JP2017057194A - Allergen-reducing and antimicrobial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that can reduce allergens present in indoors and the like, such as mite allergens, pollen allergens, and dog and cat's hair and dandruff derived allergens and at the same time that can suppress the proliferation of various bacteria.SOLUTION: Provided is an allergen-reducing and antimicrobial composition containing a zinc salt of a hydroxy acid and a cationic antimicrobial agent, and furthermore an allergen-reducing and antimicrobial composition containing a zinc salt of a hydroxy acid, a rare earth salt and a cationic antimicrobial agent, and thereby allergens such as mites and pollen that exist in the living environment can be efficiently reduced without causing coloring problems, and the proliferation of various bacteria can be suppressed.SELECTED DRAWING: None

Description

The present invention relates to liquid allergen reducing and antimicrobial compositions. Furthermore, the present invention relates to a reduction in allergens such as mites and pollen existing indoors, an allergen reduction and antibacterial composition for suppressing the propagation of various bacteria.

Allergic diseases such as asthma, atopic dermatitis, and allergic rhinitis are plagued by many people, and in recent years, the tendency has been increasing. The causes of these allergic diseases are various allergens present in the environment. Among them, mites, pet hair, pollen, and mold that inhabit indoors are typical inhalable allergens. Well known. In particular, leopard mites, which are dust mites that live in the house, are a major problem as a source of allergens. Leopard mites are a hotbed for growing textile products in the house such as tatami mats, carpets, bedding, curtains, etc., or seat sheet fabrics of moving vehicles such as trains and cars outdoors.

Among the leopard mites, Dermatophagoides farinae and Dermatophagoides 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 living environments, especially in living spaces around water, such as kitchens, washrooms, toilets, and bathrooms, it is easy for bacteria to propagate, causing unpleasant odors. In order to suppress the generation of such an odor, it is important to suppress the propagation of various germs, and even if it can be temporarily reduced by a deodorant, it has not been a fundamental solution. Various antibacterial compositions have been proposed in order to suppress the growth of various germs. Antibacterial metal salts as inorganic antibacterial agents, natural ingredients such as green tea ingredients as organic antibacterial agents, quaternary ammonium salts, etc. Such cationic antibacterial agents are used (Patent Documents 1 to 4). Recently, in addition to deodorization by suppressing the growth of various bacteria, an agent that can simultaneously reduce allergens such as mites and pollen has been demanded.

JP 2004-189606 A JP 2005-168579 A JP 2004-357746 A JP 2007-135849 A

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

As a result of intensive studies to solve such problems, the present inventors have found that a composition containing a zinc salt of a hydroxy acid and a cationic antibacterial agent, as well as a zinc salt of a hydroxy acid, a rare earth salt and a cationic property The present inventors have found that a composition containing an antibacterial agent can efficiently reduce allergens present in the living environment and suppress the propagation of various germs, thereby completing the present invention.

That is, the present invention is (1) an allergen reducing and antibacterial composition containing zinc hydroxy acid and a cationic antibacterial agent, and (2) an allergen reducing and antibacterial agent containing zinc hydroxy acid, a rare earth salt and a cationic antibacterial agent. (3) the allergen-reducing and antibacterial composition listed above, wherein the rare earth salt is one or more salts selected from lanthanum salts, cerium salts, gadolinium salts and ytterbium salts, (4) Allergen-reducing and antibacterial listed in (1) to (3), wherein the hydroxy hydroxy zinc is zinc gluconate and the cationic antibacterial agent is at least one selected from bis quaternary pyridinium salts and polyhexamethylene biguanides (5) Bis quaternary pyridinium salt is 1,4-bis (3,3 ′-(1-decyl) (1) The allergen-reducing and antibacterial composition listed in (1) to (4), which is lysium) methyloxy) butanedibromide, and (6) characterized in that the intended use is for spraying. The allergen-reducing and antibacterial composition described in (5).

Using the allergen-reducing and antibacterial composition of the present invention, in the environment, for example, indoor floors and walls, interiors such as indoor carpets, sofas, wallpaper, curtains, duvet side, duvet covers, duvet batting, sheets Further, it is possible to provide a composition that can be sprayed, applied, processed, or removed and wiped from the article on bedding such as pillow covers and mats, automobile parts such as car seats and car mats, and stuffed animals. When removing and wiping from the 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 a hydroxy acid, and the hydroxy acid is a carboxylic acid having one or more hydroxyl groups. Specific examples include glycolic acid, glyceric acid, gluconic acid, Examples include glucuronic acid, lactic acid, tartronic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, shikimic acid, etc. Of these, gluconic acid, citric acid and lactic acid are preferred, and gluconic acid is more preferred. For example, zinc gluconate has an acute oral toxicity exceeding 5000 mg / kg in rats and is very safe. It is used as a substitute for breast milk and as a health functional food for the purpose of prevention and treatment of zinc deficiency. ing.

