Antiallergen-imparting agent

Abstract

The objective is to provide an anti-allergen agent that imparts anti-allergen properties to allergens such as cedar pollen and dust mites. [Solution] An anti-allergen performance agent comprising titania nanosol particles as an active ingredient, wherein the titania nanosol particles are modified on their surface with a carboxylic acid represented by formula (1) RCO2H (wherein R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 2 carbon atoms), and the weight loss at temperatures above 200°C when heated to 600°C using a differential thermogravimetric analyzer is 5% by weight or more.

Description

[Technical Field]

[0001] The present invention relates to an anti-allergen performance-imparting agent, an anti-allergen performance-imparting product, and a method for producing an article processed to have anti-allergen performance. [Background Art]

[0002] In recent years, many allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis have become a problem. Allergic diseases may be caused by allergens present in environments such as the atmosphere and residences, in addition to food allergies caused by ingesting allergen-containing foods, for example. For example, they may occur by inhaling allergens present in the atmosphere, or by contacting allergens present on doors, walls, etc. in residential spaces. For this reason, removal of allergens in the environment and reduction of allergen-active substances are also considered important. Conventionally, for reducing allergen-active substances in the environment, preparations having an action of reducing the activity of pollen allergens and dust mite allergens, for example, have been proposed (e.g., Patent Documents 1 to 3, etc.). However, these preparations have problems such as insufficient effect of reducing allergen activity, and concerns about irritation to the skin and mucous membranes due to contained surfactants and the like, resulting in insufficient safety to humans. [Prior Art Documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Unexamined Patent Publication No. 2003-081727 [Patent Document 2] Japanese Unexamined Patent Publication No. 2019-214808 [Patent Document 3] Japanese Unexamined Patent Publication No. 2017-075420 [Summary of the Invention] [Problem to be Solved by the Invention]

[0004] The present invention aims to provide an anti-allergen performance-imparting agent that imparts anti-allergen properties to allergens such as cedar pollen and dust mites. [Means for solving the problem]

[0005] The inventors of this invention conducted extensive research to solve the above problems and discovered that titania nanosol particles modified with a specific carboxylic acid exhibit excellent anti-allergen performance against allergens such as cedar pollen and dust mites, not only in the outdoors where light is present but also in dark places where light does not reach. As a result, the inventors have solved the above problems.

[0006] The present invention is summarized in the following terms: 1. An anti-allergen performance agent comprising titania nanosol particles as an active ingredient, wherein the titania nanosol particles are modified on their surface with a carboxylic acid represented by formula (1) RCO2H (wherein R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 2 carbon atoms), and the weight loss at temperatures above 200°C when heated to 600°C using a differential thermogravimetric analyzer is 5% by weight or more. 2. The anti-allergen performance-imparting agent according to 1, wherein the average particle size of the titania nanosol particles is in the range of 1 to 5 nm. An anti-allergen product containing the anti-allergen performance-imparting agent described in 3.1 or 2. A method for producing an article that has been processed to impart anti-allergen properties, comprising incorporating an anti-allergen performance imparting agent described in 4.1 or 2 into the article or coating it on the surface of the article. [Effects of the Invention]

[0007] The anti-allergen performance imparted by the present invention exhibits excellent anti-allergen performance against allergens such as cedar pollen and dust mites, making it useful for imparting anti-allergen properties to various articles. Furthermore, titania nanosol, the active ingredient of the anti-allergen performance imparting agent of the present invention, has high transparency as well as excellent film-forming ability with high density. Therefore, by incorporating or coating an article with the anti-allergen performance imparting agent of the present invention, it is possible to exhibit excellent anti-allergen performance even in the dark, under conditions without light. [Modes for carrying out the invention]

[0008] The following describes in detail the method for manufacturing the anti-allergen performance imparting agent, the anti-allergen performance imparting product, and the anti-allergen performance imparting article of the present invention. In this specification, "titanium dioxide" or "titania" does not refer only to titanium dioxide (TiO2), but also includes titanium dioxide with oxygen depleted, such as titanium trioxide (Ti2O3), titanium monoxide (TiO), Ti4O7, Ti5O9, etc., as well as titanium hydroxide (Ti(OH)4). Furthermore, it may also contain groups other than Ti-O-Ti, which are partly due to the synthesis of titanium dioxide, as represented by terminal OH groups. In addition, it may also include titanium dioxide with a carboxylic acid represented by the following formula (1) bonded to the terminal OH group.

