JP2013064058A - Anti-allergen composition - Google Patents

Abstract

[PROBLEMS] To provide an anti-allergen composition that reduces allergenicity of allergen substances such as mites and pollen, and even if processed anti-allergen products such as non-woven fabric, fibers or fiber products processed with the anti-allergen composition are washed with water. Maintain the durability without losing the function to reduce the property, and do not cause coloration or discoloration, and use these compositions and processed products to efficiently improve the allergenicity of allergenic substances present in the environment It is to be able to reduce.
An anti-allergen composition containing particulate tungsten oxide having an average particle size of 5 μm or less is provided. The tungsten oxide may be a tungsten oxide supporting a transition metal such as platinum, copper, zinc, nickel and cobalt, and a paint, coating agent, resin product, wallpaper, processed such an anti-allergen composition, Non-woven fabric, fiber or fiber product. Furthermore, it is set as the allergen reduction method of the allergen substance which consists of using these in a human living environment.
[Selection figure] None

Description

  The present invention relates to an anti-allergen composition that reduces allergenicity of allergens such as mites and pollen, and paints, coating agents, resin products, wallpaper, nonwoven fabrics, fibers or textile products using the same, and life using them The present invention relates to a method for reducing allergenicity of allergen substances in the environment.

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 become 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 pteronyssinus 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 such allergens such as mites and pollen, there is a method of passing air to the filter using an air conditioner or an air purifier, but only allergens flying in the air can be removed, and allergens in the filter can be removed. As a result of collecting the material, there is a risk of allergen re-entrainment when changing the filter.

  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 effective as a 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. Conceivable.

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 have been made as anti-allergen agents that hardly cause coloring or discoloration. For example, methods using inorganic salts such as zinc and magnesium have been proposed (Patent Documents 1 and 6).

  However, such an inorganic salt is water-soluble, and since it is washed away by water, there is a problem that it cannot be used for applications that require washing resistance such as fibers.

Several proposals have recently been made regarding anti-allergens that are not washed away by water.
Furthermore, as an anti-allergen 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 (Patent Document 2) However, allergen inactivating agents using silicon dioxide, zinc oxide, and aluminum oxide have been proposed, but they were not satisfactory in terms of water resistance and continuous allergen inactivating performance.

  In addition, these anti-allergen agents are not water-soluble, but when processed using a resin emulsion such as an acrylic emulsion as a binder on non-woven fabrics, fibers, fiber products, plastic products, and wood materials (Patent Document 7), the amount of the binder is low. When it is sufficient, the anti-allergen agent is covered to prevent runoff, but the antiallergen performance itself is not exhibited. If the amount of the binder is small, the runoff cannot be prevented and the effect cannot often be maintained.

  In addition, those using a photocatalyst such as titanium oxide as an anti-allergen agent have been proposed (Patent Documents 3, 4, 5, 7, and 8). There is a risk that the processed substrate itself may deteriorate.

Japanese translation of PCT publication No. 2004-510717 JP 2006-239393 A JP 2007-145742 A JP 2007-146453 A JP 2006-265498 A JP 2006-241431 A JP 2008-237793 A JP 2005-278781 A

  As described above, in the background art of the present invention, since the anti-allergen agent is easily washed away (washed out or dropped out) with water, the washing resistance is not sufficient when processed into a fiber or the like. However, there is a problem that the anti-allergen agent cannot be used in applications that require these functions.

  Therefore, the problem of the present invention is to solve the above-mentioned problems of the background art, and to provide an anti-allergen composition that reduces allergenicity of allergen substances such as mites and pollen, and further processed with the anti-allergen composition, Anti-allergenic processed products such as fibers or textile products should retain durability without losing the function of reducing allergenicity even when washed with water, and will not cause coloring or discoloration. It is to be able to efficiently reduce the allergenicity of allergenic substances present in the environment using a product.

