Allergen inhibitors and allergen-inhibiting products

Abstract

The present invention provides an allergen inhibitor that exhibits excellent allergen-suppressing effects and an allergen-suppressing product using the above-mentioned allergen inhibitor. [Solution] The allergen inhibitor of the present invention contains an allergen inhibitory compound having one or more acidic functional groups and in which the acidic functional groups are bonded to a nitrogen atom via one or more carbon atoms. Therefore, it effectively suppresses the reaction of allergens with specific antibodies and exhibits an excellent allergen inhibitory effect. An allergen inhibitory product containing a base material and an allergen inhibitor exhibits an excellent allergen inhibitory effect.

Description

Technical Field

[0001] The present invention relates to an allergen inhibitor and an allergen-inhibiting product. Background Art

[0002] In recent years, many allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis have become problems. The main cause of these allergic diseases is that allergens such as allergens (Der1, Der2) of Dermatophagoides pteronyssinus, which are abundant in house dust among mites inhabiting dwellings, and Japanese cedar pollen allergens (Cryj1, Cryj2), which float in large amounts in the air mainly in spring, have been increasing in living spaces.

[0003] The allergens of Dermatophagoides pteronyssinus are not the mites themselves, but the dead bodies and feces of the mites that act as allergens. Therefore, even if the mites are exterminated, it does not lead to a fundamental solution to allergic diseases.

[0004] Furthermore, Cryj1 and Cryj2, which are Japanese cedar pollen allergens, are glycoproteins with a molecular weight of about 40 kDa and about 37 kDa, respectively. When these Japanese cedar pollen allergens adhere to the nasal mucosa or the like, they are recognized as foreign substances outside the living body and cause inflammatory reactions.

[0005] Accordingly, there is a need for a technique for inactivating allergens by removing them from living spaces or denaturing them.

[0006] Patent Document 1 discloses a cellulosic fiber having allergen treatment performance, characterized in that an allergen treatment agent containing a nitrogen-containing compound having a predetermined chemical structural formula or a solvate thereof as an active ingredient is supported on the fiber. Prior Art Literature Patent Literature

[0007] Patent Document 1 Japanese Patent Publication No. 2007-31889 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, the allergen treatment ability (allergen suppression effect) of the allergen treatment agent disclosed in Patent Document 1 is insufficient, and there was a need for an allergen suppressant that exhibits a superior allergen suppression effect.

[0009] The present invention provides an allergen inhibitor that exhibits excellent allergen-suppressing effects, and an allergen-suppressing product obtained by treating an allergen target with this allergen inhibitor. [Means for solving the problem]

[0010] The allergen inhibitor of the present invention includes an allergen inhibitory compound having one or more acidic functional groups, wherein the acidic functional groups are bonded to a nitrogen atom via one or more carbon atoms.

[0011] The allergen-suppressing product of the present invention is characterized by comprising a base material and the allergen-suppressing agent contained in the base material. [Effects of the Invention]

[0012] The allergen inhibitor of the present invention includes an allergen-inhibiting compound having one or more acidic functional groups, wherein the acidic functional groups are bonded to a nitrogen atom via one or more carbon atoms. Therefore, it can effectively suppress the reaction of allergens with specific antibodies (allergen-inhibiting effect). [Modes for carrying out the invention]

[0013] The allergen inhibitor of the present invention contains as an active ingredient an allergen inhibitory compound having one or more acidic functional groups, wherein the acidic functional groups are bonded to a nitrogen atom via one or more carbon atoms. The allergen inhibitory compound may be used alone or in combination of two or more types.

[0014] The content of the allergen-suppressing compound in the allergen suppressant is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and more preferably 100% by mass.

[0015] Allergen inhibitors exhibit excellent allergen-suppressing effects by containing allergen-suppressing compounds that have one or more acidic functional groups, in which the acidic functional groups are bonded to a nitrogen atom via one or more carbon atoms.

[0016] Here, an allergen inhibitor refers to a substance that has an allergen-inhibiting effect. The allergen-inhibiting effect can be determined, for example, by the following procedure: Dissolve the cold-dried powder of the allergen in phosphate buffer (pH 7.6) to prepare an allergen solution with a protein content of 20 μg / milliliter. As the allergen, for example, a product commercially available from Cosmo Bio under the trade name "Mite Extract-Df" can be used.

[0017] Dilute the allergen inhibitor with deionized water to prepare a 1% by mass allergen inhibitor solution.

[0018] Next, prepare a test tube containing 1 milliliter of the above allergen solution, add 100 microliters of the above allergen inhibitor dilution solution to the test tube, and shake at 25°C for 16 hours to prepare the test solution.

[0019] Next, the amount of Derf1 present in the test solution in the test tube, W1 (ng / milliliter), is measured using a measuring reagent. For example, a measuring reagent commercially available from Nichinichi Co., Ltd. under the product name "Derf1 Mite Allergen Measurement ELISA Kit" can be used.

[0020] Furthermore, the amount of Derf1 present in the test solution in the test tube, W0 (ng / milliliter), is measured in the same manner as described above, except that the test solution is prepared without adding the allergen inhibitor solution to the test tube.

[0021] Then, the allergen suppression rate (%) is calculated based on the following formula, and if the allergen suppression rate is 60% or higher, it can be determined that the product has an allergen suppression effect. Allergen suppression rate (%) = 100 - (W1 / W0) × 100

[0022] The allergen suppression rate of the allergen suppressant is preferably 70% or higher, more preferably 80% or higher, more preferably 90% or higher, and most preferably 95% or higher.

[0023] The content of the allergen-suppressing compound in the allergen suppressant is preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and more preferably 100% by mass or more.

[0024] The number of acidic functional groups in the allergen-suppressing compound is preferably 1 to 5, and more preferably 3 to 5, as this improves the allergen-suppressing effect of the allergen inhibitor.

