber
Examples include clothing, bedding, furniture, interior materials such as houses, ships, and vehicles, knitted and nonwoven fabrics used for clothing, nursing care, industrial materials, and other shapes of fibers, and fibers of other shapes.

[Prior art] <Similar products: deodorant fiber and deodorant fiber>
At present, from the main database, many Japanese patent publications, many publications, newspapers and magazine articles on similar technologies such as deodorant fibers and deodorant fibers and the drugs used in them.
Review articles are searched. For example, Vol. 16, No. The review article "Development of deodorizing materials" on pages 9, 29-36 states that although the purpose and performance of the deodorant fiber of the present invention are completely different, the chemical and physical adsorption and decomposability of the odor to the fiber are considered. Seven deodorant fibers and treatment agents that can be increased and are already on the market are described. This review article also suggests the need for the development of fibers that "do not smell the fabric" (hereinafter referred to as deodorant fibers) to reduce odor chemisorption. However, the present inventors consider this development possible in the case of fibrous fibers, but in the case of protein fibers such as wool and silk, acidic and basic odors are simultaneously produced in large quantities and rapidly by chemical reaction. Since it is adsorbed, it is considered to be technically extremely difficult to impart deodorant performance while maintaining commercial value such as the texture of these fibers. <Difference between deodorant property and deodorant property and deodorant property of fiber of the present invention> The deodorant property referred to in the present invention means that the amount of adsorption of the odor inherent in the fiber to be treated hardly increases or decreases, but the odor adsorbed after the treatment. By significantly reducing and / or delaying the amount of re-evaporation, the olfactory odor intensity of the treated fiber is significantly reduced, which is defined as performance that can be proved qualitatively and quantitatively. Drugs and fibers that obtain such an odor control have not yet been disclosed in the investigations of the present inventors.

A) In use, in addition to odors such as odors such as putrefaction odors, and fragrances such as perfume odors and incense odors during use,
Since it may be uncomfortable due to individual differences, these are collectively included in the odor to be controlled by the present invention. ), Even if the deodorant fiber is adsorbed, the amount of odor re-evaporation is significantly reduced as compared with the untreated fiber, so that the usable life of the treated fiber is about 2-3 times, depending on the type of odor. To be prolonged and to be able to regenerate the deodorant effect of the treated fiber by washing with water, washing or dry cleaning. b) As in other methods, it can be applied to almost all fiber materials regardless of a complicated method such as blending, mixing, weaving and knitting of deodorant synthetic fibers and ordinary fibers, and is an aqueous agent having an extremely low solid content. The treatment is completed by a simple method of merely impregnating and drying, and optionally performing light curing and washing. c) Unlike other methods in which an inorganic / organic deodorant is kneaded into fibers or combined with a binder and applied to the fibers, the present invention merely provides an extremely thin surface on the fibers. Since it is a method of forming a continuous film, the texture inherent in the fiber to be treated is almost completely maintained so that physical properties are not adversely affected. d) Ironing, molding press, baking, pressure treatment, heat setting, high pressure steam treatment under normal pressure or reduced pressure (decatizing), washing with water, repeated washing / dry cleaning, mechanical shrinkage of fabric at all high temperatures Maintaining the initial odor control performance of the treated fiber even after treatment (for example, sun holiz treatment). e) The number of substances in the smoke of cigarettes is determined to be 4,000 or more even for the substances identified by chemical analysis. Many other natural malodors are similarly complex in composition, so a quantitative measurement of the performance of the present invention was taken by the Environment Agency and included a panel of 6 normal olfactory and an odor judge. Was practically impossible except by using the odor measurement method, commonly known as the three-point comparison type odor bag method. When this method is employed, there is a drawback that the test method becomes very complicated as compared with the case of measuring the environmental odor. Accordingly, the present inventors have proposed a Japanese Patent Application No.