  The inventors of the present application have conducted intensive research to solve such problems, and as a result, fine tungsten oxide having an average particle diameter of 5 μm or less, preferably 0.01 μm or more, has an excellent effect as an antiallergen. And further found to be effective as an antiallergen having water resistance.

  That is, the present invention is (1) an anti-allergen composition characterized by containing a particulate tungsten oxide having an average particle diameter of 5 μm or less (preferably 0.01 μm or more), and (2) tungsten oxide is An anti-allergen composition which is tungsten oxide supporting a transition metal, and (3) an anti-allergen composition wherein the transition metal supported is one or more metals selected from platinum, copper, zinc, nickel and cobalt. (4) paints, coating agents, resin products, wallpaper, non-woven fabrics, fibers or fiber products obtained by processing these anti-allergen compositions, and (5) these anti-allergen compositions are applied to paints, coating agents, Resin products, wallpaper, non-woven fabrics, fibers or textile products, and by making these processed products exist in the living environment of human beings, This is an allergen reduction method that reduces the allergenicity of allergen substances in the environment.

  The present invention provides an anti-allergen composition that reduces the allergenicity of allergen substances such as mites and pollen by using an anti-allergen composition characterized by containing tungsten oxide having a predetermined particle size. Non-allergenic processed products such as non-woven fabrics, fibers or fiber products processed with the composition are maintained with good durability without losing the function of reducing allergenicity even when washed with water, and further, do not cause coloring or discoloration, Moreover, there exists an advantage that the allergenicity of the allergenic substance which exists in an environment can be efficiently reduced using processed products, such as these compositions, a filter, and a mask.

  The fine particulate tungsten oxide used in the present invention can be a fine powder of tungsten oxide available as an industrial raw material. If such tungsten oxide powder is dispersed in water or a solvent, it can be used in various applications. Easy to use. When dispersing, a surfactant or the like as a dispersant can be appropriately added.

  When preparing tungsten oxide carrying a metal that enhances photocatalytic properties, the metal to be carried on tungsten oxide is mixed. Alternatively, it can be obtained by mixing a metal salt to be supported on a compound to be a precursor of tungsten oxide, forming or applying the mixture as necessary, and then firing or irradiating light. .

  For example, when preparing tungsten oxide supporting platinum, it is preferable that zero-valent platinum is supported, and metallic platinum can be mixed. For example, a divalent or tetravalent platinum compound is combined with an organic substance. A tungsten oxide carrying platinum is obtained by mixing with a precursor of tungsten oxide and firing it or irradiating it with light.

  Examples of the precursor of tungsten oxide include tungstate. Various types of tungstate can be used. Examples thereof include tungstates such as sodium tungstate, potassium tungstate, and ammonium tungstate.

  Examples of the divalent and tetravalent platinum compounds described above include, but are not limited to, dichlorodiammine platinum (II), dinitroammine platinum (II), tetraammine platinum (II) chloride, platinum chloride (II), tetrachloroplatinum ( II) Potassium acid, hexachloroplatinum (IV) acid and the like can be used.

  These platinum compounds may be used in combination of two or more. In addition, there is no particular limitation on the organic substance to be mixed to reduce the metal salt, but carbon materials such as graphite, polyethylene, polypropylene, polymethyl methacrylate, polycarbonate, polystyrene, polyacrylic acid ester, polyimide, epoxy resin, starch Etc. can be used. These organic substances may be used in combination of two or more.

  The amount of the metal to be supported is usually 3.0 parts by mass or less, preferably 1.0 part by mass or less with respect to 100 parts by mass of tungsten oxide. When the amount of the metal to be supported exceeds 3 parts by mass, an efficient improvement of the antiallergen effect cannot be expected, and practicality is lost in view of the cost and amount of the metal to be supported.

  Various metals can be used as the metal to be supported, and examples include transition metals such as copper, zinc, cobalt, nickel, palladium, ruthenium, rhodium, platinum, silver, gold, iridium, and among these, platinum, copper Gold is preferred. These metals can be used in the form of fine particles, oxides, hydroxides, nitrates, sulfates, chloride salts, organic acid salts, carbonates, and phosphates, not just one type. Two or more types can be used in combination.

