JP7540685B2 - Allergen-reducing composition - Google Patents

Description

The present invention relates to an allergen-reducing composition.

Allergens such as dust mites, including Dermatophagoides farinae and Dermatophagoides pteronyssinus, and pollens, including cedar pollen and cypress pollen, have been known in recent years to cause allergic diseases, including asthma and atopic dermatitis. These allergens are present in textile products, such as clothing, curtains, and duvet covers.

Therefore, allergen-reducing compositions for inactivating allergens have been developed (Patent Document 1), and there is a demand for the development of allergen-reducing compositions that exert a more excellent allergen-reducing effect.

JP 2013-64058 A

The objective of the present invention is to provide an allergen-reducing composition that exhibits superior allergen-reducing effects.

As a result of intensive research conducted by the present inventors to solve such problems, it has been found that high allergen reduction performance can be imparted by using the composition of the present invention.
(1) An allergen-reducing composition comprising tungsten oxide and one or more compounds selected from the group consisting of titanium oxide, titanium hydroxide, and metatitanic acid.
(2) An allergen-reducing composition comprising one or more compounds selected from the group consisting of titanium oxide, titanium hydroxide and metatitanic acid, and tungsten oxide in a weight ratio of 95:5 to 50:50.
(3) A processed product comprising the allergen-reducing composition.
It is.

The present invention provides an allergen-reducing composition that has excellent allergen-reducing effects.

The compounds used in the allergen-reducing composition of the present invention include titanium oxide, titanium hydroxide, and metatitanic acid. The titanium oxide includes anatase, rutile, or brookite titanium dioxide. The titanium hydroxide includes titanium tetrahydroxide, and the metatitanic acid includes β-titanic acid.

The titanium oxide may be, for example, a titanium oxide dispersion obtained by adding commercially available titanium oxide to ion-exchanged water and pulverizing the mixture in a wet pulverizer. The average particle size of the dispersion is preferably adjusted to 5 μm or less. The titanium hydroxide may be, for example, a titanium hydroxide-containing liquid obtained by adding an alkali to an aqueous solution of a water-soluble titanium salt such as titanium tetrachloride. Another example is a titania sol obtained by peptizing the titanium hydroxide-containing liquid with a strong acid such as hydrochloric acid or nitric acid. The average particle size of the titania in the titania sol is preferably adjusted to 0.01 to 2 μm. The metatitanic acid may be, for example, a metatitanic acid-containing liquid obtained by heating and hydrolyzing a titanyl sulfate solution.

Examples of tungsten oxide used in the allergen-reducing composition of the present invention include commercially available tungsten oxide and tungsten oxide dispersions prepared by adding a dispersant to ion-exchanged water and pulverizing the mixture in a wet pulverizer. The average particle size of the tungsten oxide is preferably adjusted to 5 μm or less.

The allergen-reducing composition of the present invention is preferably formulated so that the weight ratio of one or more compounds selected from the group consisting of titanium oxide, titanium hydroxide, and metatitanic acid to tungsten oxide is 95:5 to 50:50, and more preferably 90:10 to 80:20.

The allergen-reducing composition of the present invention is usually formulated and used by adding a solvent such as water or a polar solvent. Examples of the polar solvent include ethanol, propyl alcohol, isopropyl alcohol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, N-methylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 1000 or less, polypropylene glycol having a molecular weight of 1000 or less, etc. These polar solvents can be used alone or in combination of two or more kinds.

When preparing the formulation, one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be further used, with nonionic surfactants or anionic surfactants being preferred. Examples of nonionic surfactants include polyoxyethylene alkyl phenyl ethers, polyoxyethylene styryl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of anionic surfactants include alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfates, and dialkyl sulfosuccinates. Examples of cationic surfactants include aliphatic amine salts and quaternary ammonium salts thereof. Examples of amphoteric surfactants include betaine-type surfactants and amino carboxylates.

The allergen-reducing composition of the present invention may further contain acaricides, antifungal agents, antibacterial agents, chelating agents, rust inhibitors, fragrances, scale inhibitors, defoamers, antistatic agents, thickeners, fabric softeners, fabric softeners, deodorizers, disinfectants, insecticides, and adhesives.

