JP2015089975A - Deodorant and processing method of the deodorant to fabric or yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To add excellent washing durability and odor properties to fabric or the like containing polyester fiber.SOLUTION: There are prepared a solution of an amphoteric polymer having the hydrogen ion concentration of the isoelectric point or more, a solution of an anionic polymer having the hydrogen ion concentration adjusted in a range of 5 to 9, and a solution of a crosslinking agent having a reactive group which crosslinking reacts with the amphoteric polymer and the anionic polymer. The concentration of the solution of the amphoteric polymer is adjusted to 0.1 to 10 mass%, the concentration of the solution of the anionic polymer is adjusted to 0.1 to 5.0 mass%, and the concentration of the solution of the crosslinking agent is adjusted to 0.02 to 2.0 mass%, relative to a total amount of the amphoteric polymer solution, the anionic polymer solution and the crosslinking agent solution. The amphoteric polymer solution, the anionic polymer solution and the crosslinking agent solution are used for attaching the polymer compound to fabric or the like by coating the fabric or the like with the above three kinds of solutions, drying, and then heating the fabric or the like.

Description

  The present invention provides a deodorizing agent that imparts excellent washing durability and deodorizing performance to a fabric or yarn containing polyester fibers used in clothing, bedding, materials, etc., and this deodorizing agent as a fabric described above. Or it is related with the method of processing into a thread | yarn. In this specification, the fabric is a general term including a woven fabric, a knitted fabric, and a non-woven fabric.

  In recent years, demand for comfort has increased in daily life, and deodorants have attracted attention. For example, it contains 5 to 50% by weight of a cellulose fiber obtained by graft polymerization of a carboxylic acid vinyl monomer at a graft ratio of 15 to 45%, and either one or both of an alkali metal and a divalent metal is 300 to 7000 mg / kg. Furthermore, the deodorizing property in which the ratio (B / A) of the absorbance B of the absorption peak derived from the carboxylic acid metal salt to the absorbance A of the absorption peak derived from the carboxylic acid in the infrared spectrum is 0.01 to 0.3 A cellulose fiber woven or knitted fabric is disclosed (for example, see Patent Document 1). In this deodorizing cellulose fiber woven fabric, the deodorizing property of acetic acid after washing 30 times is 85% or more, the deodorizing property of isovaleric acid is 90% or more, and the deodorizing property of ammonia is 70% or more. It is. In addition, in order to add the divalent metal salt to the cellulose fiber, it may be performed in any step of cotton, yarn, and fabric as long as it is a step after graft polymerization. It is more preferable to carry out after dyeing. The deodorant cellulose fiber woven or knitted fabric constructed in this way is excellent in sweat deodorization, that is, both acid and basic odor, and the deodorant balance against sweat odor is lost even after repeated home washing. Excellent washing durability.

  On the other hand, many methods for imparting deodorant performance to fabrics woven and knitted with synthetic fibers are known (see, for example, Patent Documents 2 to 6). Patent Document 2 contains hydroxylamine sulfate, zinc oxide, hydrotalcite and water, or contains hydroxylamine sulfate, smectite and water, or hydroxylamine sulfate, zinc oxide, hydrotalcite, smectite and Deodorants containing water are described. This deodorant is contained in the fiber and dried. Further, the deodorizer can appropriately contain a binder for fibers such as resin emulsion and rubber latex. Furthermore, the zinc oxide dispersion is prepared by putting ultrafine zinc oxide particles in water with a dispersant and stirring with a homogenizer. In the deodorant comprised in this way, the deodorizing effect can be exhibited with sufficient balance with respect to various bad odors, such as formaldehyde, acetaldehyde, and ammonia, by one liquid.

  Patent Document 3 discloses a copolymer of a sulfonic acid vinyl monomer and a polyethylene glycol divinyl monomer, or a sulfonic acid vinyl monomer, a polyethylene glycol divinyl monomer and a maleic acid copolymer as a processing agent on the fiber surface. Alternatively, an antibacterial deodorant fiber fabric to which a copolymer of a sulfonic acid vinyl monomer, a polyethylene glycol divinyl monomer and maleic anhydride is fixed is described. Examples of the fiber material include polyester, nylon, acrylic, cotton, silk, wool, rayon, vinylon, and acetate. In the antibacterial deodorant fiber fabric configured as described above, an excellent antibacterial deodorant performance can be imparted to the fabric without using an antibacterial deodorant in combination.

  Patent Document 4 discloses a deodorant in which a deodorant containing a metal hydroxide and an amine compound is attached to a fabric containing organic fibers via a synthetic resin binder having an acid value of 5 to 600 mgKOH / solid content g. A method for producing a conductive fabric is described. In this method for producing a deodorant fabric, the organic fiber is a polyester fiber. The shape of the organic fiber may be a short fiber or a long fiber (multifilament), or a false-twisted crimped yarn subjected to a normal false-twisted crimping process, and two or more kinds of constituent yarns are air-filled. It may be a mixed yarn or a composite false twisted composite yarn. The fabric is a woven or knitted fabric knitted and woven by a normal method. For example, a napped fabric obtained by knitting a tricot napped knitted fabric using polyethylene terephthalate multifilament, and then raising and shearing the fabric. Good. In the manufacturing method of the deodorant cloth comprised in this way, it has the deodorant excellent with respect to acetic acid and aldehydes, and it is hard to re-release the deodorized odor.

  Patent Document 5 discloses a cloth having a vinyl polymer containing a hydrophilic polyester and a deodorant on its surface, and has an ammonia deodorization rate after washing 30 times according to JIS L0217 103 method. A fabric is described that is 70% or more, has a frictional voltage of 800 V or less, and has a recontamination prevention grade of 4 or more. The deodorizer is a metal oxide having an average particle size of 0.01 to 10.00 μm. Examples of the fibers constituting the fabric include polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and polylactic acid. Furthermore, setting the ammonia deodorization rate within the above range can be achieved by including a predetermined amount of a deodorant in the vinyl polymer and then attaching the polymer to the fiber fabric surface in a predetermined amount. Setting to the range can be achieved by including a predetermined amount of hydrophilic polyester in the vinyl polymer and then attaching a predetermined amount of the polymer to the surface of the fiber fabric. The fabric configured as described above has deodorizing properties, antistatic properties, and antifouling properties and is excellent in washing durability, and thus can be widely applied to uniform clothing in general.

  Furthermore, Patent Document 6 describes a deodorant containing a hydrazide compound and an amphoteric surfactant. This deodorant is prepared by dissolving, dispersing or emulsifying a hydrazide compound and an amphoteric surfactant in either or both of water and an organic solvent. The deodorant is applied or impregnated into the fiber structure. The deodorant constituted in this way is not only excellent in the removal of aldehyde-based malodorous components not only at room temperature but also in a high temperature environment by containing a hydrazide compound and an amphoteric surfactant, Since it is difficult for the removed malodorous component to be re-released, it is extremely suitable for use in a vehicle room such as a narrow automobile exposed to a severe high temperature environment.

JP 2012-251265 A (Claims 1 and 4, paragraphs [0010] and [0017]) JP 2009-106736 A (Claims 1, 2, and 4, paragraphs [0010], [0039], [0045]) JP2012-12751A (Claim 1, paragraphs [0007] and [0023]) JP 2010-180515 A (Claims 1 and 2, paragraphs [0019], [0022], [0024] [0054]) JP 2010-121231 A (Claims 1 and 3, paragraphs [0008], [0010], [0030], [0033]) JP 2011-200333 A (claims 1 and 6, paragraph [0009])

  However, in the deodorant etc. shown in the above-mentioned conventional Patent Documents 1 to 5, when this deodorant etc. is attached to a cloth for clothing, etc., and washed after wearing this cloth for clothing, etc., The deodorant and the like attached to the fabric or the like is destroyed, peeled off or dropped, and the imparted deodorizing function is lost, so that there is a problem that the performance to withstand use cannot be maintained sufficiently. In particular, when polyethylene terephthalate (PET) is used as the fiber constituting the fabric, as in the conventional methods for producing deodorant fabrics shown in Patent Documents 4 and 5, deodorant or the like adheres to the fiber surface. Even if it was made to adhere, there existed a problem that the adhesive force with respect to fibers, such as a deodorizing agent, was weak and washing durability could not fully be demonstrated. Moreover, in the deodorizer shown in the above-mentioned conventional patent document 2, when the ultrafine particles of zinc oxide are uniformly dispersed in water and applied uniformly to the fiber surface with a fiber binder such as a resin emulsion or rubber latex. Because zinc oxide ultrafine particles (inorganic matter) have a higher specific gravity than organic matter, the zinc oxide ultrafine particles are separated, sticking spots appear on the fiber surface, the fiber is discolored, and the fiber is colored or stained with resin. Or the texture is hardened. Furthermore, in the deodorant shown in the above-mentioned conventional Patent Document 6, the amphoteric surfactant contained in the deodorant initially exhibits a deodorizing effect, but the fiber structure to which the deodorant is attached is used. When the body was washed repeatedly, there was a problem that the deodorizing effect was lowered due to contact with the laundry detergent together with a large amount of water, and mechanical destruction that forced physical friction and bending.

  The first object of the present invention is to provide a fabric or yarn containing polyester fibers with excellent water resistance, washing durability and deodorization performance, and processing of the deodorization finish into the fabric. It is to provide a method. A second object of the present invention is to provide a deodorizing agent that does not cause adhesion spots on the fiber surface of the fabric or thread, prevents discoloration of the fibers, occurrence of color spots on the fibers and resin stains, and does not cure the texture. Another object of the present invention is to provide a method for processing a deodorant agent into a fabric.

  A first aspect of the present invention is a deodorizing agent for attaching a polymer compound to a fabric or yarn containing polyester fiber, the polymer compound comprising an amphoteric polymer and an anionic polymer, and the hydrogen ion concentration is Prepare an aqueous solution of an amphoteric polymer adjusted to an aqueous solution having a higher isoelectric point with an acid, base or salt, and an anionic polymer whose hydrogen ion concentration is adjusted within a range of 5 to 9 with an acid, base or salt Prepare an aqueous solution, prepare an aqueous solution or emulsion of a crosslinking agent having a reactive group capable of crosslinking with an amphoteric polymer and an anionic polymer, an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution of a crosslinking agent or In the total amount of the emulsion, the concentration of the aqueous solution of the amphoteric polymer is adjusted to 0.1 to 10% by mass, the concentration of the aqueous solution of the anionic polymer is adjusted to 0.1 to 5.0% by mass, The concentration of the aqueous solution or emulsion of the crosslinking agent is adjusted to 0.02 to 2.0% by mass, and the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution or emulsion of the crosslinking agent are applied to the fabric or thread, respectively. In order to adhere the polymer compound to the fabric or yarn by further heat-treating the fabric or yarn, an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution or emulsion of a crosslinking agent are used. It is characterized by using.