The measurement results of the “air pollutant gas concentration measurement device and measurement method” (hereinafter referred to as “espo-type sensor method”) described in −284225 show excellent correlation with the results obtained by the three-point comparison type odor bag method, In addition, since it has been confirmed that there is a first-order proportional relationship between the odor concentration by this method and the measured value of this sensor, when measured by the Espo sensor method, the treated fiber is compared with the untreated fiber, and the odor is re-evaporated. For example, 50%
The purpose is to determine the selection and prescription of a treatment agent capable of obtaining a high degree of deodorizing effect or a treatment condition of the fiber.

The present invention provides (1) (A)
Amphoteric acrylamide and / or metaacyl containing only an anionic group having a molecular weight of at least 1.2 × 10 ⁷ , preferably at least 1.8 × 10 ⁷ , or an anionic group and a cationic group at the same time, as measured by an intrinsic viscosity method. Lilyamide copolymers. These are hereinafter abbreviated as poly (meth) acrylamide. And / or derivatives thereof such as, for example, an alkali salt or a quaternary ammonium salt structure thereof, and (B) hyaluronic acid and / or a derivative such as an alkali salt thereof, preferably those having a molecular weight of ¹⁰⁶ or more measured by an intrinsic viscosity method. , (C) a water-soluble and / or water-dispersible poly epoxy compound deodorant agent (hereinafter these referred to as epoxy resin.) for fiber treatment to the essential components, (2) the molecular weight of the epoxy resin is 10 ³ or more And (3) neutralizing the unreacted hydroxyl groups of the polyurethane obtained by reacting the polyester with the polyisocyanate with an alkali metal group to obtain a water-soluble and / or Or the deodorant according to the above (1) and (2), wherein the deodorant comprises an ionomer having a water-dispersible structure (hereinafter referred to as an aqueous polyurethane ionomer). 4) It is a deodorant fiber treated with a solution comprising a water-soluble and / or aqueous dispersion containing the deodorant according to the above (1) and / or (2) and / or (3). Is achieved by

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is constituted as described above, and has a composition of a deodorant used for solving the above-mentioned problems, its action, a mixing ratio, a method of treating fibers, The evaluation method of the odor control performance is as follows. <Composition of Four Components Used in Deodorant and Their Action> A) Although the range of the chargeable polyacrylamides is wide,
Examples of substances most suitable for achieving the objects of the present invention include (a) 5 to 15 mol% of acrylic acid and / or methacrylic acid (hereinafter sometimes referred to as (meth) methacrylic acid) . Aqueous solution of an anionic polyacrylamide having a molecular weight of 10 × 10 ⁷ and neutralized with an alkali metal and / or alkaline earth metal having an equivalent weight or less relative to the carboxy group thereof, and (b) more excellent An example of a substance which can obtain the above results is an amphoteric charged aqueous solution into which a dimethylaminomethyl group equivalent to the carboxyl group of (a), more preferably 80 to 95 mol%, is introduced by a Mannich reaction. Here, (meth) acrylamide and an amphoteric copolymer obtained by copolymerizing an acidic and a basic monomer are not suitable for the purpose of the present invention because the dried product is low in molecular weight and water-soluble. (C) Although not used in the present invention, an example of the compared cationic (meth) polyacrylamide (c) is poly (meth) having a molecular weight of 1.8 × 10 ⁷
Acrylamide is obtained by introducing a dimethylaminomethyl group in the form of an aqueous solution in the same manner as in (b). Here, the main properties of the diluted aqueous solutions of (a), (b) and (c) related to the present invention were as follows. 1. The films (a) and (c) obtained by drying at a decomposition temperature of about 200 ° C. or less are completely redissolved with a large amount of water, but only (b) forms intra- and inter-molecular salt bonds. Showed water swelling but was insoluble. However, in the case of (a), when the aqueous polyepoxy compound was added and dried, cross-linking was formed to show water swellability as in (b) but became insoluble. 2. In all cases, the dried film (a) adsorbed the cationic odor well and slightly adsorbed the non-odorous odor under the wet condition, but hardly adsorbed the anionic odor. The dried film (c) adsorbs anionic odor well,