[0009] <About the titania nanosol particles of this invention> The anti-allergen performance-imparting agent of the present invention contains titania nanosol particles as an active ingredient, wherein the titania nanosol particles are modified on their surface with a carboxylic acid represented by formula (1)RCO2H (wherein R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 2 carbon atoms). Here, "modified with carboxylic acid" means that the titania nanosol particle surface is in one or more of the following states: "containing carboxylic acid," "having carboxylic acid attached," or "having carboxylic acid bonded to it (covalent bond, hydrogen bond, etc.)." Examples of alkyl groups for R in formula (1) above include methyl group, ethyl group, n-propyl group, etc., and examples of hydroxyalkyl groups include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, etc. Specifically, examples of monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, etc., and examples of hydroxycarboxylic acids include glycolic acid, lactic acid, etc. Furthermore, from the viewpoint of volatility, toxicity, and decomposability, R in formula (1) above is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and from the viewpoint of water solubility and odor, a methyl group is preferred. In other words, from the viewpoint of volatility, toxicity, and decomposability, formic acid and acetic acid are preferred as monocarboxylic acids, and glycolic acid and lactic acid are preferred as hydroxycarboxylic acids. Also, from the viewpoint of water solubility and odor, acetic acid is particularly preferred. The carboxylic acids represented by formula (1) above can be used individually or in combination of two or more types.

[0010] The titania nanosol particles in this invention exhibit a weight loss of 5% by weight or more at temperatures above 200°C when heated to 600°C, as measured by a differential thermogravimetric analyzer (TG-DTA). In the present invention, the titania nanosol particles are modified with a carboxylic acid represented by formula (1) above, so the carboxylic acid represented by formula (1) is gradually eliminated in the range of 200 to 600°C. For example, if the carboxylic acid represented by formula (1) is acetic acid, the acetic acid is gradually eliminated in the range of 200 to 600°C, with a peak at approximately 260°C. As described above, the titania nanosol particles in this invention are modified with a carboxylic acid represented by formula (1), which suppresses aggregation of titania nanosol particles during drying or firing. This makes them less prone to cracking and peeling when coated, resulting in excellent coatability, transparency, and density in the coating, while also suppressing cracking and peeling. As a result of suppressing cracking and peeling, not only can the anti-allergen performance-granting effect be enhanced, but it is also useful in methods for manufacturing anti-allergen products and articles that have been processed to impart anti-allergen performance. It is generally known that when titania nanosol particles are modified with a carboxylic acid represented by formula (1) above, their performance as a photocatalyst decreases. However, in the present invention, as described above, the anti-allergen performance can be improved despite being modified with a carboxylic acid represented by formula (1) above because of its excellent crack- and peel-suppression effect. In the present invention, the titania nanosol particles are preferably modified with a large amount of carboxylic acid represented by formula (1) above. As a result, as described above, the carboxylic acid represented by formula (1) gradually detaches in the range of 200 to 600°C, and when the temperature is increased using a differential thermogravimetric analyzer, the weight loss above 200°C becomes significant. In the present invention, the titania nanosol particles, when heated to 600°C using a differential thermogravimetric analyzer, exhibit a weight loss of 5% by weight or more at temperatures above 200°C, but more preferably 7-20% by weight. In this case, the detailed conditions for the differential thermogravimetric simultaneous thermometry device (TG-DTA) are: atmosphere: air, heating rate: 3°C / min.

