JP2006321858A - Allergen rebuffing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an allergen-rebuffing agent that can effectively rebuff allergen without contamination or damage of the surface of household utensils to which allergen sticks. <P>SOLUTION: The allergen-rebuffing agent comprises 100 pts.wt. of a water-insoluble allergen-rebuffing organic compound, 1 to 1,000 pts.wt. of sulfonated benzotriazol. Accordingly, in this allergen-rebuffing agent, the water-insoluble allergen-rebuffing organic compound is decomposed by photo-irradiation and the coloration or discoloration of the allergen-rebuffing agent are almost inhibited and the reduction of the allergen rebuffing can effectively be prevented. Thus, the excellent allergen-rebuffing effect is exhibited for a long time without coloration and discoloration. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an allergen inhibitor.

  In recent years, many allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis have become a problem. The main causes of this allergic disease are mites living in the house, especially leopard mite allergens (Der1, Der2), which are abundant in indoor dust, and cedar pollen floating in the air mainly in spring. This is because allergens such as allergens (Cryj1, Cryj2) are increasing in the living space.

  And, even if the leopard mite allergen is exterminated, the dead body of the leopard mite becomes an allergen, so it is not a fundamental solution to allergic diseases. Cryj1, which is a cedar pollen allergen, is a glycoprotein having a molecular weight of about 40 kDa, and Cryj2 is a glycoprotein having a molecular weight of about 37 kDa. When the cedar pollen allergen adheres to the nasal mucosa, the cedar pollen allergen is recognized as a foreign substance and causes an inflammatory reaction.

  Therefore, in order to reduce the symptoms of allergic diseases or prevent new allergic symptoms, it is necessary to completely inactivate allergens from the living space or to inactivate allergens.

  Since allergen is a protein, it is considered that allergen loses allergenicity when it is denatured with heat, strong acid or strong alkali. However, allergens are very stable and are not easily denatured by oxidizing agents, reducing agents, heat, alkalis and acids that can be used safely at home (The Journal of Immunology Vol. 144: 1353-1360).

  If you try to denature the allergen, the daily necessities that are contaminated with allergens, such as tatami mats, carpets, floors, furniture (sofas, upholstered chairs, tables), bedding (beds, futons, sheets), in-car supplies (sheets, Child seats), kitchen supplies, baby items, curtains, wallpaper, towels, clothes, stuffed animals, other textile products, air purifiers (main body and filter) may be damaged depending on conditions.

  For this reason, a method of chemically modifying the molecular surface of the allergen under relatively mild conditions has been considered. For example, Patent Document 1 discloses a method for suppressing allergens using tannic acid, which is used for tanning of raw skin, etc., and Patent Document 2 suppresses allergens using tea extract or the like. Patent Document 3 discloses a method for suppressing an allergen using a hydroxybenzoic acid compound or a salt thereof, and Patent Document 4 discloses a method in which an aromatic hydroxy compound is chemically bonded to and / or bonded to a fiber. An allergen-reducing fiber that has been fixed has been proposed.

  However, when the above-mentioned daily necessities are treated as described above, the daily necessities are often used by being exposed to light such as sunlight. Under such circumstances, the drug used for the treatment of allergen is exposed to light. There has been a problem that coloring or discoloration may occur due to exposure, and the decorativeness of daily goods may be reduced.

JP-A 61-44821 JP-A-6-279273 JP 11-292714 A JP 2003-96670 A

  The present invention provides an allergen inhibitor that hardly causes discoloration or coloring even when exposed to sunlight and has an excellent allergen suppressing effect.

  The allergen inhibitor of the present invention comprises 100 parts by weight of a water-insoluble allergen-inhibiting organic compound and 1 to 1000 parts by weight of sulfonated benzotriazoles.

  In the allergen inhibitor, the water-insoluble allergen-inhibiting organic compound is an aromatic hydroxy compound.

  Furthermore, in the allergen inhibitor, the aromatic hydroxy compound is a compound having at least one substituent represented by the formulas (1) to (6) in the linear polymer.

  In the allergen suppressing agent, the water-insoluble allergen suppressing organic compound is an aromatic polyether compound.

  Since the allergen inhibitor of the present invention comprises 100 parts by weight of a water-insoluble allergen-inhibiting organic compound and 1 to 1000 parts by weight of sulfonated benzotriazoles, the water-insoluble allergen-inhibiting organic compound is decomposed by light irradiation, It is possible to substantially prevent the allergen inhibitor from being colored or discolored and to effectively prevent the allergen inhibitory effect of the allergen inhibitor from being lowered, and excellent without being colored or discolored over a long period of time. Demonstrate allergen suppression effect.