  A second aspect of the present invention is a deodorizing agent for attaching a polymer compound to a fabric or yarn containing polyester fiber, the polymer compound comprising an amphoteric polymer and an anionic polymer, and the hydrogen ion concentration is An aqueous solution of the amphoteric polymer adjusted to an aqueous solution having an isoelectric point higher than that by an acid, base or salt, and an anionic polymer having a hydrogen ion concentration adjusted in the range of 5 to 9 by an acid, base or salt. A mixture is prepared by mixing an aqueous solution, an aqueous solution or emulsion of a crosslinking agent having a reactive group capable of crosslinking with an amphoteric polymer and an anionic polymer, and water, and the concentration of the amphoteric polymer in the mixture is 0.00. 1 to 10% by mass, the concentration of the anionic polymer in the mixture is 0.1 to 5.0% by mass, and the concentration of the crosslinking agent in the mixture is 0.02 to 2.0% by mass. It is characterized by being

  A third aspect of the present invention is the invention based on the first or second aspect, wherein the aqueous solution of the amphoteric polymer is a diallylamine hydrochloride / maleic acid copolymer, maleic acid / diallyldimethylammonium chloride / dioxide. One or two or more aqueous solutions selected from the group consisting of a sulfur copolymer, an allylamine hydrochloride / acrylic acid copolymer, and an allylamine hydrochloride / methacrylic acid copolymer, and the average molecular weight of the amphoteric polymer is It is 1,000-200,000, and the isoelectric point of the aqueous solution of the amphoteric polymer is in the range of pH 4-9.

  A fourth aspect of the present invention is the invention based on the first or second aspect, and the aqueous solution of the anionic polymer further comprises either one or both of maleic acid and maleic anhydride and isobutylene. It is a copolymer, and the average molecular weight of the anionic polymer is 1,000 to 400,000.

  A fifth aspect of the present invention is the invention based on the first or second aspect, and the crosslinking agent aqueous solution or emulsion further comprises an oxazoline group, a carbodiimide group, a sulfite blocked isocyanate group, an oxime blocked isocyanate group, or an epoxy. One of the groups has two or more reactive groups in the molecule.

  A sixth aspect of the present invention is the invention based on the first or second aspect, wherein the acid is a water-soluble inorganic acid of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or sulfamic acid, or a mixture thereof, or Formic acid, acetic acid, propionic acid, citric acid, lactic acid, tartaric acid, maleic acid, fumaric acid, phthalic acid, salicylic acid, water-soluble organic acids, or flavonoids having phenolic hydroxyl groups, catechol, pyrogallol, catechins, gallic acid Or a hydrolyzate of polyphenols.

  A seventh aspect of the present invention is the invention based on the first or second aspect, wherein the base further comprises an alkali metal hydroxide, an alkali metal carbonate, an alkaline earth metal hydroxide, ammonia. A water-soluble base consisting of one or more selected from the group consisting of alkylamine, dialkylamine, trialkylamine, hydroxyalkylamine, dihydroxyalkylamine, trihydroxyalkylamine, and alkyldiamine And

  An eighth aspect of the present invention is the invention based on the first or second aspect, wherein the salt is one or more selected from the group consisting of sodium bicarbonate, sodium acetate, ammonium sulfate and ammonium acetate. It is characterized by being a water-soluble salt.

  A ninth aspect of the present invention is an invention based on the second aspect, wherein the mixing ratio of the amphoteric polymer and the anionic polymer is (1: 4) to (4: 1) in terms of the mass ratio of the resin component. ) Is set within the range.

  A tenth aspect of the present invention is the invention based on the first or second aspect, wherein the total amount of the resin components of the amphoteric polymer and the anionic polymer is 0 with respect to 100% by mass of the fabric or yarn. .5 to 5.0% by mass is attached.

  According to an eleventh aspect of the present invention, an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution or emulsion of a crosslinking agent described in the first aspect can be obtained from an immersion method, an adsorption method, a spray method, and a coating method. One type of coating method selected from the group consisting of two or more types, or a combination of two or more types, a polyester fiber-containing fabric or yarn can be applied in any order and dried to be amphoteric polymer, anionic To a fabric or yarn of a deodorizing agent comprising a step of attaching a polymer and a crosslinking agent to a fabric or yarn, and a step of heat-treating the fabric or yarn to which the amphoteric polymer, anionic polymer and the crosslinking agent are attached. This is a processing method.

  According to a twelfth aspect of the present invention, the deodorizing agent described in the second aspect is one type of coating method selected from the group consisting of an immersion method, an adsorption method, a spray method, and a coating method, or two or more types. A method of applying to a fabric or yarn containing polyester fiber, a step of drying the fabric or yarn coated with a deodorizing agent, and a heat treatment of the dried fabric or yarn. And a process for processing the deodorizing agent into a fabric or yarn.

  A thirteenth aspect of the present invention is the invention according to the eleventh or twelfth aspect, wherein the heat treatment of the fabric or yarn further holds the fabric or yarn at a temperature of 120 to 200 ° C. for 30 minutes to 30 seconds. It is a process.

  In the deodorizing agent according to the first aspect of the present invention, an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution or emulsion of a cross-linking agent are applied to a fabric or yarn and dried. Since an amphoteric polymer aqueous solution, an anionic polymer aqueous solution, and an aqueous solution or emulsion of a crosslinking agent were separately prepared in order to heat-treat the yarn and attach the polymer compound to the fabric or yarn, a plurality of types The combination of water-soluble polymer compounds (amphoteric polymer and anionic polymer) imparts a relatively large number of ionic functional groups to the fiber surface of the fabric or yarn. As a result, these ionic functional groups can efficiently capture malodorous components, particularly basic ammonia and acidic acetic acid gas. In addition, the water-soluble amphoteric polymer and anionic polymer having excellent deodorizing performance can be maintained even after repeated household washing more than 10 times by cross-linking them by cross-linking reaction with a cross-linking agent. Water resistance and washing durability can be imparted to fabrics or yarns. In addition, since the amphoteric polymer and anionic polymer of the deodorizing agent are water-soluble, the liquid stability can be improved and the aqueous solution of the amphoteric polymer and the aqueous solution of the anionic polymer can be uniformly applied to the cloth or yarn. Thus, uniform and stable washing durability and deodorizing performance can be imparted to the fabric or yarn. Furthermore, there are deodorizers in which ultrafine particles of zinc oxide are separated and adhesion spots appear on the fiber surface, causing discoloration of the fibers, generation of color spots and resin stains on the fibers, or hardening of the texture. Compared with, the present invention does not use ultrafine zinc oxide particles, so that no adhesion spots appear on the fiber surface of the fabric or thread, preventing discoloration of the fibers, color spots on the fibers, and resin stains. However, the texture does not harden.

  In the deodorizing agent of the second aspect of the present invention, an odor eliminating treatment comprising an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, an aqueous solution or emulsion of a crosslinking agent, and a mixture prepared by mixing water. Since the odor processing agent is applied to the fabric or yarn, dried, further heat-treated, and the polymer compound is attached to the fabric or yarn, a plurality of types of water-soluble polymer compounds (amphoteric polymers and anionic polymers) are used. ) Provides a relatively large number of ionic functional groups on the fiber surface of the fabric or yarn. As a result, the same effect as the deodorizing agent according to the first aspect can be obtained. Also, a deodorizing agent comprising a mixture in which an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution or emulsion of a crosslinking agent are mixed in a predetermined mixing ratio is prepared, and the deodorizing agent is applied to the fabric. Since the heat treatment is performed after dehydration and drying, the fabric imparted with excellent water resistance performance, washing durability performance and deodorization performance is processed more efficiently than the deodorizing agent of the first aspect. Furthermore, since the processability of the deodorizing agent into the fabric is better than the deodorizing agent of the first viewpoint, the deodorizing performance more stable than the deodorizing agent of the first aspect can be imparted to the fabric.

  In the processing method of the deodorizing agent of the eleventh aspect of the present invention into a fabric or yarn, the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution or emulsion of the crosslinking agent of the first aspect, After coating and drying the fabric or yarn containing polyester fiber in any order by a coating method such as a dipping method, the amphoteric polymer, the anionic polymer and the cross-linking agent are attached to the fabric or yarn, Since the fabric or yarn to which the amphoteric polymer, the anionic polymer, and the cross-linking agent are attached is heat-treated, the same effect as the first aspect can be obtained. In addition, when processing a deodorant into a fabric or thread, it supports a wide range of processing methods such as the adsorption method and spray method as well as the dipping method, improving the workability of the deodorant into the fabric or thread. it can.

  In the processing method of the deodorizing agent of the twelfth aspect of the present invention into a fabric or yarn, the deodorizing agent of the second aspect is applied by a coating method such as a dipping method, and the cloth or yarn containing polyester fibers. After the coating, the fabric or yarn coated with the deodorizing agent is dried, and the dried fabric or yarn is further heat-treated, so that the same effect as in the second aspect can be obtained. In addition, when processing a deodorant into a fabric or thread, it supports a wide range of processing methods such as the adsorption method and spray method as well as the dipping method, improving the workability of the deodorant into the fabric or thread. it can.

  Next, the form for implementing this invention is demonstrated.

<First Embodiment>
The deodorizing agent is used for attaching a polymer compound to a fabric containing polyester fibers, and the polymer compound is composed of an amphoteric polymer and an anionic polymer. The polyester fiber is a synthetic fiber such as polyethylene terephthalate, polypropylene terephthalate, or polyalkylene terephthalate, and is not particularly limited, and may be a modified polyester fiber such as a cationic dye-dyed polyester fiber. In addition, because it contains polyester fiber, it is blended with cotton fibers other than polyester fibers, cellulosic fibers such as rayon, tencel, acetate, animal hair such as wool, animal fibers such as silk, nylon, acrylic, etc. It may be a mixed weave. The mixing ratio of fibers other than the polyester fiber is 0 to 100% by mass with respect to 100% by mass of the polyester fiber, and is not particularly limited as long as it is within this range. Further, the fibers include either one or both of natural fibers and synthetic fibers, and include either one or both of long fibers and short fibers. Further, examples of the fabric include woven fabric, knitted fabric, and non-woven fabric. The woven fabric may be woven using only polyester yarn, or may be woven using polyester yarn and other types of yarn (mixed woven), and the knitted fabric may be knitted using only polyester yarn, or polyester yarn and other types. May be used for knitting (mixed knitting). In this embodiment, the polymer compound is attached to the fabric containing the polyester fiber, but the polymer compound may be attached to the yarn containing the polyester fiber. In this case, the yarn containing the polyester fiber may be pure spinning using only the polyester fiber or a blended yarn using the polyester fiber and other types of fibers, and a woven fabric or a knitted fabric is produced from these yarns.

  The deodorizing agent is composed of an amphoteric polymer aqueous solution, an anionic polymer aqueous solution, and a crosslinking agent aqueous solution or emulsion. In this embodiment, these three kinds of aqueous solutions are prepared in separate states without being mixed. These three kinds of aqueous solutions and the like are separately applied to the fabric and dried. Moreover, as amphoteric polymer, multiple types are mentioned as mentioned later, and the aqueous solution of the amphoteric polymer is one kind of aqueous solution among the plural kinds of amphoteric polymers, or two or more kinds of aqueous solutions. Moreover, as anionic polymer, multiple types are mentioned as mentioned later, and the aqueous solution of the anionic polymer is one type of aqueous solution of a plurality of types of amphoteric polymers, or two or more types of aqueous solutions. Furthermore, as a crosslinking agent, multiple types are mentioned as mentioned later, the aqueous solution or emulsion of a crosslinking agent is 1 type of aqueous solution or emulsion of multiple types of crosslinking agents, or 2 or more types of aqueous solution or emulsion. .

