JPH10110384A - Deodorizing nonwoven fabric and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonwoven fabric excellent in durability and comprising acrylic synthetic fiber having high deodorizing performance against various offensive odors emitted in daily life, and to provide a method for producing the nonwoven fabric. SOLUTION: This nonwoven fabric comprises acrylic synthetic fiber composed of a copolymer A with acrylonitrile as the main constituent unit and 1-40wt.% of a polymer B miscible with the copolymer A but incompatible therewith. In this case, the polymer B is in a phase-separated state, containing 0.5-20wt.% fine powder with a metal silicate or metal aluminosilicate 0.5-10μm in average particle size as active ingredient and also bearing 0.1-20wt.% of an amino compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in durability and is good against various malodors such as ammonia, amines, hydrogen sulfide, mercaptans, acetic acid and aldehydes, which are typical malodors generated in daily life. The present invention relates to a nonwoven fabric containing acrylic synthetic fibers having excellent deodorizing performance and a method for producing the same.

[0002]

2. Description of the Related Art Nonwoven fabrics are mainly used in the fields of clothing, interiors, and industrial materials. In the field of clothing, clothing interlining, middle cotton, and the like are used for front bodies, facings, collars, shoulders, and the like. , Foundations, disposable underwear and underwear, etc. In the interior field, carpets, undercarpets, curtains, blinds, etc. used indoors and vehicles, and in the industrial materials field, filters, shoes and cases used for air cleaning etc. It is used as a material, interior materials used for walls in buildings, insulation materials, building materials and other furniture furnishings, as well as surface materials, vehicle interior materials and insulation materials. With regard to imparting deodorant properties to these nonwoven fabrics, in recent years, interest in comfort in a living environment has been increasing, and proposals have been made regarding removal of offensive odors in various environments such as indoors and vehicles. In imparting the deodorizing performance to these nonwoven fabrics, a method of mixing fibers having the deodorizing performance in the process of producing the nonwoven fabric, processing of a deodorant chemical into a nonwoven fabric, and the like can be mentioned.

[0003] As a method for imparting a function of eliminating an odor which has been regarded as a problem as an offensive odor to a fiber product, a method of grafting a vinyl monomer having an acidic group onto a fiber (Japanese Patent Publication No. 3-77308, Japanese Patent Publication No. 2-58392, JP-A-62-142562, etc.), copper compounds (JP-A-61-231202, JP-A-62-69)
No. 78) and various deodorants (JP-A-61-25807).
No. 6, JP-A-56-100060) on the fiber surface. In addition, as a method of introducing a vinyl monomer having a deodorant function to the fiber,
There is a method in which a vinyl monomer having an acidic group is copolymerized and the polymer is made into a fiber.

[0004] However, among these methods, the grafting involves a change in the texture of the fiber, an inability to obtain a uniform reaction efficiency and a poor deodorizing effect, and a graft reaction similar to the dyeing process. Must be performed, and the number of steps increases, and at that time, there arises a problem such as contamination of a processing machine and wastewater by a processing liquid. In addition, if it is a vinyl monomer having an acidic group, it is often effective only for basic malodor, and it is hard to say that it has sufficient deodorizing performance.

[0005] In the post-processing of adhering the fine powder having a deodorizing effect to the fiber surface and the post-processing of dipping, applying and spraying a solution having a deodorizing effect on the fiber product, the unique texture of the fiber and the texture of the product are obtained. There are drawbacks such as a drop, and a drop in the agent due to washing with water, washing at home or dry cleaning, and insufficient washing durability.

As a method of introducing a vinyl monomer having a deodorizing function into fibers, there is a method of copolymerizing a vinyl monomer having an acidic group at the time of polymerization to produce a fiber of the polymer. Since there are more vinyl monomers having an acidic group having an odor effect inside the fiber than on the fiber surface, the rate of direct contact with malodor is small compared to the introduction rate of the vinyl monomer having an acidic group, and the deodorizing effect is poor. There are drawbacks such as sufficientness, deterioration of fiber properties, and deterioration of hand. Furthermore, because it is a vinyl monomer having an acidic group,
The effect is the same as that at the time of the grafting described above, and it is difficult to say that the deodorizing performance is sufficient.