[0025] An acidic functional group is a functional group that can release hydrogen ions (protons) in an aqueous solution. The acidic functional group is preferably an H-type acidic functional group. The acidic functional group is not particularly limited; examples include a carboxyl group (-COOH), a sulfo group (sulfonic acid group) (-SO3H), a phosphonic acid group [-P(=O)(OH)2], and a phosphate group [-OPO(OH)2]. Since the allergen inhibitor has an excellent allergen-suppressing effect, carboxyl groups, sulfo groups, and phosphonic acid groups are preferred, carboxyl groups and phosphonic acid groups are more preferred, and carboxyl groups are even more preferred.

[0026] In allergen-inhibiting compounds, the acidic functional group is bonded to the nitrogen atom via one or more carbon atoms. The acidic functional group only needs to be bonded to the nitrogen atom via one or more carbon atoms, and the carbon atoms may be either carbon atoms constituting a chain skeleton or carbon atoms constituting a cyclic skeleton. However, it is preferable, and more preferable, that the carbon atoms include those constituting a chain skeleton because they provide superior allergen-inhibiting effects for the allergen inhibitor. As for the cyclic skeleton, an alicyclic skeleton is preferred, and a cycloalkane skeleton is preferred. The chain skeleton may also include cases where there is only one carbon atom. Examples of cycloalkane skeletons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norbornene, bicyclo[1.1.0]butane, bicyclo[1.1.1]pentane, bicyclo[2.1.0]pentane, bicyclo[2.1.1]hexane, bicyclo[3.1.0]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, adamantane, diamantane, and decahydronaphthalene.

[0027] The nitrogen atom content in the allergen-suppressing compound is preferably 5% or more, and more preferably 6% or more. The nitrogen atom content in the allergen-suppressing compound is preferably 12% or less, and more preferably 11% or less. When the nitrogen atom content in the allergen-suppressing compound is within the above range, the acidic functional group of the allergen-suppressing compound and the nitrogen atom interact appropriately within the molecule, improving the allergen-suppressing effect of the allergen inhibitor.

[0028] The nitrogen atom content (%) in the allergen-suppressing compound is calculated based on the following formula. If the allergen-suppressing compound forms a hydrate, the number of atoms in the water (H2O) molecule is not included in the sum of the atomic weights of all atoms constituting the allergen-suppressing compound. Nitrogen atom content (%) = 100 × (Sum of the atomic weights of all nitrogen atoms in the allergen-suppressing compound) (The sum of the atomic weights of all atoms that make up the allergen-suppressing compound)

[0029] The pH of a 0.5% by mass aqueous solution of the allergen-suppressing compound at 25°C is preferably 4.5 or less, because this helps maintain the acidity of the acidic functional group of the allergen-suppressing compound and improves the allergen-suppressing effect of the allergen inhibitor.

[0030] As allergen-inhibiting compounds, compounds represented by the following formulas (1) and (2) are preferred. First, the allergen-inhibiting compound having the structural formula represented by formula (1) will be described. Note that the allergen-inhibiting compound represented by formula (1) may also form a hydrate.

[0031] [ka]

[0032] In formula (1), R 1 Each of these is independently a hydrogen atom, -CH2-R 3 or -A 1 -R 3 This represents the R in the allergen-suppressing compound. 1 There are two of them, but there are two R 1 They may be identical or different from one another. 3 This represents a carboxyl group, a phosphonic acid group, or a sulfo group, and since it improves the allergen-suppressing effect of the allergen inhibitor, a carboxyl group or a phosphonic acid group is preferred, and a carboxyl group is more preferred.

[0033] A 1represents a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a 4-membered ring, 5-membered ring or 6-membered ring. The carbon atoms from which hydrogen atoms are removed may be the same or different from each other. The carbon atoms from which hydrogen atoms are removed (withdrawn) are carbon atoms that directly constitute the 4-membered ring, 5-membered ring or 6-membered ring, and do not include carbon atoms that constitute a substituent bonded to the 4-membered ring, 5-membered ring or 6-membered ring. Hydrogen atoms bonded to carbon atoms of the 4-membered ring, 5-membered ring and 6-membered ring may be substituted with a substituent (e.g., an alkyl group, etc.). A 1 is preferably a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a benzene ring, an alicyclic 4-membered ring, an alicyclic 5-membered ring or an alicyclic 6-membered ring. A 1 is more preferably a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a benzene ring, cyclobutane, cyclopentane or cyclohexane.

[0034] R 2 represents -CH2-R 4 or -A 2 -R 4 . R 4 represents a carboxy group, a phosphonic acid group or a sulfo group; since this improves the allergen-inhibiting effect of the allergen inhibitor, a carboxy group or a phosphonic acid group is preferred, and a carboxy group is more preferred.

[0035] A 2 represents a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a 4-membered ring, 5-membered ring or 6-membered ring. The carbon atoms from which hydrogen atoms are removed may be the same or different from each other. The carbon atoms from which hydrogen atoms are removed (withdrawn) are carbon atoms that directly constitute the 4-membered ring, 5-membered ring or 6-membered ring, and do not include carbon atoms that constitute a substituent bonded to the 4-membered ring, 5-membered ring or 6-membered ring. Hydrogen atoms bonded to carbon atoms of the 4-membered ring, 5-membered ring and 6-membered ring may be substituted with a substituent (e.g., an alkyl group, etc.). A 2 is preferably a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a benzene ring, an alicyclic 4-membered ring, an alicyclic 5-membered ring or an alicyclic 6-membered ring. A2 The preferred substituent is a divalent substituent obtained by removing (abtracting) two hydrogen atoms from the carbon atoms of a benzene ring, cyclobutane, cyclopentane, or cyclohexane.