[0011] In the present invention, the average particle size of the titania nanosol particles is preferably in the range of 1 to 5 nm, and more preferably in the range of 2 to 4 nm. By setting the average particle diameter of the titania nanosol particles in the present invention within the above range, not only can the effect of imparting anti-allergen performance be enhanced, but also a film with high transparency and high density can be formed upon coating. Generally, when the average particle diameter of titania sol is small, the coated coating film undergoes large shrinkage during heating, so cracks and peeling from the substrate are likely to occur. However, despite the small average particle diameter of the titania nanosol particles in the present invention, they are excellent in coatability, and thus are useful in products imparted with anti-allergen performance and methods for producing articles processed to be imparted with anti-allergen performance. The average particle diameter of the titania nanosol particles in the present invention refers to a value measured by electron microscope (TEM) observation.

[0012] The specific surface area of the titania nanosol particles in the present invention is 150 to 500 m 2 / g, preferably in the range of 200 to 400 m 2 / g, and the range of / g is more preferable. By setting the specific surface area of the titania nanosol particles in the present invention within the above range, the effect of imparting anti-allergen performance can be enhanced. The specific surface area of the titania nanosol particles in the present invention refers to a value measured by the BET method.

[0013] The crystal form of the titania nanosol particles in the present invention is preferably anatase type. By adopting the anatase type, the effect of imparting anti-allergen performance can be enhanced. Further, for the same reason, there is no crystal form other than anatase type, and it is more preferable that the crystal form is 100% anatase type.

[0014] <Regarding the method for producing titania nanosol particles of the present invention> The titania nanosol particles in the present invention are (A) a step of mixing a titanium-containing substance, the carboxylic acid represented by the above formula (1) and water to obtain a dispersion; (B) a step of heating the dispersion obtained in the step (A) at a temperature higher than 80°C for 1 hour or longer, and In step (A) above, the mixing ratio of the titanium-containing substance and the carboxylic acid represented by formula (1) above can be obtained by a manufacturing method in which the amount of the carboxylic acid represented by formula (1) is 0.5 moles or more per mole of titanium in the titanium-containing substance.

[0015] Process (A) There are no particular restrictions on the titanium-containing substance as long as it becomes titanium oxide upon heating. In other words, titanium oxide and / or titanium oxide precursors are preferred as titanium-containing substances, specifically including titanium oxide; titanium hydroxide; titanium alkoxide; titanium halides such as titanium trichloride and titanium tetrachloride (especially those neutralized with a base); and metallic titanium. These titanium-containing substances can be used individually or in combination of two or more. Among these, titanium alkoxide, titanium hydroxide, or titanium halides (especially those neutralized with a base) are preferred from the viewpoint of the dispersibility, applicability, and anti-allergen performance of the resulting titania, and titanium alkoxide is more preferred from the viewpoint of purity, dispersibility, applicability, and anti-allergen performance. Examples of titanium alkoxides include titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra-n-propoxide, and titanium tetraethoxide. From the viewpoint of cost, water solubility of by-products, applicability, and anti-allergen performance, titanium tetraisopropoxide is preferred. The concentration of the titanium-containing substance in the dispersion is preferably 0.02 to 3 mol / L, and more preferably 0.05 to 3 mol / L, from the viewpoint of productivity, viscosity of the reaction solution, applicability, and anti-allergen performance. The amount of carboxylic acid represented by formula (1) above is preferably 0.5 moles or more, and more preferably 0.8 moles or more, per mole of titanium in the titanium-containing substance, from the viewpoint of dispersibility, coatability, anti-allergen performance, and cost. The more carboxylic acid represented by formula (1) above is used, the better the long-term stability and coatability during coating. There is no particular upper limit, but it is usually 10 moles per mole of titanium in the titanium-containing substance. The concentration of the carboxylic acid represented by formula (1) in the dispersion is preferably 0.005 to 2.5 mol / L, and more preferably 0.025 to 1.5 mol / L, from the viewpoint of dispersibility, applicability, anti-allergen performance, and cost.