Acaricides include pyrethroid compounds such as natural pyrethrins, fenothrin, and permethrin, organophosphorus compounds such as fenitrothion, malathion, fenthion, and diazinon, dicofol, chlorbenzilate, hexythiazox, tebufenpyrad, pyridaben, amidoflumet, benzyl alcohol, benzyl benzoate, phenyl salicylate, cinnamaldehyde, hyssop oil, and carrot seed oil.

Examples of antifungal or antibacterial agents include 5-chloro-N-methylisothiazolone, methylene bisthiocyanate, 2-bromo-2-nitropropane-1,3-diol, glutaraldehyde, iodopropynyl butylcarbamate, zinc salt of pyridinethiol-N-oxide, 1,2-benzisothiazolone, 1,2-dibromo-2,4-dicyanobutane, chlorhexidine gluconate, 2-isopropyl-5-methylphenol, 3-methyl-4-isopropylphenol, orthophenylphenol, methyl parahydroxybenzoate, ethyl parahydroxybenzoate, and propyl parahydroxybenzoate. , butyl paraoxybenzoate, parachlorometaxylenol, parachlorometacresol, polylysine, benzalkonium chloride, didecyldimethylammonium chloride, N-n-butylbenzisothiazolone, N-octylisothiazolone, 2-(4-thiazolyl)benzimidazole, 2-methylbenzimidazolylcarbamate, tetrachloroisophthalonitrile, diiodomethylparatolylsulfone, parachlorophenyl-3-iodopropargylformal, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, fatty acid glycerin esters, hinokitiol, etc.

Examples of applications of the allergen-reducing composition of the present invention include processed products containing the allergen-reducing composition of the present invention, such as paints, coatings, resin products, wallpaper, fibers, fabric softeners, deodorants, fungicides, disinfectants, insecticides, adhesives, wood, concrete, metal, stone, glass, rubber, and plastics. The amount of the allergen-reducing composition of the present invention added is preferably 0.01 to 30% by weight based on the total weight of the processed product.

Examples of paints include water-based paints, emulsion paints, polyurethane paints, polyester paints, and oil-based paints. Examples of coating agents include car wax, polymer-based coating agents, fluorine-based coating agents, and glass-based coating agents. Examples of resin products include polyethylene, polypropylene, vinyl chloride, and ABS resin. Examples of wallpapers include polyvinyl chloride resin-based, polyolefin and other plastic-based, paper-based, fiber-based, and inorganic-based products.

The fibers include natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as nylon fibers, polyester fibers, acrylic fibers, polyurethane fibers, polypropylene fibers, and vinylon fibers; semi-synthetic fibers such as rayon fibers and cupra fibers; and composite fibers using two or more of these fibers. Other examples include cleaning wet wipers, masks, filter materials, vacuum cleaner dust bags, clothing, carpets, sofas, wallpaper, curtains, and other interior items that use fibers as a base material; bedding such as futon covers, futon batting, sheets, pillowcases, and mats; car parts such as car seats, car mats, ceiling materials, and floor materials; stuffed toys, etc.

Allergens that are reduced by the allergen-reducing composition of the present invention include allergens derived from mites in house dust, allergens derived from the hair and epithelium of pets such as dogs and cats, cockroaches, feathers, and mold, as well as pollen from cedar, mugwort, Japanese laurel, cypress, ragweed, and other plants, and natural rubber latex.

The present invention will be explained in more detail with reference to examples, comparative examples, and test examples, but the present invention is not limited to these.