[0036] In equation (1), the allergen-suppressing effect of the allergen inhibitor is improved, so R 1 Each of them operates independently, -CH2-R 3 It is preferable that it be -CH2-COOH or -CH2-P(=O)(OH)2, and more preferably -CH2-COOH. Two R 1 They may be identical or different from one another.

[0037] In equation (1), the allergen-suppressing effect of the allergen inhibitor is improved, so R 2 -CH2-R 4 It is preferable that the compound is -CH2-COOH or -CH2-P(=O)(OH)2, and more preferably -CH2-COOH.

[0038] In equation (1), the allergen-suppressing effect of the allergen inhibitor is improved, so R 1 and R 2 Preferably, two or more substituents are -CH2-COOH. That is, as the allergen-suppressing compound represented by formula (1), triglycolaminic acid [formula (5)] or iminodiacetic acid [formula (18)] is preferred.

[0039] [ka]

[0040] [ka]

[0041] In equation (1), A 2Since the allergen-suppressing effect of the allergen inhibitor is improved, a divalent substituent formed by removing (extracting) two hydrogen atoms from a carbon atom of a four-membered or five-membered ring is preferred, and a divalent substituent formed by removing (extracting) two hydrogen atoms from a carbon atom of cyclobutane or cyclopentane is more preferred.

[0042] In equation (1), the allergen-suppressing effect of the allergen inhibitor is improved, so R 2 ga-A 2 -R 4 and two R 1 It is preferable that both are hydrogen atoms. In formula (1), R 2 ga-A 2 -R 4 So, A 2 A divalent substituent formed by removing (extracting) two hydrogen atoms from a carbon atom of a 5-membered or 6-membered ring, with two R 1 It is more preferable that both are hydrogen atoms. In equation (1), R 2 ga-A 2 -R 4 So, A 2 However, it is a divalent substituent formed by removing (extracting) two hydrogen atoms from the carbon atoms of a benzene ring, an alicyclic five-membered ring, or an alicyclic six-membered ring, and has two R 1 It is more preferable that both are hydrogen atoms. In equation (1), R 2 ga-A 2 -R 4 So, A 2 This is a divalent substituent formed by removing (abstracting) two hydrogen atoms from the carbon atoms of benzene, cyclopentane, or cyclohexane, with two R 1 It is preferable that both are hydrogen atoms. In formula (1), R 2 ga-A 2 -R 4 So, A 2 However, a divalent substituent formed by removing (extracting) two hydrogen atoms from the carbon atoms of benzene or cyclohexane, and with two R 1 It is more preferable that both are hydrogen atoms.

[0043] In equation (1), R 2 ga-A2 -R 4 and two R 1 Examples of allergen-suppressing compounds in which both atoms are hydrogen atoms include 1-amino-1-cyclobutanecarboxylic acid [formula (6)], cycloleucine [formula (7)], 1-aminocyclohexanecarboxylic acid [formula (8)], 3-aminocyclohexanecarboxylic acid [formula (9)], 4-aminobenzoic acid [formula (15)], 3-aminobenzoic acid [formula (16)], and 2-aminobenzoic acid [formula (17)], with 4-aminobenzoic acid [formula (15)] being preferred.

[0044] [ka]

[0045] Next, we will describe allergen-suppressing compounds having the structural formula represented by formula (2). Note that the allergen-suppressing compound represented by formula (2) may also form a hydrate.

[0046] [ka]

[0047] In formula (2), R 5 This is a hydrogen atom, -CH2-R 7 , or represents the structure shown in formula (3). 5 at least two of R 5 -CH2-R 7 Alternatively, it has the structure shown in formula (3). There are four R 5 They may be identical or different from one another. 7 R represents a carboxyl group, a phosphonic acid group, or a sulfo group. 6 This represents the structure -(CH2)n- or the structure shown in equation (4), where n is an integer between 1 and 3.

[0048] [ka] In formula (3), R 8R represents a carboxyl group, a phosphonic acid group, or a sulfo group. 9 R represents a carboxyl group, a phosphonic acid group, or a sulfo group. 7 ~R 9 They may be identical or different from one another.

[0049] [ka]

[0050] In formula (4), R 10 m represents a carboxyl group, a phosphonic acid group, or a sulfo group. However, m is an integer from 1 to 3, and p is an integer from 1 to 3.

[0051] In equation (2), R 7 Since the allergen-suppressing effect of the allergen inhibitor is improved, a carboxyl group or a phosphonic acid group is preferred, and a carboxyl group is more preferred.

[0052] In equation (2), the allergen-suppressing effect of the allergen inhibitor is improved, so the four R 5 -CH2-R 7 It is preferable that this be the case.

[0053] In equation (2), the allergen-suppressing effect of the allergen inhibitor is improved, so two R 5 The structure is shown by equation (3) and the other two R 5 Preferably, one of the atoms is a hydrogen atom, and the other nitrogen atom is R 5 A substituent having the structure shown in formula (3) and a hydrogen atom are bonded to it, and the other nitrogen atom is R 5 It is more preferable that the substituent and hydrogen atom having the structure shown in formula (3) are bonded to it.

[0054] In equation (2), the allergen-suppressing effect of the allergen inhibitor is improved, so two R atoms bonded to the same nitrogen atom 5 Of these, one R 5 has the structure shown in equation (3) and the other R 5It is preferable that it is a hydrogen atom.

[0055] In equation (3), R 8 and R 9 Since each of these enhances the allergen-suppressing effect of the allergen inhibitor, a carboxyl group or a phosphonic acid group is preferred, and a carboxyl group is more preferred.

[0056] In equation (2), R 6 -(CH2)n- is preferred, and -(CH2)2- or -(CH2)3- is more preferred, as it improves the allergen-suppressing effect of the allergen inhibitor.

