JP2017075420A - Allergen-reducing composition for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an allergen-reducing composition for fiber capable of reducing allergen having washing resistance and hardly generating coloring or discoloration on a nonwoven, a fiber or a fiber product, and a nonwoven fiber, a fiber or a fiber product having allergen-reducing performance.SOLUTION: Allergen-reducing function having washing resistance and hardly generating coloring or discoloration can be added by processing an allergen-reducing composition for fiber containing titania sol, preferably having pH of neutral region in 5 to 9, to a nonwoven, a fibber, a fiber product or the like.SELECTED DRAWING: None

Description

The present invention relates to an allergen-reducing composition for fibers, which imparts a function of reducing allergens such as mites and pollen to fibers or fiber products, and is capable of processing that is highly resistant to washing and hardly causes coloring or discoloration. Is.

Allergic diseases such as asthma, atopic dermatitis, and allergic rhinitis are plagued by many people, and in recent years, the tendency has been increasing. The causes of these allergic diseases are various allergens present in the environment. Among them, mites, pet hair, pollen, and mold that inhabit indoors are typical inhalable allergens. Well known. In particular, leopard mites, which are dust mites that live in the house, are a major problem as a source of allergens. Leopard mites are a hotbed for growing textile products in the house such as tatami mats, carpets, bedding, curtains, etc., or seat sheet fabrics of moving vehicles such as trains and cars outdoors. Among the leopard mites, Dermatophagoides farinae and Dermatophagoides pteronysinsinus are typical species, and the dead bodies and feces of these mites are strong allergen substances. In addition, pollen of various plants including cedar ( Cryptomeria japonica ) pollen scattered in early spring is also an allergen, and causes allergic rhinitis in particular. The pollen that scatters is not only cedar pollen in the early spring, but also many kinds of cypress, mugwort, ragweed, camo, etc. There is a state that some kind of pollen is scattered throughout the year, and there is a risk of causing pollen allergies at any time It is thought that there is.

In order to remove allergens such as mites and cedar pollen, there is a method of passing air through a filter using an air conditioner or an air purifier, but only allergens flying in the air can be removed. As a result, allergen substances are collected, and there is a risk that allergens will re-scatter when the filter is replaced. Also, the mask is used to prevent inhalation of cedar pollen, but the pollen attached to the mask does not lose allergenicity, so there is a risk that it will be absorbed by re-scattering. . A vacuum cleaner is an effective method for removing allergens, but a large amount of allergens contained in the sucked garbage is only stored in the dust bag, and there is a risk that the allergen will re-scatter when the dust bag is discarded. It is done.

As a drug for reducing or eliminating allergenicity of allergen substances, tannic acid has been known for a long time, and a method of applying tannic acid has been proposed. However, tannic acid has a brown color and further has a disadvantage that its use is limited by the progress of coloring over time. Thereafter, various proposals were made as an allergen reducing agent that hardly causes coloring or discoloration, and a method using an inorganic salt such as zinc or magnesium was proposed. However, since such inorganic salts are water-soluble and run away with water, there is a problem that they cannot be used for applications that require washing resistance such as fibers and textile products (Patent Document 1).

Several proposals have recently been made regarding allergen reducing agents that do not run away with water. Further, as an allergen reducing agent that does not cause coloring or discoloration and does not flow away with water, an allergen inactivating agent using a water-insoluble zinc compound or a water-insoluble zinc / metal oxide composite particle is further used. Although allergen inactivating agents using silicon, zinc oxide, and aluminum oxide have been proposed, they were not satisfactory in terms of water resistance and continuous allergen inactivating performance. These allergen reducing agents are not water-soluble, but when processed with a resin emulsion such as an acrylic emulsion as a binder to nonwoven fabrics, fibers, textile products, plastic products, and wood materials, allergens are used when the amount of binder is sufficient. The allergen reducing performance itself is not exhibited although it covers the reducing agent and prevents runoff, and if the amount of the binder is small, it is often impossible to prevent runoff and maintain efficacy (Patent Documents 2 to 2). 5). Moreover, although the thing using the photocatalytic titanium oxide as an allergen reducing agent is proposed, it was not known whether it had washing resistance by processing to a fiber (patent document 6).

Japanese translation of PCT publication No. 2004-510717 JP 2006-239393 A JP 2006-241431 A JP 2010-65114 A JP 2005-278781 A JP 2006-265498 A

An allergen-reducing composition for fibers, which imparts a function of reducing allergens such as mites and cedar pollen to non-woven fabrics, fibers or fiber products, and does not easily flow out and does not cause coloring or discoloration, and these It is an object of the present invention to provide a non-woven fabric, a fiber or a fiber product obtained by processing the allergen-reducing composition for fibers.