  When firing a mixture of the tungsten oxide precursor and the organic substance and metal salt compound, a firing apparatus such as an airflow firing furnace, a tunnel furnace, or a rotary furnace can be used. The firing temperature in that case is set in the range of 350 to 750 ° C, preferably in the range of 400 to 550 ° C. Moreover, what is necessary is just to set a calcination time suitably according to a calcination temperature and the kind of baking apparatus, However, Usually, it is set in the range of 10 minutes-30 hours, Preferably it is set in the range of 30 minutes-10 hours.

  When the average particle size of tungsten oxide or tungsten oxide supporting a metal in the present invention is 5 μm or less, a higher allergen reducing effect is exhibited. In addition, the lower limit of the average particle diameter of tungsten oxide is not particularly recognized from the operational effects of the present invention, but the average particle diameter is preferably 0.01 μm or more from a practical viewpoint, more preferably. Is 0.03 μm or more.

  When tungsten oxide, which is a normal industrial product, is dispersed in water, the average particle size shows a value of 25 μm or more, but the particle size can be reduced by performing wet grinding using glass beads or zirconia beads. .

  The average particle size of the ground tungsten oxide or the tungsten oxide supporting the metal needs to be 5 μm or less, preferably 3 μm or less, more preferably 1 μm or less, and still more preferably 0.5 μm or less. To do.

  In order to measure the average particle size, a laser diffraction particle size distribution measuring device can be used. In Examples described later, a laser diffraction particle size distribution measuring device SALD-2200 manufactured by Shimadzu Corporation is used, and the average particle size is measured. The median diameter was used as the value of. However, other particle size distribution measuring devices such as a centrifugal sedimentation type particle size distribution measuring device can also be used. In this case, it is preferable to keep a correlation with the laser diffraction type particle size distribution measuring device.

  Also, even with the same laser diffraction particle size distribution measuring device, the measured value of the average particle diameter may differ depending on the difference in equipment manufacturer and the wavelength distribution of the laser light source, and it is preferable to keep correlation between various instruments. .

  Tungsten oxide and especially tungsten oxide supporting transition metal show the performance as a photocatalyst, but the performance as an anti-allergen agent of the present invention does not necessarily require the presence of light, and the allergen reduction effect even in the dark Demonstrate.

In addition, since tungsten oxide does not dissolve in water or an organic solvent, a flowable agent is suitable for formulation. In order to prepare the flowable agent, it is possible to wet pulverize tungsten oxide together with a dispersant. In the case of a flowable agent, it is usually advantageous to prepare a formulation based on water, but it is also possible to prepare a flowable agent based on a solvent other than water.
The content of tungsten oxide in the antiallergen composition such as a flowable agent can be adjusted in the range of 0.01 to 60%, preferably 0.1 to 50%, and more preferably 1 to 30%. If it exceeds 60%, the fluidity of the agent will decrease, and if it is less than 0.01%, the amount of active ingredients will decrease and appropriate processing will be difficult.

  Although there is no restriction | limiting in particular about the solvent used for an antiallergen composition, Both a nonpolar solvent and a polar solvent can be used. Examples of such solvents are ethanol, propyl alcohol, isopropyl alcohol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethylene glycol, propylene glycol. , Butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 1000 or less), polypropylene glycol (molecular weight 1000 or less), ethyl acetate, butyl acetate, kerosene, alkylbenzene, diethylhexyl phthalate, diethyl phthalate, dioctyl phthalate, fluid Paraffin etc. are mentioned. These solvents may be used in combination of two or more.

  As the dispersant for the flowable agent, an anionic surfactant or a nonionic surfactant, or a combination thereof is usually used, but a cationic surfactant or an amphoteric surfactant may be used. Is possible. The type of the surfactant is not particularly limited, but examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, sorbitan fatty acid ester, Examples include polyoxyethylene sorbitan fatty acid esters.