[0007] In recent years, bad smells caused by smoking in indoor environments have been regarded as a problem due to an increase in non-smokers and smokers, and an increase in smoking rights. In most cases, the odor component in these living environments is not a single component but a mixture of a plurality of compounds including an acidic component, a basic component, and a neutral component. The odor caused by smoking is a mixture of thousands to tens of thousands of compounds.The main components of the odor can be divided into basic components such as ammonia and nicotine, acidic components such as acetic acid and aldehyde, and neutral components. It is said. Above all, deodorization of a part of basic odor and acidic odor is performed by the above-mentioned method and the like, but is not sufficient. Almost no aldehydes have sufficient deodorizing performance and durability. Regarding the aldehyde deodorizing method, activated carbon is adjusted to pH 7 or more (JP-A-54-74268), spinel type Activated carbon compositions containing the above-mentioned metal oxides (Japanese Patent Application Laid-Open No. 48-38291) are known, but they have problems in the effects at normal temperature, durability, processing methods, costs, and the like. As a method for eliminating odor using an amino compound, a deodorant polymer using polyalkyleneimine (Japanese Patent Application Laid-Open No. 3-218766) is known. It has drawbacks such as ineffectiveness in washing durability and basic odor.

Most of these processing methods are effective only for basic malodors such as amines and ammonia, acidic malodors such as acetic acid, or malodors such as hydrogen sulfide and mercaptans. It is known that it effectively acts on various types of odors such as malodor and hydrogen sulfide, mercaptans, and aldehydes which are said to be contained a lot in tobacco smoke, and can be used industrially safely and inexpensively for producing fibers. Absent.

As a nonwoven fabric for removing various odor components,
An air-cleaning nonwoven fabric combining a plurality of types of carriers impregnated with deodorant active ingredients having different target odors (Japanese Patent Publication No. Hei 02-226)
No. 73) and a deodorant filter (Japanese Patent Application Laid-Open No. 05-57145) to which a deodorant composition obtained by copolymerizing a vinyl sulfonate copper salt comonomer is adhered. As an aldehyde removal filter, a cigarette filter coated with a treatment solution containing polyethyleneimine and carboxylic acid (Japanese Patent Application Laid-Open No. 02-257870).
It has been known.

However, in each of these techniques, a deodorant is simply impregnated or applied to a carrier to attach a deodorant component to a fiber surface and a non-woven fabric. Changes in texture, coloration, etc., defects such as easy removal of deodorant components by washing and dry cleaning, basic odors such as amines and ammonia, acid odors such as acetic acid, or hydrogen sulfide, mercaptan It has an effect only on any of the odors such as odors, and effectively acts on both basic and acidic odors and a wide variety of odors such as hydrogen sulfide, mercaptans, and aldehydes which are said to be often contained in tobacco smoke. There are few known materials which can be used safely and inexpensively for producing fibers. There is also a method of fixing deodorant components to textiles using a resin or the like in order to prevent the deodorant components from falling off due to washing or dry cleaning, but there are drawbacks such as complicated processing steps and changes in fiber texture. In addition, it is not at a sufficiently satisfactory level because it has drawbacks such as a decrease in deodorant performance due to coating with a deodorant component.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to contain a deodorant acrylic synthetic fiber which has washing resistance, has an excellent deodorizing effect, and maintains the original performance and texture of a nonwoven fabric. An object of the present invention is to provide a nonwoven fabric and a method for producing the same.

[0012]

The gist of the present invention is to provide a copolymer (A) having acrylonitrile as a main constituent unit, and a copolymer (A) which is miscible and incompatible with the copolymer (A). In the acrylic synthetic fiber comprising 1 to 20% by weight of the polymer (B), the polymer (B) exists in a phase-separated state, and the metal silicate salt having an average particle size of 0.5 to 10 μm or An amino compound is added to a nonwoven fabric processed using a deodorant acrylic synthetic fiber containing 0.5 to 20% by weight of a fine powder containing aluminosilicate metal salt as an active ingredient.
An object of the present invention is to provide a deodorant nonwoven fabric characterized in that the nonwoven fabric adheres to a content of about 20% by weight.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The copolymer (A) containing acrylonitrile as a main constituent unit used in the present invention comprises an acrylonitrile copolymer containing at least 40% by weight of acrylonitrile, and contains any other copolymerizable monomer. It can be used together. For example, methyl acrylate, alkyl acrylates such as ethyl acrylate, methyl methacrylate, alkyl methacrylate such as ethyl methacrylate, styrene, vinyl acetate, vinyl chloride,
Neutral monomers such as vinylidene chloride, vinyl ethyl ether, and methacrylonitrile; and acidic acids such as acrylic acid, methacrylic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, and 2-acrylamide-2-methylpropanesulfonic acid. Those obtained by copolymerizing a monomer and an appropriate combination of an ammonium salt and an alkali metal salt of the monomer at a ratio of 60% by weight or less are exemplified. The acrylic copolymer may be produced by any method such as suspension polymerization, solution polymerization, emulsion polymerization and the like.