[0016] The pH of the dispersion obtained in such a process (A) is preferably in the range of 2 to less than 6, and more preferably in the range of 2.1 to less than 5, from the viewpoint of preventing corrosion of the equipment, ensuring safety during handling, and maintaining dispersibility. In step (A), there are no particular restrictions on the method of preparing the dispersion. The titanium-containing substance, the carboxylic acid represented by formula (1) above, and water (solvent) may be mixed simultaneously or sequentially. In particular, from the viewpoint of preventing aggregation and the formation of large clumps, and allowing for continued stirring, it is preferable to mix the carboxylic acid represented by formula (1) above and water (solvent) first, and then add the titanium-containing substance while stirring. In general, inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid (especially strong inorganic acids), which are often used in the hydrothermal synthesis reaction of titania nanoparticles, are not used in the present invention for the production of titania nanosol particles. These inorganic acids are generally not used in the present invention because they result in titania nanoparticles with a mixture of brookite and anatase crystal forms, as well as poor storage stability of the resulting dispersion, and from the viewpoint of equipment corrosion, impurities, and wastewater.

[0017] Process (B) The heating temperature should be higher than 80°C, preferably 82°C or higher. Below 80°C, cracks are likely to occur, resulting in poor coatability and rapid detachment, making it difficult to form a coating. There is no particular upper limit on the heating temperature, but it is usually 120°C when reacting at atmospheric pressure. During heating, stirring is preferable from the viewpoint of ensuring a sufficient reaction between the titanium-containing substance, the carboxylic acid represented by formula (1), and water. There are no particular restrictions on the method of stirring, and conventional methods can be followed. Furthermore, the stirring time is preferably 1 hour or more, and more preferably 1.5 hours or more, from the viewpoint of ensuring a sufficient reaction between the titanium-containing substance, the carboxylic acid represented by formula (1), and water. There is no particular upper limit on the stirring time, but it is usually 240 hours. The pH of the dispersion obtained in step (B) is preferably in the range of 2 to less than 6, and more preferably in the range of 2.1 to less than 5, from the viewpoint of preventing corrosion of the equipment, ensuring safety during handling, and maintaining dispersibility. Subsequently, the titania nanosol particles can be recovered by conventional methods such as precipitation and centrifugation. That is, an anti-allergen performance imparting agent of the present invention can be obtained, which contains titania nanosol particles modified with the carboxylic acid represented by formula (1) as an active ingredient.

[0018] <Dispersion of titania nanosol particles according to the present invention> The titania nanosol particle dispersion of the present invention can be made even more uniform by using the reaction solution obtained through steps (A) to (B) above and adding a dispersion step such as ultrasonic dispersion. In this case, conventional titania sol dispersions could not be obtained without using a dispersant, but the titania nanosol particle dispersion of the present invention can be made with a dispersion that is far more dispersible than conventionally known titania nanoparticles, even without adding a dispersant, although a dispersant may be added. As a result of the good dispersibility, when applied as a coating, it is possible to make a coating film with excellent crack resistance. Furthermore, since a dispersant does not need to be used, it is also possible to make a dense titania coating. In this case, in the dispersion of titania nanosol particles of the present invention, the total amount of the dispersion of titania nanosol particles of the present invention is set to 100% by mass, and the water content as the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 80% by mass or more, from the viewpoint of ease of coating and film properties of the coating.