Examples of the anionic surfactant include alkyl benzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, and dialkyl sulfosuccinate. Cationic surfactants include aliphatic amine salts and quaternary ammonium salts, and amphoteric surfactants include betaine surfactants and aminocarboxylates.
Further, these nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used alone or in combination of two or more.

  It is possible to further add a known anti-allergen component to the anti-allergen composition of the present invention. Examples of such anti-allergen components include hydroxybenzoic acid-based compounds such as 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, salts thereof, and persimmons. Can be mentioned.

  When the anti-allergen composition of the present invention is used for the purpose of removing allergens from indoor dust mites, the anti-allergen effect can be further maintained by adding and processing an acaricide.

  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, hexityazox, tebufenpyrad, pyridaben, and amidoflumet are used. be able to.

  The anti-allergen composition of the present invention can be used after being processed by a method such as dipping, coating, spraying, etc. on a nonwoven fabric, fiber or fiber product. Textiles or textile products include clothing, carpets, sofas, wallpaper, curtains and other interior items, futon sides, futon covers, futon batting, sheets, pillowcases, mats and other bedding, car seats, car mats, and ceiling materials And automobile parts such as flooring, stuffed animals, etc., and non-woven 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 anti-allergen composition of the present invention. For example, nylon, cotton, polyester, wool and the like are used, and composite fibers using two or more kinds of these fibers. There is no problem. Moreover, it can be used also for the nonwoven fabric using polyethylene and a polypropylene.

The method for processing the anti-allergen composition 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.
Processing amount of the fibers, nonwoven fabrics, relative to the weight of the fiber or fiber product is 0.01 to 10 g / ^{m 2} as tungsten oxide carrying tungsten oxide or metal, preferably 0.05 to 2 g / ^{m 2} , and still more preferably 0.1 to 1 g / ^{m 2.}

  When the anti-allergen composition of the present invention is processed into a non-woven fabric, fiber, or textile product, high wash resistance is exhibited, but a binder may be used in combination in order to further improve washing durability. As for the type of 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.

  Further, the concentration of the binder to be used is not particularly limited, but the amount of the resin to be blended is desirably equal to or less than the equivalent amount of tungsten oxide. When the amount of the binder used is too large, the anti-allergen agent is covered and the effectiveness is hardly exhibited.

  In formulating the anti-allergen composition of the present invention, in addition to the aforementioned surfactant and anti-mite agent, as necessary, chelating agent, anti-rust agent, antibacterial agent, perfume, scale inhibitor, antifoaming agent, It is also possible to add an antistatic agent, a thickener, a softening agent and the like.

As a usage form of the anti-allergen composition of this invention, a processing agent use is mainly mentioned.
In addition to fibers or textile products that require washing durability, compositions that may come into contact with people in the living environment, such as softeners, deodorants, fungicides, disinfectants, insecticides, etc. It is also possible to reduce allergens in the living environment by adding to paints, adhesives, etc., and materials that humans may come into contact with in the living environment, such as wood, wooden materials, plywood, concrete, It is also possible to reduce allergens in the living environment by processing into building materials such as metal, stone, glass, etc., molded articles made of rubber, paper, resin, plastic, and the like.

  By using the anti-allergen composition of the present invention and the nonwoven fabric, fiber or fiber product processed from the same, allergens derived from mites in house dust, pet hair and epithelium such as dogs and cats, cockroaches, feathers, Allergens derived from fungi and pollen such as cedar, mugwort, hargaya, cypress, ragweed, and natural rubber latex can be reduced, and various allergens can be substantially eliminated. Therefore, the present invention works particularly effectively when the allergen in the human living environment is a mite allergen or a plant allergen in house dust.

  Hereinafter, embodiments of the present invention will be described in more detail with reference to examples and evaluation tests. In addition,% shown below is mass% altogether.