Some nonionic odors were also adsorbed, but almost no cationic odors were adsorbed. However, the dried film of (b) adsorbed any ionic odor well, and these odor-adsorbing properties were recognized chemically by ordinary gas chromatography. 3. However, each of (a), (b) and (c) 0.003
% Aqueous solution is evenly poured in a horizontal cellophane and dried. The film obtained by drying is well adhered even at 5% RH, which is almost dry, and does not chemically adsorb any odor. For example, the aerosol of cigarette smoke adheres well to the membrane surface even at such low humidity, and at 60% RH, the odor intensity of the adsorbed film of (b) is (a) or About 40% of the case of (c) could be confirmed by the following simple olfactory method and the espo-type sensor method. 4. However, each was impregnated with 0.005% aqueous solution of (a), (b) and (c) and dried, and steamed at normal pressure for 5 minutes in a steamer. When the same comparison was made, there was no difference between the three. This was presumed to be due to the fact that the dimethylaminomethyl group was considerably hydrolyzed and vaporized by water vapor, and the cationicity of (b) on the fabric was reduced and the anionicity was increased. 5. Instead of typical synthetic fibers, polyethylene terephthalate (hereinafter abbreviated as PET), polypropylene (hereinafter abbreviated as PP), 6 nylon (hereinafter abbreviated as NY), and polyacrylnitrile (hereinafter abbreviated as AN), These films were used for the above 3. (A), (b) and (c) were flowed in the same manner as above to form a film. However, uniform wetting did not occur, and none of the dry items had any adhesion to the film, and was lightly pressed with a finger. And easily peeled off. Even if various penetrants having a large surface tension lowering effect were added to each aqueous solution, the adhesion could not be improved. Therefore, it was determined that these aqueous solutions could not be used as such as deodorants for synthetic fibers and fiber materials containing them. B) The aqueous solution of hyaluronic acid and / or its salt used in the present invention (hereinafter sometimes referred to as hyaluronic acid) is a kind of mucopolysaccharide and is β-D-glucropyranosyluronic acid- The present invention comprises repeating structural units of (1 → 3) -2-acetamido-2-deoxy-D-glucopyranose, and has various degrees of polymerization, and preferably has a molecular weight of ¹⁰⁶ or more. Now we have good results. Next, the action of this compound is as follows. 1. When the fiber contains a substance that is adsorbable or reactive with odor, the fiber becomes a deodorant fiber. For example, deodorization of a basic odor occurs when the fiber contains an acidic group or an acidic substance, and vice versa when the fiber contains a basic group or a basic substance. In addition, even when a buffering salt is contained, the acidic group and the basic group having a higher ionization degree may respectively decompose an acidic odor and a basic odor having a lower ionization degree and selectively absorb and deodorize. . Since these deodorizing reactions are often reversible under normal temperature and humidity, even if a high deodorizing rate can be proved by chemical analysis, the odor re-evaporated from the treated fiber cannot be accurately analyzed. Even when the concentration is so low as to be difficult, an odor is often perceived as a very strong odor. Both hyaluronic acid and charged poly (meth) acrylamide have the effect of preventing the re-evaporation of a very strong odor from the deodorant fiber, even in trace amounts, but when compared alone, the former is better. This prevention effect is lower than the latter. However, it can be experimentally proved that when both are used in combination, the results are higher than when either is used alone. 2. The reason for this synergistic effect is that both aqueous solutions can be mixed at an arbitrary ratio and a transparent continuous film is formed by drying, that is, the compatibility is good, and the pH of the hyaluronic acid aqueous solution is in the range of approximately 5 to 10. In other words, it is possible to further increase and reinforce the buffering property of the charged poly (meth) acrylamide due to the strong buffering property. 3. For example, an aqueous solution of sodium hyaluronate dissociates into sodium ions and extremely high acid ions of hyaluronic acid. In addition, an aqueous solution of amphoteric charged poly (meth) acrylamide alone can be used for anti-odor processing and secondary processing at 130-130.