Examples of rare earth salts used in the present invention include scandium salt, yttrium salt, lanthanum salt, cerium salt, praseodymium salt, neodymium salt, samarium salt, europium salt, gadolinium salt, terbium salt, dysprosium salt, holmium salt, erbium salt, thulium. Salts, ytterbium salts, and lutetium salts are exemplified, and lanthanum salts, cerium salts, gadolinium salts, and ytterbium salts are particularly preferable, and lanthanum salts and cerium salts 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 counter ion can be used, such as chloride salt, sulfate salt, nitrate salt, bromide salt, iodide salt, carbonate salt, phosphate salt, organic acid salt, hydroxide, etc. It can be illustrated. Examples of organic acid salts include monovalent or divalent carboxylic acids and salts of hydroxy acids. Specific examples of hydroxy acids include lactic acid, gluconic acid, tartaric acid, citric acid, and malic acid. 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 acid salts are preferable, and chloride salts, gluconates, and lactates are more preferable.

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

As the cationic antibacterial agent, a bis-quaternary pyridinium salt or 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) butanedibromide, for example, commercially available as Hygenia (registered trademark, manufactured by Tama Chemical Industry). Can be obtained by manufacturing by the methods described in the specifications such as JP-A-2005-162731 and JP-A-2006-001889, or a method analogous 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. In the formula, n 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. However, the salt sold under the name “PHMB” is usually used as the hydrochloride. Can do.

The compounding ratio of zinc hydroxy acid and rare earth salt in the allergen-reducing and antibacterial composition of the present invention is 0.01 to 9% for zinc hydroxy acid in spraying applications or processing to nonwovens, paper or fibers, Preferably, it can be used in the range of 0.1 to 5%, more preferably 0.2 to 2%. For rare earth salts, 0 to 10%, preferably 0.01 to 2%, and more preferably 0.8%. It can be used in the range of 05 to 1%. About the compounding ratio of the cationic antibacterial agent in the allergen reduction and antibacterial composition of the present invention, 0.001% to 1%, preferably 0.002 to 0.5%, more preferably 0.005 to 0.005 for spraying applications. It can be used in the range of 0.1%. Moreover, in the processing use to the nonwoven fabric of a cationic antibacterial agent, paper, or a fiber, it is 0.001%-5%, Preferably it is 0.005 to 2%, More preferably, it is used in 0.01 to 1% of range. it can.

Of the present invention, the allergens allergen-reducing and antimicrobial composition is intended, Dermatophagoides pteronyssinus (Dermatophagoides pteronyssinus) feces-derived allergen (Der p1) and parasite-derived allergen (Der p2), D. farinae of (Dermatophagoides farinae) An allergen derived from feces (Der f1) and an allergen derived from worms (Der f2) can be mentioned. Moreover, as an allergen derived from a plant, allergens such as cypress, ragweed, mugwort, camogaya, and hurghaya are mentioned, starting with the allergen (Cry j1) derived from pollen of cedar ( Cryptomeria japonica ). In addition, allergens derived from dog hair and dandruff (Can f1, Can f2), feline hair and dandruff allergens (Fel d1), cockroach-derived allergens (Brag 1, Bra g 2), fungi allergens ( Alt a1), natural rubber latex-derived allergen and the like. Among these, allergens derived from ticks and allergens derived from cedar pollen are regarded as important as allergens that particularly require reduction.

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

In addition, when formulating the allergen-reducing and antibacterial composition of the present invention, it is suitable to be a water-based solution, and the zinc salt and rare earth salt of hydroxy acid as a total of 0.01 to 5%, preferably 0.1% to 3%, more preferably 0.1 to 2%. In addition, when used as a spray, it is possible to add a volatile organic solvent in order to improve the drying property when sprayed. Although there is no restriction | limiting in particular as such an organic solvent, Ethanol is mentioned as a highly volatile solvent which does not have a safety problem. Furthermore, a fragrance | flavor, a deodorizing component, etc. can also be added to a spray agent as other components.

The above-mentioned spray can be applied to living spaces such as indoors, spaces in vehicles such as cars and trains, and reduces various allergens such as mites and pollen that are present by adhering or floating in the space. It becomes possible to do.

In carrying out the preparation, a surfactant can be added for the purpose of improving stability and dissolving oily components such as fragrances. The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. The type of the nonionic surfactant is not particularly limited. For example, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, sorbitan fatty acid ester, polyoxyalkylene alkyl ether, Examples thereof include oxyethylene 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 thereof, and amphoteric surfactants include betaine surfactants and aminocarboxylates. These nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used alone or in combination of two or more.

The allergen-reducing and antibacterial composition of the present invention can be further added with other known allergen-reducing components as long as the physical properties are not impaired. Examples of allergen-reducing components include hydroxybenzoic acid compounds such as dihydroxybenzoic acid and 2,4,6-trihydroxybenzoic acid or salts thereof, polystyrene compounds such as parahydroxypolystyrene and polystyrenesulfonate, Examples include extracts, 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 maintained by processing simultaneously with 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, hexythiazox, tebufenpyrad, pyridaben, and amidoflumet are used. be able to.