  The allergen inhibitor of the present invention comprises 100 parts by weight of a water-insoluble allergen-inhibiting organic compound and 1 to 1000 parts by weight of sulfonated benzotriazoles.

  The water-insoluble allergen-inhibiting organic compound is not particularly limited as long as it is water-insoluble and has an allergen-inhibiting effect, and water-insoluble allergen-inhibiting organic compounds such as aromatic hydroxy compounds and aromatic polyethers In addition to phenolic resins, water-soluble allergen-inhibiting organic compounds such as tannic acid are cross-linked with a crosslinking agent to make them water-insoluble, and water-soluble allergen-inhibiting organic compounds such as tannic acid are polymerized by polymerization. Water-insoluble allergen-inhibiting organic compounds such as tannic acid, inorganic carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermulite, perlite, and organic polymers such as polyethylene and polypropylene Adsorbed on a carrier to make it water-insoluble, water-soluble allergens such as tannic acid Inhibiting organic compound, such as those with non-water-soluble by binding by chemical bonding or binder such as graft are cited, may be also alone, or two or more are used alone.

  Here, water-insoluble means that the number of grams that can be dissolved in 100 g of water having a pH of 5 to 9 at 20 ° C. (hereinafter referred to as “solubility”) is 1 or less.

  The allergen-inhibiting organic compound means an allergen-inhibiting effect, and the “allergen-inhibiting effect” means a leopard mite allergen (Der1, Der2), a cedar pollen allergen (Cryj1, Cryj2) floating in the air, This refers to the effect of suppressing the reactivity of allergens to specific antibodies by denaturing or adsorbing allergens such as dogs and cats (Can f1, Fel d1). As a method for confirming such an allergen inhibitory effect, for example, a method for measuring the amount of allergen by the ELISA method using an ELISA kit commercially available from LCD Allergy Laboratories, an allergen measuring instrument (trade name, manufactured by Shinto Fine Co., Ltd.) And a method of evaluating allergenicity using a “mighty checker”).

  First, the aromatic hydroxy compound will be described. The aromatic hydroxy compound is not particularly limited as long as it has an aromatic hydroxyl group and has an allergen suppressing effect. For example, the linear hydroxy polymer is represented by the following formulas (1) to (6). Fragrance formed by polymerizing or copolymerizing a monomer containing at least one substituent represented by the formulas (1) to (6), such as an aromatic hydroxy compound having at least one of the substituents Polymers of monomers having an aromatic heterocyclic hydroxyl group, such as aromatic hydroxy compounds; aromatic heterocyclic hydroxy compounds; aromatic hydroxy compounds having an aromatic heterocyclic hydroxy group as a substituent on a linear polymer Or the aromatic hydroxy compound formed by copolymerization, the aromatic hydroxy compound which has an alicyclic structure in the principal chain of a chain polymer, etc. are mentioned.

  First, an aromatic hydroxy compound obtained by polymerizing or copolymerizing a monomer containing at least one substituent represented by formulas (1) to (6) will be described. The substituents of this aromatic hydroxy compound are represented by the following formulas (1) to (6).

  In the formulas (1) to (6), n is an integer of 0 to 5. This is because when n is 6 or more, the allergen suppression effect expressed by the substituents represented by formulas (1) to (6) becomes insufficient.

In the plurality of substituents R ¹ , R ¹ , R ¹ ... In each formula, each substituent R ¹ is hydrogen or a hydroxyl group. Furthermore, in each formula, at least one of the plurality of substituents R ¹ needs to be a hydroxyl group in order for the aromatic hydroxy compound to exhibit an allergen suppressing effect. However, if the number of hydroxyl groups is too large, the product to which the hydrogen allergen inhibitor has been applied is likely to be colored or discolored, so that the number of hydroxyl groups is preferably one. That is, in each formula, it is preferable that only ^one of a plurality of substituents R ¹ is a hydroxyl group, while all the substituents R ¹ other than this substituent are hydrogen.

  Furthermore, the position of the hydroxyl group is preferably bonded to the position having the least steric hindrance. For example, in the formula (1), the hydroxyl group is preferably bonded to the para position.

