JP2000080569A - Deodorant fiber - Google Patents

Abstract

(57) [Summary] [Problem] To provide a deodorant fiber which does not deteriorate the color of the fiber and is excellent in immediateness and sustainability of a deodorant effect. SOLUTION: The deodorant fiber comprising a deodorant base containing the following components (A) and (B) continuously or discontinuously on the fiber surface, and a method for producing the same. Component (A): High molecular substance having an amino group Component (B): High molecular substance having an acid group and / or a group in which the acid group has become a salt

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a deodorant fiber.

[0002]

2. Description of the Related Art In recent years,
Along with changes in the living environment, awareness of odors has increased, and it has been desired to quickly and continuously deodorize odors caused by body fluids generated from the body and odors generated in the living environment. Deodorization methods are roughly classified into physical deodorization, chemical deodorization, sensory deodorization (masking), and the like. Activated carbon, which is extremely excellent as a physical deodorant, is difficult to atomize. And there are problems such as difficulty in fixing on the fiber and deteriorating the color of the fiber. In the case of physical deodorization, performance such as washing is significantly reduced. In addition, the deodorant utilizing a catalytic action has a low immediate effect, and its use is limited in deodorizing by a fragrance or the like because the substance itself becomes a bad smell due to the taste of a person or causes olfactory fatigue. Become something. Among them, a method using a chemical neutralization reaction is one that can overcome the above problems while being excellent in immediate effect and sustainability.

However, in the conventional deodorizing method using a chemical neutralization reaction, the deodorizing method of one of the components is neglected in order to exhibit an adsorption performance for either an acidic substance or a basic substance as an odor component. I had to. Further, in the case of a compound having one neutralization reactive group, the acidity or basicity of the deodorant or the deodorant fiber using the compound becomes too high, so that the usable applications are further limited.
In addition, low molecular weight compounds having both an acidic group and a basic group have many disadvantages in the adsorption properties of the substances and the fiber fixing properties, so that it has been difficult to continuously exhibit the deodorizing performance.

[0004] An object of the present invention is to provide a deodorizing fiber which does not degrade the color of the fiber, has an immediate effect of deodorizing, and has excellent durability.

[0005]

According to the present invention, there is provided the following component (A):
And a deodorant fiber comprising a deodorant base containing the following component (B) continuously or discontinuously on the fiber surface, and a process for producing the same. Component (A): Polymer substance having an amino group Component (B): Polymer substance having an acid group and / or a group in which the acid group is a salt

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The deodorant base of the present invention exists continuously or discontinuously on the fiber surface, and may be, for example, a particle or a coating. In the case of particles, the average particle size is preferably from 0.01 to 100 µm, more preferably from 0.01 to 50 µm. The average particle size can be confirmed by an electron microscope. In the case of a coating, the coating may be continuous or may have discontinuous portions.

The component (A) of the deodorant base includes polygalactosamine, chitosan (polyglucosamine), chitin, polyethyleneimine, polyaniline and the like. From the viewpoint of stability as a polymer and low odor of the polymer itself, Particularly, chitosan is preferred. The weight average molecular weight of this component (A) is 5,
A range from 000 to 500,000 is preferred.

As the component (B) of the deodorant base, polycarboxylic acids such as polyacrylic acid, polymethacrylic acid, polycrotonic acid, polyitaconic acid and polymaleic acid are preferably used, having the lowest acidity and other acidic odors. Preference is given to polyacrylic acid or polymethacrylic acid, especially polymethacrylic acid, which is easily salt-exchanged with the substance. The component (B) is a component such as acrylamide, methylacrylamide, dimethylacrylamide, diethylacrylamide, or 3-acrylamide-N, N-dimethylpropylamine which interacts with an electron donating substance (eg, ketones) which is a malodorous component. It may be a copolymer of various amide monomers. Further, some or all of the acid groups of component (B) may be in the form of a salt,
Alkali metal salts such as lithium, sodium and potassium,
Alkaline earth metal salts such as calcium, organic amine salts such as methylamine, ethylamine, and butylamine; amino acid salts such as alanine and glycine; and the like. From the viewpoint of low cost and low odor, alkali metal salts such as sodium and potassium are included. preferable. Further, a part of the acid groups of the component (B) may be esterified. The weight average molecular weight of component (B) is 5,000
A range from 0 to 500,000 is preferred.

