JP2002011084A - Deodorizer and textile product using the samel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorizer that has excellent deodorizing effect and with which the textile products treated for deodorization, in particular, have a good touch and retain the deodorizing effect after repeated washings. SOLUTION: This is a deodorizer which is made by containing a hydrotalcite compound, bivalent or trivalent metal oxide, acrylic emulsion and organopolysiloxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant suitable for fiber processing and a fiber product processed using the same. More specifically, the present invention relates to a deodorant which has an excellent deodorizing effect, does not impair the texture of fibers, and maintains a high deodorizing effect even after repeated washing, and a fiber product processed using the deodorant.

[0002]

2. Description of the Related Art In recent years, there has been a demand for a deodorizing treatment of fibers such as for preventing bad odors such as socks and stockings and for preventing adhesion of tobacco odors on curtains and garments. In response to this, a method of fixing a hydrotalcite compound capable of deodorizing to fibers with a urethane-based binder (Japanese Unexamined Patent Publication No.
No. 52478), a method of blending an aluminum silicate compound and zinc oxide into a fiber raw material (JP-A-6-10830).
No. 4) has been proposed as a method for deodorizing fibers. However, the conventional fiber processing deodorant gives a hard feel to the deodorized fiber, so that the texture becomes worse, the fiber becomes whitish due to the powder of the deodorant compound, or the fiber is decolorized. There has been a drawback such that the deodorant drops off after repeated washing and the deodorant performance is reduced.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a deodorant which has a large deodorizing effect, does not deteriorate the texture of deodorized fibers, and does not decrease the deodorizing effect even after repeated washing. Another object of the present invention is to provide a deodorant that does not impair the color of the fiber, and to provide a fiber product processed using these deodorants. .

[0004]

As a result of intensive studies, the present inventors have found that the above object can be achieved by fixing a hydrotalcite compound and a specific metal compound to a fiber using a specific binder. Based on this finding, the present invention has been completed.

Thus, according to the present invention, (1) a deodorant comprising a hydrotalcite compound, an oxide of a divalent or trivalent metal, an acrylic emulsion and an organopolysiloxane; 0.1-2 μm hydrotalcite compound dispersion, average particle size 0.01-
A 2 μm dispersion of an oxide of a divalent or trivalent metal, an acrylic emulsion and a deodorant containing an organopolysiloxane, and (3) the above (1) or (2)
A textile product obtained by performing a deodorizing process using the described deodorant.

Further, in a preferred embodiment of the present invention,
(4) The deodorant is a hydrotalcite compound 100
20 to 150 parts by weight of an oxide of a divalent or trivalent metal, 5 to 25 parts by weight of an acrylic emulsion (in terms of solid content), and 0.1 to 10 parts by weight of a polyorganosiloxane. (5) The deodorant according to (1) or (2), (5) the deodorant according to (1) or (2), wherein the polyorganosiloxane is an organopolysiloxane having a methoxy group at a terminal, and (6) The above-mentioned (1) or (2), wherein the polymer constituting the acrylic emulsion contains at least 50% by weight of a (meth) acrylate-based monomer and has a glass transition temperature of -30 to 30 ° C. A deodorant is provided.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The deodorant of the present invention comprises a hydrotalcite compound, a divalent or trivalent metal oxide, an acrylic emulsion and an organopolysiloxane.

The hydrotalcite compound used in the present invention
The product has the general formula [Mg_1-xAl_x (OH)₂]_X ⁺
[(CO₃ )_{x / 2}・ MH₂0]_X ⁻Represented by
Positively charged base layer [Mg
_1-xAl_x(OH)₂ ]_X ⁺And negatively charged
Intermediate layer [(CO₃)_{x / 2}・ MH₂0] _X ⁻
And an inorganic substance having a layered crystal structure. This
Here, X is a number greater than 0 and less than or equal to 0.33.
Natural products are Mg₆Al₂(OH)₁₆CO₃・ 4
H₂O, and the synthetic product is mainly Mg
_4.5Al₂(OH)₁₃CO₃・ 3.5H₂
The O form is commercially available. Examples of synthesis methods
For example, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-300
No. 39, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 6
Examples of known methods described in 1-1174270 are exemplified.
can do.