[0019] It is also possible to extract the titania nanosol particles from the dispersion of titania nanosol particles of the present invention and change the solvent from water to another solvent. Alternatively, water may be removed from the reaction solution by centrifugation or filtration and replaced with an organic solvent. In this case, it is preferable not to dry the titania nanosol particles of the present invention from the viewpoint of dispersibility and transparency. Organic solvents used in dispersions include alcohols. These alcohols include aliphatic alcohols with 1 to 6 carbon atoms such as methanol, ethanol, and isopropanol, as well as non-aliphatic alcohols such as α-terpineol; glycol solvents such as butyl carbitol (diethylene glycol monobutyl ether), hexylene glycol (2-methyl-2,4-pentanediol), ethylene glycol-2-ethylhexyl ether, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; and diols such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. In addition to alcohols, any solvent that has affinity for titania and other solvents (water, alcohol, etc.) is acceptable, and examples include diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate, triethylene glycol diacetate, and tetraethylene glycol diacetate. Among these, diethylene glycol monobutyl ether acetate and tetraethylene glycol dimethyl ether are preferred from the viewpoint of boiling point, etc.

[0020] <Allergens> The anti-allergen agent of the present invention exhibits excellent anti-allergen performance against dust mite-derived allergens in house dust, pet hair and epithelium from dogs and cats, cockroaches, feathers, and mold-derived allergens, and plant allergens such as pollen from cedar, mugwort, sweet vernal grass, cypress, ragweed, and natural rubber latex. Among these, it is particularly effective when the environmental allergens are dust mite allergens or plant allergens in house dust. Due to the manifestation of this anti-allergen property, the anti-allergen performance imparting agent of the present invention can impart anti-allergen properties to a variety of articles.

[0021] <Method for manufacturing articles with anti-allergen properties> The anti-allergen performance imparting agent of the present invention can be used to manufacture articles that have been processed to impart anti-allergen performance, such as by incorporating it into an article or coating it on the surface of an article. This allows for the production of articles that have been processed to impart anti-allergen performance. By incorporating or coating an article with the anti-allergen performance imparting agent of the present invention, anti-allergen performance can be imparted, and the article can then exhibit anti-allergen performance. In this invention, articles that can be processed to impart anti-allergen properties include industrial products and their raw materials used in various fields. Specific examples of industrial products include paints, adhesives, synthetic rubber latex, inks, resin films, resin products, gypsum boards, roofing materials, wall materials, flooring materials, joinery, coated paper, wallpaper, exterior floor coverings, office automation equipment, home appliances, air conditioning equipment, vacuum cleaners, desks, chairs, sofas, benches, windows, straps, handles, seats, automatic ticket gates, automatic ticket vending machines, vending machines, doors, fences, handrails, tableware, cooking utensils, packaging films, packaging bags, bottles, containers, packaging packs, sinks, toilets, stationery, books, shelves, toothbrushes, mirrors, filters, masks, coats, and jackets. Examples include trousers, skirts, dress shirts, knit shirts, blouses, sweaters, cardigans, nightwear, underwear, diapers, supporters, socks, tights, stockings, hats, scarves, mufflers, neck wraps, stoles, gloves, clothing linings, clothing interlinings, clothing padding, work clothes, uniforms, school uniforms, etc., as well as curtains, screen doors, bedding fabric, bedding cotton, bedding covers, pillowcases, sheets, mats, carpets, towels, handkerchiefs, wall coverings, bandages, bandages, etc., and composite materials of these.

[0022] In the present invention, "incorporating into an article" is not particularly limited as long as the article contains titania nanosol particles, which are the active ingredient of the anti-allergen performance imparting agent of the present invention (preferably, in a manner in which the titania nanosol particles, which are the active ingredient, are present on the surface of the article), and can be appropriately selected depending on the type of article. Examples of incorporation include mixing into an article, kneading into the article during the manufacturing process, and impregnating an article (for example, an article made of a fiber aggregate). In the present invention, "coating the surface of an article" is not particularly limited as long as titania nanosol particles, which are the active ingredient of the anti-allergen performance imparting agent of the present invention, are present on the surface of the article, and can be appropriately selected depending on the type of article. Examples of coating methods include applying to the surface of the article, spraying onto the surface of the article, or immersing the surface of the article. The coating methods include both methods in which the titania nanosol particles, which are the active ingredient of the anti-allergen performance imparting agent of the present invention, are fixed to the surface of the article, and methods in which they are not fixed. The anti-allergen performance imparting agent of the present invention is preferably prepared by adjusting the viscosity of a titania nanosol particle dispersion according to the application. For example, a low viscosity is preferred when used for spin coating, dip coating, spraying, etc., a higher viscosity is preferred when used for brush coating, squeegeeing, etc., and an even higher viscosity is preferred when used for screen printing to suppress fluidity during coating. The resulting coating film is, as described above, highly transparent and dense, thereby exhibiting excellent effects. The amount of the anti-allergen performance imparting agent of the present invention can be appropriately selected depending on the manner of use, the type of article to which it is applied, the period for which anti-allergen performance is expected, etc. For example, when incorporated into industrial products, the amount of titania nanosol particles, which are the active ingredient of the anti-allergen performance imparting agent of the present invention, can be 10 to 50,000 mg per 1 kg of industrial product. [Examples]