[0009] In the deodorant base, component (A) and component (B) may be a mixture or a complex.
The presence of the component (A) and the component (B) in a complex can be confirmed by observing the deodorant base section with an electron microscope (magnification 10,000).
Within the range of 1 μm square, component (A) and component (B)
Is confirmed by the presence of both high molecular substances.
When component (A) and component (B) do not satisfy this condition,
Component (A) and component (B) form a mixture. In the present invention, the components of the deodorant base in terms of immediateness and persistence of the deodorant effect
Preferably, (A) and component (B) are present in a composite on the fiber surface.

Regardless of whether component (A) and component (B) are present in a mixture or in a complex, the ratio by weight of component (A) / component (B) is 0.5 / 99.5. ~ 99.5 / 0.5
Is preferable, and 20/80 to 75/25 is more preferable. In this range, the excellent deodorizing effect desired by the present invention is achieved.

The deodorant fiber of the present invention is obtained, for example, by the following production method 1 or 2. Production method 1: Particles containing component (A) and component (B) (hereinafter, referred to as particles)
The fiber is brought into contact with the fibers or a dispersion of the particles in water and / or an organic solvent and the fibers are brought into contact with each other to form a particulate deodorant base (hereinafter referred to as deodorant particles) on the fiber surface. Method of forming.

In carrying out this method, a binder may be used, but may not be used. However, it is preferable to use a binder from the viewpoint of washing resistance. As a binder, silicone, acrylic, urethane,
Examples thereof include vinyl acetate. In this case, in addition to the binder, a softening agent, an antibacterial agent, a fluorescent dye, an antishrinking agent such as glyoxal, a fixing agent, and the like can be used according to the purpose.

As a method for bringing fibers into contact with deodorant particles or a dispersion of these particles in water and / or an organic solvent, a pad-dry method using a mangle, a dryer, a win
An immersion method using a cheese dyeing machine, a liquid jet dyeing machine or the like is generally used, but a spraying method, a coating method, a printing method, and a kneading method for rayon, acrylic fiber and the like are also possible. When a binder is used, its amount is preferably 0.01 to 20% by weight, more preferably 0.1 to 20% by weight, based on the weight of the deodorizing particles.
~ 15% by weight.

Contacting a fiber with a dispersion of deodorant particles in water and / or an organic solvent (hereinafter referred to as a deodorant particle dispersion);
In the case of adhering on the fiber surface, a method of immersing the fiber in the dispersion and then drying, or a method of spraying the dispersion with the fiber and then drying the fiber is exemplified.

When a deodorant particle dispersion is used, water and / or an organic solvent can be used as a dispersion medium, and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, heptanol and octanol can be used as the organic solvent. And polar solvents such as acetone, acetonitrile, tetrahydrofuran, dioxane and ethyl acetate, and non-polar solvents such as cyclohexane, hexane, heptane and octane. Such a solvent can be used by mixing with water in any ratio.

In the deodorized particle dispersion, the average particle size of the deodorized particles is preferably 0.01 to 100 μm, more preferably 0.01 to 100 μm.
To 50 μm, particularly preferably 0.1 to 10 μm. The average particle size can be measured with a laser diffraction type particle size distribution analyzer (LA-910).

The following method is exemplified as a method for preparing the deodorant particle dispersion and the deodorant particles. Component (A) in water or a mixture of water and an organic solvent (methanol, ethanol, etc.)
And a polymerizable monomer having an acid group and / or a group in which the acid group has become a salt (hereinafter, referred to as a raw material monomer of the component (B)), and a polymerization initiator is added thereto to carry out a polymerization reaction. And the obtained deodorant particle dispersion can be used as it is or after being neutralized with a base. Here, as the raw material monomer of the component (B), for example, at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and salts thereof is used. Further, esterification products of these acids may be copolymerized.