Further, as the hydrotalcite compound, a Zn-modified type in which a part of Mg in the hydrotalcite compound is substituted with Zn may be used.

In the present invention, as the hydrotalcite compound, the hydrotalcite compound is reacted with a perhalic acid such as perchloric acid, perbronic acid, perfluoric acid, etc. in water at an arbitrary ratio to obtain a hydrotalcite compound. Perhalogenic acid partially introduced type or perhalic acid introduced type in which part or all of CO ₃ in the site compound is substituted with a perhalogen acid radical such as ClO ₄ (hereinafter, referred to as “perhalic acid type hydrotalcite”) As a practical example, it is preferable to use hydrotalcite such as "perchloric acid type hydrotalcite". This is because perhalic acid-type hydrotalcite has a large effect of removing basic odors such as ammonia and amines. As a method for obtaining a perhalic acid type hydrotalcite compound, for example, a predetermined amount of an aqueous solution of perhalic acid or a metal perhalate is added to water in which the hydrotalcite compound is suspended, and the mixture is stirred well and then filtered. And drying methods.

The hydrotalcite compound often takes the form of fine particles agglomerated, and the average particle size is usually 0.01 to 50 μm, preferably 0.01 to 5 μm.
m. When deodorizing the fiber with the deodorant of the present invention, the color of the textile is white, such as off-white, no special consideration is required, but the color of the textile is other than black, red, etc. For example, in the case of a color, the color tends to change to a whitish color caused by the hydrotalcite compound powder. In such a case, as the hydrotalcite compound, a finer, preferably average particle size of 0.01 to 2 is used.
It is desirable to use a resin having a thickness of μm, more preferably 0.01 to 1.5 μm, because it is possible to suppress a change in the color of a textile product. In order to stably disperse the fine particles, it is preferable to adopt a method of dispersing the fine particles in an aqueous medium with a dispersant.

The divalent or trivalent metal oxide used in the present invention is an oxide of an element belonging to Groups 2, 3, 12, and 13 of the periodic table. Specifically, oxides of Group 2 elements such as beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide; oxides of Group 3 elements such as scandium oxide and yttrium oxide; zinc oxide; Oxides of Group 12 elements such as cadmium; oxides of Group 13 elements such as boron oxide, aluminum oxide, gallium oxide, and indium oxide are exemplified. Of these, oxides of elements of Groups 2, 12, and 13 are preferable, and magnesium oxide, zinc oxide, or aluminum oxide is particularly preferable. These may be used alone or in combination of two or more.

The particle diameter of the oxide of the divalent or trivalent metal is often in the form of fine particles aggregated, and the average particle diameter is usually 0.01 to 50 μm, preferably 0.01 to 5 μm.
It is. When the fiber is deodorized with the deodorant of the present invention, the oxide of a divalent or trivalent metal also has a tint to a whitish color when the color of the fiber product is colored, like the hydrotalcite compound. Tends to change. In this case, a divalent or trivalent metal oxide having a finer, preferably average particle size of 0.01 to 2 μm, more preferably 0.1 to 2 μm is used.
It is desirable to use the one having a thickness of from 01 to 1.5 μm, because it is possible to suppress a change in the color of the textile product. In order to stably disperse the fine particles, it is preferable to adopt a method of dispersing the fine particles in an aqueous medium with a dispersant.

The amount of the divalent or trivalent metal oxide used is as follows:
Usually per 100 parts by weight of the hydrotalcite compound,
20 to 150 parts by weight, preferably 50 to 120 parts by weight. If the amount of the divalent or trivalent metal oxide is excessively small, the effect as a deodorant may be reduced. On the other hand, if the amount is excessively large, the texture of the fiber may be reduced.