When exposed to dry heat or steam heat in the range of 200 ° C, dimethylaminomethyl groups, and dimethylamine and formaldehyde generated by decomposition of the dimethylaminomethyl groups, evaporate out of the system, generating a bad smell,
Although the cationicity decreases, the coexistence of hyaluronic acid and high acid valence ions prevents these decomposition products from volatilizing outside the system, and prevents a large change in the anion group / cation group ratio on the deodorant fiber after drying. What can be done is also a major reason for the synergistic effect. 4. Although the aqueous solution of hyaluronic acid and a salt thereof is used alone or in combination with an aqueous solution of charged poly (meth) acrylamide, the adhesiveness to the above-mentioned hydrophilic natural fibers is excellent, but the above-mentioned hydrophobic synthetic fiber There is no adhesiveness with any kind. C) The aqueous polyurethane ionomer used in the present invention can be uniformly mixed with the aqueous solution of the above-mentioned charged polyacrylamides and hyaluronic acid, and forms a transparent dry film.
Further, since the polymer itself is anionic and is an alkali salt of a polyvalent anion group of the polymer, it can be solubilized or dispersed in water so as to be fine particles of 0.1 μm or less. According to the present invention, the 100% modulus of the dried film is 150-250k.
g / cm ² is preferred. Such aqueous polyurethane ionomers can have various compositions, for example,
When a diisocyanate is reacted with a polyester obtained from an aliphatic dibasic acid diol having 4 to 6 carbon atoms or a disodium salt thereof and isophthalic acid or terephthalic acid, the molecular weight is 1
Those 0 ⁴ ~2 × 10 ⁴ obtained by dissolving or dispersing in water. 1. Treating fibers with this aqueous polyurethane ionomer hardly improves odor control, but it is used because it contains no surfactant, so it has excellent adhesion to most synthetic fibers, and Acts as an anchoring agent for these synthetic fibers without inhibiting the excellent odor control effect on the excellent fibers possessed by the mixture of the above-mentioned charged polyacrylamides and hyaluronic acid, and efficiently removes by washing, dry cleaning and friction. This is because it can be prevented. 2. A mixed aqueous solution of these three types of polymer compounds provides an excellent effect as a film-enhancing component of a deodorant such as a knitted woven fabric or a nonwoven fabric in which a synthetic fiber or a natural fiber is mixed with a synthetic fiber. Can also be used in cases. D) The aqueous polyepoxy resin used in the present invention has an oxirane ring (epoxy group) number of 2 or more in one molecule,
It is mainly produced by reacting epichlorohydrin with polyols having 2 to 4 hydroxyl groups. Examples of compounds suitable for the present invention are sorbitol tetraglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol tetraglycidyl ether, diglycerol tri (and di) glycidyl ether, trimethylolpropane tri (and di) glycidyl ether, polytetra O / W emulsions of methylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A epoxy resin, and mixtures thereof. 1. These aqueous polyepoxy resins are used as a cross-linking agent for the above two or three kinds of mixed polymer compounds. The moderate cross-linking determined by the experiment significantly improved the water resistance, washing resistance, heat resistance, steam heat resistance, dry cleaning resistance, frictional properties and odor control effect as shown in the examples. 2. The use of an amino resin, such as a water-soluble melamine resin, as a cross-linking agent was also considered, but this methylene addition-type cross-linking reaction involves curing at a high temperature where amine odor and formaldehyde odor are likely to occur, and basic It is necessary to use an acid catalyst that easily binds to the offensive odor, and furthermore, two or three types of water-soluble polymer compounds used in the present invention may be aggregated during processing, and are excluded because they are not suitable for the present invention. 