  Amphoteric polymers are water-soluble and have the following chemical structure. That is, the amphoteric polymer is a copolymer of a cationic group (X) and an anionic group (Y), or a copolymer of a cationic group (X), an anionic group (Y) and a neutral group (Z). And, it has a chemical structure (basic structure) of X · Y or X · Y · Z. The main compounds of these chemical structures (basic structures) are diallylamine hydrochloride / maleic acid copolymer, maleic acid / diallyldimethylammonium chloride / sulfur dioxide copolymer, allylamine hydrochloride / acrylic acid copolymer, or allylamine. Hydrochloride / methacrylic acid copolymer. Cationic monomers represented by X are allylamine, diallylamine, N-alkylallylamine, N-allyl-N-trialkylammonium salt and the like, and anionic monomers represented by Y are methacrylic acid, acrylic acid, Maleic acid, maleic anhydride and the like, and nonionic monomers represented by Z are alkylene, alkene, vinyl acetate, vinyl hydroxide, methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid amide, acrylic acid Amides, sulfur dioxide, etc. Of these water-soluble amphoteric polymers, diallylamine hydrochloride / maleic acid copolymer is most preferable. The average molecular weight of these amphoteric polymers is set to 1,000 to 200,000, preferably 6,000 to 20,000. Furthermore, these aqueous solutions of amphoteric polymers have different isoelectric points (pI), and the hydrogen ion concentration (pH) of the aqueous solution of amphoteric polymers is adjusted to be higher than the isoelectric point, Preferably, it is adjusted within the range of 4 to 9 (weakly acidic to weakly basic). Here, the average molecular weight of the amphoteric polymer is limited to the range of 1,000 to 200,000 because the solubility in water becomes strong when the molecular weight is less than 1,000, and the water resistance and washing durability performance of the intended fabric. If the molecular weight exceeds 200,000, the viscosity of the aqueous solution of the amphoteric polymer increases, the effective concentration cannot be increased, and is inefficient and difficult to handle. is there. Further, the preferable range of the hydrogen ion concentration (pH) of the aqueous solution of the amphoteric polymer is limited to the range of 4 to 9. If it is less than 4, the pH of the fabric is lowered due to the effect of the resin applied to the polyester fiber. There is a possibility that the quality of the fiber may deteriorate or the skin irritation may become strong, and the deodorizing ability of the acidic odor gas may be remarkably reduced, and if it exceeds 9, the pH of the fabric containing the polyester fiber becomes high. This is because the fabric containing the polyester fiber may become brittle, and the deodorizing ability of the basic odor gas is remarkably lowered.

  The anionic polymer is a water-soluble polymer having one or both of maleic acid and maleic anhydride as its basic structural unit and copolymerized with isobutylene. Maleic anhydride may be partially or fully hydrolyzed with a base, and may be hydrolyzed with ammonia and partially amidated. The average molecular weight of the anionic polymer is set to 1,000 to 400,000, preferably 50,000 to 160,000. Furthermore, the hydrogen ion concentration (pH) of the aqueous solution of these anionic polymers is adjusted within a range of 5 to 9 (weakly acidic to weakly basic). Here, the average molecular weight of the anionic polymer is limited to the range of 1,000 to 400,000 because the solubility in water is strong at less than 1,000, and the water resistance performance and washing durability of the intended fabric are as follows. It becomes difficult to impart performance, and when the molecular weight exceeds 400,000, the viscosity of the aqueous solution of the anionic polymer increases, the effective concentration cannot be increased, and it is inefficient and difficult to handle. It is. In addition, the hydrogen ion concentration (pH) of the aqueous solution of the anionic polymer was limited to the range of 5 to 9 (weakly acidic to weakly basic) because the hydrogen at the isoelectric point (pI) of the aqueous solution of the amphoteric polymer. This is because the hydrogen ion concentration (pH) is higher than the ion concentration (pH) and the practical performance and deodorizing performance of the polyester fiber are exhibited. Specifically, the hydrogen ion concentration (pH) of the aqueous solution of the anionic polymer is limited to the range of 5 to 9 (weakly acidic to weakly basic). This is because the durability to washing, which maintains the deodorizing performance even after repeated washing, decreases when the number exceeds 9. The hydrogen ion concentration (pH) of the aqueous solution of the anionic polymer is higher than the hydrogen ion concentration (pH) at the isoelectric point (pI) of the aqueous solution of the amphoteric polymer, and the polyester A mixed solution when an aqueous solution of an anionic polymer is mixed with an aqueous solution of an amphoteric polymer by limiting it to a range of 5 to 9 (weakly acidic to weakly basic) that exhibits practical performance and deodorant performance of the fiber The stability of the mixed solution can be maintained by reducing the fluctuation of the hydrogen ion concentration (pH). Furthermore, the hydrogen ion concentration (pH) of the aqueous solution of the anionic polymer for the polyester fiber to exert its practical performance is the hydrogen ion concentration (pH) of the aqueous solution when the fabric using the polyester fiber is extracted with hot water. Is preferably neutral to slightly acidic, and when the dough using polyester fibers is extracted with hot water, the hydrogen ion concentration (pH) of the aqueous solution becomes basic, causing discoloration. Since the dough may come into contact with the skin, basicity is determined because it is not preferable. In this specification, the average molecular weight of the amphoteric polymer and the anionic polymer is the weight average molecular weight, and the sum of the values obtained by multiplying the molecular weight of each polymer by the mass of the polymer is the total molecular weight. It is the value divided by the mass.

  The crosslinking agent is a compound capable of crosslinking reaction with the functional group of the amphoteric polymer and anionic polymer, that is, a hydroxyl group, a carboxylic acid group, an amino group, contained in the molecular structure of the water-soluble amphoteric polymer and anionic polymer, It is a compound that can undergo intermolecular crosslinking by chemically reacting with a functional group such as an amide group. The crosslinking agent has a main skeleton composed of polyacrylate ester or polystyrene, and one or more selected from the group consisting of an oxazoline group, a carbodiimide group, a blocked isocyanate group, and an epoxy group in its molecule. A compound having two or more functional groups, which is an aqueous solution or an emulsion, is desirable. Specifically, the crosslinking agent is an aqueous solution or emulsion of a polymer having an oxazoline group as a functional group, and two or more oxazoline groups in the molecule of the copolymer or acrylic acid polymer of styrene / acrylic acid. It is a compound having a functional group or a polymer having a carbodiimide group as a functional group, which is an aqueous solution or emulsion, and two or more carbodiimide groups in the styrene / acrylic acid copolymer or acrylic acid polymer. It is a compound having a functional group, a water-soluble compound having at least two sulfite blocked isocyanate groups or oxime blocked isocyanate groups, which are blocked isocyanate groups, in the molecule, or an epoxy. Water having two or more glycidyl ether groups as functional groups in the molecule Either sex compound, or it is further desirable blocked isocyanate group and an epoxy group in the molecule a water-soluble compound having a two or more functional groups.

  In the aqueous solution of amphoteric polymer and the aqueous solution of anionic polymer, the hydrogen ion concentration is adjusted by acid, base or salt, respectively. The reason why the hydrogen ion concentration is adjusted in this way is that the amphoteric polymer and the anionic polymer each have an ionic functional group, and the solubility in water greatly depends on the pH in the system. Examples of the acid include water-soluble inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid or mixtures thereof, formic acid, acetic acid, propionic acid, citric acid, lactic acid, tartaric acid, maleic acid, fumaric acid, phthalic acid, It is possible to use one or more acids selected from water-soluble organic acids such as salicylic acid, flavonoids having phenolic hydroxyl groups, catechol, pyrogallol, catechins, gallic acid, polyphenol hydrolysates, etc. preferable. Bases include alkali metal hydroxide, alkali metal carbonate, alkaline earth metal hydroxide, ammonia, alkylamine, dialkylamine, trialkylamine, hydroxyalkylamine, dihydroxyalkylamine, and trihydroxyalkyl. It is preferable to use one or more bases selected from amines, alkyldiamines and the like. Further, as the salt, it is preferable to use one or more water-soluble salts selected from sodium hydrogen carbonate (weakly basic), sodium acetate (weakly basic), ammonium sulfate (weakly acidic), ammonium acetate and the like. . It is more preferable to use hydrochloric acid, sulfuric acid, acetic acid, citric acid, polyphenol hydrolyzate, etc. as the acid, and as the base, sodium hydroxide, ammonia, monoethanolamine, diethanolamine, triethanolamine, etc. More preferably, it is used.

  On the other hand, the concentration of the amphoteric polymer aqueous solution in the total amount of the amphoteric polymer aqueous solution, the anionic polymer aqueous solution, and the crosslinking agent aqueous solution or emulsion is 0.1 to 10% by mass, preferably 0.5 to 5%. The concentration of the aqueous solution of the anionic polymer is adjusted to 0.1 to 5.0% by mass, preferably 0.5 to 3.0% by mass, and the concentration of the aqueous solution or emulsion of the crosslinking agent Is adjusted to 0.02 to 2.0 mass%, preferably 0.05 to 0.5 mass%. Moreover, the hydrogen ion concentration of the aqueous solution of the amphoteric polymer is adjusted to be higher than the isoelectric point (pI) by an acid, base or salt, and preferably within a range of 4 to 9 (from weakly acidic to weakly basic). The hydrogen ion concentration of the aqueous solution of the anionic polymer is higher than the hydrogen ion concentration (pH) at the isoelectric point (pI) of the aqueous solution of the amphoteric polymer due to the acid, base or salt ( pH) and is adjusted within a range of 5 to 9 (weakly acidic to weakly basic) that exhibits practical performance and deodorizing performance of the polyester fiber. Here, the concentration of the aqueous solution of the amphoteric polymer was limited to the range of 0.1 to 10% by mass with respect to the total amount, and the work efficiency of attaching the amphoteric polymer to the fabric was less than 0.1% by mass. This is because the viscosity of the aqueous solution of the amphoteric polymer becomes high and handling becomes difficult when it exceeds 10% by mass. In addition, the concentration of the aqueous solution of the anionic polymer is limited to the range of 0.1 to 5.0% by mass with respect to the above total amount. This is because the working efficiency is lowered, and if it exceeds 5.0% by mass, the viscosity of the aqueous solution of the anionic polymer becomes high and handling becomes difficult. Furthermore, the concentration of the aqueous solution or emulsion of the crosslinking agent was limited to the range of 0.02 to 2.0% by mass with respect to the total amount. In addition, the washing durability performance of maintaining the deodorizing performance even after repeated washing is deteriorated, and if it exceeds 2.0% by mass, the fabric deodorizing performance is deteriorated due to excessive crosslinking and the fabric texture is cured. Because it ends up.

