JP7007540B2 - Allergen reduction and antibacterial composition - Google Patents

Description

The present invention relates to liquid allergen reduction and antibacterial compositions. Further, the present invention relates to reduction of allergens such as mites and pollen existing in a room and the like, reduction of allergens for suppressing the growth of various germs, and an antibacterial composition.

Allergic diseases such as asthma, atopic dermatitis, and allergic rhinitis are plagued by many people, and have been increasing in recent years. The causes of these allergic diseases are various allergens existing in the environment, and among them, mites, pet hair, pollen, and mold that live indoors are typical inhalable allergens. Well known. In particular, house dust mites, house dust mites, have become a major problem as a source of allergens. For house dust mites, textile products in the house such as tatami mats, rugs, bedding, and curtains, or even outdoors, seat fabrics for moving vehicles such as trains and automobiles are hotbeds for growth.

Among the house dust mites, Dermatophagoides farinae and Dermatophagoides pteronysinus are typical species, and the carcasses and feces of these mites are strong allergen substances. In addition, pollen of various plants, including pollen of Sugi ( Cryptomeria japonica ) scattered in early spring, is also an allergen and causes allergic rhinitis in particular. There are many types of pollen scattered throughout the year, including not only cedar pollen in early spring, but also hinoki, mugwort, ragweed, and Dactylis, and there is a risk of causing allergies due to pollen at any time. It is thought that there is.

In the living environment, especially in the living space around water such as kitchens, washrooms, toilets, and bathrooms, germs are likely to propagate, which causes an unpleasant odor. In order to suppress the generation of such an odor, it is important to suppress the growth of various germs, and although it could be temporarily reduced by a deodorant, it was not a fundamental solution. Various antibacterial compositions have been proposed to suppress the growth of various germs, such as antibacterial metal salts as inorganic antibacterial agents, natural components such as green tea components as organic antibacterial agents, and quaternary ammonium salts. Cationic antibacterial agents such as the above are used (Patent Documents 1 to 4). Recently, there has been a demand for an agent that can reduce allergens such as mites and pollen at the same time as deodorizing by suppressing the growth of various germs.

Japanese Unexamined Patent Publication No. 2004-189606 Japanese Unexamined Patent Publication No. 2005-168579 Japanese Unexamined Patent Publication No. 2004-357746 Japanese Unexamined Patent Publication No. 2007-135489

It is an object of the present invention to provide an allergen-reducing and antibacterial composition capable of reducing allergens existing in a living environment such as mites and cedar pollen and further suppressing the growth of various germs in the treated portion.

As a result of diligent research to solve such problems, the present inventors have conducted a composition containing a zinc salt of hydroxy acid and a cationic antibacterial agent, as well as a zinc salt of hydroxy acid, a rare earth salt and cationic. The present invention has been completed by finding that a composition containing an antibacterial agent can efficiently reduce allergens present in a living environment and suppress the growth of various germs.

That is, the present invention is (1) an allergen-reducing and antibacterial composition containing zinc hydroxyate and a cationic antibacterial agent, and (2) an allergen-reducing and antibacterial composition containing zinc hydroxyate, a rare earth salt and a cationic antibacterial agent. It is an antibacterial composition, and (3) the allergen-reducing and antibacterial composition mentioned above, wherein the rare earth salt is one or more salts selected from lanthanum salt, cerium salt, gadrinium salt and itterbium salt, and (4). The allergen reduction and antibacterial agents listed in (1) to (3), wherein the zinc hydroxyate is zinc gluconate and the cationic antibacterial agent is at least one selected from the bisquatic pyridinium salt and the polyhexamethylene biguanide. It is a composition, and (5) a bisquatic pyridinium salt is 1,4-bis (3,3'-(1-decylpyridinium) methyloxy) butanedibromid, listed in (1) to (4). The allergen-reducing and antibacterial composition according to (1) to (5), which is an allergen-reducing and antibacterial composition, and is characterized in that (6) the intended use is for spraying.