It is an essential condition that the polymer (B) used in the present invention is miscible and incompatible with the polymer (A). Being miscible means that the polymers are
The property that the polymer solutions can be mixed well without agglomeration or gelation, and the incompatibility means that when the solution of the copolymer (A) and the solution of the polymer (B) are mixed, Phase separation without dissolving, or solvent removal, phase separation of copolymer (A) and polymer (B) during molding, or mixing of copolymer (A) and polymer (B) It means that after melt-kneading, they are not uniformly blended with each other but are phase-separated. In general, the phase separation state is preferably such that the polymer (B) is spherical or spheroidal, more preferably spherical having a more uniform size. Although it is possible to use two or more polymers as the polymer (B), it is necessary that the polymer (B) be miscible and incompatible with the polymer (A). Confirmation of phase separation when the solution of the copolymer (A) and the solution of the polymer (B) are mixed,
It can be carried out by a general method, for example, a phase-contrast optical microscope or the like, as long as phase separation is performed in a solution state.

The polymer (B) is not particularly limited as long as it is miscible and incompatible with the copolymer (A).
Cellulose derivatives such as acetyl cellulose, acetyl propionyl cellulose, acetyl butyl cellulose,
Polyvinyl acetal such as polyvinyl formal, polyvinyl butyral, polyvinyl alcohol derivatives such as cyanoethylated polyvinyl alcohol, polyvinyl acetate,
Vinyl acetate copolymers such as vinyl acetate-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Vinyl chloride polymers such as acrylonitrile copolymers, polystyrene, styrene polymers such as acrylonitrile-butadiene-styrene copolymers, polymethyl methacrylate, copolymers containing methyl methacrylate as a main component, and the like. Cellulose derivatives or polyvinyl alcohol derivatives are preferred.

In the present invention, the polymer (B) is contained in the copolymer (A) in an amount of 1 to 20% by weight, preferably 2 to 15% by weight. If the amount of the polymer (B) is less than 1% by weight, a good phase separation state cannot be obtained, and if it exceeds 20% by weight, the fiber performance deteriorates, and it is difficult to produce easily and inexpensively industrially. Become.

As the fine powder used in the present invention, SiO ₂ : 5 to 80 mol% MO _{n / 2} : 5 to 65 mol% Al ₂ O ₃ : 0 to 60 mol in three component composition ratios expressed as oxides % (M is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, magnesium or zirconium, and n represents the valency of the metal) Alternatively, a metal aluminosilicate is used as an active ingredient. Such metal salts are
The crystals have both properties of solid acid and solid base, and exist independently on the surface of one solid particle without neutralizing each other, forming an amphoteric adsorption surface. It has an excellent deodorizing effect due to chemical adsorption to acidic malodors, and has a large specific surface area, excellent contact efficiency with malodors, and also has a physical adsorption function, so it can be effectively deodorized. . When M of the metal MO _{n / 2} , which is one component in the fine powder, is zinc, copper, or silver, it exhibits antibacterial properties. If antibacterial properties are important, use the corresponding fine powder. I just need.

The average particle size of the fine powder containing a metal silicate or aluminosilicate used as an active ingredient in the present invention depends on the particle size distribution, but is preferably 0.1 to 10 μm, and more preferably 1 to 10 μm.
７7 μm. If the average particle size of the fine powder is less than 0.1 μm, agglomeration is likely to occur, and uniform dispersion is difficult unless a special dispersing device or dispersant is used. If it exceeds 10 μm, the filtration pressure increases during spinning and the yarn breaks. Etc. occur, which is not preferable in operation.

The fine powder containing a metal silicate or aluminosilicate used as an active ingredient in the present invention has a BET specific surface area of 100 m ² / g or more, preferably 150 m ² / g or more. This BET specific surface area is 100
If it is lower than m ² / g, the efficiency of contact with malodor decreases, and the deodorizing ability cannot be sufficiently exhibited.