 As a result of earnest research to solve such problems, the present inventor can reduce various allergens by processing a composition containing titania sol into a nonwoven fabric, fiber or fiber product, The present invention has been completed by finding that it has washing resistance and can be processed without causing coloring or discoloration.

  That is, the present invention is (1) an allergen-reducing composition for fibers characterized by containing titania sol, and (2) an allergen-reducing composition for fibers in which the pH range of titania sol is 5 to 9, (3) A non-woven fabric, fiber or fiber product obtained by processing this fiber allergen-reducing composition without using a binder. (4) The above-mentioned fiber allergen-reducing composition is made of non-woven fabric, fiber or fiber product. And allergens that come into contact with these non-woven fabrics, fibers or textile products are reduced.

By using the composition of the present invention, it becomes possible to impart a function of reducing allergens such as mites and cedar pollen to nonwoven fabrics, fibers or fiber products, and further has wash resistance and causes discoloration and coloring. In addition, it is possible to provide a non-woven fabric that can be used for fibers or fiber products having a function of reducing allergens, filter materials, masks, and the like.

The titania sol in the present invention can be a commercially available industrial product, but can also be prepared by a known method. It is disclosed that titania sol can be produced by peptizing titanium hydroxide precipitated by adding an alkali to an aqueous solution of a water-soluble titanium salt such as titanium tetrachloride with an acid, particularly a strong acid such as hydrochloric acid or nitric acid. Has been.

Moreover, by hydrolyzing titanyl sulfate as an aqueous solution by heating, etc., by neutralizing, filtering and washing the precipitated titanium hydroxide, the cake obtained by peptizing with a strong acid such as hydrochloric acid or nitric acid It is also possible to produce a titania sol. Since the titania sol as described above is strongly acidic, there is a possibility that the fiber or the fiber product processed from the titania sol may come into contact with human skin, and considering the suppression of corrosiveness to metals, the pH is 5-9. What was adjusted to the neutral area | region is especially suitable. In order to adjust to neutral pH range, it can carry out by methods, such as addition of various stabilizers, alkali neutralization, ion exchange, ultrafiltration, and dialysis. Also disclosed is a method in which an aqueous phosphoric acid solution is mixed with a sol and coated with a hydrated titanium phosphate compound produced by a reaction between a titanium compound in the aqueous solution and a phosphoric acid compound.

The average particle diameter of the titania sol is in the range of 0.01 to 2 μm, preferably in the range of 0.1 to 1 μm. In order to obtain such an average particle size, it is possible to use a method such as wet grinding using glass beads or zirconia beads, a ball mill, a sand mill, or a homomixer.

The titania sol has a solid content concentration of 5 to 40%, preferably 10 because the solid concentration of the titania sol is so high that the viscosity becomes high and handling becomes difficult. It is preferable to set it in a range of ˜30%.

The method for treating the titania sol into the fiber or the fiber product is not particularly limited, and examples thereof include a method by immersing the fiber in a titania sol dilution, or a method of spraying the titania sol dilution on the fiber or fiber product. After the titania sol dilution is processed into fibers or fiber products, it is dried by air drying or heating. There is no particular limitation on the drying temperature, and air drying at room temperature or forced drying by heating can be performed. About the temperature to heat, 200 degrees C or less is preferable from thermal efficiency, and 150 degrees C or less is more preferable.

To the allergen-reducing composition for fibers of the present invention, it is possible to further add an allergen-reducing component that is already known within a range not affecting the physical properties and the like. Examples of the allergen-reducing component include hydroxybenzoic acid-based compounds such as 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, or salts thereof, and persimmon astringents. .

The allergen-reducing composition for fibers of the present invention, when used for the purpose of reducing allergens in indoor dust mites, can be further sustained by reducing the allergen by processing it simultaneously with an acaricide. is there. The acaricide used is not particularly limited as long as it has a lethal and repellent effect on indoor dust mites. For example, benzyl alcohol, benzyl benzoate, phenyl salicylate, cinnamaldehyde, hyssop oil, carrot seed oil In addition, pyrethroid compounds such as natural pyrethrin, phenothrin, and permethrin, organophosphorus compounds such as fenitrothion, malathion, fenthion, and diazinon, dicofol, chlorbenzilate, hexythiazox, tebufenpyrad, pyridaben, and amidoflumet are used. be able to.