3. The two or three types of high molecular compounds used in the fiber treating deodorant of the present invention do not penetrate into the fine structure of the fiber during the processing, regardless of the type of the fiber. In addition, since the above synthetic fibers have a high degree of crystallinity, the penetration of the drug including the relatively low molecular weight aqueous epoxy resin into the fiber microstructure hardly occurs, and the deodorant film is formed on the fiber surface. It is formed. Therefore, it is hardly affected by the molecular weight of the aqueous epoxy resin used. 4. However, the hydrophilic protein fiber, the regenerated protein fiber, the fibrous fiber, the regenerated fibrous fiber, and the fiber material in which these are mixed with the synthetic fiber, the larger the molecular weight of the water-based epoxy resin used, the more the amorphous region of the fiber Therefore, it is necessary to select a compound having as large a molecular weight as possible. When a compound having a molecular weight of 10 ³ or more is used, unnecessary internal penetration into the fine structure of the fiber can be reduced, so that the treated fiber has a reduced tensile strength, a deteriorated texture, and a reduced anti-odor effect such as washing resistance. Could be reduced. E) The auxiliaries to be added to the deodorant of the present invention include a preservative for the deodorant solution, a bacteriostat for the deodorant fiber, a fungicide, an antistatic agent, a softener, an acaricide, and an insect repellent. Agents, softeners and the like. The properties required for these auxiliaries are insolubility in water and dry cleaning solvents, non-cationic, anionic and amphoteric in the presence of water, chemical and / or physical adsorption and reactivity with odorants No, no pre-dispersed in fine particles, pre-dispersed in uniform fine particles so as not to cause aggregation in each polymer compound of the deodorant, one that does not hinder the deodorant performance of the present invention These need to be considered in advance in preliminary tests. <Compounding ratio of deodorant and deodorizing treatment method for fiber> The solid content concentration of the aqueous solution of the fiber deodorant of the present invention was found to exhibit a good deodorant effect in the range of 0.001 to 0.01% with respect to many fabrics by the following evaluation method. ,
Reasonable concentrations range from 0.002 to 0.01%. However, the optimum concentration needs to be determined by conducting experiments for each fiber material to be treated. 2. The deodorant of the present invention has three components,
This is shown in (Table 1) since components may be required. (Table 1) 3. It is necessary to determine the optimum blending ratio of the deodorant of the present invention in the case of three components and in the case of four components, respectively, by performing a test for each fiber to be treated. An excellent deodorant effect was given to the fiber material that was used. (In the case of a three-component formulation) Chargeable polyacrylamide: hyaluronic acid and / or its salt: aqueous epoxy resin = 45%: 15%: 40% (In the case of a four-component formulation) Chargeable polyacrylamide: hyaluronic acid and / or its 3. Salt: aqueous polyurethane ionomer: aqueous epoxy resin = 30%: 10%: 40%: 20% The main precautions of the deodorant treatment method using the deodorant of the present invention are as follows. a) If substances that ionize in water such as detergents, softeners, salts, acids, and bases remain in the textile material to be processed, these act as deodorants against the malodor of the opposite charge, resulting in reversible adsorption. It is necessary to wash and remove it beforehand. b) If the pH of the deodorant aqueous solution is adjusted to the range of 5.0 to 7.5, the stability of the polymer compound of the main compounding component can be maintained even during long-time operation. For protein fiber,
If a small amount of citric acid or the like is added to adjust the pH of the treatment solution to be close to the isoelectric point of the fiber to be treated, possible selective adsorption of the drug is reduced. c) For impregnation and drying of each fiber material, an ordinary method suitable for the form of the material is applied. For example, in the case of knitted fabrics and nonwoven fabrics, squeeze by mangle rolls and then dry with a stenter; in the case of dyed yarns, socks, and knitted yarns, impregnate and centrifugally dehydrate and then dry with hot air. Drying with hot air after centrifugal dehydration or treatment at the raw fiber stage may be used, but other methods may be used. In addition, the treatment of the interior fiber of the automobile and the carpet already laid can be performed by spraying, wiping with a mop, wiping with a mop, or the like, followed by natural drying or hot air drying. d) When impregnated with 100% synthetic fiber material, the entire surface is completely wetted with the deodorant aqueous solution of the present invention.