The acrylic emulsion used in the present invention is a (meth) acrylate-based polymer (this term is used in the meaning of an acrylate-based or methacrylate-based polymer). Is an emulsion containing 10 to 40% by weight. Here, the (meth) acrylate-based polymer is a polymer containing a (meth) acrylate-based monomer in an amount of 50% by weight or more of the polymer constituent unit. In the fiber processing deodorant of the present invention, the acrylic emulsion serves as a binder for fixing the hydrotalcite compound to the fiber. Therefore, the acrylic emulsion preferably has a film-forming property at room temperature, and the glass transition temperature (Tg) of the constituent polymer is usually -30 to 30.
° C, preferably -20 to 20 ° C.

In order to obtain the (meth) acrylate-based polymer, a (meth) acrylate-based monomer having a Tg of the homopolymer within the above-mentioned range is homopolymerized, or a single polymer having a Tg higher than the above-mentioned range is obtained. A method of copolymerizing a monomer giving a coalescence and a monomer giving a homopolymer having a sufficiently low Tg is adopted. In terms of emulsion production costs, methyl methacrylate (a homopolymer having a Tg of 105 ° C.), which is the most widely used and readily available monomer, is copolymerized with a monomer which gives a homopolymer having a sufficiently low Tg. Is preferred. Monomers that give low Tg homopolymers include methyl acrylate (Tg of homopolymer 8 ° C.),
Ethyl acrylate (-22 ° C), n-propyl acrylate (-52 ° C), n-butyl acrylate (-54 ° C), isobutyl acrylate (-24 ° C),
n-octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-85 ° C), n-lauryl acrylate (15 ° C), n-tetradecyl acrylate (20 ° C), methoxyethyl acrylate (-8)
5 ° C), ethoxyethyl acrylate (-50 ° C),
Acrylates such as cyclohexyl acrylate (15 ° C) and benzyl acrylate (6 ° C); n-amyl methacrylate (10 ° C), n-octyl methacrylate (-20 ° C), n-decyl methacrylate (-65 ° C) ), N-lauryl methacrylate (-65)
C.) and methacrylates such as n-cetyl methacrylate (15 ° C.); conjugated dienes such as butadiene and isoprene. One of these monomers may be used alone, or two or more thereof may be used in combination.

It is also possible to use a third monomer copolymerizable with the above monomers. Such copolymerizable monomers include styrene, vinyl toluene, α
Aromatic vinyl compounds such as methylstyrene; unsaturated nitriles such as (meth) acrylonitrile and vinylidene cyanide; 2-hydroxyethyl fumarate, hydroxybutyl vinyl ether, monobutyl maleate,
Glycidyl methacrylate, butoxyethyl methacrylate and the like can be mentioned.

As a method for producing the acrylic emulsion, a method is usually used in which the above-mentioned monomer is polymerized by an emulsion polymerization method or a fine suspension polymerization method to obtain an emulsion. Although the polymerization temperature is not particularly limited, it is preferably 30 to 80 ° C.

In the emulsion polymerization method, water is used as a dispersion medium, an anionic or nonionic surfactant is used as an emulsifier, a water-soluble peroxide is used as a polymerization initiator, and a surfactant-containing micelle layer containing a monomer is used. The polymerization is advanced to obtain microspherical polymer particles having a particle size of about 0.05 to 0.3 μm as latex. The seeding emulsion polymerization method is a method in which polymer particles in a latex obtained by emulsion polymerization in advance are used as seeds, and the seeds are coated with a monomer.

In the fine suspension polymerization method, water (dispersion medium),
In this method, a mixture of a monomer, an emulsifier, an oil-soluble polymerization initiator, and the like is homogenized using a homogenizer or the like, dispersed into fine droplets, and then polymerized.

The acrylic emulsion is used in an amount of 5 to 50 parts by weight, preferably 10 to 10 parts by weight, as a solid content in the emulsion per 100 parts by weight of the total of the hydrotalcite compound and the oxide of the divalent or trivalent metal. It is an amount of up to 40 parts by weight. If the amount is excessively small, the hydrotalcite compound may fall off from the fibers deodorized with the deodorant of the present invention. Conversely, if the amount of the acrylic emulsion is excessively large, the deodorizing effect tends to decrease. The amount of acrylic emulsion used is 25-40
If the amount is larger than the above range, the effect of preventing the whitening of the deodorant of the present invention from the fibers of the color is observed.