As a method for using the allergen-reducing composition for fibers of the present invention, it can be processed by a method such as dipping, coating, spraying, etc. on a nonwoven fabric, fiber or textile product. Interiors such as sofas, wallpaper, curtains, futon side, futon covers, futon batting, sheets, pillow covers, mats and other bedding, car seats, car mats, car parts such as ceiling and flooring, plush toys, etc. Nonwoven fabrics include wet wipers for cleaning, masks, filter materials, dust collection bags for vacuum cleaners, and the like.

There are various non-woven fabrics and fibers that can process the allergen-reducing composition for fibers of the present invention, and examples thereof include nylon, cotton, polyester, wool, rayon, acrylic, silk, and the like. Even if it is a composite fiber using two or more types. It can also be used for non-woven fabrics using polyethylene or polypropylene. The method for processing the allergen-reducing composition for fibers of the present invention into a non-woven fabric, fiber or fiber product is not particularly limited, and immersion treatment, spray treatment, exhaustion processing, and the like can be performed. The processing amount to the fiber or fiber product is 0.01 to 20 g / m ² , preferably 0.1 to 10 g / m ² as the solid content of the titania sol with respect to the weight of the nonwoven fabric, fiber or fiber product. , more preferably from 0.5 to 2 g / ^{m 2.}

When the fiber allergen-reducing composition of the present invention is processed into a non-woven fabric, fiber, or fiber product, the combined use of a binder is not preferable, but it may be used in a limited range. As for the type of the binder, any type of resin emulsion such as acrylic or urethane can be used. The urethane binder may be any type such as an ester type, an ether type, and a polycarbonate type, and may be anionic, anionic, cationic, or nonionic. Although there is no restriction | limiting in particular about the use density | concentration of a binder, It is desirable that the quantity of resin mix | blended is 1/5 or less of solid content of a titania sol. When the usage-amount of a binder increases too much, it will result in covering the fiber allergen reduction composition of this invention, and an effect will become difficult to be exhibited.

In formulating the fiber allergen-reducing composition of the present invention, in addition to the above-mentioned acaricide, a surfactant, chelating agent, rust inhibitor, antibacterial agent, perfume, scale inhibitor, It is also possible to add foaming agents, antistatic agents, thickeners, softening agents and the like.

By using non-woven fabrics, fibers or fiber products processed with the fiber allergen-reducing composition of the present invention, mite-derived allergens in house dust that come into contact with non-woven fabrics, fibers or fiber products, pets such as dogs and cats, etc. Allergens derived from hair, epithelium, cockroaches, feathers, mold, and pollen such as cedar, mugwort, hargaya, cypress, ragweed, natural rubber latex, etc. can be reduced, and allergens are virtually eliminated. be able to.

The present invention will be described in more detail with reference to examples and test examples, but the present invention is not limited thereto. In addition, all% shown below are weight%.

(Example 1) Preparation of acidic titania sol 2.0 g of sodium hexametaphosphate (made by Yoneyama Chemical Co., Ltd.) was dissolved in 600 g of ion-exchanged water, and 80 g of titanyl sulfate (made by Kishida Chemical Co., Ltd.) was dispersed and boiled. Heated in a hot water bath for 2 hours. Next, the solution was cooled to 70 ° C. and adjusted to pH 6.0 with 25% aqueous ammonia (Wako Pure Chemical Industries, Ltd.). Suction filtration was performed using a 12.5 cm diameter Nutsche laid with 5C filter paper, and further washed with ion-exchanged water to obtain 150 g of a cake. This cake was dispersed in 100 g of ion-exchanged water, and 10 g of hydrochloric acid (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added to peptize.

  This dispersion was wet-ground for 20 minutes using glass beads having a diameter of 1 mm to obtain a titania sol (solid content: 15%). When the average particle size of the titania sol was measured using a particle size distribution analyzer SALD-2100 (manufactured by Shimadzu Corporation), the average particle size was 0.8 μm. As a result of measuring the pH, the pH was 1.2.

(Example 2) Preparation of neutral titania sol 3.0 g of sodium hexametaphosphate (made by Yoneyama Chemical Co., Ltd.) was dissolved in 600 g of ion-exchanged water, and 80 g of titanyl sulfate (made by Kishida Chemical Co., Ltd.) was dispersed and boiled. Heated in a hot water bath for 2 hours. Next, the mixture was cooled to 70 ° C., and the pH was adjusted to 6.3 using 25% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.). Suction filtration was performed using a 12.5 cm diameter Nutsche laid with 5C filter paper, and further washed with ion-exchanged water to obtain 150 g of a cake. This cake was dispersed in 100 g of ion-exchanged water, and 10 g of hydrochloric acid (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added to peptize. 10.7 g of titanium tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to this dispersion, and 2.1 g of 85% phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added. Stirring was continued for 2 hours, and the pH was adjusted to 5.5 again using 25% aqueous ammonia. No. Suction filtration was performed using a Nutsche 12.5 cm in diameter on which 5C filter paper was laid, and further washed with ion-exchanged water to obtain 185 g of a cake. 120 g of ion-exchanged water was added to the cake, and wet pulverization was performed for 20 minutes using glass beads having a diameter of 1 mm to obtain titania sol (solid content: 15%). When the average particle size of the titania sol was measured using a particle size distribution analyzer SALD-2100, the average particle size was 0.7 μm. Moreover, as a result of measuring pH, pH was 5.6.