The amount of the fine powder containing the metal silicate or metal aluminosilicate used in the present invention as an active ingredient is 0.5 to 20 with respect to the acrylonitrile copolymer.
%, Preferably 1 to 15% by weight. If the content of the fine powder is less than 0.5% by weight, sufficient deodorizing performance cannot be provided, and if it exceeds 20% by weight, spinnability, fiber quality and spinnability in spinning are undesirably reduced.

In the fiber of the present invention, the deodorizing effect is remarkably improved due to the localization of the fine powder in the phase-separated polymer (B). Although the reason is not clear, the macrovoids formed by the phase-separated polymer (B) partially have pores opened on the surface communicating with the internal pores, and the malodorous substance is contained in the acrylic fiber. It is considered that the deodorizing effect is improved by making it easier to enter and increasing the contact area with the fine powder. This localization can be confirmed in the same manner as the method for confirming the phase separation. Further, it is considered that the obtained pores can be easily provided to the inside when the amino compound is provided, and the amino compound retained in the fine pores further improves the durability to washing and the like. Further, the amino compound held inside the pores increases the contact area with the malodor as in the case of the fine powder, and improves the deodorizing effect.

As the solvent used in the present invention, any solvent may be used as long as it can dissolve the acrylonitrile copolymer. For example, organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone and the like can be mentioned, which are preferable in terms of solubility, solvent recovery and handling.

In the present invention, the concentration of the solution of the polymer (B) in the organic solvent is 5 to 40% by weight, preferably 10 to 30% by weight. If this concentration is less than 5% by weight, the concentration of the spinning dope decreases, the spinnability decreases, and the fiber properties decrease. On the other hand, when the content exceeds 40% by weight, not only is it difficult to uniformly disperse the fine powder due to an increase in viscosity, but also the spinnability is reduced, and it becomes difficult to produce easily in an industrial manner.

In the present invention, the dispersion concentration of the organic solvent in the fine powder containing metal silicate or metal aluminosilicate as an active ingredient is 5 to 40% by weight, preferably 10 to 35% by weight. If the concentration is less than 5% by weight, the concentration of the spinning dope decreases, and the spinnability decreases and the fiber properties decrease. On the other hand, if the content exceeds 40% by weight, a good dispersion state cannot be obtained, and it is difficult to produce easily industrially.

A method for obtaining a spinning solution by adding and mixing a fine powder containing the polymer (B) and a metal silicate or a metal aluminosilicate as an active ingredient to the acrylonitrile-based copolymer (A) is used. A dispersion in which the polymer (B) and a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient are dispersed in an organic solvent is added to a solution obtained by dissolving the compound (A) in an organic solvent, and the dispersion is added immediately before spinning and mixed. Just do it. The polymer (B) used in the present invention and a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient are dispersed in an organic solvent,
The dissolving method and the method of adding and mixing the prepared solution to the spinning solution containing the acrylonitrile copolymer can be sufficiently mixed by a usual mixer.

The obtained spinning dope is spun out from an ordinary spinneret. As for the spinning method, any known wet spinning method can be applied, and the spinning method may be performed under the same conditions as those for ordinary acrylic synthetic fibers. More preferably, by performing a secondary stretching of 3 times or less with moist heat, macrovoids can be effectively imparted to the fiber, and the deodorizing performance can be improved.

The amino compound used in the present invention is a compound having an amino group in its structure.

Embedded image An aliphatic primary amine, an aromatic amine represented by R—NH ₂ (R is an alkyl group or an aryl group) and a general formula

A diamine compound represented by R- (NH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

An amide compound represented by R-CONH ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

Embedded image A diamide compound represented by R- (CONH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

A hydrazide compound represented by R-CONHNH ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

A dihydrazide compound represented by R- (CONHNH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

Embedded image A trihydrazide compound represented by R- (CONHNH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

Embedded image H ₂ N— (CH ₂ —CH ₂ —NH) _n —H (where n is an integer of 1 or more) or