The organopolysiloxane used in the present invention is generally referred to as silicone oil and is a siloxane polymer having the following structure. R ¹ and R ² are hydrogen,
It is a methyl group or a phenyl group. R ² may be partially or entirely a methoxy group.

[0023]

Embedded image The kinematic viscosity of an organopolysiloxane at 25 ° C. is usually
1 to 1,000,000 cs, preferably 10 to 10
000 cs. The weight average molecular weight is usually 100 to 1,000,000, preferably 1,000.
0 to 100,000.

The textile product deodorized by the deodorant of the present invention containing an organopolysiloxane has an effect that the deodorizing performance is hardly reduced even after repeated washing.

The amount of the organopolysiloxane used is 0.1 to 10 parts by weight per 100 parts by weight of the total of the hydrotalcite compound and the oxide of the divalent or trivalent metal.
Preferably it is 1 to 5 parts by weight. If the amount of the organopolysiloxane in the deodorant is too small, the deodorizing effect is significantly reduced when the textile is repeatedly washed. Conversely, if the amount of the organopolysiloxane is excessively large, the hydrotalcite compound and the oxide of a divalent or trivalent metal tend to fall off.

The deodorant of the present invention is usually in the form of a solution or dispersion in which a hydrotalcite compound, an oxide of a divalent or trivalent metal, an acrylic emulsion and an organopolysiloxane are dispersed in water or an organic solvent. Used in. The solids concentration in the solution or dispersion is usually 5
５０50% by weight, preferably 10-30% by weight. As the organic solvent, methyl alcohol, ethyl alcohol, diethyl ether and the like can be used. The mixer for mixing is not limited, and a stirring mixer, a Hobart mixer, a homomixer, a homogenizer, or the like is appropriately used.

The above hydrotalcite compound and 2
The oxide of a trivalent or trivalent metal is preferably finely dispersed in water using a suitable dispersant.

Examples of such a dispersant for fine dispersion include sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl ether phosphate, sodium polyoxyethylene alkyl phenyl ether phosphate, and fatty acid. Sodium monoglyceride sulfate, sodium alkylnaphthalenesulfonate, sodium salt of naphthalenesulfonic acid formaldehyde condensate,
Anionic surfactants such as cresol shefate formaldehyde condensate sodium salt, sodium alkyldiphenyl ether disulfonate, sodium polyacrylate, sodium carboxymethylcellulose, sodium salt of olefin-maleic acid copolymer; polyglycerin fatty acid partial ester, polyoxyethylene Alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester, polyoxyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyoxyethylene polyoxypropylene block polymer, hydroxyethyl cellulose , Polyvinyl alcohol, polyvinylpyrrolidone, methylcell Polymeric nonionic surfactant caustic agent such as over the scan; and polymer inorganic salts such as tripolyphosphate, sodium phosphate is used. These may be used alone or in combination of two or more. It is also possible to use different dispersants for the hydrotalcite compound and the oxide of the divalent or trivalent metal. The amount of the dispersant used is usually 0.05 to 5 parts by weight, preferably 0.2 to 1 part by weight, per 100 parts by weight of the hydrotalcite compound or the divalent or trivalent metal oxide to be dispersed. It is.

By deodorizing fibers using the deodorant of the present invention, a fiber product having deodorizing performance can be obtained.
Examples of the fibers that can be deodorized include polyamide fibers, polyurethane fibers, polyester fibers, polyethylene fibers, polypropylene fibers, and polyvinylidene chloride fibers. Of these, polyamide fibers are preferred.

As a method for deodorizing fibers using the deodorant of the present invention, the fiber to be deodorized is immersed in an aqueous solution or suspension of the above-mentioned deodorant, then taken out and dewatered. There are a method of drying, a method of spreading the fiber, applying or spraying the suspension on the fiber, and then drying.

Preferable examples of the application of the present invention include applications for preventing the odor caused by the fermentation of sweat such as socks, stockings, and underwear, and for preventing the adhesion of tobacco odors such as curtains and garments.