Examples of the fragrance include ethyl acetoacetate, anisaldehyde, methyl anthranilate, anethole, ethyl vanillin, eugenol, geraniol, benzyl acetate, methyl salicylate, citral, citronellal, citronellol, cineol, n-decyl alcohol, α-terpineol, vanillin , Pinene, benzyl succinate, methyl eugenol, limonene, linalool and the like. Natural essential oils such as orange oil, cinnamon oil, perilla oil, spearmint oil, sage oil, thyme oil, tea tree oil, nutmeg oil, basil oil, pimento oil, peppermint oil, lavender oil, lemon oil, rosemary Oil, eucalyptus oil and the like.

In the allergen reduction and formulation of the antibacterial composition of the present invention, in addition to the aforementioned surfactant and anti-mite agent, chelating agent, anti-rust agent, scale inhibitor, antifoaming agent, antistatic agent as necessary 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%.

For the preparation of Examples and Comparative Examples, the following reagents and the like were used as raw materials.

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

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

Examples 1 to 5 and Comparative Examples 1 to 6 were prepared by mixing, stirring and dissolving in the formulations shown in Tables 1 and 2.

[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). A strain of Staphylococcus aureus pre-cultured in a TGC liquid medium is suspended in sterilized water, and 5 mL of the bacterial solution adjusted so that the viable cell count is about 10 ⁶ CFU / mL is dispensed into test tubes. Examples 1 to 5 and Comparative Examples 1 to 6 were added to the bacterial solution so as to have a predetermined concentration (0.5% or 2%) with respect to the bacterial solution. After a predetermined time (30 minutes and 1 hour) had elapsed after the addition, 100 μL was collected from each test tube and placed in a petri dish, and 15 mL of medium was added to dissolve uniformly. After culturing at 37 ° C. for 3 days, the number of viable bacteria was measured by counting the number of colonies generated. Sterile water was used as a blank. The results are shown in Table 3.

[Test Example 2] Measurement of mite allergen reducing effect Example 1 to 1 mL of allergen solution containing mite allergen Der f2 and about 900 ng / 1 mL {phosphate buffer (pH 7.2)} of protein. 5. Comparative Examples 1 to 6 were reacted with 150 μL or 500 μL, respectively. About these samples, the mite allergen reduction effect was measured 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 a blocking reagent {1 wt% bovine serum albumin + phosphate buffer (pH 7.2)} was added per well and reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2).

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

[Test Example 3] Measurement of reduction effect of cedar pollen allergen Example 1-5 with respect to 1 mL of allergen solution of about 12.5 ng / 1 mL {phosphate buffer (pH 7.2)} as cedar pollen allergen Cry j1. In Comparative Examples 1 to 6, 150 μL or 500 μL was reacted. These samples were measured for the effect of reducing cedar pollen allergen by the sandwich method of Cry j1 enzyme immunoassay (ELISA). First, Cry j1 monoclonal antibody 013 diluted to 2 μg / mL with phosphate buffer (pH 7.4, containing 0.1 wt% NaN ₃ ) was added per well of F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC). 100 μL each was added and sensitized at 4 ° C. for 1 day or longer. After sensitization, the solution was discarded, and a blocking reagent {1% by weight bovine serum albumin + phosphate buffer (pH 7.2, containing 0.1% by weight NaN ₃ )} was added in an amount of 200 μL per well. Reacted for 1 minute. After the reaction, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate).

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

Use of the allergen-reducing and antibacterial composition containing zinc hydroxy acid and a cationic antibacterial agent of the present invention, and further an allergen reducing and antibacterial composition containing zinc hydroxy acid, a rare earth salt and a cationic antibacterial agent Thus, the allergenicity of allergens such as mites and pollen can be reduced without causing coloring problems, and the propagation of germs can be suppressed.

Claims (6)

An allergen-reducing and antibacterial composition comprising zinc hydroxy acid and a cationic antibacterial agent. The allergen-reducing and antibacterial composition according to claim 1, comprising zinc hydroxy acid, a rare earth salt and a cationic antibacterial agent. The allergen-reducing and antibacterial composition according to claim 2, wherein the rare earth salt is one or more salts selected from lanthanum salts, cerium salts, samarium salts, gadolinium salts and ytterbium salts. The hydroxy hydroxy zinc is zinc gluconate, and the cationic antibacterial agent is at least one selected from bis quaternary pyridinium salts and polyhexamethylene biguanides. Allergen-reducing and antibacterial compositions. The allergen according to claim 1, wherein the bis-quaternary pyridinium salt is 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide. Reduced and antimicrobial composition. The allergen-reducing and antibacterial composition according to any one of claims 1 to 5, wherein the use is for spraying.