[Example 1]
30 g of tungsten oxide (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of an anionic surfactant (manufactured by Kao Corporation: Poise 520) and 69 g of water are mixed, and wet grinding is performed using glass beads having a diameter of 1 mm for 15 minutes. The glass beads were removed with a 30 mesh wire mesh. This dispersion was diluted 3 times with ion-exchanged water to obtain a 10% tungsten oxide dispersion. It was 0.4 micrometer when the average particle diameter of the tungsten oxide was measured with the laser diffraction type particle size distribution measuring apparatus (Shimadzu Corporation make: SALD2200).

[Example 2]
30 g of tungsten oxide (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of an anionic surfactant (manufactured by Kao Corporation: Poise 520) and 69 g of water are mixed, and wet pulverization is performed using glass beads having a diameter of 1 mm for 2 minutes. The glass beads were removed with a 30 mesh wire mesh. This dispersion was diluted 3 times with ion-exchanged water to obtain a 10% tungsten oxide dispersion. It was 5.0 micrometers when the average particle diameter of the tungsten oxide was measured with the laser diffraction type particle size distribution measuring apparatus.

[Example 3]
According to the method described in Example 1 of WO 11/068095, a dispersion of 10% tungsten oxide supporting platinum was obtained. It was 0.4 micrometer when the average particle diameter of the obtained tungsten oxide was measured with the laser diffraction type particle size distribution measuring apparatus.

[Comparative Example 1]
30 g of tungsten oxide (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of an anionic surfactant (manufactured by Kao Corporation: Poise 520) and 269 g of water were mixed and shaken well to obtain a dispersion of tungsten oxide 10%. The average particle diameter of tungsten oxide in this dispersion was 28 μm as measured with a laser diffraction particle size distribution analyzer.

[Comparative Example 2]
20 g of anatase-type titanium oxide (Ishihara Sangyo Co., Ltd .: ST-01), 1.0 g of an anionic surfactant (Kao Co., Ltd .: Poise 520) and 79 g of water are mixed, and wet using glass beads having a diameter of 1 mm. Grinding was carried out for 20 minutes to obtain a dispersion of titanium oxide. The average particle diameter of the titanium oxide was measured with a laser diffraction particle size distribution measuring device and was 2.7 μm.

[Comparative Example 3]
30 g of zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.), 1.0 g of an anionic surfactant (manufactured by Kao Corporation: Poise 520) and 69 g of water are mixed, and wet grinding is performed for 15 minutes using glass beads having a diameter of 1 mm. And a zinc oxide dispersion was obtained. The average particle diameter of zinc oxide was measured with a laser diffraction particle size distribution measuring device and found to be 0.7 μm.

[Comparative Example 4]
25 g of tannic acid (manufactured by Fuji Chemical Industry Co., Ltd.), 60 g of water and 15 g of ethanol were mixed and dissolved to obtain a tannic acid solution.

[Evaluation Test 1] (Measurement of Mite Allergen Reduction Effect by Anti-Allergen Composition)
Example 1 to 3 and Comparative Examples 1 to 3 with ion-exchanged water 10 times each of mite allergen Der f2 about 900 ng / mL {phosphate buffer solution (pH 7.2)} solution contained in standard house dust The diluted solution and 50 μL of distilled water as a control were reacted in the dark. These samples were measured for the mite allergen reducing effect by the sandwich method of Der f2 enzyme immunoassay (ELISA).

  First, 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 an F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC), and then added to 4 ° C. Sensitized for more than 3 days. After sensitization, the solution was discarded, and 200 μL of blocking reagent {1% by mass 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 reacting the mite allergen and the above composition 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). Then, the 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. 100 μL per well of 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 Added.

  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 (Wako Pure Chemical Industries, Ltd .: 13 mg Table) 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 (OD490 nm) was measured with a spectrophotometer for microplate (manufactured by Tecan Japan Co., Ltd.). Indicated.

  As is clear from the results in Table 1, the reduction rate of the mite allergen amount of Examples 1 to 3 is sufficiently larger than that of Comparative Examples 1 to 3, and the anti-allergen composition reduces the allergenicity of mite allergen. It can be seen that is obtained.