(Comparative Example 1)
Photocatalytic titanium oxide AMT-600 (manufactured by Teika Co., Ltd.) 45 g, poise 520 (manufactured by Kao Corporation) 2.5 g, sodium hexametaphosphate (manufactured by Yoneyama Chemical Co., Ltd.) 0.6 g, Kelzan S (manufactured by Sanki Co., Ltd.) 0.3 g and 270 g of ion-exchanged water were mixed, and wet pulverization was performed using glass beads having a diameter of 1 mm to obtain a dispersion having a photocatalytic titanium oxide concentration of 15%. When the average particle size of the titanium oxide dispersion was measured using a particle size distribution analyzer SALD-2100, the average particle size was 0.9 μm.

(Comparative Example 2)
30 g of tungsten oxide (manufactured by Inorganic Chemical Industry Co., Ltd.), 2.5 g of poise 520 (manufactured by Kao Corp.), 0.6 g of sodium hexametaphosphate (manufactured by Yoneyama Chemical Co., Ltd.), Kelzan S (manufactured by Sanki Co., Ltd.) 3 g and 270 g of ion exchange water were mixed, and wet pulverization was performed using glass beads having a diameter of 1 mm to obtain a dispersion having a tungsten oxide concentration of 10%. When the average particle size of the tungsten oxide dispersion was measured using a particle size distribution analyzer SALD-2100, the average particle size was 1.0 μm.

(Processing to fiber)
For nylon jersey fabric (120 g / m ² ) 15 cm × 20 cm, the processing concentration of the solid content of Examples 1-2 or Comparative Examples 1-2 is 0.2 g / m ² or 0.4 g / m ^2. After diluting to a predetermined concentration, the dough was dipped, squeezed at a squeezing rate of about 250%, and then heated and dried at 100 ° C. for 15 minutes.

In addition, for nylon jersey fabric (120 g / m ² ) of 15 cm × 20 cm, the processing concentration of the solid content of Example 1 or Comparative Example 1 is set to 0.2 g / m ² or 0.4 g / m ^2. Dilute to a concentration, and further add Adekabon titer HUX-350 (manufactured by Adeka Co., Ltd., 30% solid content) as a urethane binder, half the solid content of Example 1 or Comparative Example 1 (15% as the solid content of the binder) and The dough was soaked in the solution so added and squeezed at a squeezing rate of about 250%, and then heat-dried at 100 ° C. for 15 minutes.

(Washing method)
Half of the processed nylon jersey fabric (15 cm × 10 cm) was placed in 200 mL of a solution obtained by adding 2 mL of JAFET standard combination detergent to 1.5 L of ion-exchanged water, and 200 r. p. m. And squeezed at a squeezing rate of about 250%. Next, the sample dough was put in 200 mL of ion-exchanged water, and 200 r. p. m. And rinsed twice for 10 minutes.

(Test Example 1) Measurement of reduction effect of processed nylon jersey fabric against mite allergen Nonwoven fabric processed from Examples 1 to 2 or Comparative Examples 1 to 2 (processing concentration, 0.2 g / m ² or 0. 4 g / m ² ) is cut into 5 cm x 5 cm, placed in a plastic bag with a chuck, 1 mL of a standard mite allergen suspension (allergen amount 900 ng / mL, but converted to total protein amount) is added, and the sample and allergen are brought into contact. I let you. After 1 hour, the allergen solution was squeezed out of the plastic bag with a chuck, and the mite allergen reducing effect was measured by the sandwich method of Der f2 enzyme immunoassay (ELISA) for these sample solutions after centrifugation.

First, 100 μL of anti-Der f2 monoclonal antibody 15E11 diluted to 2 μg / mL with phosphate buffer (pH 7.4) was added in an amount of 100 μL per well of F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC). Sensitized for more than 3 days. After sensitization, the solution was discarded, and 200 μL of a blocking reagent {1 wt% bovine serum albumin + phosphate buffer (pH 7.2)} was added per well and reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2). Next, 100 μL of the extract obtained by bringing the mite allergen and the nylon jersey dough into contact with each other was dropped and reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2).