  The monomer containing at least one substituent represented by the above formulas (1) to (6) is not particularly limited as long as it has a substituent represented by the formula (1) to (6). Examples thereof include monomers having a monovalent phenol group such as vinylphenol, tyrosine, and 1,2-di (4-hydroxyphenyl) ethene (formula (7)).

  Furthermore, the monomer containing at least one substituent represented by the formulas (1) to (6), preferably one or more monovalent phenol groups within a range not inhibiting the allergen suppressing effect of the aromatic hydroxy compound. You may copolymerize the monomer which can be copolymerized with this monomer with this monomer.

  Examples of such monomers include ethylene, acrylate, methacrylate, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and styrene.

  And as a linear polymer to which the substituent shown by Formula (1)-(6) has couple | bonded, it does not specifically limit, A vinyl polymer, polyester, polyamide, etc. are mentioned. The chemical bond between the linear polymer and the substituents represented by formulas (1) to (6) is not particularly limited, and examples thereof include a carbon-carbon bond, an ester bond, an ether bond, and an amide bond. .

  Here, examples of the aromatic hydroxy compound having at least one of the substituents represented by the formulas (1) to (6) in the linear polymer include (1) formulas (1) to (6). A polymer or copolymer of a monomer containing at least one substituent represented by formula (1), a monomer containing at least one substituent represented by formulas (1) to (6), Examples thereof include a copolymer of a monomer and a copolymerizable monomer.

  Specific examples of the aromatic hydroxy compound having at least one of the substituents represented by the formulas (1) to (6) on the linear polymer include poly (3,4,5- (Hydroxybenzoate), polyvinylphenol, polytyrosine, poly (1-vinyl-5-hydroxynaphthalene), poly (1-vinyl-6-hydroxynaphthalene) and poly (1-vinyl-5-hydroxyanthracene) are preferable.

  The molecular weight of the aromatic hydroxy compound obtained by polymerizing the monomer is not particularly limited, but is preferably an aromatic hydroxy compound obtained by polymerizing two or more monomers, and includes five monomers. An aromatic hydroxy compound obtained by polymerization as described above is more preferable.

  In addition, the aromatic heterocyclic hydroxy compound is not particularly limited as long as it has an allergen suppressing effect, and examples thereof include 2-hydroxyfuran, 2-hydroxythiophene, hydroxybenzofuran, and 3-hydroxypyridine.

  Next, an aromatic hydroxy group obtained by polymerizing or copolymerizing a monomer having an aromatic heterocyclic hydroxy group such as an aromatic hydroxy compound having an aromatic heterocyclic hydroxy group as a substituent on a linear polymer. The compound will be described.

  Examples of the aromatic heterocyclic hydroxy group include those in which a hydroxy group is bonded to a heterocyclic skeleton such as thiophene and furan (formulas (8) and (9)), and a skeleton having a heterocyclic ring and an aromatic ring. Are bonded to each other (formula (10)), a heterocyclic skeleton is bonded to a hydroxy group and an alkyl group having 5 or less carbon atoms, and a skeleton having a heterocyclic ring and an aromatic ring is bonded to a hydroxy group and 5 or less carbon atoms. And those having an alkyl group bonded thereto.

  The linear polymer to which the aromatic heterocyclic hydroxy group is bonded is not particularly limited, and examples thereof include vinyl polymers, polyesters, and polyamides. The chemical bond between the linear polymer and the aromatic heterocyclic hydroxy group is not particularly limited, and examples thereof include a carbon-carbon bond, an ester bond, an ether bond, and an amide bond.

  Examples of the compound obtained by polymerizing or copolymerizing a monomer having an aromatic heterocyclic hydroxy group include, for example, (1) a polymer or copolymer of a monomer having an aromatic heterocyclic hydroxy group. And (2) a copolymer of a monomer having an aromatic heterocyclic hydroxy group and a monomer copolymerizable with this monomer.

  Examples of the monomer copolymerizable with the monomer having an aromatic heterocyclic hydroxy group include ethylene, acrylate, methacrylate, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate. , Hydroxypropyl methacrylate, styrene and the like.

  Subsequently, an aromatic hydroxy compound having an alicyclic structure in the main chain of the chain polymer will be described. The aromatic hydroxy compound having an alicyclic structure in the main chain of the chain polymer has an alicyclic structure in the main chain of the chain polymer and a phenol group in the main chain or side chain of the chain polymer. The alicyclic structure is preferably the formula (11) or the formula (12) from the viewpoint that the texture of household goods is not impaired.