[Evaluation Test 2] (Measurement of reduction effect of cedar pollen allergen Cry j1 by anti-allergen composition)
Examples 1 to 3 and Comparative Examples 1 to 3 were each diluted with ion-exchanged water so that the active ingredient was 0.2%. The cedar pollen allergen Cry j1 contained in the cedar pollen is reacted with about 12.5 ng / mL {phosphate buffer (pH 7.2)} of 1 ml of these diluted solutions and 50 μL of distilled water as a control in the dark. It was. About these samples, the reduction effect of the cedar pollen allergen was measured by the sandwich method of Cry j1 enzyme immunoassay (ELISA).

First, Cry j1 monoclonal antibody 013 diluted to 2 μg / mL with a phosphate buffer (pH 7.4, containing 0.1% by mass 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% by mass polyoxyethylene (20) sorbitan monolaurate).

  Next, 100 μL of an extract obtained by reacting the cedar pollen allergen and the above composition was added dropwise at a temperature of 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1% by mass polyoxyethylene (20) sorbitan monolaurate). Peroxidase-labeled Cry j1 monoclonal antibody 053 was dissolved in distilled water at 200 μg / mL, and the solution was dissolved in phosphate buffer {pH 7.2, 1% by weight bovine serum albumin and 0.1% by weight 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 mass% polyoxyethylene (20) sorbitan monolaurate).

100 μL per well of 13 mol of 0.1 mol / L phosphate buffer (pH 6.2) plus ortho-phenylenediamine dihydrochloride (26 mg Table, manufactured by SIGMA CHEMICAL CO.) And 13 μL of 30% hydrogen peroxide solution The mixture was added and reacted 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 (OD490 nm) was measured with a microplate spectrophotometer (manufactured by Tecan Japan Co., Ltd.). The results are shown in Table 2. It was.

  As is clear from the results in Table 2, the reduction rate of the cedar pollen allergen amount of Examples 1 to 3 is sufficiently larger than that of Comparative Examples 1 to 3, and the anti-allergen composition reduces the allergenicity of the pollen allergen. You can see that things are being obtained.

[Measurement of mite allergen reduction effect by processed products]
(Processing Example 1, Processing to Nonwoven Fabric)
A non-woven fabric (20 cm × 30 cm) of 80 g / m ² was immersed for 1 minute in 50 g of a solution obtained by diluting Examples 1 to 2 or Comparative Examples 1 and 4 with ion-exchanged water 80 times, and after treatment at a squeezing rate of 200%, It was dried at 110 ° C. for 10 minutes (processing amount was 2 g / m ² ). The nonwoven fabric processed in this way was cut into two pieces, one was immersed in 4 L of ion exchange water, stirred for 30 minutes, taken out, air-dried at room temperature, and used as a sample after washing with water.

[Evaluation Test 3] (Measurement of mite allergen reducing effect of anti-allergen composition processed nonwoven fabric)
The nonwoven fabric or blank cloth processed in Processing Example 1 was cut into 5 cm × 5 cm, put into a plastic bag with a chuck, 1 mL of a standard mite allergen suspension (allergen amount 900 ng / mL) was added, and the sample and the allergen were brought into contact with each other. The contact was performed under the condition that no light was irradiated. After 1 hour, the allergen solution was squeezed out of the plastic bag with the chuck, and the mite allergen reducing effect was measured by the sandwich method of Der f2 enzyme immunoassay (ELISA) for these samples after centrifugation.