[0023] The present invention will be described in more detail below with reference to test examples, etc., but the present invention is not limited to these examples. The present invention's anti-allergen performance-imparting agent exhibits an anti-allergen performance-imparting effect, as demonstrated in the test examples.

[0024] (1) Preparation of test specimens for the examples 142.1 g (0.5 mol) of titanium tetraisopropoxide was mixed with 30 g (0.5 mol) of acetic acid and stirred for 60 minutes. Then, 538 g of water was added, and the mixture was stirred at atmospheric pressure (0.10 MPa) at 95°C for 3 hours. Subsequently, a dispersion containing titanium dioxide nanoparticles was obtained by high-pressure dispersion treatment. The pH of this dispersion was 2.6. When this dispersion was applied to glass by spin coating and dried, a transparent coating film was obtained. This dispersion was dried to obtain titania nanoparticles, which were used as the example test sample. TEM observation of these titania nanoparticles revealed an average particle size of approximately 3 nm. Furthermore, X-ray diffraction analysis of the obtained titania nanoparticles showed that they were 100% anatase-type, with no other crystalline forms present. The TG-DTA titania nanoparticles, which were dried using a moisture meter at 200°C until weight loss ceased, were then heated to 600°C under an air atmosphere at a rate of 3°C / min. The weight loss above 200°C was 10%. This weight loss above 200°C corresponds to the weight loss due to the elimination of acetic acid, the carboxylic acid represented by formula (1) above. Since the liberated acetic acid almost completely volatilizes below 200°C, a weight loss of 10% above 200°C indicates that the surface of the titania nanoparticles of the present invention is modified with the carboxylic acid represented by formula (1) above.

[0025] (2) Preparation of comparative test specimens 2.0 g of sodium hexametaphosphate was dissolved in 600 g of deionized water, and 80 g of titanyl sulfate was further dispersed. The mixture was heated in a boiling water bath for 2 hours. Next, it was cooled to 70°C, the pH was adjusted to 6.0 using 25% ammonia water, and after suction filtration, it was washed with deionized water to obtain 150 g of cake. This cake was dispersed in 100 g of deionized water, and 10 g of hydrochloric acid was added to dissolve it. This dispersion was wet-milled using 1 mm diameter glass beads for 20 minutes to obtain titania sol (solid content 15%), which was used as the comparative example test sample. The average particle size of this thianya sol was 0.8 μm. The pH was measured to be 1.4.