This is a condition for obtaining a high degree of odor control effect, and a substantial change in the solid content concentration of the processing solution during the process does not occur, so that the quality can be easily controlled. On the other hand, in the case of a hydrophilic fiber or a mixed material of a synthetic fiber and a hydrophilic fiber, the polymer component of the deodorant stays on the fiber surface in its entirety and does not penetrate into the non-crystalline region of the fiber. Only water and water selectively penetrate into the non-crystalline region of the hydrophilic fiber, and there is a high possibility that the concentration of the treatment liquid fluctuates during the process. As a measure to prevent this, the moisture content of the fiber material is determined experimentally so that the concentration of the treatment liquid can be kept constant.
A high degree of concentration control can be achieved if the treatment is performed by a method such as pressing twice. e) When the treatment liquid is impregnated, drying at room temperature, hot air drying at 100 ° C. or less, and drying in an oven at 130 ° C. or less until the weight becomes constant, the deodorant of the present invention completely completes the crosslinking reaction. I do. After processing, even if washed with warm water, the odor control does not decrease,
Rather, they confirmed the tendency to improve. <Evaluation method of odor control performance> The quantitative evaluation of the deodorant effect of the present invention can be performed very accurately by the three-point comparison odor bag method, but the experiment is easy,
Since it has been confirmed that there is a first-order proportional relationship between the sensor and the sensitivity to odor, the reliability of the evaluation results is high in both methods. 2. In the test by the espo sensor method, mainly the smoke odor of tobacco was used as the test odor. In this method, first, the smoke aerosol of cigarettes is sealed in a plastic bag with an artificial smoking device, the smoke disappears and the tar is deposited in the bag. This was diluted with fresh, low humidity air to give a test odor. After absorbing the test odor under a certain condition to each of the untreated and deodorized fiber samples, transfer each sample to a separate plastic bag and send a certain amount of low humidity fresh air. The odor generated from the sample was measured by a sensor. The odor emitted from the untreated sample and the deodorized sample is measured (the unit of the sensor reading is Hz), and the odor of each deodorized sample is defined assuming that the residual odor rate of the untreated sample is 100%. Was converted to a percentage and compared. 3. In parallel with this sensor method, a simple olfactory test devised by the present inventors was also employed. In this test, a mixed odor having a slow volatilization rate and a complex composition, for example, an ethanol solution of perfume, a mixed solvent solution of ethanol / water of incense fume odor of 80/20, and an ethanol / water of cigarette tar of 90/10 were obtained. A mixed solvent solution, garlic extract, etc. were used as test odor sources, and a certain amount was dropped onto each of the deodorized fiber materials.Then, apply hot air or cold air from a hair dryer under certain conditions to these samples. In this method, the order of the residual odor intensity is determined by three sets of normal olfactory panels of three persons. Repeated comparison between the results of this simple olfactory test and the results obtained by the sensor method in the test for the same purpose showed that 90%
Because of the above correct answer rate, this test method greatly contributed to the completion of the present invention. 4. The odor with which textile materials such as clothing come into contact in normal living and working spaces is rare in the case of a single odor, and is mostly a mixed odor with a complex composition. The measurement of the deodorant effect by the method or gas chromatography was not adopted because it is of little value in practical use, but in the present invention, the chemical analysis is used to clearly grasp the difference between the deodorant property and the deodorant property. Some of the results are described in Example 4 and Reference Example 11.