Using the allergen-reducing and antibacterial composition of the present invention, interior materials such as carpets, sofas, wallpapers, curtains, etc. in the environment, such as indoor floors and walls, duvet side areas, duvet covers, duvet batting, sheets. , Pillowcases, bedding such as mats, car seats, automobile parts such as car mats, stuffed animals and the like can be provided with a composition that can be sprayed, applied, processed or removed or wiped from the above-mentioned articles. When removing or wiping from the above-mentioned article, the allergen-reducing and antibacterial composition of the present invention can be processed into paper, non-woven fabric, fiber or the like to form a wiper, towel, sheet or the like.

The zinc salt used in the present invention is a zinc salt of hydroxy acid, and the hydroxy acid is a carboxylic acid having one or more hydroxyl groups, and specific examples thereof include glycolic acid, glyceric acid, and gluconic acid. Examples thereof include glucuronic acid, lactic acid, tarthronic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitrate acid, leucic acid, mevalonic acid, pantoic acid, ricinolic acid, chymic acid and the like. Of these, gluconic acid, citric acid and lactic acid are preferable, and gluconic acid is more preferable. For example, zinc gluconate has an acute oral toxicity of more than 5000 mg / kg in rats, is extremely safe, and is used as a food substitute for breast milk and as a food with health claims for the purpose of prevention and treatment of zinc deficiency. ing.

The rare earth salts used in the present invention include scandium salt, ytterbium salt, lanthanum salt, cerium salt, placeodium salt, neodymium salt, samarium salt, europium salt, gadolinium salt, terbium salt, disprosium salt, formium salt, elbium salt and turium. Examples thereof include salt, ytterbium salt and lutethium salt, and lanthanum salt, cerium salt, gadolinium salt and ytterbium salt are particularly preferable, and lanthanum salt and cerium salt are more preferable. As these rare earth salts, those commercially available as general reagents or industrial raw materials can be used.

As the salt, any salt having any counterion can be used, and chloride salts, sulfates, nitrates, bromide salts, iodide salts, carbonates, phosphates, organic acid salts, hydroxides and the like can be used. It can be exemplified. Examples of the organic acid salt include monovalent or divalent carboxylic acids and salts of hydroxy acids, and specific examples of the hydroxy acids include lactic acid, gluconic acid, tartrate acid, citric acid, and malic acid, and monovalent or divalent. Examples of the valent carboxylic acid include acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and azelaic acid. Of these, chloride salts and hydroxy salts are preferable, and chloride salts, gluconate salts and lactates are more preferable.

As the hydroxy acid rare earth salt, commercially available reagents or industrial raw materials can be used, but it can also be prepared as an aqueous solution from hydroxy acid and a general-purpose inorganic rare earth salt or rare earth oxide. It is possible. As these hydroxy acids for preparation, those commercially available as reagents or industrial raw materials can be generally used. The preparation includes a method of directly reacting a rare earth oxide with an aqueous solution of hydroxy acid. Further, an alkali metal hydroxide is reacted with an aqueous solution of an inorganic rare earth salt such as chloride to prepare a rare earth salt hydroxide in advance, and then hydroxy acid is reacted with the hydroxide to prepare a rare earth hydroxy acid. It is possible. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and sodium hydroxide is preferable.

As the cationic antibacterial agent, a bis-quaternary pyridinium salt or a polyhexamethylene biguanide is preferable, and two or more of these may be used in combination. Examples of the bis quaternary pyridinium salt include 1,4-bis (3,3'-(1-decylpyridinium) methyloxy) butanedibromid, which is commercially available as Hygenia (registered trademark, manufactured by Tama Chemical Industry Co., Ltd.), for example. It can be obtained by manufacturing the product, the method described in Japanese Patent Laid-Open No. 2005-162731, JP-A-2006-001889, or a method similar thereto.

Polyhexamethylene biguanide is a compound represented by the following chemical formula (I), which is a polymer in which hexamethylene groups and biguanide groups are alternately bonded, and n in the formula is an integer in the range of 10 to 16, and n is different. It is also possible to use a mixture of compounds. As the salt of polyhexamethylene biguanide, any salt such as hydrochloride, sulfate, organic acid salt, etc. can be used, but usually, the salt salt commercially available under the name such as "PHMB" should be used. Can be done.