[0026] (3) Test to confirm the performance of inactivating cedar pollen allergens The effectiveness test for conferring anti-cedar pollen allergen performance was commissioned to an external testing institution. The outline of the testing method is as follows: A dispersion of titania sol particles of the example test sample or comparative example test sample is placed on a 5cm x 5cm glass plate, with a titanium dioxide content of 100mg / m². 2 Each test specimen was prepared by applying the mixture with a brush in the manner described above. Glass plates without the test sample coating were considered unprocessed. The concentration of the allergen suspension was adjusted (509.4 ng / mL) so that the purified cedar pollen allergen Cry j1 concentration was approximately 100 ng / test specimen. 0.2 mL of this suspension was dropped onto each test specimen, and the specimens were subjected to either dark conditions (4 hours) or light irradiation conditions (black light: Toshiba FL20S-BLB, 0.25 mW / cm²). 2 The reaction was carried out under conditions of light irradiation (4 hours). After the reaction, samples were collected from each test specimen using PBS + Tween20 (10 mL), and the Cry j1 concentration was quantified using an ELISA measurement kit for Cry j1. Unprocessed samples were also subjected to the same procedure for Cry j1 concentration quantification after being placed in the dark or under light irradiation conditions for 4 hours. The detection limit for these samples was 0.1 ng / test specimen. The cedar pollen allergen inactivation performance of the examples and comparative examples was evaluated using the values ​​calculated by the following formulas 1 to 3. The reduction rate (%) of cedar pollen allergens in untreated samples under dark conditions and light-irradiated conditions was calculated as C1 (dark) and C1 (light-irradiated) using the calculation formula 1 below. [Calculation Formula 1] C1 = {1 - (Amount of Cry j1 recovered from the test specimen ÷ Amount of Cry j1 recovered from the unprocessed product)} × 100 The reduction rate (%) of cedar pollen allergens due to light irradiation was calculated as ΔC1 using the calculation formula 2 below. [Calculation formula 2] ΔC1 = C1 (light exposure) - C1 (darkness) The reduction rate (%) of cedar pollen allergens in the example, comparative example, or unprocessed product was calculated as C2 (darkness) and C2 (light irradiation) using the calculation formula 3 below. [Calculation Formula 3] C2 = {1 - (Amount of Cry j1 recovered from the test specimen or unprocessed product ÷ Amount of Cry j1 inoculated (= 101.9 ng / test specimen))} × 100 Table 1 below shows the concentration of cedar pollen allergen Cry j1 (ng / test specimen) in the samples recovered from each test specimen or unprocessed product as "Recovered Cry j1 Concentration," the reduction rate of cedar pollen allergen compared to the unprocessed product (%) as "C1," the reduction rate of cedar pollen allergen by light irradiation (%) as "ΔC1," and the reduction rate of cedar pollen allergen by the example, comparative example test specimen or unprocessed product (%) as "C2."

[0027] [Table 1]

[0028] As shown in Table 1, the examples of the anti-allergen performance imparting agent of the present invention clearly demonstrated excellent allergen inactivation performance against cedar pollen allergen not only under light irradiation conditions but also under dark conditions. This result clearly demonstrates that the anti-allergen performance imparting agent of the present invention exhibits excellent anti-allergen performance imparting effects against cedar pollen allergen even indoors where ultraviolet light is difficult to reach. In contrast, a comparative example using conventionally known titania sol as the active ingredient showed an allergen-reducing effect against cedar pollen allergens under light irradiation conditions, but it was confirmed that it could not exert a sufficient allergen-reducing effect under dark conditions.