Embedded image And hydrazine, alkylhydrazine derivatives, hydrazine salts and the like. As aliphatic primary amines, decylamine, undecylamine, tridecylamine, cetylamine, etc .; as aromatic amines, benzylamine, naphthylamine, etc .; as diamine compounds,
As aliphatic diamines such as ethylenediamine, hexamethylenediamine and octamethylenediamine, aromatic diamines such as phenylenediamine, and amide compounds represented by the general formula H ₂ N (CH ₂ ) _n NH ₂ (where n is an integer of 2 or more) Are lauric amide, azelainamide, sebacin monoamide, etc., as diamide compounds, adipic amide, sebacin diamide, azelaic diamide, etc., as hydrazide compounds, benzhydrazide, acetohydrazide, etc., and as dihydrazide compounds, carbodihydrazide, Adipic acid dihydrazide, sepasic acid dihydrazide, dodecane diacid dihydrazide, isophthalic acid hydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide and the like; and alkylene imines such as diethylene triamine, trie Rentetoramin, tetraethylene pentamine, pentaethylene hexamine and the like, polyalkylene imines such as polyethylene imine, polypropylene imine, poly (2-ethyl-aziridinyl Din) and the like,
As hydrazine and alkylhydrazine derivatives, hydrazine salts such as hydrazine hydrate, monomethylhydrazine, dimethylhydrazine, tert-butylhydrazine salts, benzophenone hydrazone, acetone thiosemicarbazone, semicarbazide hydrochloride, polyhydrazine hydrazine, trihydrazide citrate, etc. Examples thereof include, but are not limited to, hydrazine sulfate, hydrazine carbonate, hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine phosphate, hydrazine bromate, and thiosemicarbazide hydrochloride.

The content of the amino compound used in the present invention is 0.1 to 20% by weight, preferably 0.1 to 20% by weight, based on the nonwoven fabric.
5 to 10% by weight. Although it depends on the type of amino compound, if the content is less than 0.1% by weight, sufficient deodorizing performance cannot be imparted, and if it exceeds 20% by weight, the fiber texture and post-processability are undesirably reduced.

As a method for applying such an amino compound to a nonwoven fabric, a spinning solution is spun from a die by wet spinning, and a fiber obtained by primary drawing is washed with water, dried and densified,
A method of immersing the nonwoven fabric processed using the obtained fibers into a solution of an amino compound, and a method of spraying the solution of the amino compound and drying and preferably heat-treating the solution are used. In the nonwoven fabric of the present invention, since a deodorant acrylic synthetic fiber having macrovoids and high water absorbency is used, the method by immersion can be performed in a short time, and the amount of adhesion is adjusted by the concentration of the amino compound in the liquid. And drying, preferably heat treatment. In the method by spraying, the processed nonwoven fabric is placed on a conveyor or the like, and a certain amount of the amino compound solution is sprayed from above and / or below, followed by drying, preferably heat treatment.

The addition of titanium oxide, a flame retardant, a light stabilizer, a heat storage agent, a pigment, a polymer used for the purpose of improving shrinkage, etc., which are usually used within the range not impairing the characteristics of the present invention, dyeing, Gel tow processing and oil application for the purpose of imparting flammability and the like are optional. In addition, an additive may be used when producing a fine powder containing a metal silicate or aluminosilicate as an active ingredient within a range that does not impair the characteristics of the present invention, and may be added for improving the dispersibility of the fine powder. The use of objects is optional.

The nonwoven fabric according to the present invention is obtained by adding amino acid to a nonwoven fabric processed using a deodorant acrylic synthetic fiber containing a polymer (B) and a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient. Except that the compound is attached in an amount of 0.1 to 20% by weight, a generally used processing method may be used. Processing such as dyeing and printing can also be performed. Also, the mechanical properties of the nonwoven fabric,
For example, strength, area, air permeability, heat resistance, chemical resistance, and the like differ depending on the application to be used. Therefore, the material, thickness, structure, and the like should be appropriately selected and are not particularly limited. Although the nonwoven fabric of the present invention may use only the deodorant acrylic synthetic fiber of the present invention, synthetic fibers such as polyethylene, polypropylene, polyester, polyurethane, nylon, acrylic, vinylon, and aramid, acetate, rayon, cupra, etc. After mixing with recycled fibers, natural fibers such as cotton, wool, and hemp, carbon fibers, glass fibers, and the like, processing the resulting mixture into a nonwoven fabric, an amino compound may be added. The mixing ratio of the deodorant acrylic synthetic fiber containing the fine powder containing the metal silicate or the metal aluminosilicate of the present invention as an active ingredient and other fibers is not particularly limited. When importance is placed on functions, for example, flame retardancy, heat retention, moisture absorption, etc., about 5% to 50%, more preferably 5% to 30%
As long as it is at the same level, the obtained nonwoven fabric can have sufficient deodorizing performance.