The blending ratio of zinc hydroxyate and rare earth salt in the allergen reduction and antibacterial composition of the present invention is 0.01 to 9% for zinc hydroxyate for spraying use or processing into non-woven fabric, paper or fiber. It can be preferably used in the range of 0.1 to 5%, more preferably 0.2 to 2%, 0 to 10% for rare earth salts, preferably 0.01 to 2%, still more preferably 0. It can be used in the range of 05 to 1%. The blending ratio of the cationic antibacterial agent in the allergen reduction and antibacterial composition of the present invention is 0.001% to 1%, preferably 0.002 to 0.5%, more preferably 0.005 to 0.005 to 1% for spraying applications. It can be used in the range of 0.1%. Further, in the application for processing a cationic antibacterial agent into a non-woven fabric, paper or fiber, it may be used in the range of 0.001% to 5%, preferably 0.005 to 2%, and more preferably 0.01 to 1%. can.

The allergens targeted by the allergen-reducing and antibacterial composition of the present invention include allergens derived from the feces of Dermatophagoides pteronysinus ( Dermatophagoides pteronysinus ), allergens derived from worms (Der p2), and Dermatophagoides farinae (Dermatophagoides). Examples include fecal-derived allergens (Der f1) and insect body-derived allergens (Der f2). Examples of plant-derived allergens include pollen-derived allergens (Cry j1) of Sugi ( Cryptomeria japonica ), and allergens such as hinoki, ragweed, yomogi, kamogaya, and harugaya. In addition, allergens derived from dog hair and dandruff (Can f1, Can f2), allergens derived from cat hair and dandruff (Fel d1), allergens derived from cockroaches (Brag1, Bra g2), and allergens derived from mold (Brag1, Brag2). Alt a1), allergens derived from natural rubber latex and the like can be mentioned. Among these, mite-derived allergens and cedar pollen-derived allergens are regarded as particularly important as allergens that need to be reduced.

Bacteria targeted by the allergen-reducing and antibacterial composition of the present invention include generally propagating bacteria such as Staphylococcus aureus , Escherichia coli , and Pseudomonas aeruginosa . Resistant bacteria such as MRSA can also be mentioned as the target bacteria.

Further, when the allergen-reducing and antibacterial composition of the present invention is formulated, it is suitable to use a water-based liquid preparation, and the zinc salt of the hydroxy acid and the rare earth salt are used as the total active ingredient from 0.01 to 0.01. It is contained in the range of 5%, preferably 0.1% to 3%, and more preferably 0.1 to 2%. When used as a spraying agent, it is also possible to add a volatile organic solvent in order to improve the drying property when sprayed. There are no particular restrictions on such an organic solvent, but ethanol is an example of a highly volatile solvent that does not pose a safety problem. Further, it is also possible to add a fragrance, a deodorant component, or the like as other components to the spray agent.

The above spraying agent can be applied to living spaces such as indoors and spaces in vehicles such as cars and trains, and reduces various allergens such as mites and pollen that are present in the space due to adhesion or floating. It becomes possible to do.

It is possible to add a surfactant for the purpose of improving stability and dissolving oily components such as fragrances in the preparation. The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. The type of nonionic surfactant is not particularly limited, but for example, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, sorbitan fatty acid ester, poly. Examples thereof include oxyethylene sorbitan fatty acid ester. Examples of the anionic surfactant include alkylbenzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, dialkyl sulfosuccinate and the like. Examples of the cationic surfactant include aliphatic amine salts and quaternary ammonium salts thereof, and examples of the amphoteric surfactant include betaine-type 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 also possible to further add other known allergen-reducing components to the allergen-reducing and antibacterial composition of the present invention as long as the physical properties are not impaired. Examples of the allergen-reducing component include hydroxybenzoic acid-based compounds such as dihydroxybenzoic acid and 2,4,6-trihydroxybenzoic acid or salts thereof, polystyrene-based compounds such as parahydroxypolystyrene and polystyrene sulfonate, and natural products such as persimmon astringent. Examples thereof include extracts and inorganic salt compounds such as calcium salts and strontium salts.