Here, in Formula (11) (12), R < ² > -R < ⁹ > is hydrogen, a hydrocarbon group, or a phenol group. Examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups, alkenyl groups such as vinyl groups, and cycloalkenyl groups such as cyclobutenyl groups. Group, an aryl group such as a phenyl group and an ethylphenyl group, and an aralkyl group.

Further, the alicyclic structure portion preferably has a substituent represented by the formula (13), and at least one substituent of R ^{2 to} R ^{5 in} the formula (11) is represented by the formula (13). More preferably, it is a substituent.

Here, in Formula (13), R ^{10 to} R ¹⁴ are hydrogen or a hydroxyl group, and at least one of R ^{10 to} R ¹⁴ is a hydroxyl group. This is because when at least one of R ^{10 to} R ¹⁴ is not a hydroxyl group, the allergen suppressing effect of the water-insoluble allergen suppressing organic compound may be lowered. However, as the number of hydroxyl groups increases, the colorability of the water-insoluble allergen-inhibiting organic compound may increase, so that only one substituent among R ^{10 to} R ¹⁴ in formula (13) is a hydroxyl group. And the remaining substituent is preferably hydrogen, and since steric hindrance is small, it is more preferable that R ¹² is a hydroxyl group and R ¹⁰ , R ¹¹ , R ¹³ and R ¹⁴ are hydrogen. .

  In Formula (13), X is a direct bond or a hydrocarbon group, and examples of such a hydrocarbon group include a methylene group, an ethylene group, a propylidene group, and a butylidene group.

  The aromatic hydroxy compound having an alicyclic structure represented by the formula (11) in the main chain of the chain polymer and having a substituent represented by the formula (13) in the alicyclic structure portion is a liquid. It can be synthesized using polybutadiene and phenol as raw materials, and is commercially available, for example, under the trade name “PP series” from Shin Nippon Oil Co., Ltd., and the fat represented by the formula (12) in the main chain of the chain polymer Aromatic hydroxy compounds having a cyclic structure can be synthesized using dicyclopentadiene and phenol as raw materials, and are commercially available, for example, under the trade names “DPP series” and “DPA series” from Nippon Oil Corporation. .

  Furthermore, examples of the aromatic polyether compound include epoxy resin, phenoxy resin, polyethersulfone, polysulfone, polyallylsulfone, polyetherketone, polyphenylene ether, polyetherimide, polyarylate, and the like. Since coloring can be more effectively prevented, epoxy resin, phenoxy resin, polyethersulfone, polysulfone, polyallylsulfone, and polyetherketone are preferable, and epoxy resin, phenoxy resin, polyethersulfone, and polysulfone are more preferable.

Among the aromatic polyether compounds, an epoxy obtained by polymerization by a polycondensation or oxidative coupling reaction between a monomer such as bisphenol A, tetrachlorobisphenol A, bisphenol F, or bisphenol S and epichlorohydrin. Resin and phenoxy resin: Fragrance of polycondensation by heating an alkali metal salt of bisphenol and an aromatic dihalide activated by an electron-withdrawing group such as —SO ₂ —, —CO—, and —CN in a polar solvent Aromatic nucleophilic substitution polymerization method and aromatic electrophilic substitution polymerization method applying Friedel-Crafts sialylation reaction in which an aromatic compound rich in electrons such as diphenyl ether and aromatic diacid chloride are polymerized under a Lewis acid catalyst Obtained by polysulfone, polyallylsulfone, polyether Sulfone or polyether ketone is more preferable.

  Furthermore, since the coloring to the daily necessities can be particularly effectively prevented, the aromatic polyether compound contains the structural unit represented by the formula (14) and / or the formula (15) as a main repeating unit. Those are preferred.

(R ^{15 to} R ²⁶ are hydrogen or a hydrocarbon group, which may be the same or different. X is selected from the group consisting of a methylene group, an ethylene group, a propylidene group, a butylidene group, and a sulfonyl group. A divalent organic group or a direct bond, and Z ¹ and Z ² are a divalent organic group selected from the group consisting of a methylene group, an ethylene group, a propylene group, a hydroxytrimethylene group, and a butylene group, and a phenylsulfonyl structure A divalent organic group having a direct bond or a direct bond.)