[0032]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The number of copies is based on weight unless otherwise specified.

(1) Preparation of acrylic emulsion In a stainless steel reactor, 150 parts of water, 40 parts of methyl methacrylate, 60 parts of n-butyl acrylate, 1 carbon atom
1 part of sodium alkyl sulfate having 2 to 18 alkyl groups and 0.1 part of potassium persulfate were added, and the temperature was raised with stirring, and emulsion polymerization was performed at a temperature of 55 ° C. The reaction was terminated at a polymerization rate of 96% to obtain an acrylic emulsion having a solid content of 39% by weight. The copolymer has a glass transition temperature (Tg) of −10 ° C., a weight average molecular weight (Mw) of 7,
800,000.

(2) For the measurement of the concentration of each gas component, the following tubes were used as detection tubes for each odor component: Ammonia: manufactured by Komei Rikagaku Kogyo KK 105S
D isovaleric acid: manufactured by Komei Rikagaku Kogyo Co., Ltd .; 216S
And GT No. 81L was used.

(3) Measurement of Average Particle Size The average particle size of the hydrotalcite compound and the oxide of the divalent or trivalent metal can be determined by a particle size analyzer [SALD2000J, manufactured by Shimadzu Corporation] using a laser diffraction scattering method. Was measured. That is, the sample powder is added to water and dispersed well for 3 minutes with an ultrasonic cleaner, and then the volume-based cumulative particle size distribution is measured with the above particle size measuring device, and the particle size corresponding to a cumulative value of 50% is determined. The average particle size was used.

(4) Preparation of deodorant for textile processing Deodorant (a1) Perchloric acid type hydrotalcite (average particle size 5 μm) 1
Parts, 1 part of magnesium oxide (average particle size: 5 μm), 1.4 parts of an acrylic emulsion having a solid content of 39% by weight,
A deodorant (a1) was prepared by mixing 0.02 parts of a methoxy-terminated dimethylpolysiloxane and 128 parts of water.

Deodorant (a2) Perchloric acid type hydrotalcite (average particle size 5 μm) 1
Parts, 1 part of aluminum oxide (average particle size: 5 μm), 1.4 parts of the acrylic emulsion, 0.02 part of methoxy-terminated dimethylpolysiloxane and 128 parts of water,
A deodorant (a2) was prepared.

Deodorant (a3 ) 1 part of hydrotalcite (average particle size: 0.5 μm) was added to water 4
, 25 parts of hydrotalcite fine dispersion prepared by high-speed stirring with a homomixer together with 0.02 part of sodium tripolyphosphate, 4 parts of water, 1 part of zinc oxide (average particle size: 0.3 μm), and 0 part of sodium polyacrylate. Zinc oxide fine dispersion 2 prepared by high-speed stirring with a homomixer together with 0.05 parts
5 parts, 50 parts of the acrylic emulsion and 0.7 part of methoxy-terminated dimethylpolysiloxane were mixed to prepare a deodorant (a3).

Deodorant (b1) Deodorant (a1) except that magnesium oxide was not added.
A deodorant (b1) was prepared in the same manner as described above.

Deodorant (b2) A deodorant (b2) was prepared in the same manner as the deodorant (a1), except that the terminal methoxylated organopolysiloxane was not added.

Deodorant (b3) Deodorant (a) except that no acrylic emulsion was added.
Deodorant (b3) was prepared in the same manner as in 1).

(5) Deodorization of Textile Products A piece of black cloth (10 cm × 20 cm) made of 5 g of fiber is immersed in a deodorant for deodorant fiber processing, taken out, and placed on a paper towel to absorb moisture. After that, the sample was dried at 90 ° C. for 1 hour to prepare a sample.

(6) Measurement of Deodorization Rate Cloth pieces before washing and after washing 10 times (JIS L 021)
7), the deodorization rate was measured as follows. A sample of the deodorized textile was placed in a 3 liter Tedlar bag, the air in the bag was evacuated, and then 3 liters of air containing 50 ppm of ammonia was injected. The ammonia concentration in the sample was measured with a detector tube, and the rate of decrease from the initial concentration was defined as the deodorization rate. The larger the value, the greater the deodorizing effect (unit%).