[0032]

Next, the present invention will be described in detail with reference to examples. Parts and% in Examples are "parts by weight" and "% by weight" unless otherwise specified. [Deodorant] Evaluation of the deodorant performance of textile products is based on the basic smell of daily life, such as ammonia smell, which is a basic smell (rot odor of meat, components of tobacco smoke, decomposition products of sweat and urine, etc.) , Trimethylamine odor (fish rot odor, etc.), mercaptan odor (vegetable rot odor, etc.), acetic acid odor (body odor due to decomposition of sweat component, tobacco smoke component, etc.), acetaldehyde (tobacco smoke component) Etc.) were performed by the following method.

1. Trimethylamine (hereinafter referred to as TMA) removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, TMA was sealed so as to have a concentration of 10 ppm, and after allowing to stand for 1 hour, the gas concentration was measured with a detector tube. 10 pp of TMA in empty Tedlar bag as control
m and then left for 1 hour, the gas concentration was measured with a detector tube, and the TMA removal rate was calculated from the decrease rate of the concentration.

2. Ammonia removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, ammonia was sealed to a concentration of 40 ppm, and the mixture was allowed to stand for 1 hour, and then the gas concentration was measured with a detector tube. Add 4 ammonia to empty Tedlar bag as control
After sealing the mixture to a concentration of 0 ppm and leaving it to stand for 1 hour, the gas concentration was measured with a detector tube, and the removal rate of ammonia was calculated from the decrease rate of the concentration.

3. Ethyl mercaptan (hereinafter referred to as EMP) removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, EMP was sealed so as to have a concentration of 20 ppm, and after allowing to stand for 1 hour, the gas concentration was measured with a detector tube. 20 pp of EMP in empty Tedlar bag as control
m and then left for 1 hour, the gas concentration was measured with a detector tube, and the EMP removal rate was calculated from the concentration decrease rate.

4. Acetic acid removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, acetic acid was sealed so as to have a concentration of 20 ppm, and the mixture was allowed to stand for 1 hour, and then the gas concentration was measured with a detector tube.
As a control, acetic acid was sealed in an empty Tedlar bag so as to have a concentration of 20 ppm. After leaving for 1 hour, the gas concentration was measured with a detector tube, and the acetic acid removal rate was calculated from the decrease rate of the concentration.

5. Acetaldehyde removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, acetaldehyde was sealed to a concentration of 25 ppm, and the mixture was allowed to stand for 1 hour, and then the gas concentration was measured with a detector tube. As a control, acetaldehyde was sealed in an empty Tedlar bag so as to have a concentration of 25 ppm, and after allowing to stand for 1 hour, the gas concentration was measured with a detector tube, and the acetaldehyde removal rate was calculated from the decrease rate of the concentration.

[Washing resistance] The washing resistance test was conducted according to JIS L
Performed according to 1018 “Home Electric Washing Method”.

[Porosity] In the present invention, the polymer (B)
The macro voids obtained by the method described above were evaluated by the water absorption rate for convenience because the macro voids opened on the surface communicated with the internal macro voids to improve the water absorption performance, and were measured by the following method. The water absorption is a measured value of 100% of the deodorant acrylic synthetic fiber of the present invention. 0.5 g of cotton is immersed in pure water for 5 minutes and then treated with a centrifuge for 2 minutes to remove water between fibers, measure the weight (W0), and further dry the cotton to dry weight (W1) was measured, and the water absorption was calculated by the following equation. Water absorption (%) = (W0−W1) / W1 × 100 *

Examples 1 to 5 and Comparative Examples 1 to 5 The production of an acrylonitrile copolymer was carried out by using acrylonitrile (hereinafter referred to as AN) / methyl acrylate / 2-acrylamide-2-methylpropanesulfonic acid sodium (hereinafter referred to as SAM). ) = 91.2 / 8.0 / 0.8 is polymerized in dimethylformamide (hereinafter referred to as DMF) using azobisisobutyronitrile as an initiator to remove residual monomers. Do
Thereafter, the copolymer concentration was adjusted to 20 to 30%.