  In addition, a softening agent, a penetrating agent, etc. can be used together with the deodorizing agent of this invention. Examples of the softener include aqueous solutions or emulsions of modified silicone oils, alkylamide surfactants, cationic surfactants, anionic surfactants, higher fatty acid esters, high melting point waxes, polyester resins, and the like. Examples of penetrants include nonionic surfactants such as higher synthetic alcohols or natural alcohol ethylene oxide adducts, higher synthetic alcohols or natural alcohol propylene oxide adducts, polyethylene glycol-modified silicones, higher synthetic alcohols or natural alcohols. Examples include anionic surfactants such as alcohol sulfonates, higher synthetic alcohols or sulfates of natural alcohols, and amphoteric surfactants such as alkylbetaines. When a nonionic surfactant is used as the penetrant, the hydrophobic site has an alkyl carbon number of 8 to 16, and an HLB (Hydrophile-Lipophile Balance) value of 9 to 13, preferably 10 to 12 It is desirable. Here, the HLB value is a value indicating the degree of affinity of the surfactant with water and oil (an organic compound insoluble in water), and the HLB value takes a value from 0 to 20 and is close to 0. The higher the lipophilicity, the higher the hydrophilicity the closer to 20. Furthermore, functional processing agents such as antibacterial processing agents, bacteriostatic processing agents, insect repellents, water / oil repellents, antifouling processing agents, and water-absorbing quick-drying processing agents can be used in combination.

  A method of processing the deodorant agent thus configured into a fabric will be described. First, an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution or emulsion of a cross-linking agent are applied to one or two kinds of coating methods selected from the group consisting of an immersion method, an adsorption method, a spray method and a coating method. By the coating method which combined the above, it apply | coats to a fabric containing a polyester fiber in arbitrary order, and it dries, and attaches an amphoteric polymer, an anionic polymer, and a crosslinking agent to a fabric or a thread | yarn. For example, an aqueous solution of an amphoteric polymer is applied to a fabric containing polyester fibers and dried, then an aqueous solution of an anionic polymer is applied to the fabric and dried, and then an aqueous solution or emulsion of a crosslinking agent is applied to the fabric. And dry. However, it is not limited to this order. Further, the dipping method of the coating method includes a mangle padding method in which a cloth dipped in an aqueous solution of an amphoteric polymer is squeezed with a mangle (roller) to uniformly apply the aqueous solution of the amphoteric polymer to the fabric. The coating method includes a brush coating method in which an aqueous solution of an amphoteric polymer is applied with a brush, and a roll coater method in which an aqueous solution of an amphoteric polymer is applied to a rotating roller and applied to a fabric. Furthermore, since the amphoteric polymer and the anionic polymer of the deodorizing agent are water-soluble, the liquid stability can be improved, and the aqueous solution of the amphoteric polymer and the aqueous solution of the anionic polymer can be uniformly applied to the cloth or yarn. Can be applied.

  On the other hand, drying includes dehydration drying, room temperature air drying, hot air drying, and the like. The drying conditions evaporate water in which the amphoteric polymer is dissolved when an aqueous solution of the amphoteric polymer is applied to the fabric. When the fabric is dried at room temperature or hot air, room temperature or hot air of room temperature to 140 ° C., preferably hot air of 70 to 120 ° C. is used. In consideration of efficiency and the like, it is desired that the drying condition is maintained in hot air at 50 to 140 ° C. for 30 to 1 minute, preferably in hot air at 90 to 120 ° C. for 10 to 2 minutes. Specifically, when using hot air of 50 ° C. in the above drying conditions, hold in the hot air for about 30 minutes, gradually reducing the holding time as the temperature of the hot air rises, and using 140 ° C. hot air, Hold in this hot air for about 1 minute. In addition, when using 90 ° C hot air under the preferable conditions for drying, the hot air is kept for about 10 minutes, the holding time is gradually shortened as the temperature of the hot air rises, and when 120 ° C hot air is used, Hold in hot air for about 2 minutes. By such a drying treatment, excess water is removed from the fabric coated with the aqueous solution of the amphoteric polymer and the amphoteric polymer, the anionic polymer, and the crosslinking agent adhere to the fabric. That is, a thin film made of an amphoteric polymer, an anionic polymer and a crosslinking agent is formed on the fiber surface of the fabric.

  Next, the fabric to which the amphoteric polymer, the anionic polymer and the crosslinking agent are attached is heat-treated. Specifically, a heat treatment is performed in which the fabric to which the amphoteric polymer or the like is attached is kept in dry air at 120 to 200 ° C. for 30 to 30 seconds. In this heat treatment, when using 120 ° C. dry air, hold for 30 minutes, gradually reduce the holding time as the temperature of the dry air rises, and when using 200 ° C. dry air, hold for 30 seconds. To do. In consideration of efficiency and the like, it is desired that the heating condition is maintained in 120 to 200 ° C. dry air for 30 to 0.5 minutes, preferably 130 to 180 ° C. for 3 to 1 minutes. In this heating condition, when using 120 ° C. dry air, hold it in this dry air for about 30 minutes, and gradually reduce the holding time as the temperature of the dry air rises, and when using 200 ° C. dry air, Hold in dry air for about 0.5 minutes. Also, in the preferred heating conditions, when using 130 ° C. dry air, hold in this dry air for about 30 minutes, gradually reduce the holding time as the temperature of the dry air rises, and when using 180 ° C. dry air, Hold in this dry air for about 1 minute. Here, the heating temperature in the heat treatment is limited to the range of 120 to 200 ° C. The reason why the crosslinking reaction between the water-soluble resin and the crosslinking agent does not sufficiently proceed when the temperature is less than 120 ° C. This is because the water resistance performance of maintaining the performance decreases, and the washing durability performance of maintaining the deodorizing performance even by repeated washing decreases, and when the temperature exceeds 200 ° C., the fiber fabric deteriorates. Moreover, the reason for limiting the heating time in the heat treatment to the range of 30 minutes to 30 seconds is that the improvement of the washing durability performance is not recognized even if it exceeds 30 minutes, and the work efficiency is lowered, and it is less than 30 seconds. This is because the reaction time for the crosslinking reaction is insufficient, and the water resistance and the washing durability cannot be sufficiently obtained. Furthermore, the total amount of amphoteric polymer and anionic polymer resin adhering to the fabric is 0.5 to 5.0% by mass with respect to 100% by mass of the fabric. Here, the total amount of the amphoteric polymer and the anionic polymer adhering to the fabric was limited to the range of 0.5 to 5.0% by mass with respect to 100% by mass of the fabric. If the amount is less than 5% by mass, the deodorizing rate of the odor gas cannot be sufficiently increased. If the amount exceeds 5.0% by mass, the fabric texture is hardened due to excessive resin adhesion, or various physical properties of the fiber ( This is because, for example, physical properties such as tearability, burst strength, colorability, and color fading (whitening phenomenon) are reduced.

  By such heat treatment, a dehydration condensation reaction occurs between the water-soluble amphoteric polymer and the anionic polymer, and a water-resistant resin layer is formed on the fiber surface of the fabric. Since this resin layer has a relatively large number of ionic functional groups, malodorous components, particularly basic ammonia and acidic acetic acid gas can be efficiently collected by these ionic functional groups. In addition, the amphoteric polymer and anionic polymer in the resin layer having the excellent deodorizing performance are intermolecularly crosslinked by a crosslinking reaction with a crosslinking agent, so that the deodorizing performance is maintained even after repeated household washing 10 times or more. It is possible to impart water resistance and washing durability to the fabric. Thus, uniform and stable washing durability and deodorizing performance can be imparted to the fabric. In addition, by using a penetrant in combination with an aqueous solution of an amphoteric polymer, the processability of the deodorant and the stability of washing durability and deodorizing performance can be improved. A softener is used in combination with an aqueous solution of an amphoteric polymer. By doing so, the texture of the fabric can be made soft and the design can be improved. In addition, since a resin layer having sufficient mechanical strength is formed on the fabric having the washing durability performance and the deodorizing performance, the fabric can be reused by using an arbitrary tumbler, a shrinking machine, a dyeing machine, or the like. Scouring is also possible.

<Second Embodiment>
In this embodiment, an aqueous solution of an amphoteric polymer whose hydrogen ion concentration is adjusted to an aqueous solution higher than the isoelectric point by an acid, base or salt, and an aqueous solution of the amphoteric polymer which has a hydrogen ion concentration by an acid, base or salt An aqueous solution of an anionic polymer adjusted to the same hydrogen ion concentration, an aqueous solution or emulsion of a crosslinking agent having a reactive group capable of crosslinking with an amphoteric polymer and an anionic polymer, and water are mixed to form a mixture. A deodorizing agent is prepared. The concentration of the amphoteric polymer in the deodorizing agent is 0.1 to 10% by mass, preferably 0.5 to 5.0% by mass, and the concentration of the anionic polymer in the deodorizing agent is 0.00. 1 to 5.0% by mass, preferably 0.5 to 3.0% by mass, and the concentration of the crosslinking agent in the deodorizing agent is 0.02 to 2.0% by mass, preferably 0.05 to 0%. 0.5% by mass. Here, the concentration of the amphoteric polymer in the deodorizing agent is limited to the range of 0.1 to 10% by mass. If the concentration is less than 0.1% by mass, more processing is performed on the fabric including the polyester fiber. It is inefficient because it is necessary to apply an agent, and if it exceeds 10% by mass, the viscosity of the processing liquid increases, and it becomes difficult to apply the processing liquid to a fabric containing polyester fibers, resulting in a decrease in workability. It is. In addition, the concentration of the anionic polymer in the deodorizing agent is limited to the range of 0.1 to 5.0% by mass of less than 0.1% by mass of the processing liquid to be applied to the fabric containing polyester fibers. When the amount increases, the efficiency decreases. When the amount exceeds 5.0% by mass, the viscosity of the processing liquid increases, and it becomes difficult to apply the processing liquid to the fabric containing the polyester fiber, and the workability decreases. Because. Furthermore, the concentration of the cross-linking agent in the deodorizing agent is limited to the range of 0.02 to 2.0% by mass, and if it is less than 0.02% by mass, the deodorizing performance is maintained even by repeated washing. If the durability performance cannot be obtained and the content exceeds 2.0% by mass, the texture of the fabric is cured, and various physical properties of the fiber (for example, physical properties such as tearing property, bursting strength, coloring property, color fading property (whitening phenomenon)). It is because it falls. Note that the types of the amphoteric polymer, the anionic polymer, and the crosslinking agent are the same as those in the first embodiment.

  On the other hand, the compounding ratio of the amphoteric polymer and the anionic polymer is preferably set within the range of (1: 4) to (4: 1) in terms of the mass ratio of the resin component. Here, the compounding ratio of the amphoteric polymer and the anionic polymer is limited to the range of (1: 4) to (4: 1) by the mass ratio of the resin component. If it is less than, the kind of odor gas that can be deodorized is limited, and it is not possible to obtain a washing durability performance that maintains the deodorizing performance even by repeated washing, and if it exceeds 4: 1 (4/1), the same as above This is because the type of odor gas that can be deodorized is limited, and the washing durability performance cannot be obtained. Other than the above, the configuration is the same as that of the first embodiment.

  A method of processing the deodorant agent thus configured into a fabric will be described. First, a deodorizing agent comprising a mixture prepared by mixing an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, an aqueous solution or emulsion of a cross-linking agent, and the remainder of the water, an immersion method, an adsorption method, a spray It coats on the cloth containing a polyester fiber with the coating method of either the method or the apply | coating method. At this time, since the amphoteric polymer and the anionic polymer in the deodorizing agent are water-soluble, the liquid stability can be improved, and the deodorizing agent containing the amphoteric polymer and the anionic polymer can be used as a fabric or yarn. Can be applied uniformly. The coating method is the same as that in the first embodiment.