First, Der f2 monoclonal antibody 15E11 diluted to 2 μg / mL with phosphate buffer (pH 7.4, containing 0.1% by mass NaN ₃ ) was added to each well of F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC). 200 μL each was added and sensitized at 4 ° C. for 3 days or more. 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% by mass polyoxyethylene (20) sorbitan monolaurate). Next, 100 μL of the mite 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% by mass polyoxyethylene (20) sorbitan monolaurate). The peroxidase-labeled Der f2 monoclonal antibody was dissolved in distilled water at 200 μg / mL, and was dissolved in phosphate buffer {pH 7.2, 1% by weight bovine serum albumin and 0.1% by weight polyoxyethylene (20) sorbitan monolaur. A solution diluted 1000 times with a rate containing} 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 mass% polyoxyethylene (20) sorbitan monolaurate) and then with distilled water. 100 μL per well of 13 mol of 0.1 mol / L phosphate buffer (pH 6.2) plus ortho-phenylenediamine dihydrochloride (26 mg Table, manufactured by SIGMA CHEMICAL CO.) And 13 μL of 30% hydrogen peroxide solution The mixture was added and reacted at 37 ° C. for 5 minutes. Thereafter, 2 mol / L H ₂ SO ₄ was immediately added in 50 μL portions to stop the reaction, and the absorbance (OD490 nm) was measured with a spectrophotometer for microplate (manufactured by Tecan Japan Co., Ltd.). The results are shown in Table 3. .

  As is clear from the results in Table 3, the mite allergen reduction rate of Examples 1 and 2 maintains a relatively high value even after washing with water, and the anti-allergen composition reduces allergenicity even when washed with water. It can be seen that it is retained with good durability without losing the function to make it. Further, in Comparative Example 1 using tungsten oxide having a large particle size of 28 μm, the reduction rate of mite allergen was low from the beginning, and the same result was obtained after washing with water.

[Evaluation Test 4] (Measurement of reduction effect of cedar pollen allergen of anti-allergen composition processed nonwoven fabric)
Cut the non-woven fabric or blank cloth processed in Processing Example 1 into 5 cm x 5 cm, put it in a plastic bag with a chuck, add 1 mL of standard cedar pollen allergen suspension (allergen amount 12.5 ng / mL), and contact the sample with the allergen. It was. The contact was performed under the condition that no light was irradiated. One hour later, the allergen solution was squeezed out from the plastic bag with a chuck, and the mite 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 a phosphate buffer (pH 7.4, containing 0.1% by mass 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% by mass 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% by mass polyoxyethylene (20) sorbitan monolaurate). Peroxidase-labeled Cry j1 monoclonal antibody 053 was dissolved in distilled water at 200 μg / mL, and the solution was dissolved in phosphate buffer {pH 7.2, 1% by weight bovine serum albumin and 0.1% by weight 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 mass% polyoxyethylene (20) sorbitan monolaurate). 100 μL per well of 13 mol of 0.1 mol / L phosphate buffer (pH 6.2) plus ortho-phenylenediamine dihydrochloride (26 mg Table, manufactured by SIGMA CHEMICAL CO.) And 13 μL of 30% hydrogen peroxide solution The mixture was added and reacted at 37 ° C. for 5 minutes. Thereafter, 2 mol / L H ₂ SO ₄ was immediately added in 50 μL portions to stop the reaction, and the absorbance (OD490 nm) was measured with a spectrophotometer for microplate (manufactured by Tecan Japan Co., Ltd.). The results are shown in Table 4. .

  As is clear from the results in Table 4, the cedar pollen allergen reduction rate of Examples 1 and 2 maintains a relatively high value even after washing with water, and the anti-allergen composition exhibits allergenicity even when washed with water. It can be seen that durability is maintained without losing the function of reducing. In Comparative Example 1 using tungsten oxide having a large particle size of 28 μm, the reduction rate of cedar pollen allergen was initially 13%, but it was almost lost after washing, and the effect was lost by washing. I understand that.

[Processing Example 2, Processing to Nonwoven Fabric]
A non-woven fabric (20 cm × 20 cm) of 80 g / m ² was immersed in 50 g of a solution obtained by diluting Example 3 65 times or 130 times with ion-exchanged water for 1 minute, treated at a squeeze rate of 160%, and then at 110 ° C. for 10 minutes. It was dried (the processing amount was about 1 g / m ² or about 2 g / m ² ). The nonwoven fabric processed in this way was cut into two pieces, one was immersed in 4 L of ion exchange water, stirred for 30 minutes, taken out, air-dried at room temperature, and used as a sample after washing with water.