[0029] (4) Test to confirm dust mite allergen inactivation performance The test to confirm the effect of imparting anti-mite allergen performance was commissioned to an external testing institution. The outline of the test method is as follows: A dispersion of titania sol particles of the example test sample or comparative example test sample is placed on a 5cm x 5cm glass plate, with a titanium dioxide content of 100mg / m². 2 Each test specimen was prepared by applying the mixture with a brush in the manner described above. Glass plates without the test sample coating were considered unprocessed. The allergen suspension was adjusted to a concentration of 843.7 ng / mL so that the Der f1 concentration in the crude extract of house dust mite was 100 ng / test specimen. 0.1 mL of this suspension was dropped onto each test specimen, and the specimens were subjected to either dark conditions (4 hours) or light irradiation conditions (black light: Toshiba FL20S-BLB, 0.25 mW / cm²). 2 The reaction was carried out under irradiation conditions (irradiation time: 4 hours). After the reaction, samples were collected from each test specimen using PBS + Tween20 (10 mL), and the Der f1 concentration was quantified using an ELISA measurement kit for Der f1. For the unprocessed samples, the Der f1 concentration was quantified in the same manner after being left in the dark or under light irradiation conditions for 4 hours. The detection limit for these samples was 0.1 ng / test specimen. The dust mite allergen inactivation performance of the examples and comparative examples was evaluated using the values ​​calculated by formulas 4 to 6 below. The reduction rate (%) of dust mite allergens for untreated products under dark conditions and light irradiation conditions was calculated as C1 (dark) and C1 (light irradiation) respectively using the calculation formula 4 below. [Calculation Formula 4] C1 = {1 - (Amount of Der f1 recovered from the test specimen ÷ Amount of Der f1 recovered from the unprocessed product)} × 100 The reduction rate (%) of dust mite allergens due to light irradiation was calculated as ΔC1 using the following formula 5. [Calculation formula 5] ΔC1 = C1 (light exposure) - C1 (darkness) The reduction rate (%) of dust mite allergens in the example, comparative example, test specimen, or unprocessed product was calculated as C2 (darkness) and C2 (light irradiation) using the calculation formula 6 below. [Calculation formula 6] C2 = {1 - (Amount of Der f1 recovered from the test specimen or unprocessed product ÷ Amount of Der f1 inoculated (= 84.4 ng / test specimen))} × 100 Table 2 below shows the dust mite allergen Der f1 concentration (ng / test specimen) in the samples recovered from each test specimen or unprocessed product as "Recovered Der f1 Concentration", the reduction rate of dust mite allergens compared to the unprocessed product (%) as "C1", the reduction rate of dust mite allergens by light irradiation (%) as "ΔC1", and the reduction rate of dust mite allergens by the example, comparative example test specimen or unprocessed product (%) as "C2".

[0030] [Table 2]

[0031] As shown in Table 2, the examples of the anti-allergen performance imparting agent of the present invention clearly demonstrate excellent allergen inactivation performance against dust mite allergens, not only under light irradiation conditions but also under dark conditions. This result clearly demonstrates that the anti-allergen performance imparting agent of the present invention exhibits excellent anti-allergen performance imparting effects against dust mite allergens even in indoor environments where ultraviolet light is difficult to reach. The anti-allergen performance imparting agent of the present invention is thought to exhibit excellent allergen inactivation performance even in the dark, due to the high transparency of its active ingredient, titania nanosol particles, as well as its film-forming ability which is excellent in both transparency and density. It has been confirmed that it exhibits excellent allergen inactivation performance not only against cedar pollen allergens but also against dust mite allergens. [Industrial applicability]

[0032] The anti-allergen performance imparted to the present invention exhibits excellent anti-allergen performance against allergens such as cedar pollen allergens and dust mite allergens, making it useful for imparting anti-allergen performance to various articles. Furthermore, titania nanosol, the active ingredient of the anti-allergen performance imparting agent of the present invention, has high transparency as well as excellent film-forming ability with high density. Therefore, by incorporating or coating an article with the anti-allergen performance imparting agent of the present invention, it is possible to exhibit excellent anti-allergen performance even in the dark, under conditions without light.

Claims

1. The active ingredient is titania nanosol particles, and the titania nanosol particles have a surface of formula (1) RCO ２ An anti-allergen agent characterized by being modified with a carboxylic acid represented by H (wherein R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 2 carbon atoms), and exhibiting a weight loss of 5% by weight or more at temperatures above 200°C when heated to 600°C using a differential thermogravimetric analyzer.

2. The anti-allergen performance-imparting agent according to claim 1, wherein the average particle size of the titania nanosol particles is in the range of 1 to 5 nm.

3. An anti-allergen performance-imparting product containing the anti-allergen performance-imparting agent described in claim 1 or 2.

4. A method for producing an article that has been processed to impart anti-allergen properties, comprising incorporating the anti-allergen performance imparting agent described in claim 1 or 2 into the article or coating it on the surface of the article.

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