  Next, the fabric coated with the deodorizing agent is dried. This drying includes dehydration drying, room temperature air drying, hot air drying and the like. The drying conditions are the same as the drying conditions in the first embodiment. By such a drying treatment, excess water is removed from the fabric coated with the aqueous solution of the amphoteric polymer and the amphoteric polymer, the anionic polymer, and the crosslinking agent adhere to the fabric. That is, a thin film made of an amphoteric polymer, an anionic polymer and a crosslinking agent is formed on the fiber surface of the fabric. Further, the fabric that has been dried and to which the amphoteric polymer, the anionic polymer, and the cross-linking agent are attached is heat-treated. This heat treatment is performed in the same manner as the heat treatment of the first embodiment. The heating conditions are the same as those in the first embodiment.

  By such heat treatment, a dehydration condensation reaction occurs between the water-soluble amphoteric polymer and the anionic polymer, and a water-resistant resin layer is formed on the fiber surface of the fabric. Since this resin layer has a relatively large number of ionic functional groups, malodorous components, particularly basic ammonia and acidic acetic acid gas can be efficiently collected by these ionic functional groups. In addition, since the amphoteric polymer and the anionic polymer in the resin layer having the excellent deodorizing performance are cross-linked by the cross-linking reaction by the cross-linking agent, the deodorizing performance can be maintained even if the home laundry is repeated 10 times or more. It can hold | maintain and can provide water resistance and washing durability performance to a fabric. Also, a deodorizing agent comprising a mixture in which an aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution or emulsion of a crosslinking agent are mixed in a predetermined mixing ratio is prepared, and the deodorizing agent is applied to a fabric. Since the heat treatment is performed after coating, dehydrating and drying, a fabric imparted with excellent water resistance, washing durability and deodorization performance is efficiently processed. Furthermore, since the processability of the deodorizing agent into the fabric is better than that in the first embodiment, it is possible to impart more stable deodorizing performance to the fabric than in the first embodiment. Since operations other than those described above are substantially the same as those in the first embodiment, repeated description will be omitted.

  Next, examples of the present invention will be described in detail together with comparative examples.

<Example 1>
50% by weight aqueous solution of diallylamine hydrochloride / maleic acid copolymer (resin content 40%), 25% -sodium hydroxide aqueous solution (base) 10% by weight, 2,2′-diiminoethanolamine (base) 10 The aqueous solution of the amphoteric polymer having a concentration of 30% by mass and a hydrogen ion concentration (pH) of 8.6 is prepared by mixing the mass% and the remainder of the water. An aqueous solution of an amphoteric polymer whose concentration was adjusted to 5% by mass was prepared. The isoelectric point of this amphoteric polymer aqueous solution was 4.3, and the average molecular weight of the amphoteric polymer was 30,000. Also, 2% by mass of polyphenol hydrolyzate (acid) is dissolved in 68% by mass of water, and 30% by mass of ammonia hydrolyzate of maleic anhydride / isobutylene copolymer (average molecular weight: about 14,000) is added and dissolved. An anionic polymer aqueous solution having a concentration of 30% by mass and a hydrogen ion concentration (pH) of 6.5 was prepared, and the aqueous solution of the anionic polymer was diluted with water to a concentration of 5% by mass. A prepared aqueous solution of an anionic polymer was prepared. The average molecular weight of this anionic polymer was about 14,000. Furthermore, an aqueous solution (concentration 1% by mass) of Epocros WS-700 (manufactured by Nippon Shokubai Co., Ltd., registered trademark) having an oxazoline group as a crosslinking agent was prepared. The concentration of the aqueous solution of the amphoteric polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent is 1.0% by mass, and the concentration of the aqueous solution of the anionic polymer is Each aqueous solution was adjusted so that the concentration of the aqueous solution of the crosslinking agent was 1.5% by mass and the concentration of the aqueous solution of the crosslinking agent was 0.2% by mass.

First, an aqueous solution of an amphoteric polymer having a concentration of 1.0% by mass in the total amount of the above three types of aqueous solutions is padded on a fabric of a regular polyester knit (weight per unit: 240 g / m ² , manufactured by Color Dye), and then immediately with a mangle. Squeezing (dehydration drying), the pickup rate was 100% by mass. The fabric was dried with a hot air dryer at 110 ° C. (hot air drying). Next, the fabric to which the amphoteric polymer was adhered was immersed in an aqueous solution of anionic polymer having a concentration of 1.5% by mass in the total amount of the above three types of aqueous solution, and then immediately squeezed with mangle (dehydrated and dried), and picked up. The rate was 100% by mass. The fabric was dried with a hot air dryer at 110 ° C. (hot air drying). Further, the fabric to which the amphoteric polymer and the anionic polymer were adhered was immersed in an aqueous solution of a crosslinking agent having a concentration of 0.2% by mass in the total amount of the three aqueous solutions, and then immediately squeezed with mangle (dehydration). Drying), the pickup rate was 100% by mass. And after drying this fabric with a 110 degreeC hot air dryer (hot air drying), it heat-processed for 1 minute with a 160 degreeC hot air dryer. A fabric to which the amphoteric polymer and the anionic polymer were attached in this manner was designated as Example 1.

<Example 2>
5% by weight of an amphoteric polymer aqueous solution having a concentration prepared in Example 1 of 30% by mass and a hydrogen ion concentration (pH) of 8.6, the concentration prepared in Example 1 being 30% by mass, and 5% by mass of an aqueous solution of anionic polymer having a hydrogen ion concentration (pH) of 6.5, 1% by mass of an aqueous solution of a crosslinking agent having a concentration of 1% by mass prepared in Example 1, and the remainder of water were mixed. A deodorizing agent comprising a total of 100% by mass of the mixture was prepared. The concentration of the amphoteric polymer in the deodorizing agent is 1.0% by mass, the concentration of the anionic polymer in the deodorizing agent is 1.5% by mass, and the crosslinking agent in the deodorizing agent The concentration of the aqueous solution was 0.2% by mass. Next, this deodorizing agent was padded on a fabric of regular polyester knit (weight per unit: 240 g / m ² , manufactured by Color Dye) and immediately squeezed with a mangle (dehydrated and dried) to obtain a pickup rate of 100% by mass. The fabric was dried with a hot air dryer at 110 ° C. (hot air drying). Furthermore, this fabric was heat-treated for 1 minute with a 160 ° C. hot air dryer. A fabric to which the amphoteric polymer and the anionic polymer were attached in this manner was designated as Example 2.

<Example 3>
The amphoteric polymer and the anion were the same as in Example 2 except that a fabric of 90% cationic dyeable polyester (CDP) and 10% polyurethane spandex (PU) (weight per unit area: 110 g / m ² ) was used as the fabric. A fabric to which a conductive polymer and a crosslinking agent were attached was prepared. This fabric was referred to as Example 3.

<Example 4>
The amphoteric polymer and the anionic polymer were adhered in the same manner as in Example 2 except that a 50% polyester and 50% cotton knit (mesh weight: 200 g / m ² , manufactured by Color Dye) was used as the fabric. A finished fabric was produced. This fabric was referred to as Example 4.

<Example 5>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that Carbodilite SV-2 (registered trademark, manufactured by Nittobo Chemical Co., Ltd.) was used as a crosslinking agent. This fabric was referred to as Example 5.

<Example 6>
A fabric to which an amphoteric polymer and an anionic polymer were attached was produced in the same manner as in Example 2 except that Denacol EX-313 (manufactured by Nagase Chemitex, registered trademark) was used as a crosslinking agent. This fabric was designated as Example 6.

<Example 7>
A fabric to which an amphoteric polymer and an anionic polymer were attached was prepared in the same manner as in Example 2 except that BAYPRET USV (manufactured by Tanatex Chemicals Japan) was used as a crosslinking agent. This fabric was designated as Example 7.

<Example 8>
50% by weight aqueous solution of maleic acid / diallyldimethylammonium chloride / sulfur dioxide copolymer (resin content 30%), 25% -sodium hydroxide aqueous solution (base) 6% by weight, 2,2′-diiminoethanolamine (Base) 6% by mass and the remaining water were mixed to prepare an aqueous solution of an amphoteric polymer having a concentration of 50% by mass and a hydrogen ion concentration (pH) of 8.0. 10% by mass of this amphoteric polymer aqueous solution, 5% by mass of an aqueous anionic polymer solution having a concentration of 30% by mass and a hydrogen ion concentration (pH) of 6.8 prepared in Example 1, 1% by mass of an aqueous solution of a crosslinking agent having a concentration of 1% by mass prepared in 1 and the remaining water were mixed to prepare a deodorizing agent having a total of 100% by mass. The concentration of the amphoteric polymer in the deodorizing agent is 0.75% by mass, the concentration of the anionic polymer in the deodorizing agent is 1.5% by mass, and the crosslinking agent in the deodorizing agent The concentration of the aqueous solution was 0.2% by mass. Except for the above, a fabric to which an amphoteric polymer and an anionic polymer were attached was produced in the same manner as in Example 2. This fabric was referred to as Example 8.

<Example 9>
30% by mass of an aqueous solution of diallylamine hydrochloride / maleic acid copolymer (resin content 40%), 25% -sodium hydroxide aqueous solution (base) 10% by mass, triethanolamine (base) 8% by mass, ammonium sulfate ( Salt) 2% by mass and the remainder of the water were mixed to prepare an aqueous solution of an amphoteric polymer having a concentration of 30% by mass and a hydrogen ion concentration (pH) of 8.6. 7% by mass of this amphoteric polymer aqueous solution, 5% by mass of an aqueous anionic polymer solution having a concentration of 30% by mass and a hydrogen ion concentration (pH) of 6.8 prepared in Example 1, 1% by mass of an aqueous solution of a crosslinking agent having a concentration of 1% by mass prepared in 1 and the remaining water were mixed to prepare a deodorizing agent having a total of 100% by mass. The concentration of the amphoteric polymer in the deodorizing agent is 0.84% by mass, the concentration of the anionic polymer in the deodorizing agent is 1.5% by mass, and the crosslinking agent in the deodorizing agent The concentration of the aqueous solution was 0.2% by mass. Except for the above, a fabric to which an amphoteric polymer and an anionic polymer were attached was produced in the same manner as in Example 2. This fabric was designated as Example 9.

<Example 10>
Acrylate / acrylamide / diallylamine hydrochloride polymer aqueous solution (resin content 20%) 50% by mass, 25% -sodium hydroxide aqueous solution (base) 5% by mass, 2,2′-diiminoethanolamine (base) ) 5% by mass and the remaining water were mixed to prepare an aqueous solution of an amphoteric polymer having a concentration of 50% by mass and a hydrogen ion concentration (pH) of 7.6. 10% by mass of the aqueous solution of the amphoteric polymer, 5% by mass of the aqueous solution of the anionic polymer having the concentration prepared in Example 1 of 30% by mass and the hydrogen ion concentration (pH) of 6.8, 1% by mass of an aqueous solution of a crosslinking agent having a concentration of 1% by mass prepared in 1 and the remaining water were mixed to prepare a deodorizing agent having a total of 100% by mass. The concentration of the amphoteric polymer in the deodorizing agent is 1.0% by mass, the concentration of the anionic polymer in the deodorizing agent is 1.5% by mass, and the crosslinking agent in the deodorizing agent The concentration of the aqueous solution was 0.2% by mass. Except for the above, a fabric to which an amphoteric polymer and an anionic polymer were attached was produced in the same manner as in Example 2. This fabric was referred to as Example 10.