In carrying out this polymerization reaction, the emulsion or suspension polymerization can be carried out in the presence or absence of a surfactant, but is preferably carried out in the presence of a surfactant.
As the surfactant used in the present invention, anionic, nonionic, cationic and amphoteric ordinary surfactants can be used. For example, anionic surfactants such as dodecyl sulfate, dodecylbenzenesulfonate, and sulfate salts of polyoxyethylene nonylphenyl ether; cationic surfactants such as octadecyltrimethylammonium chloride; polyoxyethylene dodecyl ether, polyoxyethylene Nonionic surfactants such as cetyl ether, polyoxyethylene nonylphenyl ether, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, polyoxyethylene sorbitan monostearate, and polyoxyethylene are exemplified. The use amount thereof is preferably 0.5 to 5.0% by weight based on the raw material monomer.

The polymerization initiator used in the polymerization reaction is as follows:
Radical decomposition in the presence of heat or a reducing substance initiates the addition polymerization of monomers, and water-soluble or oil-soluble peroxodisulfates, peroxides, azobis compounds and the like are used. For example, potassium persulfate, ammonium persulfate,
Peroxides such as hydrogen peroxide and t-butyl hydroperoxide; and azo compounds such as 2,2'-azobis-2-amidinopropane salts and 4,4'-azobis-4-cyanopentanoic acid. . If necessary, it can be used as a redox initiator in combination with a reducing agent. These polymerization initiators can be used alone or in combination of two or more. The polymerization reaction is performed at a temperature in the range of 20 to 80 ° C. The polymerization is completed between 0.1 and 24 hours. The thus-obtained deodorant particle dispersion may be used as it is, or the dispersion and a hydrophobic organic solvent may be mixed to precipitate deodorant particles and used in the form of deodorant particles. Good.

Production method 2: A method in which the raw material monomers of component (A) and component (B) are mixed, and the monomer is polymerized on the fiber surface to form a film-like deodorizing base.

The fibers are immersed in an aqueous solution of the raw material monomers of the components (A) and (B) and squeezed with a mangle.
The polymerization reaction is carried out at 90 ° C, more preferably 70-80 ° C, for 5 hours. Thereafter, drying is performed to obtain deodorant fibers.

The fibers used in the present invention include natural fibers such as cotton and hemp, regenerated fibers such as rayon, cupra and tencel, semi-synthetic fibers such as acetate, diacetate and triacetate, polyester, nylon, acrylic and vinylon. And synthetic fibers such as polypropylene, polyurethane and the like. In addition, the form of the fiber of the present invention can be applied to various types such as staple fiber, thread, nonwoven fabric, knitted fabric, and woven fabric.

In the deodorant fiber of the present invention, the deodorant base is preferably present in the deodorant fiber at a ratio of 0.01 to 10.0% by weight.

[0024]

According to the present invention, it is possible to obtain a deodorant fiber excellent in the immediateness and persistence of the deodorant effect.

[0025]

EXAMPLES In the examples,% is% by weight.

Example 1 Water was added to 40 g of chitosan (SK-10 manufactured by Koyo Chemical Co., Ltd., degree of deacetylation: 85 to 88%, weight average molecular weight: 130,000).
The amount was adjusted to 900 g, and 120 g of methacrylic acid was added thereto and dissolved at 60 ° C. with stirring to prepare an aqueous solution of chitosan and methacrylic acid. To this, a solution prepared by dissolving 3 g of potassium persulfate in 100 g of ion-exchanged water was added, followed by stirring at 25 ° C. for 5 minutes. The sorbitan monolaurate is added to this chitosan solution.
A 1.0% cyclohexane solution was added at a ratio of 1/1 by weight and reacted at 70 ° C. for 5 hours. Then, 1 kg of isopropyl alcohol was added and the mixture was stirred and solid-liquid separated. Thereafter, the operation of adding 500 g of isopropyl alcohol and performing solid-liquid separation is performed in two steps.
This was repeated and dried under reduced pressure at 50 ° C. to obtain fine particle powder. Disperse 2.5 g of these fine particles in 500 mL of water, apply to cotton fiber,
After squeezing the applied solution to 20% with respect to the cotton fiber, it was dried to obtain a deodorant fiber.

Example 2 Water was added to 20 g of the same chitosan as in Example 1 to make 700 g.
Add 50 g of methacrylic acid and 30 g of acrylic acid to this, and add
And dissolved under stirring to prepare an aqueous solution of chitosan, methacrylic acid and acrylic acid. To this, a solution prepared by dissolving 3 g of potassium persulfate in 100 g of ion-exchanged water was added.
Stirred at C for 5 minutes. This chitosan solution is applied to cotton fiber, squeezed out so that the solid content of the applied solution is 20% of the cotton fiber, reacted at 75 ° C. for 5 hours, and washed by adding 300 g of ethyl alcohol. After drying, a deodorized fiber was obtained.