Peroxidase-labeled anti-Der f2 monoclonal antibody was dissolved in phosphate buffer {pH 7.2, containing 1% by weight bovine serum albumin and 0.05% by weight polyoxyethylene (20) sorbitan monolaurate} at 200 μg / mL, A solution obtained by diluting it with phosphate buffer (pH 7.2, containing 1% by weight bovine serum albumin and 0.05% by weight polyoxyethylene (20) sorbitan monolaurate) 1200 times was added at 100 μL per well. . After reacting at 37 ° C. for 60 minutes, the plate was washed with a phosphate buffer (pH 7.2). To 6.5 mL of 0.1 mol / L phosphate buffer (pH 6.2), add 1 tablet of ortho-phenylenediamine dihydrochloride (13 mg Table, manufactured by Wako Pure Chemical Industries, Ltd.) and 6.5 μL of 30% hydrogen peroxide solution. 100 μL per well was added and reacted at 37 ° C. for 3 minutes. Immediately thereafter, 50 μL of 1 mol / L H ₂ SO ₄ was added to stop the reaction, and the absorbance (OD 490 nm) was measured with a spectrophotometer for microplate (manufactured by Tecan Japan Co., Ltd.). The results are shown in Tables 1 and 2.

(Test Example 2)
Measurement of reduction effect of cedar pollen allergen Cry j1 by fiber allergen-reducing composition Nylon jersey fabric processed from Examples 1-2 or Comparative Examples 1-2 (processing concentration, 0.2 g / m ² as solid content or 0.4 g / m ² ) was cut into 5 cm × 5 cm, put into a plastic bag with a chuck, 1 mL of a standard cedar pollen allergen suspension (allergen amount 12.5 ng / mL) was added, and the sample and the allergen were brought into contact with each other. One hour later, the allergen solution was squeezed out of the plastic bag with a chuck, and the cedar pollen allergen reducing effect was measured by the sandwich method of Cry j1 enzyme immunoassay (ELISA) for these samples after centrifugation.

First, Cry j1 monoclonal antibody 013 diluted to 2 μg / mL with phosphate buffer (pH 7.4, containing 0.1 wt% NaN ₃ ) was added per well of F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC). 100 μL each was added and sensitized at 4 ° C. for 1 day or longer. After sensitization, the solution was discarded, and a blocking reagent {1% by weight bovine serum albumin + phosphate buffer (pH 7.2, containing 0.1% by weight NaN ₃ )} was added in an amount of 200 μL per well. Reacted for 1 minute. After the reaction, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate). Next, 100 μL of a cedar pollen allergen extract solution contacted with the processed non-woven fabric was added dropwise per well and reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate).

Peroxidase-labeled Cry j1 monoclonal antibody 053 was dissolved in distilled water to 200 μg / mL, and then dissolved in phosphate buffer {pH 7.2, 1 wt% bovine serum albumin and 0.1 wt% polyoxyethylene (20) sorbitan mono A solution diluted 1200 times with laurate contained} was added at 100 μL per well. After reacting at 37 ° C. for 60 minutes, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate). 100 μL per well of ortho-phenylenediamine dihydrochloride (26 mg Table, manufactured by SIGMA CHEMICAL CO.) And 13 μL of hydrogen peroxide solution was added to 13 mL of 0.1 mol / L phosphate buffer (pH 6.2). And allowed to react at 37 ° C. for 5 minutes. Immediately thereafter, 50 μL of 2 mol / L H 2 SO 4 was added to stop the reaction, and the absorbance (OD 490 nm) was measured with a spectrophotometer for microplate (manufactured by Tecan Japan Co., Ltd.). The results are shown in Tables 3 and 4.

According to the present invention, an allergen-reducing composition for fibers that can reduce allergens such as mites and pollen and imparts a function of reducing allergens to a non-woven fabric, fiber or fiber product, which is washable. , And a non-woven fabric, fiber or fiber product that can reduce allergens.

Claims (4)

  An allergen-reducing composition for fibers, comprising a titania sol.   The allergen-reducing composition for fibers according to claim 1, wherein the titania sol has a pH range of 5-9. A non-woven fabric, fiber or fiber product obtained by processing the fiber allergen-reducing composition according to claim 1 or 2 without using a binder. A method for reducing the allergen that contacts the nonwoven fabric, fiber, or fiber product by processing the fiber allergen-reducing composition according to claim 1 or 2 into a nonwoven fabric, fiber, or fiber product.