When the allergen-reducing and antibacterial composition of the present invention is used for the purpose of removing allergens from indoor dust mites, the allergen-reducing effect can be further sustained by processing at the same time as the acaricide. .. The acaricide used is not particularly limited as long as it has a lethal effect or a repellent effect on indoor dust mites, and is, for example, benzyl alcohol, benzyl benzoate, phenyl salicylate, cinnamaldehyde, hisop oil, carrot seed oil. Etc., and pyrethroid compounds such as natural pyrethrin, phenothrin, permethrin, organophosphorus compounds such as phenothrin, malathion, fenthion, and diadinone, dichophor, chlorbenzylate, hexithiazox, tebufenpyrado, pyridaben, amide flumeth, etc. are used. be able to.

Examples of the fragrance include ethyl acetoacetate, anisaldehyde, methyl anthranilate, anethole, ethylvanillin, eugenol, geraniol, benzyl acetate, methyl salicylate, citral, citronellal, citronellol, cineole, n-decyl alcohol, α-terpineol, vanillin. , Pinene, benzyl succinate, methyleugenol, limonene, linalol and the like. Natural essential oil-based fragrances include orange oil, katsura oil, perilla oil, sparemint oil, sage oil, thyme oil, tea tree oil, nutmeg oil, basil oil, pimento oil, peppermint oil, lavender oil, lemon oil, and rosemary. Examples include oil and eucalyptus oil.

In the allergen reduction and the formulation of the antibacterial composition of the present invention, in addition to the above-mentioned surfactant and anti-tick agent, a chelating agent, a rust preventive agent, an anti-scale agent, an antifoaming agent and an antistatic agent are required. It is also possible to add an agent, a resin binder, a thickener, a softening agent and the like.

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

The following reagents and the like were used as raw materials for the preparation of Examples and Comparative Examples.

Zinc gluconate trihydrate (Helcious Zn (registered trademark), manufactured by Fuso Chemical Industry Co., Ltd.)
Lanthanum chloride heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
Lanthanum oxide (manufactured by Wako Pure Chemical Industries, Ltd.)
90% lactic acid (manufactured by Musashino Chemical Laboratory Co., Ltd.)
Proxel IB (PHMB 20% solution, registered trademark, Lonza Japan Co., Ltd.)
Hygenia S-100 (manufactured by Tama Chemical Co., Ltd.)

Preparation of Lactic Acid Lantern Aqueous Solution 4.5 g of 90% lactic acid solution and 69.0 g of ion-exchanged water were mixed in a 100 mL volume Erlenmeyer flask equipped with a condenser cooling tube, and 1.2 g of lanthanum oxide was further added. The mixture was heated to 75 ° C. in a hot water bath and stirred for 3 hours to dissolve lanthanum oxide. The mixture was allowed to cool to obtain an aqueous solution of lactic acid lanthanum.

The formulations shown in Tables 1 and 2 were prepared by mixing, stirring and dissolving.

[Test Example 1] Bactericidal activity test In order to evaluate the antibacterial activity against bacteria, a bactericidal activity test was performed using Staphylococcus aureus (NBRC12732). Staphylococcus aureus strains pre-cultured in TGC liquid medium were suspended in sterile water, and 5 mL of the bacterial solution adjusted so that the viable cell count was about ¹⁰⁶ CFU / mL was dispensed into test tubes. Each composition was added to the bacterial solution to a predetermined concentration (0.5% or 2%) with respect to the bacterial solution. After a predetermined time (30 minutes and 1 hour) had elapsed from the addition, 100 μL was collected from each test tube and collected in a petri dish, and 15 mL of the medium was added to uniformly dissolve the mixture. The viable cell count was measured by culturing at 37 ° C. for 3 days and counting the number of colonies generated. Sterilized water was used as the blank. The results are shown in Table 3.

[Test Example 2] Measurement of reduction effect of mite allergen Each composition is added to 1 mL of an allergen solution containing the mite allergen Der f2 and having a protein amount of about 900 ng / 1 mL {phosphate buffer solution (pH 7.2)}. , 150 μL or 500 μL, respectively.