[Evaluation Test 5] (Measurement of mite allergen reducing effect of anti-allergen composition processed nonwoven fabric)
The nonwoven fabric or blank cloth processed in Processing Example 2 was cut into 5 cm × 5 cm, put into a plastic bag with a chuck, 1 mL of a standard mite allergen suspension (allergen amount 900 ng / mL) was added, and the sample and the allergen were brought into contact with each other. This was prepared by subjecting a 20 W fluorescent lamp to irradiation at 6000 lux for 1 hour and storing it in a dark place for 1 hour. Next, the allergen liquid was squeezed out from 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 samples after centrifugation.

First, Der f2 monoclonal antibody 15E11 diluted to 2 μg / mL with phosphate buffer (pH 7.4, containing 0.1% by mass NaN ₃ ) was added to each well of F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC). 200 μL each was added and sensitized at 4 ° C. for 3 days or more. 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% by mass polyoxyethylene (20) sorbitan monolaurate). Next, 100 μL of the mite 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% by mass polyoxyethylene (20) sorbitan monolaurate). The peroxidase-labeled Der f2 monoclonal antibody was dissolved in distilled water at 200 μg / mL, and was dissolved in phosphate buffer {pH 7.2, 1% by weight bovine serum albumin and 0.1% by weight polyoxyethylene (20) sorbitan monolaur. A solution diluted 1000 times with a rate containing} 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 mass% polyoxyethylene (20) sorbitan monolaurate) and then with distilled water. 100 μL per well of 13 mol of 0.1 mol / L phosphate buffer (pH 6.2) plus ortho-phenylenediamine dihydrochloride (26 mg Table, manufactured by SIGMA CHEMICAL CO.) And 13 μL of 30% hydrogen peroxide solution The mixture was added and reacted at 37 ° C. for 5 minutes. Thereafter, 50 μL of ₂ mol / L H ₂ SO ₄ was immediately added to stop the reaction, and the absorbance (OD490 nm) was measured with a microplate spectrophotometer (manufactured by Tecan Japan Co., Ltd.). The results are shown in Table 5. It was.

  As is clear from the results in Table 5, in Example 3 using the anti-allergen composition using tungsten-supported platinum, the allergen reduction effect was activated by light irradiation, and the reduction rate was increased. In addition, Example 3 had the allergen reduction effect which endures use even if it is not irradiated with light. Moreover, the allergen reduction effect is not changed before and after washing with or without light irradiation, and even if washed with water, the allergen reduction effect is maintained with good durability without losing the function of reducing allergenicity. You can see that

  According to the present invention, the allergenicity of allergenic substances such as mites and pollen can be reduced, and the antiallergen for imparting a function of reducing the allergenicity of a nonwoven fabric, fiber or textile product with durability to washing. Compositions and paints, plastic products, vinyl chloride wallpaper, nonwoven fabrics, fibers or textiles that can reduce allergens can be provided.

Claims (5)

  An anti-allergen composition comprising fine tungsten oxide having an average particle size of 5 μm or less.   The anti-allergen composition according to claim 1, wherein the tungsten oxide is a tungsten oxide supporting a transition metal.   The anti-allergen composition according to claim 2, wherein the transition metal is one or more metals selected from the group consisting of platinum, copper, zinc, nickel and cobalt.   The coating material, coating agent, resin product, wallpaper, nonwoven fabric, fiber, or textiles which processed the anti-allergen composition in any one of Claims 1-3.   An allergen substance obtained by processing the anti-allergen composition according to any one of claims 1 to 3 into a paint, a coating agent, a resin product, a wallpaper, a nonwoven fabric, a fiber or a fiber product, and using them in a human living environment. Method for reducing allergens.