The polymer (B) was prepared using acetyl cellulose, which is a cellulose derivative, so as to have a DMF content of 20 to 30%.

In the fine powder, the composition ratio of the active ingredient metal aluminosilicate is SiO ₂ : 58 mol%, Al ₂ O
₃ : 7 mol%, ZnO: 35 mol%, an average particle diameter of 3.5 μm, and a specific surface area of 200 m ² / g were used, and the DMF was adjusted to 20 to 25%.

The amino compound was prepared by using adipic acid dihydrazide in distilled water at a concentration of 1 to 20%.

The DMF solution of acetyl cellulose obtained and the dispersion of the fine powder were added to the acrylonitrile copolymer at the addition rates shown in Table 1 and mixed to obtain a spinning stock solution.

The above spinning stock solution was spun into a 58% aqueous solution of DMF at 22 ° C., and subjected to primary stretching six times in three steps while removing the solvent, and then washed with water at 60 ° C. to remove DMF.
Thereafter, drying was performed at 130 ° C. with a heater roller under tension, secondary stretching was performed at 1.2 times under moist heat at 100 ° C., and after crimping, moist heat treatment was performed at 105 ° C. moist heat.
mm. Using this fiber, the basis weight is 150 gr /
created the m ² of needle punched nonwoven fabric. An amino compound was applied to this nonwoven fabric so as to have the adhesion amount shown in Table 1 to prepare a deodorant nonwoven fabric.

In Comparative Examples 1 to 5, the polymer (B), the fine powder and the amino compound used in Examples 1 to 5 were added and added to the acrylonitrile copolymer at a ratio out of the range. Each step and each evaluation were performed in the same manner as in Examples 1 to 5.

Example 6 The same procedure as in Examples 1 to 5 was carried out except that isophthalic hydrazide was used as the amino compound, and the deodorizing performance and the feeling were evaluated. Table 1 summarizes the above results.

[0048]

[Table 1]

As is evident from Table 1, the product of the example has a superior deodorizing performance as compared with the product of the comparative example.
In the case of Comparative Examples 1 and 2 in which the addition ratio of the copolymer (B) and the fine powder to the acrylonitrile-based polymer was increased outside the range, the filtration pressure increased during spinning, and yarn breakage occurred, making spinning impossible. Was. In the case where the addition ratio of the fine powder was reduced outside the range as in Comparative Example 3, the spinning operability and the fiber quality were good, the water absorption was high, and macrovoids were formed. Was not obtained. In Comparative Example 4 in which the content of the amino compound was reduced outside the range, the deodorizing performance against acetaldehyde was insufficient, and satisfactory performance was not satisfied. Further, in Comparative Example 5 in which the content of the amino compound was increased outside the range, the deodorizing performance was good, but the texture of the nonwoven fabric was lowered and the nonwoven fabric could not have sufficient quality. Also, it can be seen that Examples 6 to 8 using an amino compound different from Examples 1 to 5 also have excellent deodorizing performance as compared with Comparative Examples 6 and 7.

Examples 9 to 12 The fiber (C) used in Examples 1 to 5 and polyester 3 denier 51 mm (D) were mixed at a ratio shown in Table 3 to process a needle punched nonwoven fabric having a basis weight of 160 gr / m ^2. After preparing and adding the amino compound used in Examples 1 to 5,
Deodorizing performance and texture evaluation were performed. As is clear from Table 3, the product of the example had excellent deodorizing effect, durability, texture and quality of the nonwoven fabric even when used by mixing with other fibers.

[0051]

[Table 3]

Examples 13 to 15 and Comparative Examples 8 to 10 An acrylonitrile copolymer consisting of AN / vinylidene chloride / SAM = 57/40/3 was polymerized in DMF using azobisisovaleronitrile as an initiator. The remaining monomer is removed, and then the copolymer concentration is reduced to 20 to 30.
%.

The polymer (B) was prepared using polyvinyl butyral so as to have a DMF content of 20 to 30%.

The fine powder used was the same as in Examples 1 to 5, and was adjusted to 15 to 20% in DMF.

The obtained DMF solution of polyvinyl butyral and the dispersion of the fine powder were added to the acrylonitrile copolymer at the addition ratio shown in Table 4 and mixed to obtain a spinning stock solution.