Further, in the Tedlar bag, isovaleric acid 10
Three liters of air containing 0 ppm was injected, and the isovaleric acid concentration was measured 30 minutes and 120 minutes later using a detector tube, and the rate of decrease in the initial concentration was defined as the deodorization rate.

(7) Evaluation of Color Before the texture test, the textile product whose deodorization rate was measured was examined to determine whether the color had changed due to the deodorizing process, and evaluated according to the following criteria.

：: The color of the black piece of cloth changed before and after the deodorizing process and was not seen.

Δ: The cloth piece after the deodorizing process looks slightly whiter than before the deodorizing process.

×: The cloth piece after the deodorizing process looks whiter than before the deodorizing process.

(8) Evaluation of texture The deodorizing rate was measured, and the fiber product which had been subjected to the color test was rubbed with both hands. ○: soft touch, Δ: slightly soft touch, ×: hard touch And

Examples 1-3, Comparative Examples 1-3 Black nylon / polyurethane blended fiber products were deodorized using deodorants (a1)-(b3), and were repeated 10 times before washing. After washing, the deodorizing rate, texture and color were evaluated. The results are shown in Table 1.

[0051]

[Table 1] As shown in Table 1, deodorants (a1), (a1) containing a hydrotalcite compound, a divalent or trivalent metal oxide (magnesium oxide, aluminum oxide or zinc oxide), an acrylic emulsion and an organopolysiloxane
Textile products deodorized by using 2) or (a3) (Examples 1, 2 and 3) have a good texture, and the deodorization rate with respect to ammonia and isovaleric acid improves over time. It was confirmed that there was almost no decrease even after washing twice. Further, in Example 3 in which a deodorant using a fine hydrotalcite compound and a metal oxide was applied, the color of the black fiber did not change.

On the other hand, in the case of the fiber deodorized by using the deodorant (b1) containing no divalent or trivalent metal oxide (Comparative Example 1), the deodorant of the present invention was used. The deodorizing rate of isovaleric acid after 30 minutes was reduced as compared with the case where the deodorizing process was used (Examples 1 to 3). In addition, in the case of the sample deodorized by using the deodorant (b2) containing no organopolysiloxane (Comparative Example 2), the feeling is lowered, and in particular, the deodorizing effect of ammonia after washing 10 times repeatedly. Has dropped significantly. In the case of using the deodorant (b3) to which the acrylic emulsion was not added (Comparative Example 3), the deodorization rate of both ammonia and isovaleric acid was significantly reduced after washing, and
Since the texture is not reduced, it is understood that these are the results of desorption of the deodorant.

[0053]

The deodorant for textile processing of the present invention is effective for deodorizing ammonia and lower fatty acids which are odor components of feet and lower fatty acids which are a main component of tobacco odor, so that soots, stockings, curtains, etc. Has the effect of preventing bad smell of the fiber and does not impair the texture and color of the fiber. In addition, these effects are maintained even after repeated washing.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 83/04 C08L 83/04 D06M 11/45 D06M 15/263 15/263 15/643 15/643 11/10 F term (Reference) 4C080 AA03 AA05 AA07 BB02 CC02 CC08 CC12 HH05 JJ05 KK08 LL05 LL10 MM02 NN02 NN04 NN26 NN29 QQ03 4J002 BG04W BG05W BG06W BG07W CP03X CP04X DE077 DE087 DE097 DE13 A03 A03 DA03 A03 DA03 A02 A

Claims (3)

[Claims] 1. A deodorant comprising a hydrotalcite compound, a divalent or trivalent metal oxide, an acrylic emulsion and an organopolysiloxane. 2. A dispersion of a hydrotalcite compound having an average particle size of 0.01 to 2 μm, a dispersion of a divalent or trivalent metal oxide having an average particle size of 0.01 to 2 μm, an acrylic emulsion, and an organopolysiloxane. A deodorant comprising: 3. A textile product which is deodorized using the deodorant according to claim 1 or 2.