<Example 11>
66% by mass of water, 30% by mass of ammonia hydrolyzate of maleic anhydride / isobutylene copolymer (average molecular weight: 60,000), 2% by mass of ammonium acetate (salt), 2% by mass of ammonium sulfate (salt) Was added to prepare an aqueous solution of an anionic polymer having a concentration of 30% by mass and a hydrogen ion concentration (pH) of 8.5. 5% by weight of an aqueous solution of this anionic polymer, 5% by weight of an aqueous solution of an amphoteric polymer having a concentration prepared in Example 1 of 30% by weight and a hydrogen ion concentration (pH) of 8.6, 1% by mass of an aqueous solution of a crosslinking agent having a concentration of 1% by mass prepared in 1 and the remaining water were mixed to prepare a deodorizing agent having a total of 100% by mass. The concentration of the amphoteric polymer in the deodorizing agent is 1.0% by mass, the concentration of the anionic polymer in the deodorizing agent is 1.5% by mass, and the crosslinking agent in the deodorizing agent The concentration of the aqueous solution was 0.2% by mass. Except for the above, a fabric to which an amphoteric polymer and an anionic polymer were attached was produced in the same manner as in Example 2. This fabric was determined as Example 11.

<Comparative Example 1>
A fabric to which an amphoteric polymer and an anionic polymer were attached was produced in the same manner as in Example 2 except that the crosslinking agent was not used. This fabric was referred to as Comparative Example 1.

<Comparative Example 2>
A fabric to which an amphoteric polymer and an anionic polymer were attached was prepared in the same manner as in Example 2 except that no heat treatment was performed on the fabric subjected to coating and drying of the deodorizing agent. . This fabric was designated as Comparative Example 2.

<Comparative Example 3>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that an aqueous solution of polyacrylic acid was used as the anionic polymer. This fabric was designated as Comparative Example 3.

<Comparative test 1 and evaluation>
A deodorizing performance test was performed on the fabrics of Examples 1 to 11 and Comparative Examples 1 to 3. Specifically, first, a test piece having a length × width of 5 cm × 4 cm is placed in a 0.9 liter sample bottle from a fabric, exposed to a gas containing 120 ppm of ammonia and 100 ppm of acetic acid, and gas is detected using a gas detector tube. The deodorization rate was measured from the amount of decrease. Here, the exposure means holding in a gas at 55 ° C. for 15 minutes and holding in a gas at 20 ° C. for 2 hours in a dark place. The deodorizing performance test was conducted at the initial stage of processing (immediately after processing the deodorizing agent on the fabric), immediately after 10 consecutive home washings, and immediately after 30 consecutive home washings. However, 30 consecutive home washings were performed only on the fabrics of Examples 2-4.

  Ten consecutive home washings were performed as follows. Put 40 ml of laundry detergent (JAFET standard detergent) into a household washing machine, combine the fabric and load cloth (100% polyester knit), wash 1 kg with 30 liters of water, and then dehydrate by first washing for 50 minutes. Then, 20 minutes of rinsing was performed for dehydration, then 20 minutes of running water rinsing was performed for dehydration, and the fabric was further dried.

  30 consecutive home washings were performed as follows. Put 40 ml of laundry detergent (JAFET standard detergent) into a household washing machine, combine the fabric and load cloth (100% polyester knit), wash with 30 liters of water, first wash for 5 minutes and dehydrate. Subsequently, rinsing for 2 minutes was performed for dehydration, followed by rinsing with running water for 2 minutes for dehydration, and the above washing, dehydration, rinsing, dehydration, running water rinsing and dehydration operations were repeated 30 times. These results are shown in Table 2.

In Table 1, each type of fabric, amphoteric polymer, anionic polymer, cross-linking agent, and acid, base, or salt is shown.
Moreover, each symbol in Table 1 is the following material.
F1: Fabric with 90% cationic dyeable polyester (CDP) and 10% polyurethane spandex (PU) (weight per unit: 110 g / m ² )
F2: 50% polyester and 50% cotton knit (weight per unit: 200 g / m ² , manufactured by Color & Color Co., Ltd.)
A1: Diallylamine hydrochloride / maleic acid copolymer A2: Maleic acid / diallyldimethylammonium chloride / sulfur dioxide copolymer A3: Acrylate / acrylamide / diallylamine hydrochloride polymer B1: Maleic anhydride / isobutylene copolymer C1 : Epocros WS-700 having an oxazoline group (manufactured by Nippon Shokubai Co., Ltd., registered trademark)
C2: Carbodilite SV-2 (manufactured by Nittobo Chemical Co., Ltd., registered trademark)
C3: Denacol EX-313 (manufactured by Nagase Chemitex, registered trademark)
C4: BAYPRAT USV (manufactured by Tanatex Chemicals Japan)
D1: 25% -aqueous sodium hydroxide solution (base)
D2: 2,2′-diiminoethanolamine (base)
D3: Polyphenol hydrolyzate (acid)
D4: Triethanolamine (base)
D5: Ammonium sulfate (salt)
D6: Ammonium acetate (salt)

  As is clear from Table 2, the deodorization rate of ammonia after 10 consecutive home washings in Comparative Examples 1 to 3 was as low as 3 to 40%, whereas in Examples 1 to 11, 10 consecutive times. The deodorization rate of ammonia after home washing was maintained as high as 70 to 93%. In Comparative Examples 1 to 3, the deodorization rate of acetic acid after 10 consecutive home washings was reduced to 2 to 60%, whereas in Examples 1 to 11, acetic acid after 10 consecutive home washings was reduced. The deodorization rate was maintained as high as 78 to 97%. Furthermore, in Examples 2 to 4, the deodorization rate of ammonia after 30 consecutive home washings was maintained as high as 88 to 90%, and the deodorization rate of acetic acid after 30 consecutive home washings was 90 to 92%. And kept high. As a result, it was found that when the deodorizing agent of the present invention was processed into a fabric, washing durability and deodorizing performance could be imparted to the fabric.

<Example 12>
In the same manner as in Example 1, except that the concentration of the amphoteric polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.1% by mass. A fabric to which a polymer and an anionic polymer were attached was prepared. This fabric was designated as Example 12.

<Example 13>
In the same manner as in Example 1, except that the concentration of the amphoteric polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 5.0% by mass. A fabric to which a polymer and an anionic polymer were attached was prepared. This fabric was designated as Example 13.

<Example 14>
In the same manner as in Example 1, except that the concentration of the amphoteric polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 10% by mass. And the fabric to which the anionic polymer was adhered was produced. This fabric was referred to as Example 14.

<Example 15>
Except that the concentration of the anionic polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.1% by mass, A fabric having an amphoteric polymer and an anionic polymer attached thereto was prepared. This fabric was determined as Example 15.

<Example 16>
Except that the concentration of the anionic polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.5% by mass, A fabric having an amphoteric polymer and an anionic polymer attached thereto was prepared. This fabric was referred to as Example 17.

<Example 17>
Except that the concentration of the anionic polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 3.0% by mass, A fabric having an amphoteric polymer and an anionic polymer attached thereto was prepared. This fabric was referred to as Example 17.

<Example 18>
Except that the concentration of the anionic polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 5.0% by mass, A fabric having an amphoteric polymer and an anionic polymer attached thereto was prepared. This fabric was referred to as Example 18.

<Example 19>
In the same manner as in Example 1, except that the concentration of the crosslinking agent in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.02% by mass, Fabrics to which molecules and anionic polymers were attached were prepared. This fabric was referred to as Example 19.

<Example 20>
In the same manner as in Example 1, except that the concentration of the crosslinking agent in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.05% by mass, Fabrics to which molecules and anionic polymers were attached were prepared. This fabric was referred to as Example 20.

<Example 21>
In the same manner as in Example 1, except that the concentration of the crosslinking agent in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.5% by mass, Fabrics to which molecules and anionic polymers were attached were prepared. This fabric was referred to as Example 21.

<Example 22>
In the same manner as in Example 1, except that the concentration of the crosslinking agent in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 2.0% by mass, Fabrics to which molecules and anionic polymers were attached were prepared. This fabric was referred to as Example 22.

<Example 23>
A fabric with an amphoteric polymer and an anionic polymer adhered thereto was prepared in the same manner as in Example 1 except that the hydrogen ion concentration of the amphoteric polymer aqueous solution was adjusted to 4. This fabric was designated as Example 23.

<Example 24>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 1 except that the hydrogen ion concentration of the amphoteric polymer aqueous solution was adjusted to 9. This fabric was referred to as Example 24.

<Example 25>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 1 except that the hydrogen ion concentration of the aqueous solution of the anionic polymer was adjusted to 5. This fabric was referred to as Example 25.

<Example 26>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 1 except that the hydrogen ion concentration of the aqueous solution of the anionic polymer was adjusted to 9. This fabric was designated as Example 26.

<Comparative Example 4>
In the same manner as in Example 1, except that the concentration of the amphoteric polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.08% by mass. A fabric to which a polymer and an anionic polymer were attached was prepared. This fabric was designated as Comparative Example 4.

<Comparative Example 5>
In the same manner as in Example 1, except that the concentration of the amphoteric polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 12% by mass. And the fabric to which the anionic polymer was adhered was produced. This fabric was designated as Comparative Example 5.

<Comparative Example 6>
Except that the concentration of the anionic polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.08% by mass, A fabric having an amphoteric polymer and an anionic polymer attached thereto was prepared. This fabric was designated as Comparative Example 6.

<Comparative Example 7>
Except that the concentration of the anionic polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 7.0% by mass, A fabric having an amphoteric polymer and an anionic polymer attached thereto was prepared. This fabric was designated as Comparative Example 7.

<Comparative Example 8>
In the same manner as in Example 1, except that the concentration of the crosslinking agent in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 0.005% by mass, Fabrics to which molecules and anionic polymers were attached were prepared. This fabric was designated as Comparative Example 8.

<Comparative Example 9>
In the same manner as in Example 1, except that the concentration of the crosslinking agent in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution of the crosslinking agent was adjusted to 4.0% by mass. Fabrics to which molecules and anionic polymers were attached were prepared. This fabric was designated as Comparative Example 9.

<Comparative Example 10>
In the same manner as in Example 1, except that the hydrogen ion concentration (pH) of the aqueous solution of the amphoteric polymer was adjusted to 3.5 (value lower than the isoelectric point 4.3 of the aqueous solution of the amphoteric polymer), Fabrics to which molecules and anionic polymers were attached were prepared. This fabric was designated as Comparative Example 10.

<Comparative Example 11>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 1 except that the aqueous solution hydrogen ion concentration (pH) of the amphoteric polymer was adjusted to 9.5. This fabric was designated as Comparative Example 11.

<Comparative Example 12>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 1 except that the hydrogen ion concentration of the aqueous solution of the amphoteric polymer was adjusted to 8.6. This fabric was designated as Comparative Example 12.

<Comparative Example 13>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 1 except that the hydrogen ion concentration of the aqueous solution of the anionic polymer was adjusted to 9.5. This fabric was designated as Comparative Example 13.

<Comparative test 2 and evaluation>
The same deodorizing performance test as Comparative Test 1 was performed on the fabrics of Examples 12 to 26 and Comparative Examples 4 to 13. This deodorization performance test was performed at the initial stage of processing (immediately after processing the deodorizing agent on the fabric) and immediately after 10 consecutive home washings. The results are shown in Table 3. In Table 3, the deodorization rate of Example 1 is also described.