[0057] In equation (4), R 10 Since the allergen-suppressing effect of the allergen inhibitor is improved, a carboxyl group or a phosphonic acid group is preferred, and a carboxyl group is more preferred.

[0058] Preferred allergen-suppressing compounds represented by formula (2) include ethylenediaminetetraacetic acid [formula (10)], 1,3-diaminopropanetetraacetic acid [formula (11)], ethylenediaminedisuccinic acid [formula (12)], diethylenetriaminepentaacetic acid [formula (13)], and ethylenediaminetetra(methylenephosphonic acid) [formula (14)].

[0059] [ka]

[0060] Allergen inhibitors contain an allergen-inhibiting compound as an active ingredient. However, the method for producing allergen inhibitors is not particularly limited, and allergen inhibitors can be produced by mixing the allergen-inhibiting compound with compounds to be added as needed in a general manner.

[0061] Next, the usage instructions for the above-mentioned allergen inhibitors will be explained. Allergen inhibitors exert an allergen-suppressing effect against various allergens through the action of allergen-suppressing compounds.

[0062] Allergens targeted by allergen suppressants include animal allergens such as dust mite allergens (Der1, Der2), allergens caused by dogs and cats (Can f1, Fel d1), and plant allergens such as cedar pollen allergens (Cryj1, Cryj2) and pollen that float in the air. While any type of mite allergen can be targeted, particularly those found in indoor dust, especially bedding, and are a common cause of allergic diseases, this product is especially effective against house dust mites, particularly house dust mites, which are abundant in indoor dust and bedding. It is particularly effective against house dust mites, which are a common cause of allergic diseases. (These include mites with dorsal spiracles, mites with tetraspiracles, mites with posterior spiracles, mites with posterior spiracles, mites with mesospiracles, mites with mesospiracles, mites with anterior spiracles, mites with stag beetle mites and broad mites, house dust mites such as Dermatophagoides pteronyssinus, mites with anaspiracles, and mites with hidden spiracles, such as house dust mites and ornamental red dust mites.)

[0063] The allergen inhibitor may be used by adhering (supporting) it to the surface of the base particles. By adhering the allergen inhibitor compound to the surface of the base particles, the allergen inhibitor can be uniformly dispersed on the substrate described later without forming clumps. Therefore, the surface area of ​​the allergen inhibitor can be increased, ensuring sufficient contact between the allergen inhibitor and the allergen, and allowing the allergen inhibitor to exert its full allergen-inhibiting effect.

[0064] The base particles used to adhere the allergen inhibitor are not particularly limited, as long as they do not inhibit the allergen-inhibiting effect of the allergen inhibitor. The base particles include resin particles and inorganic particles. The base particles may be used alone or in combination of two or more types.

[0065] Examples of synthetic resins constituting the resin particles include styrene-based resins, acrylic-based resins, urethane-based resins, vinyl chloride-based resins, ABS resins, and synthetic rubbers such as styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR). Acrylic resins and styrene-based resins are preferred, and polystyrene is more preferred.

[0066] The styrene-based resin is not particularly limited and includes, for example, homopolymers or copolymers containing styrene monomers such as styrene, methylstyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, chlorostyrene, and bromostyrene as monomer units, and copolymers containing a styrene monomer and one or more vinyl monomers copolymerizable with the styrene monomer as monomer units.

[0067] Examples of vinyl monomers copolymerizable with styrene monomers include acrylic monomers such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, butyl acrylate, etc.), methacrylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.), maleic anhydride, and acrylamide.

[0068] The acrylic resin is not particularly limited and includes, for example, homopolymers or copolymers containing acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate as monomer units, and copolymers containing acrylic monomers and one or more vinyl monomers copolymerizable with the acrylic monomer as monomer units. (Meth)acrylate means acrylate or methacrylate.

[0069] Examples of vinyl monomers copolymerizable with acrylic monomers include acrylonitrile, methacrylonitrile, maleic anhydride, and acrylamide.

[0070] The inorganic compounds (inorganic materials) that make up the inorganic particles are not particularly limited, and examples include zeolites, hydrotalcite, calcium carbonate, calcium citrate, magnesium carbonate, and magnesium hydroxide.

[0071] The synthetic resin constituting the resin particles preferably contains aromatic rings. The aromatic rings attract the hydrophobic portion of the allergen-suppressing compound attached to the surface of the resin particles, causing the acidic functional groups to be oriented outward, thereby allowing the allergen-suppressing effect of the allergen inhibitor to be exerted more effectively.

[0072] The aromatic ring may be a monocyclic aromatic ring or a compound fused aromatic ring (fused aromatic ring). The aromatic ring is not particularly limited and examples include benzene rings, naphthalene rings, anthracene rings, biphenyls, and phenoxyphenyls. In an aromatic ring, one or more hydrogen atoms bonded to a carbon atom that directly constitutes the aromatic ring or fused aromatic ring are abstracted and covalently bonded to other atoms.

[0073] The amount of allergen-suppressing compound attached to the base particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of base particles. When the amount of allergen-suppressing compound attached is 1 part by mass or more, the allergen-suppressing agent can be uniformly attached to the surface of the base particles, and the allergen-suppressing effect of the allergen-suppressing agent can be exerted more effectively.

[0074] The amount of allergen-suppressing compound attached to the base particles is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, per 100 parts by mass of base particles. When the amount of allergen-suppressing compound attached is 50 parts by mass or less, the allergen suppressants do not bind to each other, and the allergen suppressants are efficiently arranged on the surface of the base particles, improving the allergen-suppressing effect.