Here, in Formula (14) (15), R < ¹⁵ > -R < ²⁶ > is hydrogen or a hydrocarbon group. Examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups, alkenyl groups such as vinyl groups, and cycloalkenyl groups such as cyclobutenyl groups, An aryl group such as a phenyl group and an ethylphenyl group, an aralkyl group and the like can be mentioned, and it is preferable that all of R ^{15 to} R ²⁶ are hydrogen.

  Further, in the formula (14), X is a divalent organic group or a direct bond selected from the group consisting of a methylene group, an ethylene group, a propylidene group, a butylidene group and a sulfonyl group, and is a methylene group, a propylidene group, a sulfonyl group Groups are preferred.

In the formulas (14) and (15), Z ¹ and Z ² are a divalent organic group selected from the group consisting of a methylene group, an ethylene group, a propylene group, a hydroxytrimethylene group and a butylene group, and a phenylsulfonyl structure. A divalent organic group or a direct bond having a methylene group, a hydroxytrimethylene group, or a divalent organic group having a phenylsulfonyl structure or a direct bond, and Z ¹ represents a hydroxytrimethylene group or a phenylsulfonyl structure. A divalent organic group or a direct bond is more preferable, and Z ² is more preferably a divalent organic group having a phenylsulfonyl structure.

  And although it does not specifically limit as a bivalent organic group which has the said phenylsulfonyl structure, For example, the organic group which has a structure shown to following formula (16)-(18) is mentioned.

  When the aromatic polyether compound is a compound containing the structural unit represented by formula (14) and / or formula (15) as a main repeating unit, the structural unit of formula (14) or formula (15) is selected. The main repeating unit may be used, or the constituent units of the formula (14) and the formula (15) may be used as the main repeating unit, and other constituent units may be contained.

  Specific examples of the compound containing the structural unit represented by the above formula (14) as a main repeating unit include polysulfone obtained by polycondensation of bisphenol A and bis (4-chlorophenyl) sulfone; Epoxy resins obtained by polycondensation of bisphenol F and epichlorohydrin are preferred.

  As the compound containing the structural unit represented by the above formula (15) as the main repeating unit, specifically, by a solution polycondensation method using a potassium salt of 4-chloro-4′-hydroxydiphenylsulfone. Polyethersulfone obtained, polyethersulfone obtained by solution polycondensation method using potassium salt of 4-fluoro-4'-hydroxydiphenylsulfone; polycondensation of 4,4'-biphenyldisulfonyl chloride and diphenyl ether The resulting polyallylsulfone is preferred.

  If the weight average molecular weight of the aromatic polyether compound is small, the allergen suppressing effect may not be manifested. Therefore, 1500 or more is preferable, and 2500 or more is more preferable. If too large, the allergen suppressing organic compound is handled. Since the property may deteriorate, 500,000 or less is preferable.

  And in the allergen inhibitor of this invention, in order to prevent a water-insoluble allergen suppression organic compound from being decomposed | disassembled by light irradiation and coloring or discoloring, sulfonated benzotriazole is contained.

  In particular, when the water-insoluble allergen-inhibiting organic compound is an aromatic hydroxy compound, the aromatic hydroxy compound is decomposed by light irradiation to generate quinones, which may cause coloring or discoloration. It is effective in preventing discoloration.

  Examples of the sulfonated benzotriazoles include sodium 2-benzotriazole sulfonate, 2- (2H-benzotriazol-2-yl) sulfonic acid, and the like. The sulfonated benzotriazoles are preferably anionic sulfonated benzotriazoles commercially available from Ciba Specialty Chemicals under the trade name “Ciba CIBAFAST W liq”.

  The content of the sulfonated benzotriazoles in the allergen inhibitor is preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, with respect to 100 parts by weight of the water-insoluble allergen-inhibiting organic compound. -300 parts by weight are particularly preferred.

  This is because if the content of the sulfonated benzotriazoles is small, the allergen inhibitor cannot give a sufficient coloring / discoloration suppressing effect, whereas if the content is large, the allergen suppressing effect of the allergen inhibitor may be suppressed. This is because when the allergen inhibitor is contained in the fiber, the strength of the fiber is lowered or the quality is impaired.

  In addition, the allergen suppressant, as long as it does not inhibit the allergen inhibitory effect, is a formulation aid such as a dispersion aid, wetting agent, thickener, antioxidant, ultraviolet absorber, acaricide, bactericidal agent, Additives such as antifungal agents and deodorants may be added.