  As is apparent from Table 3, in Comparative Example 4 where the concentration of the amphoteric polymer is as low as 0.08% by mass, the deodorization rate of acetic acid at the initial stage of processing is as low as 30%, and ammonia after 10 consecutive home washings In Comparative Example 5 in which the concentration of the amphoteric polymer was as high as 12% by mass, the deodorization rate of acetic acid at the initial stage of processing was as high as 90%. In addition, the deodorization rate of ammonia and acetic acid after continuous 10 home washings is as high as 96% and 90%, and the concentration of the amphoteric polymer is 1.0% by mass, 0.1% by mass, and 5.0% by mass, respectively. In Examples 1 and 12 to 14 of 10% by mass and 10% by mass, the deodorization rate of acetic acid at the initial stage of processing is as high as 69 to 90%, and the deodorization rates of ammonia and acetic acid after 10 consecutive home washings are respectively It became high with 84 to 94% and 66 to 91%. From this, it was found that when the concentration of the amphoteric polymer was 0.1% by mass or more, the deodorization rates of ammonia and acetic acid after 10 consecutive home washings were improved. In Comparative Example 5, although the deodorization rate of ammonia and acetic acid at the initial stage of processing and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings were improved, the concentration of the amphoteric polymer was 12% by mass. Therefore, there was a problem that the fabric was discolored, the texture was hardened, the flexibility was lacked, or the strength was lowered.

  Further, as is apparent from Table 3, in Comparative Example 6 where the concentration of the anionic polymer is as low as 0.08% by mass, the deodorization rate of ammonia at the initial stage of processing is as low as 41% and 10 home washings are performed continuously. In Comparative Example 7, the deodorization rates of ammonia and acetic acid after that were 20% and 65%, respectively, and the anionic polymer concentration was as high as 7.0% by mass. While the odor rate was as low as 63%, the concentrations of the anionic polymer were 0.1% by mass, 0.5% by mass, 3.0% by mass, and 5.0% by mass, respectively. 18, the deodorization rate of ammonia at the initial stage of processing was as high as 82 to 99%, and the deodorization rates of ammonia and acetic acid after 10 consecutive home washings were as high as 72 to 98% and 73 to 85%, respectively. It was. From this, it is found that the deodorization rate of ammonia and acetic acid after 10 consecutive home washings is improved when the concentration of the anionic polymer is in the appropriate range of 0.1 to 5.0% by mass. It was.

  Further, as apparent from Table 3, in Comparative Example 8 where the concentration of the crosslinking agent is as low as 0.005% by mass, the deodorization rates of ammonia and acetic acid after 10 consecutive home washings were 32% and 74%, respectively. In contrast to Comparative Example 9, where the concentration of the crosslinking agent was as high as 4.0% by mass, the deodorization rate of ammonia and acetic acid after 10 consecutive home washings was increased to 83% and 85%. In Examples 19 to 22 in which the concentration of the agent is 0.02% by mass, 0.05% by mass, 0.5% by mass and 2.0% by mass, respectively, the consumption of ammonia and acetic acid after 10 consecutive home washings The odor rate increased to 60-97% and 82-92%, respectively. From this, it was found that when the concentration of the crosslinking agent is 0.2% by mass or more, the deodorization rates of ammonia and acetic acid after 10 consecutive home washings are improved. In Comparative Example 9, although the deodorizing rate of ammonia and acetic acid at the initial stage of processing and the deodorizing rate of ammonia and acetic acid after 10 consecutive home washings were improved, the concentration of the crosslinking agent was 4% by mass. Since it was high, the fabric was discolored, the texture was hardened, the flexibility was lacking, or the strength was reduced.

  Further, as apparent from Table 3, in Comparative Example 10 where the pH of the aqueous solution of the amphoteric polymer is as low as 3.5, the deodorization rate of acetic acid at the initial stage of processing is as low as 58% and after 10 consecutive home washings. In Comparative Example 11 where the deodorization rate of acetic acid was as low as 62% and the pH of the aqueous solution of the amphoteric polymer was as high as 9.5, the deodorization rate of acetic acid at the initial stage of processing was 70% low and the household was continuously 10 times. In Examples 23 and 24 in which the pH of the aqueous solution of the amphoteric polymer was 4 and 9, respectively, while the deodorization rates of ammonia and acetic acid after washing were 41% and 58%, respectively, acetic acid at the initial stage of processing Deodorization rate of 75% and 84% respectively, and ammonia deodorization rate after 10 consecutive home washings increased to 95% and 80%, respectively, and acetic acid after 10 consecutive home washings The deodorization rate was as high as 82% and 87%, respectively. From this, when the pH of the aqueous solution of the amphoteric polymer is limited within the range of 4 to 9, the deodorization rate of acetic acid at the initial stage of processing and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings are respectively It turns out that it improves.

  Furthermore, as is clear from Table 3, in Comparative Example 12 where the pH of the aqueous solution of the anionic polymer is as low as 4.5, the deodorization rate of acetic acid at the initial stage of processing is as low as 68%, and 10 home washings are performed continuously. In Comparative Example 13 where the deodorization rate of acetic acid afterwards is as low as 72% and the pH of the aqueous anionic polymer solution is as high as 9.5, the deodorization rate of ammonia after 68 consecutive home washings is 68%. In contrast, in Examples 25 and 26, in which the pH of the aqueous solution of the anionic polymer was 5 and 9, respectively, the deodorization rate of acetic acid at the initial stage of processing was increased to 78% and 88%, respectively. The ammonia deodorization rate after 96 home washings was as high as 96% and 81%, respectively, and the acetic acid deodorization rate after 10 consecutive home washings was as high as 80% and 88%, respectively. From this, when the pH of the aqueous solution of the anionic polymer is limited within the range of 5 to 9, the deodorization rate of acetic acid at the initial stage of processing and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings It turns out that each improves.

<Example 27>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the amphoteric polymer in the deodorizing agent was adjusted to 0.1% by mass. This fabric was designated as Example 27.

<Example 28>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the amphoteric polymer in the deodorizing agent was adjusted to 0.5% by mass. This fabric was designated as Example 28.

<Example 29>
A fabric to which the amphoteric polymer and the anionic polymer were attached was prepared in the same manner as in Example 2 except that the concentration of the amphoteric polymer in the deodorizing agent was adjusted to 5.0% by mass. This fabric was determined as Example 29.

<Example 30>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the amphoteric polymer in the deodorizing agent was adjusted to 10% by mass. This fabric was referred to as Example 30.

<Example 31>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the anionic polymer in the deodorizing agent was adjusted to 0.1% by mass. This fabric was determined as Example 31.

<Example 32>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the anionic polymer in the deodorizing agent was adjusted to 0.5% by mass. This fabric was determined as Example 32.

<Example 33>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the anionic polymer in the deodorizing agent was adjusted to 3.0% by mass. This fabric was determined as Example 33.

<Example 34>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the anionic polymer in the deodorizing agent was adjusted to 5.0% by mass. This fabric was determined as Example 34.

<Example 35>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the crosslinking agent in the deodorizing agent was adjusted to 0.02% by mass. This fabric was determined as Example 35.

<Example 36>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the crosslinking agent in the deodorizing agent was adjusted to 0.05% by mass. This fabric was designated as Example 36.

<Example 37>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the crosslinking agent in the deodorizing agent was adjusted to 0.5% by mass. This fabric was determined as Example 37.

<Example 38>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the crosslinking agent in the deodorizing agent was adjusted to 2.0% by mass. This fabric was designated as Example 38.

<Example 39>
A fabric to which the amphoteric polymer and the anionic polymer were attached was prepared in the same manner as in Example 2 except that the hydrogen ion concentration of the amphoteric polymer aqueous solution was adjusted to 4. This fabric was designated as Example 39.

<Example 40>
A fabric having an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the hydrogen ion concentration of the amphoteric polymer aqueous solution was adjusted to 9. This fabric was designated as Example 40.

<Example 41>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the hydrogen ion concentration of the aqueous solution of the anionic polymer was adjusted to 5. This fabric was determined as Example 41.

<Example 42>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the hydrogen ion concentration of the aqueous solution of the anionic polymer was adjusted to 9. This fabric was determined as Example 42.

<Comparative example 14>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the amphoteric polymer in the deodorizing agent was adjusted to 0.05% by mass. This fabric was designated as Comparative Example 14.

<Comparative Example 15>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the amphoteric polymer in the deodorizing agent was adjusted to 12% by mass. This fabric was designated as Comparative Example 15.

<Comparative Example 16>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the anionic polymer in the deodorizing agent was adjusted to 0.05% by mass. This fabric was designated as Comparative Example 16.

<Comparative Example 17>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the anionic polymer in the deodorizing agent was adjusted to 7.0% by mass. This fabric was designated as Comparative Example 17.

<Comparative Example 18>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the crosslinking agent in the deodorizing agent was adjusted to 0.005% by mass. This fabric was designated as Comparative Example 18.

<Comparative Example 19>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the concentration of the crosslinking agent in the deodorizing agent was adjusted to 4.0% by mass. This fabric was designated as Comparative Example 19.

<Comparative Example 20>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the hydrogen ion concentration (pH) of the aqueous solution of the amphoteric polymer was adjusted to 3.5. This fabric was designated as Comparative Example 20.

<Comparative Example 21>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the hydrogen ion concentration (pH) of the amphoteric polymer was adjusted to 9.5. This fabric was determined as Comparative Example 21.

<Comparative Example 22>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the hydrogen ion concentration (pH) of the aqueous solution of the anionic polymer was adjusted to 4.5. This fabric was designated as Comparative Example 22.

<Comparative Example 23>
A fabric with an amphoteric polymer and an anionic polymer attached thereto was prepared in the same manner as in Example 2 except that the hydrogen ion concentration (pH) of the aqueous solution of the anionic polymer was adjusted to 9.5. This fabric was designated as Comparative Example 23.

<Comparative test 3 and evaluation>
The same deodorizing performance test as Comparative Test 1 was performed on the fabrics of Examples 27 to 42 and Comparative Examples 14 to 23. This deodorization performance test was performed at the initial stage of processing (immediately after processing the deodorizing agent on the fabric) and immediately after 10 consecutive home washings. The results are shown in Table 4. In Comparative Example 20, agglomeration occurred during the preparation of the deodorizing agent, and the deodorizing agent could not be applied to the polyester fiber. Therefore, the deodorizing performance test could not be performed, and ammonia after home washing at the initial stage of processing. In addition, the deodorization rate of acetic acid and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings could not be measured. Table 4 also describes the deodorization rate of Example 2.