[0075] The method for adhering the allergen inhibitor to the base particle surface is not particularly limited. For example, it may be done by the adhesive strength of the allergen inhibitor itself, or by using a binder resin to adhere the allergen inhibitor to the surface of the base particle. However, it is preferable that the allergen inhibitor is adhered to the surface of the base particle by the adhesive strength of the allergen inhibitor compound itself, as this allows the allergen inhibitory effect of the allergen inhibitor to be effectively exerted.

[0076] Allergen inhibitors are used, for example, by being incorporated into a substrate to which an allergen-inhibiting effect is to be imparted, thereby constituting an allergen-inhibiting product. A substrate containing an allergen inhibitor exhibits an allergen-inhibiting effect as an allergen-inhibiting product. The form in which the allergen inhibitor is incorporated into the substrate is not particularly limited, and examples include attaching the allergen inhibitor to the surface of the substrate or kneading the allergen inhibitor into the substrate.

[0077] By dissolving or dispersing an allergen inhibitor in a solvent to obtain an allergen inhibitor solution or dispersion, and then coating this allergen inhibitor solution or dispersion onto a substrate, the allergen inhibitor can be attached to the substrate surface.

[0078] Examples of the solvents mentioned above include water (preferably deionized water), alcohols (methyl alcohol, ethyl alcohol, propyl alcohol, etc.), hydrocarbons (toluene, xylene, methylnaphthalene, kerosene, cyclohexane, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), and amides (N,N-dimethylformamide, etc.), with water and alcohols being preferred.

[0079] The allergen inhibitor solution or dispersion may be applied to the substrate surface by spraying. That is, the allergen inhibitor solution or dispersion may be filled into a spray-type container and used.

[0080] The content of the allergen inhibitor in 100% by mass of the allergen inhibitor solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 1% by mass or more. The content of the allergen inhibitor in 100% by mass of the allergen inhibitor solution is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0081] The allergen-suppressing solution may contain additives such as aqueous solvents, oils, emulsions, and suspensions as needed.

[0082] The content of the allergen inhibitor in 100% by mass of the allergen inhibitor dispersion is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 1% by mass or more. The content of the allergen inhibitor in 100% by mass of the allergen inhibitor dispersion is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0083] The allergen suppressant dispersion may contain additives such as dispersants and thickeners, as needed.

[0084] Examples of dispersants include surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Anionic surfactants are preferred as dispersants because they improve the dispersibility of allergen inhibitors in the solution.

[0085] Examples of anionic surfactants include alkylbenzene sulfonates, salts of naphthalene sulfonic acid formalin condensate, aromatic sulfonates such as polystyrene sulfonates, alkanesulfonates, α-sulfo fatty acid salts, alkyl sulfosuccinates, α-olefin sulfonates, alkyl sulfates, alkyl sulfate esters, alkyl ethoxysulfate esters, and phosphate esters.

[0086] Examples of cationic surfactants include fatty amine salts, quaternary ammonium salts, and alkylpyridinium salts.

[0087] Examples of nonionic surfactants include polyoxyethylene derivatives such as polyoxyethylene obtained by polymerizing polyoxyethylene with oligomer-phenol complexes or tripenzylated phenols such as styrene, propylene, and butylene, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and other long-chain alkyl-phenyl ethers of polyoxyethylene, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and fatty acid alkanolamides.

[0088] Examples of amphoteric surfactants include tertiary amine oxides, betaines, and alkylbetaines.

[0089] The thickening agent may be a natural polymer compound or a synthetic polymer compound. Examples of natural polymer compounds include pectin, gelatin, carrageenan, xanthan gum, gum arabic, glucomannan, gellan gum, and alginic acid. Examples of synthetic polymer compounds include polyethylene glycol, polyvinyl alcohol, and polyacrylic acid.

[0090] The substrates for which the allergen inhibitor is contained are not particularly limited as long as they can contain the allergen inhibitor, and examples include synthetic resin molded articles, paints, coatings, wallpaper, decorative sheets, flooring materials, fibers, textile products (woven fabrics, nonwoven fabrics, knitted fabrics), interior accessories and interior materials for vehicles (e.g., cars, airplanes, ships, etc.) (seats, child seats and the foams that make them up, etc.), kitchenware, baby products, and building interior materials.

[0091] Building interior materials are not particularly limited and can include, for example, flooring, wallpaper, ceiling materials, paint, doorknobs, switches, switch covers, and wax.

[0092] Vehicle interior accessories and vehicle interior materials are not particularly limited and may include, for example, seats, child seats, seat belts, car mats, seat covers, doors, ceiling materials, floor mats, door trims, instrument panels, consoles, glove boxes, straps, handrails, etc.

[0093] The synthetic resin constituting the molded synthetic resin article is not particularly limited and includes, for example, thermoplastic resins (e.g., polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, Teflon®, acrylonitrile butadiene styrene resin, acrylonitrile styrene resin, acrylic resin, polyvinyl alcohol, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyester, polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, polyetheretherketone, thermoplastic polyimide, polyamideimide, etc.) and thermosetting resins (e.g., phenolic resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, silicone resin, polyurethane, thermosetting polyimide, etc.). The synthetic resin may be used alone or in combination of two or more types.

[0094] The allergen inhibitor may be kneaded into the synthetic resin. One method for kneading the allergen inhibitor into the synthetic resin is to mix the allergen inhibitor with the raw material synthetic resin to create a resin composition. This resin composition can then be used to obtain a molded allergen-inhibiting product of a desired shape using a general-purpose synthetic resin molding method. Examples of general-purpose synthetic resin molding methods include extrusion molding, injection molding, and blow molding. Alternatively, the synthetic resin and the allergen inhibitor may be mixed to form a masterbatch for synthetic resin molding containing the synthetic resin and allergen inhibitor. The masterbatch for synthetic resin molding can then be mixed with the raw material synthetic resin to produce a synthetic resin molded product of the allergen-inhibiting product using a general-purpose synthetic resin molding method.