(Preparation of titania sol)
1. 3.0 g of sodium hexametaphosphate (manufactured by Yoneyama Chemical Industry Co., Ltd.) was dissolved in 600 g of ion-exchanged water, and 80 g of titanyl sulfate (manufactured by Kishida Chemical Industry Co., Ltd.) was further dissolved therein. The mixture was then heated to 100° C. and heated for 2 hours to prepare titanium hydroxide.
2. The liquid containing the titanium hydroxide was cooled to 70° C., and the pH was adjusted to 6.3 using 25% aqueous ammonia (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The liquid was then subjected to suction filtration using a 12.5 cm diameter Nutsche filter with No. 5C filter paper laid thereon, and further washed with 50 g of ion-exchanged water to obtain 150 g of a cake.
3. The cake was dispersed in 100 g of ion-exchanged water, and 10 g of hydrochloric acid (special grade reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto to deflocculate the cake, thereby obtaining a dispersion liquid.
4. 10.7 g of titanium tetrachloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 2.1 g of 85% phosphoric acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added to the dispersion and then mixed for 2 hours.
5. The pH was then adjusted to 5.5 using 25% aqueous ammonia (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was subjected to suction filtration using a 12.5 cm diameter Nutsche filter with No. 5C filter paper laid thereon, and then washed with ion-exchanged water to obtain 185 g of a cake.
6. 185 g of the cake, 45 g of ion-exchanged water, and 500 g of glass beads having a diameter of 1 mm were placed in a wet mill container and ground for 30 minutes to obtain a titania sol (solid content 20%).
7. The average particle size of the particles in the thianiasol was measured using a particle size distribution analyzer SALD-2200 (manufactured by Shimadzu Corporation) and was found to be 0.5 μm. The pH was 5.5.

(Preparation of Tungsten Oxide Dispersion)
1. 3 g of Poise 520 (manufactured by Kao Corporation) was dissolved in 165 g of ion-exchanged water, 56 g of tungsten trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was added, and the mixture was pulverized for 30 minutes in a wet mill using 500 g of glass beads having a diameter of 1 mm to obtain a dispersion liquid.
2. 40 g of a 1% solution of xanthan gum (manufactured by Sansho Co., Ltd.) was added to 160 g of the dispersion liquid, and mixed using a stirrer to obtain a tungsten oxide dispersion liquid (solid content 20 wt %).
3. The average particle size of the tungsten oxide was measured using a particle size distribution analyzer SALD-2200 (manufactured by Shimadzu Corporation) and was found to be 0.6 μm.

Preparation of Formulations
The titania sol and tungsten oxide were mixed so as to obtain the weight ratio shown in Table 1, thereby preparing allergen-reduced compositions of Formulations 1 to 6.

[Table 1]

[Test Example 1]
Measurement of mite allergen reduction rate 1. Anti-Der f2 monoclonal antibody 15E11 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) diluted to 2 μg/mL with PBS (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added at 100 μL per well of an F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC Corporation) and allowed to stand at 4° C. for 3 days.
2. After standing, the liquid was discarded, and 200 μL of a blocking reagent {PBS containing 1% by weight bovine serum albumin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)} was added per well, and the plate was left to stand at 37° C. for 60 minutes.
3. The plate was rinsed with PBS (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
4. 12.5 μL of each of Preparations 1 to 6 diluted 10-fold with ion-exchanged water was mixed with 1 mL of an allergen solution containing the mite allergen Der f2 {a solution prepared by diluting PBS-T (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 10 times to give a protein content of 900 ng/mL converted to Der f2} (hereinafter referred to as the standard mite allergen solution).
5. 100 μL of these mixtures were dropped into each well and allowed to stand at 37° C. for 60 minutes.
6. The plate was rinsed with PBS (Fujifilm Wako Pure Chemical Industries, Ltd.).
7. Peroxidase-labeled anti-Der f2 monoclonal antibody 13A4 (manufactured by Fuji Film Wako Shibayagi Co., Ltd.) was dissolved at 200 μg/mL in PBS-T (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) containing 1% by weight of bovine serum albumin, and then diluted 1200-fold with PBS-T (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) containing 1% by weight of bovine serum albumin.
8. 100 μL of the 1200-fold diluted solution was added to each well and allowed to stand at 37° C. for 60 minutes.
9. The plate was rinsed with PBS (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
10. 6.5 mL of 0.2 mol/L phosphate buffer (pH 6.2) was mixed with one tablet of ortho-phenylenediamine dihydrochloride (13 mg Tablet, Fujifilm Wako Pure Chemical Industries, Ltd.) and 6.5 μL of 30% hydrogen peroxide solution, and 100 μL of the mixture was added per well and allowed to stand at 37° C. for 3 minutes.
11. 50 μL of 1 mol/L _H2SO4 was added per well, and the absorbance (OD 490 nm) was measured using a microplate spectrophotometer (manufactured by Tecan Japan Co., Ltd.) The protein concentration converted to Der _f2 was calculated from the absorbance, and the mite allergen reduction rate was calculated using formula (1).
Mite allergen reduction rate (%) = (900 - (protein amount converted to Der f2)) / 900 x 100 (1)

Table 2 shows the Der f2-equivalent protein concentration and allergen reduction rate.