  In addition, when using an allergen inhibitor for daily necessities, a hygroscopic compound is added to the allergen inhibitor to form a reaction field that can cause interaction with the allergen by collecting water molecules in the air. It is preferable to do.

  Examples of the hygroscopic compound include inorganic substances such as calcium chloride, magnesium chloride and silica gel, polyethers such as polyethylene glycol, polypropylene glycol and polyoxymethylene; polyalcohols such as polyvinyl alcohol; and polymer salts such as sodium polyacrylate. A polymer compound containing a polymer acid such as polyacrylic acid, and the like. Polyether is preferable because it easily releases water molecules captured in the system as well as hygroscopicity.

  Next, the method for producing the allergen inhibitor of the present invention is not particularly limited. For example, after dissolving a water-insoluble allergen-inhibiting organic compound in a solvent, sulfonated benzotriazoles in this solvent, and It can be produced by adding and dissolving other additives as necessary.

  Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and propylene glycol, hydrocarbons such as toluene, xylene, methylnaphthalene, kerosene, and cyclohexane, and ethers such as dimethyl ether, tetrahydrofuran, and dioxane. , Ketones such as acetone and methyl ethyl ketone, amides such as N, N-dimethylformamide, and the like. Alcohols, ethers, and ketones are preferable. May be. In addition, you may mix water with a solvent in the range which does not impair the solubility to the solvent of a water-insoluble allergen suppression organic compound.

  Then, the allergen suppressor of the present invention is supplied by spraying or applying to an object in which the allergen is present, that is, an object for which the allergen is to be suppressed (hereinafter referred to as “allergen object”). Or allergens can be suppressed by wiping allergen objects with this wiping sheet by impregnating a fiber assembly such as non-woven fabric or woven fabric with an allergen inhibitor to make a wiping sheet. . In addition, the allergen inhibitor may be used by adding it to a detergent or softening agent, or the allergen inhibitor may be treated on the human skin or mucous membrane.

  In addition, as said allergen target object, the household goods etc. which become a hotbed of allergen in living space are mentioned. Examples of such daily items include tatami mats, carpets, floors, furniture (sofas, cloth chairs, tables), bedding (beds, futons, sheets), in-car items (seats, child seats, door trim materials, ceiling materials, floor carpets, Floor mats, seat belts, fabrics for trunk rooms, car seat covers), kitchen items, baby items, curtains, wallpaper, towels, clothing, stuffed animals, textile products, air purifiers (main body and filters), and the like. Furthermore, in addition to the above, the allergen inhibitor can also exert an allergen inhibitory effect by being added to a detergent, a softener or the like.

  In addition, the allergen inhibitor can be used by general-purpose usage methods such as a spray type, an aerosol type, a smoke type, a heat evaporation type, and a liquid agent. In addition, a spray type means the usage method which applies a pressure to the allergen inhibitor under normal pressure, and sprays the allergen inhibitor in a mist form.

  Then, by adding a solid carrier (talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermulite, perlite, etc.) to the spray-type allergen inhibitor, the allergen inhibitor is made aerosol type. Can do.

  Here, the aerosol type means that the allergen inhibitor is sealed in a container in a state where the propellant is compressed together with the propellant, and the allergen inhibitor is sprayed in a mist state by the pressure of the propellant. Say. Examples of the propellant include nitrogen, carbon dioxide, dimethyl ether, and LPG.

  In addition to the spray-type allergen suppressor, oxygen supply agent (potassium perchlorate, potassium nitrate, potassium chlorate, etc.), combustion agent (sugar, starch, etc.), exothermic regulator (guanidine nitrate, nitroguanidine, phosphoric acid) The allergen inhibitor can be smoked by adding a guanylurea or the like) or an auxiliary agent for decomposing oxygen supply agents (potassium chloride, copper oxide, chromium oxide, iron oxide, activated carbon, etc.). The smoke type means a method of use in which an allergen inhibitor is made into fine particles to form a smoke and dispersed.

  The allergens targeted by the water-insoluble allergen-inhibiting organic compound include plant allergens such as animal allergens and pollen. Particularly effective animal allergens include mite allergens (mites, arthropod ginsengs-mite organisms, which are mainly divided into seven subtypes. , Anterospira represented by ticks, mite, posterior genus represented by spider mite, middle antrum represented by house dust mite, spider mite, anterior genus represented by staghorn tick, nymph mite, leopard mites such as mite It can be any of the types such as anatomical typified by Kenagakonadani mites, Jesa Saladani, and Hidden mosquitoes typified by Kasari Mite, but it is often found in indoor dust, especially in bedding, and is a cause of allergic diseases. Is particularly effective.