[0095] The content of the allergen inhibitor in 100% by mass of the masterbatch for molding synthetic resin is preferably 5% by mass or more, and more preferably 10% by mass or more. The content of the allergen inhibitor in 100% by mass of the masterbatch for molding synthetic resin is preferably 80% by mass or less, and more preferably 70% by mass or less.

[0096] The content of the allergen inhibitor in 100% by mass of the synthetic resin molded article is preferably 1% by mass or more, and more preferably 3% by mass or more. The content of the allergen inhibitor in 100% by mass of the synthetic resin molded article is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0097] Allergen-inhibiting fibers may be manufactured by physically fixing an allergen inhibitor to fibers. Methods for physically fixing an allergen inhibitor to fibers include, for example, (1) preparing an allergen inhibitor solution by dissolving or dispersing the allergen inhibitor in a solvent, and impregnating the fibers with this allergen inhibitor solution; (2) applying or spraying the above allergen inhibitor solution onto the fiber surface; (3) immersing the fibers in a binder resin containing the dissolved or dispersed allergen inhibitor to fix the allergen inhibitor to the fibers with the binder resin; and (4) applying or spraying a binder resin containing the dissolved or dispersed allergen inhibitor onto the fiber surface to fix the allergen inhibitor to the fibers with the binder resin. Note that in methods (1) and (2) above, the allergen inhibitor solution may contain a binder resin. The solvent is the same as described above, so its explanation is omitted.

[0098] The binder resin is not particularly limited as long as it can fix the allergen inhibitor to the fiber surface. For example, examples of binder resins include urethane resins such as one-component urethane resins and two-component urethane resins, silicone resins, acrylic resins, urethane acrylate resins, polyester resins, unsaturated polyester resins, alkyd resins, vinyl acetate resins, vinyl chloride resins, epoxy resins, and epoxy acrylate resins, with urethane resins being preferred.

[0099] Allergen inhibitors may be incorporated into paints and used as allergen-inhibiting paints. Conventional paints can be used, such as oil-based paints (e.g., mixed paints, oil varnishes, etc.), cellulose paints, and synthetic resin paints. Paints also include photocurable paints that polymerize to produce binder resins upon irradiation with radiation such as ultraviolet light.

[0100] Paints may contain additives such as pigments, plasticizers, hardeners, fillers, antioxidants, thickeners, and surfactants, to the extent that they do not impair the physical properties of the paint. Methods for incorporating allergen inhibitors into paints include, for example, supplying the allergen inhibitor and paint to a dispersion device and mixing them uniformly. Examples of dispersion devices include high-speed mills, ball mills, and sand mills.

[0101] The content of the allergen inhibitor in 100% by mass of the allergen-suppressing paint is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The content of the allergen inhibitor in 100% by mass of the allergen-suppressing paint is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0102] The content of the allergen inhibitor in 100% by mass of the allergen-suppressing product is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The content of the allergen inhibitor in 100% by mass of the allergen-suppressing paint is preferably 40% by mass or less, and more preferably 30% by mass or less. [Examples]

[0103] The present invention will be described more specifically below with reference to examples, but the present invention is not limited thereto.

[0104] The following compounds were prepared as allergen-suppressing compounds. These allergen-suppressing compounds were used as allergen inhibitors.

[0105] 4-aminobenzoic acid Triglycolaminic acid [Formula (5)] • 1,3-diaminopropanetetraacetic acid [Formula (11)] • Diethylenetriaminepentaacetic acid [Formula (13)] • Iminodiacetic acid [Formula (18)] • Ethylenediamine disuccinic acid trihydrate [Trihydrate of the compound shown in formula (12)] • Ethylenediaminetetra(methylenephosphonic acid) [Formula (14)] • Sebacinic acid • Suberic acid ·benzoic acid • Diethylenetriamine iron pentaacet diammonium salt

[0106] The nitrogen atom content of the allergen-suppressing compound and the pH of a 0.5% by mass aqueous solution of the allergen-suppressing compound at 25°C are shown in the "Nitrogen Content" and "pH (25°C)" columns of Table 1, respectively.

[0107] (Examples 1-7 and Comparative Examples 1-4) Allergen inhibitors containing the allergen-inhibiting compounds (100% by mass) shown in Table 2 were prepared.

[0108] Anti-allergen tests were conducted on allergen suppressants using dust mite allergen (Derf1) and pollen allergen (Cryj1), and the results are shown in Table 2.

[0109] (Drug-Antiallergen Test) [Dust mite allergen] A freeze-dried dust mite allergen (Derf1) powder (manufactured by Cosmo Bio, product name "Mite Extract-Df") was dissolved in phosphate buffer (pH 7.6) to prepare an allergen solution with a protein content of 20 μg / ml.

[0110] An allergen inhibitor containing an allergen-inhibiting compound was prepared by adding deionized water to the allergen inhibitor to prepare a diluted solution of the allergen inhibitor with an allergen-inhibiting compound concentration of 1% by mass.

[0111] Next, a test tube containing 1 milliliter of the above allergen solution was prepared. 100 microliters of the above allergen inhibitor dilution solution was added to the test tube, and the mixture was shaken at 25°C for 16 hours to prepare the test solution.

[0112] Next, the amount of Derf1 present in the test solution in the test tube, W1 (ng / milliliter), was measured using a measuring reagent (Nichinichi Co., Ltd., product name "Derf1 Mite Allergen Measurement ELISA Kit").

[0113] Furthermore, the amount of Derf1 present in the test solution in the test tube, W0 (ng / milliliter), was measured in the same manner as described above, except that the test solution was prepared without adding the allergen inhibitor solution to the test tube.