  As is clear from Table 4, in Comparative Example 14 where the concentration of the amphoteric polymer is as low as 0.05% by mass, the deodorization rate of acetic acid at the initial stage of processing is as low as 32%, and ammonia after 10 consecutive home washings In Comparative Example 15 in which the concentration of the amphoteric polymer was as high as 12% by mass, the deodorization rate of acetic acid at the initial stage of processing was as high as 90%. In addition, the deodorization rates of ammonia and acetic acid after 10 consecutive home washings were as high as 96% and 91%, respectively, and the concentrations of amphoteric polymers were 0.1%, 0.5%, and 5.0%, respectively. In Examples 27 to 30 which are 10% by mass and 10% by mass, the deodorization rate of acetic acid at the initial stage of processing is as high as 70 to 92%, respectively, and the deodorization rates of ammonia and acetic acid after 10 consecutive home washings are respectively It became high with 81-98% and 70-93%. From this, when the concentration of the amphoteric polymer is 0.1% by mass or more, the deodorization rate of acetic acid at the initial stage of processing and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings are improved. I understood. In Comparative Example 15, although the deodorization rate of ammonia and acetic acid at the initial stage of processing and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings were improved, the concentration of the amphoteric polymer was 12% by mass. Therefore, there was a problem that the fabric was discolored, the texture was hardened, the flexibility was lacked, or the strength was lowered.

  Further, as is apparent from Table 4, in Comparative Example 16, where the concentration of the anionic polymer is as low as 0.05% by mass, the deodorization rate of acetic acid at the initial stage of processing is as low as 68%, and 10 home washings are performed continuously. In Comparative Example 17, the deodorization rate of ammonia afterwards was as low as 30%, and the concentration of the anionic polymer was as high as 7.0% by mass. The deodorization rate of acetic acid after a single home wash was as low as 60%, whereas the concentrations of anionic polymer were 0.1%, 0.5%, 3.0% and 5. In Examples 31 to 34, which are 0% by mass, the ammonia and deodorization rates of acetic acid at the initial stage of processing were as high as 88 to 99% and 68 to 88%, respectively. The odor rate increased to 81-99% and 72-83%, respectively. From this, when the concentration of the anionic polymer is within a suitable range of 0.2 to 5.0% by mass, the deodorization rate of ammonia and acetic acid at the initial stage of processing, and ammonia after 10 consecutive home washings and It was found that the deodorization rate of acetic acid was improved.

  Further, as is clear from Table 4, in Comparative Example 18, where the concentration of the crosslinking agent is as low as 0.005% by mass, the deodorization rate of ammonia after 10 consecutive home washings was as low as 30%. In Comparative Example 19 where the concentration of the crosslinking agent is as high as 4.0% by mass, the deodorizing rate of ammonia after 10 consecutive home washings is as high as 92%, and the concentration of the crosslinking agent is 0.02% by mass, In Examples 35-38 which are 0.05 mass%, 0.5 mass%, and 2.0 mass%, the deodorization rate of ammonia after 10 consecutive home washings was as high as 55-92%, respectively. From this, it was found that when the concentration of the crosslinking agent is 0.2% by mass or more, the deodorization rate of ammonia after 10 consecutive home washings is improved. In Comparative Example 19, although the deodorization rate of ammonia and acetic acid at the initial stage of processing and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings were improved, the concentration of the crosslinking agent was 4% by mass. Since it was high, the fabric was discolored, the texture was hardened, the flexibility was lacking, or the strength was reduced.

  Further, as is clear from Table 4, in Comparative Example 20 where the pH of the aqueous solution of the amphoteric polymer is as low as 3.5, aggregation occurs during the preparation of the deodorizing agent, and the deodorizing agent is applied to the polyester fiber. In Comparative Example 21, the deodorizing performance test could not be performed because the pH of the aqueous solution of the amphoteric polymer was as high as 9.5, and the deodorizing rate of acetic acid at the initial stage of processing was as low as 0% and 10 times in succession. In Examples 39 and 40 in which the pH of the aqueous solution of the amphoteric polymer was 4 and 9, respectively, while the deodorization rates of ammonia and acetic acid after home washing were as low as 70% and 0%, ammonia at the initial stage of processing Deodorization rate of 99% and 85%, respectively, acetic acid deodorization rate at the initial stage of processing increased to 79% and 85%, respectively, and ammonia deodorization rate after 10 consecutive home washings was 95 respectively. % And 82%, 10 times deodorization rate of acetic acid after the household washing was as high as 81%, respectively and 88%. From this, when the pH of the aqueous solution of the amphoteric polymer is limited to the range of 4 to 9, the deodorization rate of ammonia and acetic acid at the initial stage of processing, and the deodorization rate of ammonia and acetic acid after 10 consecutive home washings It was found that each improved.

  Furthermore, as is clear from Table 4, in Comparative Example 22 where the pH of the aqueous solution of the anionic polymer is as low as 4.5, the deodorization rate of acetic acid at the initial stage of processing is as low as 66%, and 10 home washings are performed continuously. In Comparative Example 23, the subsequent deodorization rate of acetic acid was as low as 72%, and the pH of the aqueous anionic polymer solution was as high as 9.5, and the deodorization rate of ammonia after 10 consecutive home washings was 58%. In Examples 41 and 42 in which the pH of the anionic polymer was 5.0 and 9.0, respectively, whereas the deodorization rate of acetic acid at the initial stage of processing was increased to 81% and 89%, respectively, The deodorization rate of ammonia after 10 consecutive home washings was as high as 96% and 81%, respectively, and the deodorization rate of acetic acid after 10 consecutive home washings was as high as 82% and 90%, respectively. Therefore, when the pH of the aqueous solution of the anionic polymer is adjusted within the range of 5.0 to 9.0, the deodorization rate of acetic acid at the initial stage of processing and the elimination of ammonia and acetic acid after 10 consecutive home washings. It was found that the odor rate was improved.

Claims (13)

A deodorizing agent for attaching a polymer compound to a cloth or yarn containing polyester fiber,
The polymer compound comprises an amphoteric polymer and an anionic polymer;
Prepare an aqueous solution of the amphoteric polymer whose hydrogen ion concentration is adjusted to an aqueous solution higher than the isoelectric point by an acid, base or salt,
Preparing an aqueous solution of the anionic polymer having a hydrogen ion concentration adjusted within a range of 5 to 9 with an acid, base or salt;
Prepare an aqueous solution or emulsion of a crosslinking agent having a reactive group that undergoes a crosslinking reaction with the amphoteric polymer and the anionic polymer,
The concentration of the aqueous solution of the amphoteric polymer in the total amount of the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution or emulsion of the crosslinking agent is adjusted to 0.1 to 10% by mass, and the anion The concentration of the aqueous solution of the functional polymer is adjusted to 0.1 to 5.0% by mass, the concentration of the aqueous solution or emulsion of the crosslinking agent is adjusted to 0.02 to 2.0% by mass,
By applying the aqueous solution of the amphoteric polymer, the aqueous solution of the anionic polymer, and the aqueous solution or emulsion of the cross-linking agent to the cloth or the yarn, respectively, and drying the fabric or the yarn, In order to attach the polymer compound to the fabric or the yarn, an aqueous solution of the amphoteric polymer, an aqueous solution of the anionic polymer, and an aqueous solution or emulsion of the crosslinking agent are used. . A deodorizing agent for attaching a polymer compound to a cloth or yarn containing polyester fiber,
The polymer compound comprises an amphoteric polymer and an anionic polymer;
An aqueous solution of the amphoteric polymer whose hydrogen ion concentration is adjusted to an aqueous solution higher than the isoelectric point by an acid, base or salt, and the anion whose hydrogen ion concentration is adjusted within a range of 5 to 9 by an acid, base or salt A mixture is prepared by mixing an aqueous solution of a functional polymer, an aqueous solution or emulsion of a crosslinking agent having a reactive group capable of crosslinking with the amphoteric polymer and the anionic polymer, and water,
The concentration of the amphoteric polymer in the mixture is 0.1 to 10% by mass, the concentration of the anionic polymer in the mixture is 0.1 to 5.0% by mass, and the concentration in the mixture is The concentration of the crosslinking agent is 0.02 to 2.0% by mass.   The aqueous solution of the amphoteric polymer includes diallylamine hydrochloride / maleic acid copolymer, maleic acid / diallyldimethylammonium chloride / sulfur dioxide copolymer, allylamine hydrochloride / acrylic acid copolymer, and allylamine hydrochloride / methacrylic acid copolymer. One or two or more aqueous solutions selected from the group consisting of polymers, the average molecular weight of the amphoteric polymer is 1,000 to 200,000, and the isoelectric point of the aqueous solution of the amphoteric polymer is pH 4 The deodorant processing agent according to claim 1 or 2, wherein the deodorizing agent is in a range of -9.   The aqueous solution of the anionic polymer is a copolymer composed of one or both of maleic acid and maleic anhydride and isobutylene, and the average molecular weight of the anionic polymer is 1,000 to 400,000. The deodorizing agent according to claim 1 or 2.   The aqueous solution or emulsion of the crosslinking agent has any one of an oxazoline group, a carbodiimide group, a sulfite blocked isocyanate group, an oxime blocked isocyanate group, and an epoxy group as two or more reactive groups in the molecule. Deodorant processing agent of description.   The acid is a water-soluble inorganic acid of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or sulfamic acid or a mixture thereof, or formic acid, acetic acid, propionic acid, citric acid, lactic acid, tartaric acid, maleic acid, fumaric acid, phthalic acid, 3. The deodorizing agent according to claim 1 or 2, which is a water-soluble organic acid of salicylic acid, or a hydrolyzate of flavonoids having a phenolic hydroxyl group, catechol, pyrogallol, catechins, gallic acid, or polyphenols.   The base is alkali metal hydroxide, alkali metal carbonate, alkaline earth metal hydroxide, ammonia, alkylamine, dialkylamine, trialkylamine, hydroxyalkylamine, dihydroxyalkylamine, trihydroxyalkylamine. And a water-soluble base consisting of one or more selected from the group consisting of alkyldiamines.   The deodorizing agent according to claim 1 or 2, wherein the salt is one or more water-soluble salts selected from the group consisting of sodium hydrogen carbonate, sodium acetate, ammonium sulfate and ammonium acetate.   The deodorizing agent according to claim 2, wherein a blending ratio of the amphoteric polymer and the anionic polymer is set within a range of (1: 4) to (4: 1) in terms of a mass ratio of a resin component.   The deodorant according to claim 1 or 2, wherein the total amount of the resin components of the amphoteric polymer and the anionic polymer is adhered to 0.5 to 5.0% by mass with respect to 100% by mass of the fabric or the yarn. Processing agent. An aqueous solution of an amphoteric polymer, an aqueous solution of an anionic polymer, and an aqueous solution or emulsion of a crosslinking agent according to claim 1, wherein the coating solution is one kind selected from the group consisting of an immersion method, an adsorption method, a spray method, and a coating method. A coating method or a coating method in which two or more types are combined, and each of the amphoteric polymer, the anionic polymer and the cross-linking agent is applied to a fabric or yarn containing polyester fibers in an arbitrary order and dried. Attaching to the fabric or the yarn;
And a step of heat-treating the cloth or yarn to which the amphoteric polymer, the anionic polymer and the cross-linking agent are attached. The deodorizing agent according to claim 2 is a polyester fiber produced by a coating method selected from the group consisting of an immersion method, an adsorption method, a spray method, and a coating method, or a combination of two or more types. Applying to a fabric or thread comprising
Drying the fabric or yarn coated with the deodorizing agent;
A method of processing a deodorizing agent into a fabric or yarn, comprising the step of heat-treating the dried fabric or yarn.   The heat treatment of the fabric or the yarn is a treatment of holding the fabric or the yarn at a temperature of 120 to 200 ° C for 30 minutes to 30 seconds, to the fabric or yarn of the deodorizing agent according to claim 11 or 12. Processing method.