Examples and Reference Examples Hereinafter, the present invention will be described with reference to Examples and Reference Examples. (Examples 1-3 and Reference Examples 1-10)
As shown in Table 2, 170 g / m ² of a 100% wool plain woven fabric (Reference Example 1), which had been dried to remove ionic impurities and was dried only once, was separately formulated according to the present invention (Example 1). To 3), impregnating the four types of the deodorant of the present invention alone and the mixed aqueous solution thereof (Reference Examples 2 to 10) described in each section of the above (Embodiments of the invention), and picking up with a roll 60 %, Completely dried at 130 ° C., and then boiled the samples of Examples 1 and 2 and Reference Example 2 for 10 minutes and dried. The sample was prepared by using the smoke of cigarette as the test smell. The intensity of the odor re-evaporated after each sample was adsorbed was measured by the Espo sensor method (measurement of the odor control effect). (Table 2) (Example 4 and Reference Example 11) Same fabric as in Example 3 on the same fabric as the standard raw material of 280 g / m ² scoured and bleached 100% wool ayaji (Reference Example 11) purchased from Shimosen Co., Ltd. Four samples each having a size of 10 cm × 10 cm were cut out from the woven fabric (Example 4) that had been subjected to the odor control under the conditions described above and placed in a nylon bag coated with nylon having a low permeability and a capacity of 5 liters. After attaching the stopcock, each sample was placed one by one, and in each bag, four types of odorous gases having a known concentration as shown in (Table 3) were pumped into each bag for 5 times.
After sending each liter, the initial concentration and the concentration of each offensive odor gas after a lapse of a predetermined time are measured using a Kitagawa gas detector tube, and then each sample is taken out. A cooler was applied to the dryer vertically from 30 cm above for 2 minutes each, and the intensity of residual odor was compared by the sense of smell of the panel. (Table 3) The wool fabric (Reference Example 11) is an excellent deodorant fiber even in an untreated fabric because it deodorizes a large amount of ionic odor, but the above results show that the wearer does not volatilize the odor adsorbed by the wearer. It indicates that the user feels pleasure. The results of the simple olfaction test showed that the deodorized fabric (Example 4) did not show any increase or decrease in deodorant properties within the range of the analysis accuracy, but had the property of hardly re-evaporating the absorbed odor. Here, another test confirms that the rapid decrease in the concentration of ammonia and acetic acid in the bag containing no fiber adsorbed the nylon resin as a coating agent for the polyethylene film. (Examples 5 to 6 and Reference Examples 12 to 16) A plain woven fabric having a PET / wool blend ratio of 70/30, 190 g / m ² , scouring, bleaching, and water washing was prepared according to the formulation shown in Table 4 below. The process under the same conditions as in No. 3 was performed. However, instead of the boiling test after processing, after performing a steaming treatment for 30 minutes under reduced pressure assuming decatizing, a measurement test of the deodorant effect on the smoke odor of the cigarette was performed by the same method using the Espo sensor method. . (Table 4) (Example 7 and Reference Example 17) Same deodorizing treated fabric as in Example 5 (Example 7) and untreated fabric of Reference Example 12 (Reference Example 17)
Was placed on a horizontal surface, and 1 ml of a perfume (Chanel No. 5 made in France) diluted with 4 times the volume of ethyl alcohol was dropped dropwise with a pipette, and the hair was blown with a cool air hair dryer at room temperature of 25 ° C. for 8 minutes. Sample was placed in a polyethylene bag fitted with a separate two-way stopcock, 10 liters of fresh air was introduced, and then left at room temperature for 24 hours.