[0114] The allergen suppression rate (%) was calculated based on the following formula. The results obtained are listed in the "Dust Mite (Derf1)" column under "Allergen Suppression Rate (%)" in Table 2. Allergen suppression rate (%) = 100 - (W1 / W0) × 100

[0115] [Pollen allergens] The allergen suppression rate was measured in the same manner as when using dust mite allergen (Derf1), except that freeze-dried powder of pollen allergen (Cryj1) (product name "Japanese Cedar Pollen Extract" manufactured by ITEA Co., Ltd.) was used instead of dust mite allergen (Derf1), and the measurement reagent (product name "Japanese Cedar Pollen Allergen Cryj1 Measurement ELISA Kit" manufactured by Nichinichi Co., Ltd.) was used instead of the measurement reagent (product name "Derf1 Dust Mite Allergen Measurement ELISA Kit" manufactured by Nichinichi Co., Ltd.) was used. The obtained results are listed in the "Pollen (Cryj1)" column of "Allergen Suppression Rate (%)" in Table 2 under "Medicine".

[0116] (Coating film - anti-allergen test) The same dust mite allergen (Derf1) and measurement reagent, as well as the pollen allergen (Cryj1) and measurement reagent used in the above-mentioned (drug-anti-allergen test), were used.

[0117] To 10 parts by mass of the allergen inhibitor obtained in the examples and comparative examples, a binder resin (Showa Denko Co., Ltd., product name "Polysol AM-200", solvent: water, solids content: 40% by mass) was added to prepare an allergen-inhibiting coating by adding 90 parts by mass of solids. Next, a polyester film was prepared as a substrate. The allergen-inhibiting coating was applied to one side of this substrate to a film thickness of 10 μm after drying, and then dried in an oven at 120°C for 1 hour to prepare an allergen-inhibiting product with a coating film formed on one side.

[0118] The freeze-dried powders of the above allergens were separately dissolved in purified water to prepare allergen aqueous solutions containing 10 μg / mL of each allergen. Then, PBS-T (phosphate buffer containing 0.05% by mass of Tween 20 (manufactured by Tokyo Chemical Industry Co., Ltd.), pH: 7.4) was added to the allergen aqueous solutions and mixed uniformly to prepare an allergen solution containing 15 ng / mL of each allergen.

[0119] The above allergen-suppressing product was cut into a flat square with sides of 5 cm, 0.4 mL of the above allergen solution was dropped onto the coating film, and then the product was covered with a flat square polyethylene film with sides of 4 cm and left at 25°C for 24 hours to prepare the test solution. Next, the amount of allergen W1 (ng / mL) in the test solution was measured using the above measurement reagent.

[0120] Blank products were prepared in the same manner as described above, except that a binder resin (Showa Denko Corporation, product name "Polysol AM-200", solvent: water, solids content: 40% by mass) was used as the blank coating instead of the allergen-suppressing coating. The amount of allergens present in the test solution W0 (ng / mL) was measured in the same manner as described above, except that a blank product was used instead of the allergen-suppressing coating. The allergen suppression rate (%) was calculated based on the following formula. The obtained results are recorded in the "Dust Mites (Derf1)" and "Pollen (Cryj1)" columns under "Coating Film" in "Allergen Suppression Rate (%)" in Table 2, respectively. Allergen suppression rate (%) = 100 - (W1 / W0) × 100

[0121] (Fiber-Anti-Allergen Test) The same dust mite allergen (Derf1) and measurement reagent, as well as the pollen allergen (Cryj1) and measurement reagent used in the above-mentioned (drug-anti-allergen test), were used.

[0122] Purified water was added to 1 g of the allergen inhibitor obtained in the examples and comparative examples and mixed uniformly to prepare an allergen inhibitor dispersion containing 1% by mass of the allergen inhibitor.

[0123] Next, as the base material, we use polyester fiber (Toray Polyester Tropical, manufactured by Irozome Co., Ltd., weight: 120g / m²). 2A solution was prepared. The fibers were immersed in 100g of the above allergen inhibitor dispersion for 2 minutes. The immersed polyester fibers were squeezed with a manual mangle and dried at 120°C for 10 minutes to produce allergen-inhibiting fibers in which the allergen inhibitor was fixed to the polyester fibers. In the allergen-inhibiting fibers, the allergen inhibitor was 1g / m 2 It contained it.

[0124] The freeze-dried powders of the above allergens were separately dissolved in purified water to prepare allergen aqueous solutions containing 10 μg / mL of each allergen. Then, PBS-T (phosphate buffer containing 0.05% by mass of Tween 20 (manufactured by Tokyo Chemical Industry Co., Ltd.), pH: 7.4) was added to the allergen aqueous solutions and mixed uniformly to prepare an allergen solution containing 15 ng / mL of each allergen.

[0125] 0.4 g of allergen-suppressing fiber was placed in a resealable plastic bag, 1 mL of the above allergen solution was added dropwise, and the bag was sealed and left at 25°C for 2 hours to prepare the test solution.

[0126] Next, the amount of allergen W1 (ng / mL) in the test solution was measured using the above-mentioned measurement reagent.

[0127] Except for not placing the allergen-suppressing fibers in the resealable plastic bag, the amount of allergen present in the test solution W0 (ng / mL) was measured in the same manner as described above. The allergen suppression rate (%) was calculated based on the following formula. The obtained results are recorded in the "Dust Mites (Derf1)" and "Pollen (Cryj1)" columns under "Fibers" in the "Allergen Suppression Rate (%)" column of Table 2, respectively. Allergen suppression rate (%) = 100 - (W1 / W0) × 100

[0128] (Spray - Anti-allergen test) An aqueous solution of the allergen inhibitor was prepared by mixing 5 parts by mass of the allergen inhibitor obtained in Examples 1, 5, and 6, and Comparative Examples 1 and 4, 5 parts by mass of polyethylene glycol (Wako Pure Chemical Industries, Ltd.: Mw7500), and 90 parts by mass of water. The obtained aqueous solution of the allergen inhibitor was filled into a spray bottle and sprayed at a rate of 4 μL / cm² onto polyester fiber (Toray Polyester Tropical, manufactured by Irozome Co., Ltd., basis weight: 120 g / m²). 2 The material was sprayed evenly to create an allergen-suppressing fiber, which was then left to dry at room temperature for 8 hours.