[Table 2]

[Test Example 2]
Measurement of reduction rate of cedar pollen allergen 1. Cry j1 monoclonal antibody 013 (Bio Dynamics Institute Co., Ltd.) diluted to 2 μg/mL with PBS (Fujifilm Wako Pure Chemical Industries, Ltd.) was added at 100 μL per well of an F16 MAXISORP NUNC-IMMUNO MODULE plate (NUNC Corporation), and allowed to stand at 4° C. for 1 day.
2. After standing, the liquid was discarded, and 200 μL of a blocking reagent {PBS containing 1% by weight bovine serum albumin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)} was added per well, and the plate was left to stand at 37° C. for 60 minutes.
3. The plate was rinsed with PBS (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
4. 12.5 μL of each of preparations 1 to 6 diluted 10-fold with ion-exchanged water was mixed with 1 mL of a 12.5 ng/mL allergen solution of cedar pollen allergen Cry j1 (a solution prepared by diluting PBS-T (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 10 times to give a concentration of 12.5 μg/mL) (hereinafter referred to as standard cedar pollen allergen solution).
5. 100 μL of the mixture was dropped into each well and allowed to stand at 37° C. for 60 minutes.
6. The plate was rinsed with PBS (Fujifilm Wako Pure Chemical Industries, Ltd.).
7. Peroxidase-labeled Cry j1 monoclonal antibody 053 (Bio Dynamics Laboratory Co., Ltd.) was dissolved in distilled water at 200 μg/mL, and the solution was diluted 1200-fold with PBS-T (Fujifilm Wako Pure Chemical Industries, Ltd.) containing 1% by weight of bovine serum albumin. 100 μL of the solution was added per well and allowed to stand at 37° C. for 60 minutes.
8. The plate was rinsed with PBS (Fujifilm Wako Pure Chemical Industries, Ltd.).
9. 6.5 mL of 0.2 mol/L phosphate buffer (pH 6.2) was mixed with ortho-phenylenediamine dihydrochloride (13 mg tablet, Fujifilm Wako Pure Chemical Industries, Ltd.) and 6.5 μL of 30% hydrogen peroxide solution, and 100 μL of the mixture was added per well and allowed to stand at 37° C. for 5 minutes.
10. 50 μL of 2 mol/L H ₂ SO ₄ was added per well, and the absorbance (OD 490 nm) was measured using a microplate spectrophotometer (manufactured by Tecan Japan Co., Ltd.).
11. The Cry j1 concentration was determined from the absorbance, and the cedar pollen allergen reduction rate was calculated using formula (2).
Cedar pollen allergen reduction rate (%) = (12.5 - (Cry j1 amount)) / 12.5 x 100 (2)

Table 3 shows the Cry j1 concentration and the reduction rate of cedar pollen allergens.

[Table 3]

(Preparation of fibers treated with allergen-reducing composition)
Each of the allergen-reducing compositions of formulations 1 to 6 was diluted 500-fold with ion-exchanged water, and polyester fiber (basis weight: 240 g/ ^m2 ) measuring 9 cm x 23 cm was immersed in 50 mL of the diluted solution, and wrung to a wringing ratio of 220% (wringing ratio = (weight of fiber after immersion - weight of fiber before immersion) / weight of fiber before immersion x 100), and then heated and dried in a dryer at 105°C for 15 minutes to obtain an allergen-reducing composition-treated fiber.

(Creating laundry-processed fibers)
The allergen-reducing composition processed fiber cut to a size of 9 cm x 11.5 cm was placed in 200 mL of detergent solution obtained by adding 2 mL of JAFET standard detergent to 1.5 L of ion-exchanged water, and stirred for 25 minutes at 300 rpm with a mixer equipped with two pitch blades (φ=60 mm), and squeezed to a wringing rate of 300%. Next, the allergen-reducing composition processed fiber after squeezing was placed in 200 mL of ion-exchanged water, stirred for 25 minutes at 300 rpm with a mixer, and squeezed to a wringing rate of 300%. These operations were repeated to obtain a washing-processed fiber.