Next, 100 μL of the extract obtained by reacting the mite allergen with the above composition was added dropwise per well, and the mixture was reacted at 37 ° C. for 60 minutes. After the reaction, the plates were washed with phosphate buffer (pH 7.2). Peroxidase-labeled anti-Der f2 monoclonal antibody was dissolved in phosphate buffer {pH 7.2, containing 1 wt% bovine serum albumin and 0.05 wt% polyoxyethylene (20) sorbitan monolaurate} at 200 μg / mL. A solution obtained by diluting it 1200 times with a phosphate buffer solution (pH 7.2, containing 1 wt% bovine serum albumin and 0.05 wt% polyoxyethylene (20) sorbitan monolaurate) was added in an amount of 100 μL per well. .. After reacting at 37 ° C. for 60 minutes, the plates were washed with phosphate buffer (pH 7.2). To 6.5 mL of 0.1 mol / L phosphate buffer (pH 6.2), add 1 tablet of ortho-phenylenediamine dihydrochloride (13 mg Tablet, manufactured by Wako Pure Chemical Industries, Ltd.) and 6.5 μL of 30% hydrogen peroxide solution. 100 μL of hydrogen peroxide was added per well, and the mixture was reacted at 37 ° C. for 3 minutes. Immediately after that, 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 microplates (manufactured by Tecan Japan Co., Ltd.). The results are shown in Table 4.

[Test Example 3] Measurement of reduction effect of cedar pollen allergen Each composition is added to 1 mL of an allergen solution of about 12.5 ng / 1 mL {phosphate buffer (pH 7.2)} as cedar pollen allergen Cry j1. 150 μL or 500 μL was reacted.

Next, 100 μL of the extract sample obtained by reacting the cedar pollen allergen with the above composition was added dropwise per well, and the mixture was reacted at 37 ° C. for 60 minutes. After the reaction, the plates were washed with phosphate buffer {pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate}. Peroxidase-labeled Cry j1 monoclonal antibody 053 was dissolved in distilled water at 200 μg / mL and dissolved in phosphate buffer {pH 7.2, 1 wt% bovine serum albumin and 0.1 wt% polyoxyethylene (20) sorbitanmono. A solution diluted 1200-fold with laurate-containing} was added in an amount of 100 μL per well. After reacting at 37 ° C. for 60 minutes, the plates were washed with phosphate buffer {pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate}. Add 100 μL of ortho-phenylenediamine dihydrochloride (manufactured by SIGMA CHEMICAL CO.: 26 mg Tablet) and 13 μL of hydrogen peroxide solution to 13 mL of 0.1 mol / L phosphate buffer (pH 6.2). , 37 ° C. for 5 minutes. Immediately after that, 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 spectrophotometer for microplates (manufactured by Tecan Japan Co., Ltd.). The results are shown in Table 5.

To use the allergen-reducing and antibacterial composition of the present invention containing zinc hydroxyate and a cationic antibacterial agent, as well as the allergen-reducing and antibacterial composition containing zinc hydroxyate, a rare earth salt and a cationic antibacterial agent. Therefore, the allergen property of allergens such as mites and pollen can be reduced without causing the problem of coloring, and the growth of various germs can be suppressed.

Claims (3)

Floors, walls containing 0.01-9% zinc hydroxyate as an allergen reducing agent, one or more cationic antibacterial agents and rare earth salts selected from the group consisting of bisquatic pyridinium salts and polyhexamethylene biguanides. , Carpets, sofas, wallpapers, curtains, duvet sides, duvet covers, duvet batting, sheets, pillowcases, mats, car sheets, car mats and stuffed animals.
Or an allergen-reducing and antibacterial composition for processing into at least one of the group consisting of paper, non-woven fabrics and fibers .
Further, the zinc hydroxyate is zinc gluconate,
An allergen-reducing and antibacterial composition, wherein the allergen is at least one allergen selected from the group consisting of mite allergens and cedar pollen allergens. The allergen-reducing and antibacterial composition according to claim 1, wherein the rare earth salt is one or more salts selected from a lanthanum salt, a cerium salt, a samarium salt, a gadolinium salt and a ytterbium salt. The allergen reduction and allergen reduction according to claim 1 or 2, wherein the bisquatic pyridinium salt is 1,4-bis (3,3'-(1-decylpyridinium) methyloxy) butanedibromid. Antibacterial composition.