[0129] Using the obtained allergen-suppressing fibers, the allergen suppression rate (%) was calculated in the same manner as in the above (fiber-anti-allergen test). The results obtained are recorded in the "Allergen Suppression Rate (%)" column for "Spray" under "Dust Mites (Derf1)" and "Pollen (Cryj1)" in Table 2.

[0130] (Molded material - anti-allergen test) The same dust mite allergen (Derf1) and measurement reagent, as well as the pollen allergen (Cryj1) and measurement reagent used in the above-mentioned (drug-anti-allergen test), were used.

[0131] A masterbatch for synthetic resin molding was prepared by melt-kneading and mixing 50 parts by mass of the allergen inhibitors obtained in Examples 2-5 and Comparative Examples 1-3 with 50 parts by mass of polypropylene (Novatec PP BC6C, manufactured by Nippon Polypropylene Co., Ltd.).

[0132] A resin composition was prepared by melt-kneading 30 parts by mass of the obtained masterbatch for synthetic resin molding and 70 parts by mass of separately prepared polypropylene (manufactured by Nippon Polypropylene Co., Ltd., product name "Novatec PP BC6C") at 180°C for 5 minutes. The obtained resin composition was press-molded to obtain a sheet-like synthetic resin molded article with an average thickness of 1 mm.

[0133] Furthermore, a sheet-like synthetic resin molded body with an average thickness of 1 mm was prepared using only polypropylene (product name "Novatec PP BC6C" manufactured by Nippon Polypropylene Co., Ltd.), and this synthetic resin molded body was used as a blank synthetic resin molded body.

[0134] Using synthetic resin molded articles containing an allergen inhibitor and blank synthetic resin molded articles, the allergen inhibition rate (%) was calculated in the same manner as in the above (coating film-anti-allergen test). The obtained results are recorded in the "Allergen Inhibition Rate (%)" column for "Molded Article" under "Dust Mites (Derf1)" and "Pollen (Cryj1)" in Table 2.

[0135] [Table 1]

[0136] [Table 2] [Industrial applicability]

[0137] The allergen inhibitor of the present invention can effectively suppress the reaction of allergens with specific antibodies. By incorporating the allergen inhibitor into a base material, an allergen-suppressing product with excellent allergen-suppressing effects can be manufactured.

[0138] (Cross-reference of related applications) This application claims priority under Japanese Patent Application No. 2022-167899, filed on 19 October 2022, and the disclosures of this application are incorporated herein by reference to those applications in their entirety.

Claims

1. An allergen inhibitor characterized by containing an allergen-inhibiting compound having one or more acidic functional groups, wherein the acidic functional groups are bonded to a nitrogen atom via one or more carbon atoms.

2. The allergen inhibitor according to claim 1, characterized in that the above-mentioned acidic functional group is a carboxyl group, a phosphonic acid group, or a sulfo group.

3. The allergen-suppressing compound is characterized by being represented by formula (1), as described in claim 1 or 2. 【Chemistry 1】 [In formula (1), R 1 are each independently a hydrogen atom, -CH 2 -R 3 or -A 1 -R 3 ; the two R 1 may be the same or different from each other. R 3 represents a carboxy group, a phosphonic acid group or a sulfo group. A 1 represents a divalent substituent formed by removing two hydrogen atoms from carbon atoms of a 4-membered, 5-membered or 6-membered ring. R 2 is -CH 2 -R 4 or -A 2 -R 4 . R 4 represents a carboxy group, a phosphonic acid group or a sulfo group. A 2 represents a divalent substituent formed by removing two hydrogen atoms from carbon atoms of a 4-membered, 5-membered or 6-membered ring.]]

4. The allergen-suppressing compound is characterized by being represented by formula (2) as described in claim 1 or 2. 【Chemistry 2】 [In formula (2), R 5 This is a hydrogen atom, -CH 2 -R 7 , or representing the structure shown in formula (3), with at least two R 5 is, -CH 2 -R 7 Alternatively, it has the structure shown in formula (3). There are four R 5 They may be identical or different from one another. 7 ~R 9 Each of these represents a carboxyl group, a phosphonic acid group, or a sulfo group. 6 is, -(CH 2 ) Represents the structure shown by n- or formula (4). However, n is an integer between 1 and 3. 【Transformation 3】 【Chemistry 4】 [In formula (4), R 10 [where m represents a carboxyl group, a phosphonic acid group, or a sulfo group, and p is an integer between 1 and 3.]

5. The allergen inhibitor according to claim 1 or 2, characterized in that the above-mentioned acidic functional group is a carboxyl group or a phosphonic acid group.

6. The allergen inhibitor according to claim 1 or 2, characterized in that the nitrogen atom content in the allergen-inhibiting compound is 5 to 12%.

7. The allergen inhibitor according to claim 1 or 2, characterized in that the above-mentioned acidic functional group is a carboxyl group.

8. The allergen inhibitor according to claim 1 or 2, characterized in that the pH of a 0.5% by mass aqueous solution of the above allergen-inhibiting compound at 25°C is 4.5 or less.

9. An allergen-suppressing product characterized by comprising a base material and an allergen-suppressing agent according to claim 1 or claim 2 contained in the base material.

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