  When the allergen inhibitor of the present invention is processed into the above-mentioned daily necessities, the water-insoluble allergen-inhibiting organic compound may not exhibit an allergen-inhibiting effect if the amount used is small, whereas if it is large, the above-mentioned daily items may be damaged. Therefore, it is preferable to treat the water-insoluble allergen-inhibiting organic compound in an amount of 0.01 to 100 parts by weight, and 0.02 to 80 parts by weight with respect to 100 parts by weight of daily necessities. It is more preferable to process, and it is especially preferable to process so that it may become 0.03-50 weight part.

  According to the above-mentioned procedure for using the allergen inhibitor, the allergen inhibitor is supplied to the allergen object as necessary, thereby suppressing the reactivity of the allergen present in the allergen object to the specific antibody. It was.

  The allergen-suppressing agent can be contained in a fiber to form an allergen-suppressing fiber, and an allergen-suppressing effect can be imparted to the fiber itself. By producing the above-mentioned daily necessities using this allergen-suppressing fiber, the allergen-inhibiting effect can be imparted to the daily necessities in advance.

  Examples of the method for incorporating the water-insoluble allergen-inhibiting organic compound in the allergen-suppressing agent into the fiber include a method in which the water-insoluble allergen-inhibiting organic compound is chemically bonded to or physically fixed to the fiber. The fiber is not particularly limited as long as it can contain a water-insoluble allergen-inhibiting organic compound. For example, synthetic fiber such as polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, acetate, etc. Examples thereof include semi-synthetic fibers such as fibers, regenerated fibers such as cupra and rayon, natural fibers such as cotton, hemp, wool, and silk, or composite fibers and mixed cottons of these various fibers.

  Examples of the method of chemically binding the water-insoluble allergen-inhibiting organic compound in the allergen inhibitor to the fiber include a method of chemically binding the water-insoluble allergen-inhibiting organic compound to the fiber by grafting reaction. The grafting reaction is not particularly limited.For example, (1) a graft polymerization method in which a polymerization initiation point is created in a trunk polymer that becomes a fiber, and a water-insoluble allergen-inhibiting organic compound is polymerized as a branch polymer; (2) water-insoluble A polymer reaction method in which an allergen-inhibiting organic compound is chemically bonded to a fiber by a polymer reaction.

  Examples of the graft polymerization method include (1) a method in which a chain transfer reaction to a fiber is used to generate and polymerize radicals, and (2) a second cerium salt or silver sulfate salt such as alcohol, thiol or amine. A method in which a reducing substance is allowed to act to form a redox system (redox system), and free radicals are generated in the fiber for polymerization. (3) Fiber and a single amount used as a raw material for water-insoluble allergen-inhibiting organic compounds A method of irradiating the fiber with γ rays or accelerated electron beams in the state of coexisting with the body, and (4) irradiating only the fibers with γ rays or accelerated electron beams, (5) Oxidizing the polymer constituting the fiber to introduce a peroxy group or introducing a diazo group from the side chain amino group, and using this as a polymerization starting point Polymerization method, (6) hydroxyl group, amino group, Examples thereof include a method using a polymerization initiation reaction of an epoxy, lactam, polar vinyl monomer or the like by a side chain active group such as a boxyl group.

  Next, a method for physically fixing the allergen inhibitor to fibers will be described. Examples of the method of physically fixing the allergen inhibitor to the fiber include, for example, (1) a water-insoluble allergen-inhibiting organic compound obtained by immersing the fiber in the allergen inhibitor and containing the allergen inhibitor in the fiber. And a method of fixing sulfonated benzotriazoles to the fiber, (2) a method of applying the allergen inhibitor to the fiber surface by means of spraying, etc., (3) dissolving or dispersing the binder in the allergen inhibitor. , A method in which fibers are immersed in the allergen inhibitor, the fiber contains an allergen inhibitor, and the water-insoluble allergen-inhibiting organic compound and sulfonated benzotriazoles are fixed to the fiber with a binder, (4) allergen Dissolve or disperse the binder in the inhibitor, and apply this allergen inhibitor to the fiber surface using a means such as spraying. And a method of fixing the water-insoluble allergen-inhibiting organic compound and the sulfonated benzotriazole to the fiber with a binder.