The spinning solution was spun into a 57% aqueous solution of DMF at 18 ° C., stretched 5.9 times in three steps while removing the solvent, and then washed with water at 60 ° C. to remove DMF. After that, the fiber in the gel swelling state is dried at 130 ° C. by a heater roller under tension, the secondary stretching is performed at 1.2 times under the moist heat of 100 ° C., and after the crimp is applied, the moist heat treatment is performed at 105 ° C. , 51 mm.

The basis weight 16 processed using the obtained fiber
A needle-punched nonwoven fabric of 0 gr / m ² was impregnated with an aqueous solution of an amino compound by padding, and then squeezed with a mangle roller so as to obtain the adhesion amount shown in Table 4. The nonwoven fabric is tenter dried at 100 ° C. for 2 minutes, and then dried at 150 ° C. for 1 minute.
Bake for minutes. In addition, polyethyleneimine (SP-003 manufactured by Nippon Shokubai Kagaku Co., Ltd.) was used as the amino compound. Comparative Examples 8 to 10 are Examples 13 to 1 of the above nonwoven fabric.
The amount of the amino compound used in Example 5 was outside the range, and each step and each evaluation were performed in the same manner as in Examples 13 to 15.

Table 4 summarizes the above results.

[0059]

[Table 4]

As is evident from Table 4, it can be seen that the product of the example has superior deodorizing performance as compared with the product of the comparative example.
In the case of Comparative Example 8 in which the addition ratio of the fine powder was reduced outside the range, spinning operability and fiber quality were good, the water absorption was high, and macrovoids were formed. Therefore, the deodorizing performance was insufficient, and satisfactory performance could not be satisfied. In Comparative Example 9 in which the amount of amino compound attached was reduced outside the range, the deodorizing performance against acetaldehyde was insufficient, and satisfactory performance was not satisfied. In Comparative Example 10 in which the addition rate of the polymer (B) was reduced outside the range, the addition amount of the fine powder and the adhesion amount of the amino compound were within the range, but the addition rate of the copolymer (B) was less than the range. For this reason, formation of macrovoids was insufficient, and sufficient deodorizing performance could not be obtained. In contrast,
In the examples, satisfactory results were obtained in deodorizing performance, durability, texture of the nonwoven fabric, and quality.

[0061]

The deodorant nonwoven fabric of the present invention is obtained by mixing a conventionally used acrylonitrile-based copolymer (A) with a miscible and incompatible polymer (A) with the copolymer (A). B) and a deodorizing nonwoven fabric obtained by admixing an amino compound to a nonwoven fabric made of an acrylic fiber obtained by mixing a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient. And a nonwoven fabric provided with excellent deodorizing performance having washing resistance without lowering the feel, color and strength of the nonwoven fabric when using acrylic fibers. The nonwoven fabric obtained by the present invention is mixed with other fibers such as polyester, nylon, wool, and cotton in the same process and under the same conditions as ordinary acrylic synthetic fibers only by using the deodorant acrylic synthetic fibers of the present invention. Deodorizing nonwoven fabric which is inexpensive and has excellent deodorizing performance and washing resistance in the fields of clothing, interiors, industrial materials, etc., which require deodorizing performance, and its production It is very industrially significant because it can provide a method.

[Table 2]

Claims (2)

[Claims] 1. A copolymer (A) containing acrylonitrile as a main constituent unit, and a polymer (B) miscible and incompatible with the copolymer (A) in an amount of 1 to 20% by weight. In the acrylic synthetic fiber, the polymer (B) is present in a phase-separated state, and a fine powder containing an active ingredient of a metal silicate or aluminosilicate having an average particle size of 0.5 to 10 μm is used as a powder. A nonwoven fabric processed using a deodorant acrylic synthetic fiber containing 0.5 to 20% by weight, wherein an amino compound is attached at a ratio of 0.1 to 20% by weight. Deodorant nonwoven fabric. 2. A copolymer (A) containing acrylonitrile as a main constituent unit and 1 to 20% by weight of a polymer (B) miscible and incompatible with the copolymer (A). In the acrylic synthetic fiber, the polymer (B) is present in a phase-separated state, and a fine powder containing an active ingredient of a metal silicate or aluminosilicate having an average particle size of 0.5 to 10 μm is used as a powder. 0.1 to 20% by weight of an amino compound attached to a nonwoven fabric processed using a deodorant acrylic synthetic fiber containing 0.5 to 20% by weight by immersion or spraying. Method for producing odorous nonwoven fabric.