[Test Example 3] (Test for reducing mite allergens using fibers treated with allergen-reducing composition)
The allergen-reducing composition processed fiber and the washed fiber cut into 4 cm x 4 cm pieces were placed in a zippered plastic bag, and 1 mL of standard mite allergen liquid was added. After 1 hour, the mite allergen liquid was squeezed out of the zippered plastic bag, and the squeezed mite allergen liquid was centrifuged, and the supernatant was used as a mite allergen extract. The mite allergen extract was subjected to a mite allergen reduction test according to the procedure of the mite allergen reduction test described in [0026]. The results are shown in Table 4.

[Table 4]

[Test Example 4] (Test on the reduction of cedar pollen allergens by fibers treated with an allergen-reducing composition)
The allergen-reducing composition processed fiber and the washed fiber cut into 4cm x 4cm were placed in a zippered plastic bag, and 1mL of standard cedar pollen allergen liquid was added. After 1 hour, the cedar pollen allergen liquid was squeezed out of the zippered plastic bag, the squeezed liquid was centrifuged, and the supernatant was used as cedar pollen allergen extract. The cedar pollen allergen extract was subjected to a cedar pollen allergen reduction test according to [0029]. The results are shown in Table 5.

[Test Example 5]
Allergen reduction test for wallpaper treated with allergen-reducing composition

Preparation of PVC wallpaper 100g of PVC powder with an average degree of polymerization of 700 (PQB83, manufactured by Shin-Daiichi PVC Co., Ltd.), 50g of plasticizer diisononyl phthalate (DINP, manufactured by Taoka Chemical Co., Ltd.), 3g of stabilizer Adeka STAB (registered trademark) FL100 (manufactured by ADEKA Corporation), and 7g of isoparaffin (IP Solvent 2028, manufactured by Idemitsu Kosan Co., Ltd.) were mixed using a stirrer to obtain a PVC wallpaper surface layer liquid. The PVC wallpaper surface layer liquid was applied to an A4-sized PPC paper as a base layer so as to be 200g/ ^m2 , and heated in a dryer at 220°C for 1 minute to obtain a PVC wallpaper.

Formulations 1, 3, 4 and 6 were added to a PVC resin emulsion (Vinyblan HD-057 (registered trademark), manufactured by Nissin Chemical Industry Co., Ltd.) so that the content of each was 10% by weight, and the mixture was mixed uniformly to obtain a surface treatment agent. The surface treatment agent was applied to the PVC wallpaper so as to be 15 g/ ^m2 , and the wallpaper was heated in a dryer at 110°C for 15 minutes to obtain a wallpaper treated with an allergen-reducing composition.

A 5 mm portion of an allergen-reducing composition-treated wallpaper cut into a circle with a diameter of 8 cm was folded so that the surface coated with the surface treatment agent was concave, and 1 mL of standard mite allergen solution was dropped near the center of the allergen-reducing composition-treated wallpaper. A 5 mm portion of another allergen-reducing composition-treated wallpaper was folded from above so that the surface coated with the surface treatment agent was convex, and the two surfaces coated with the surface treatment agent were placed in a zippered plastic bag and stored at room temperature for 1 hour. 100 μL of the allergen solution was collected with a micropipette, and the amount of mite allergen was measured using the same method as in [Test Example 1]. The same operation was performed using standard cedar pollen allergen solution instead of the standard mite allergen solution, and the amount of cedar pollen allergen was measured using the same method as in [Test Example 2]. The results are shown in Table 6.

The present invention makes it possible to provide an allergen-reducing composition that can reduce allergens such as mites and pollen and that can impart the function of reducing allergens to paints, coating agents, resin products, wallpaper, and fibers, as well as processed products such as paints, coating agents, resin products, wallpaper, and fibers that can reduce allergens.

Claims (3)

An allergen-reducing composition for use against dust mites or cedar pollen, comprising tungsten oxide and one or more compounds selected from the group consisting of titanium oxide, titanium hydroxide and metatitanic acid. The allergen-reducing composition for mites or cedar pollen according to claim 1, characterized in that the weight ratio of one or more compounds selected from the group consisting of titanium oxide, titanium hydroxide and metatitanic acid to tungsten oxide is 95:5 to 50:50. A processed product comprising the allergen-reducing composition targeted against mites or cedar pollen according to claim 1 or 2.