When the stopcock was opened and the bag in the bag was pushed out and the panel with 3 persons / set x 3 sets was used to make the panel with the stronger odor judge, all of the perfumes in the bag of the deodorant-treated fabric were re-used. The volatile odor was determined to be significantly weaker than the untreated fabric. (Examples 8 to 11 and Reference Example 18) Untreated 70 g / m ²
A roll of a spunbond made of PP (Reference Example 18) was impregnated with a 50% pickup with an aqueous deodorant shown in the following Table 5 and completely dried and finished in an oven at 130 ° C. (Example 8). ) Taking out and absorbing and adhering the smoke odor of cigarettes to these samples as in Example 1, the odor intensity of each sample volatilized into the space by the applicant's sensor method was compared and measured. (Table 5) (Treatment agent used in deodorant) A-1. Aqueous solution of sodium salt of polyacrylamide copolymer having anionic properties, molecular weight of 2 × 10 ⁷ and anion content of 10 mol% A-2. A. Aqueous solution of polyacrylamide copolymer having amphoteric charge, molecular weight 2 × 10 ⁷ , cation group / anion group ratio of 0.91 / 1 mol%, and cation group / anion group content of 10 mol% Aqueous solution of sodium hyaluronate having a molecular weight of 2 × 10 ⁶ C.I. A. aqueous solution of an aqueous polyurethane ionomer having a molecular weight of 1.5 × 10 ⁴ D) Glycerol diglycidyl ether having a calculated molecular weight of 248 and having 2 epoxy groups

The present invention is configured as described above and exhibits the following effects. (1) Materials containing amphoteric protein fibers have strong chemical adsorption to various types of odors. In addition, various fibrous fibers, which are essentially neutral substances, are produced through severe chemical treatment, so that carboxyl groups are generated on the side chains of the cellulose polymer, and various finishing processes are performed. Has been found to be easier to adsorb. Most synthetic fibers are hydrophobic, NY, AN, PET, PP
, The degree of hydrophobicity becomes stronger. Synthetic fibers are highly hydrophobic and / or highly adsorbent to highly sticky odorants, such as tobacco tar, just as PP with the highest hydrophobicity is used as an oil collector. As described above, the odor-absorbing property of the fiber is high regardless of hydrophilicity and hydrophobicity, and it is reversible, so that the odor once adsorbed by the fiber is re-evaporated by the movement of the adsorption equilibrium, and emits an odor that is unpleasant. . Therefore, even if appropriate deodorizing treatment can be performed on the fiber material and the deodorizing performance can be analytically proved, the olfactory perception of a strong mixed odor such as cigarette smoke from the treated fiber should be significantly prevented or delayed. Was impossible. The present invention, even if odor is adsorbed to most fiber materials,
The degree of olfactory odor sensing is reduced to at least 50% or less of that of the untreated fiber, which provides a technique that can be quantitatively and qualitatively confirmed. (2) In addition to deodorant fibers, the industry has pointed out the need to develop fibers that do not smell the fabric. Here, when the fiber having no bad odor adsorbing property is defined as “deodorant fiber”, the undeodorized fiber of the present invention has an untreated fiber that is chemically analyzed to have an odor.
Although it does not prevent sorption and adsorption, it cannot be made into deodorant fiber. However, when evaluated by a quantitative olfactory test, the amount of odor re-evaporation clearly decreases, so it can be considered as a kind of deodorant fiber.However, since it lacks accuracy, it is difficult to smell even if the odor is absorbed by the fabric. The fiber of the present invention which gives performance is defined as "anti-odor fiber", and a technique for obtaining such a fiber having a high practical value and a chemical for treating the fiber is provided. (3) Processing can be applied to most fibers and the drug concentration is extremely low, so the texture, appearance, flexibility, various physical strengths, water resistance, washing resistance, dry cleaning resistance, steaming resistance due to processing An object of the present invention is to provide a deodorant and a deodorant fiber for fiber treatment which can be easily processed by ordinary fiber processing equipment without causing deterioration or deterioration such as offensive odor.

Claims (4)

[Claims] (A) A copolymer of acrylamide and / or methacrylamide containing only an anionic group or an anionic group and a cationic group simultaneously and having a molecular weight of 1.2 × 10 ⁷ or more as measured by an intrinsic viscosity method. Or a derivative thereof,
(B) a deodorant for treating fibers, comprising, as essential components, hyaluronic acid and / or a derivative thereof; and (C) a water-soluble and / or water-dispersible polyepoxy compound. 2. The deodorant according to claim 1, wherein the polyepoxy compound has a molecular weight of 10 ³ or more. 3. An ionomer having a structure in which an unreacted hydroxyl group of a polyurethane obtained by reacting a polyester with a polyisocyanate is neutralized with an alkali metal to make it water-soluble and / or water-dispersible. 2. The deodorant according to 2. 4. A deodorant fiber which is treated with an aqueous solution and / or aqueous dispersion containing the deodorant according to claim 1 and / or 3, and dried.