Example 3 The same chitosan (50 g) as in Example 1 was added to water to make 900 g,
To this, 100 g of methacrylic acid was added and dissolved with stirring at 60 ° C. to prepare an aqueous solution of chitosan and methacrylic acid. 70 g of lauryl methacrylate and 1 g of lauryl peroxide were added thereto, and the mixture was irradiated with ultrasonic waves for 5 minutes to prepare an emulsion. After reacting this at 75 ° C. for 2 hours, a solution prepared by dissolving 2 g of potassium persulfate in 20 g of ion-exchanged water was added.
The reaction was performed at 75 ° C. for 3 hours. Thereafter, a 1N aqueous solution of sodium hydroxide was dropped and neutralized so that 75% of the polymethacrylic acid was neutralized. This was applied to cotton fibers, squeezed so that the solid content of the applied solution was 10% based on the cotton fibers, and dried under reduced pressure at 90 ° C. for 5 hours to obtain deodorized fibers.

Examples 4 to 7 In the same manner as in Example 3, emulsions were prepared with the monomer compositions shown in Table 1, and immobilized on the fibers shown in Table 1, to obtain deodorized fibers.

Comparative Example 1 Chitosan powder was mechanically pulverized (crushed particle size: about 5 μm).
m), an aqueous solution was applied onto cotton fibers and dried as they were to obtain deodorized fibers.

Comparative Example 2 The procedure of Example 3 was repeated, except that 25 g of acetic acid was added to 75 g of chitosan and dissolved. The same operation as in Example 3 was applied to cotton fiber and dried. A deodorant fiber was obtained.

The deodorizing fibers obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to a deodorizing test by the following method. Table 1 shows the results.

<Deodorizing test method> Four 100 ppm gases of acetic acid, ammonia, acetaldehyde and methyl mercaptan were sealed in a 1 m ³ glass container, and 1 g of each sample described in Table 1 was placed therein, and a gas detection tube was used. After 30 minutes, the amount of gas was quantified, and the decrease from the initial stage was defined as the deodorization rate. If the deodorization rate is 100%, it means that all the gases in the system have been deodorized.

[0034]

[Table 1]

Note) * 1 Ratio of each component in deodorant base * 2 MAA: methacrylic acid AA: acrylic acid MAA-Na: sodium methacrylate AA-Na: sodium acrylate LMA: lauryl methacrylate SMA: methacrylic acid Stearyl * 3 Indicates the weight fraction of fiber component to deodorant base.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Tsuneo Yasumura 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term (reference) 4K090 AA03 AA08 BA46 BA47 BA48 CA06 CA07 CA35 DA09 DA21 DA23 4D012 CA09 CB01 CG01 CG04 4G066 AA13D AA47D AB07A AC01A AC01B AC17B AD10B AD15B BA16 CA02 CA25 CA29 CA52 CA56 DA03 FA07 4L033 AB01 AC10 AC15 BA19 CA02 CA18 DA02

Claims (5)

[Claims] 1. A deodorant fiber comprising a deodorant base containing the following components (A) and (B), which is continuously or discontinuously present on the fiber surface. Component (A): Polymer substance having an amino group Component (B): Polymer substance having an acid group and / or a group in which the acid group is a salt 2. The deodorant fiber according to claim 1, wherein the component (A) and the component (B) are present in a complex. 3. The deodorant fiber according to claim 1, wherein the component (A) is chitosan, and the component (B) is polyacrylic acid, polymethacrylic acid and / or a salt thereof. 4. A component (A) comprising contacting a fiber with particles containing components (A) and (B), or contacting a fiber with water and / or an organic solvent dispersion of the particles. Ingredient (B)
The method for producing a deodorant fiber according to claim 1, wherein a particulate deodorant base containing is present on the fiber surface. 5. A mixture of component (A) and a polymerizable monomer having an acid group and / or a group in which the acid group has become a salt, and polymerizing the monomer on the fiber surface. 2. A film-like deodorizing base containing the component (A) and the component (B) is present on the fiber surface.
The method for producing the described deodorant fiber.