  The binder is not particularly limited as long as the water-insoluble allergen-inhibiting organic compound and the sulfonated benzotriazole can be fixed to the fiber surface. For example, as a binder made of a synthetic resin, a one-component urethane resin, Urethane resins such as two-component urethane resins, acrylic resins, urethane acrylate resins, polyester resins, unsaturated polyester resins, alkyd resins, vinyl acetate resins, vinyl chloride resins, epoxy resins, epoxy acrylate resins, silicone resins, etc. Of these, urethane resins and silicone resins are preferred.

  In the above description, the allergen inhibitor is chemically bonded to a separately manufactured fiber or physically fixed, thereby explaining how to contain the allergen inhibitor in the fiber. Fibers may be produced by spinning fiber raw materials chemically bonded with organic compounds and containing sulfonated benzotriazoles.

  The production method of the fiber raw material in which the water-insoluble allergen-inhibiting organic compound is chemically bound is not particularly limited. For example, a polymerizable monomer having a water-insoluble allergen-inhibiting organic compound as a substituent, Examples thereof include a method of producing a fiber raw material by copolymerizing a polymerizable monomer serving as a fiber raw material.

Example 1
3 parts by weight of water-insoluble condensed tannin (trade name “Oshibu: medium viscosity” manufactured by Osugi Paper Industries Co., Ltd.) and 3 parts by weight of sulfonated benzotriazole (trade name “CIBAFAST W liq” manufactured by Ciba Specialty Chemicals) Was dissolved in a mixed solvent consisting of 50 parts by weight of ethanol and 50 purified water to obtain an allergen inhibitor.

In this allergen inhibitor, a white nonwoven fabric made of polyethylene terephthalate fibers (5 cm × 2 cm flat rectangular shape, basis weight: 100 g / m ² ) was totally immersed and then slowly pulled up, and the nonwoven fabric was heated at 100 ° C. for 30 minutes. It was made to dry over and the allergen suppression nonwoven fabric was obtained.

(Example 2)
100 parts by weight of propylene glycol solution, 10 parts by weight of 4-vinylphenol, 1 part by weight of sulfonated benzotriazoles (trade name “CIBAFAST W liq” manufactured by Ciba Specialty Chemicals) and polyethylene glycol (Wako Pure) Yakuhin Co., Ltd. weight average molecular weight Mw: 7500) 20 parts by weight was added and mixed uniformly to obtain a monomer solution.

  Next, in the monomer solution, 1 part by weight of benzoyl peroxide (reagent manufactured by Sigma-Aldrich, purity: 75% first grade) as a polymerization initiator, sodium lauryl sulfate (trade name “manufactured by Kao Corporation” as an anionic surfactant, After adding 1 part by weight of “Emar 2F Needle”, active ingredient or solid content: 90% by weight, 10 parts by weight of chlorobenzene (purity 99.5% special grade standard manufactured by Sigma-Aldrich) and 1000 parts by weight of purified water, the above single amount The body solution was stirred.

Subsequently, in the monomer solution, a white nonwoven fabric made of polyethylene terephthalate fibers (planar rectangular shape of 5 cm × 2 cm, basis weight: 100 g / m ² ) was entirely immersed in the monomer solution. Heat at 100 ° C. for 60 minutes to graft polymerize 4-vinylphenol as a branched polymer to polyethylene ethephthalate fiber, chemically bond poly (4-vinylphenol) to polyethylene terephthalate fiber, and sulfonated benzotriazoles Was adhered to the nonwoven fabric to obtain an allergen-suppressed nonwoven fabric. In addition, 0.2 weight% of 4-vinylphenol was unreacted.

(Example 3)
In a mixed solvent consisting of 50 parts by weight of ethanol and 50 parts by weight of purified water, 10 parts by weight of poly (4-vinylphenol), sulfonated benzotriazoles (trade name “CIBAFAST W liq” manufactured by Ciba Specialty Chemicals) 1 1 part by weight and 1 part by weight of sodium lauryl sulfate (trade name “Emar 2F Needle” manufactured by Kao Corporation, active ingredient or solid content: 90%) as an anionic surfactant is added and mixed to obtain an allergen inhibitor It was.

After filling this allergen inhibitor in a spray container (made by Canyon) and spraying it on a white nonwoven fabric (5 cm × 2 cm flat rectangular shape, basis weight: 100 g / m ² ) made of polyethylene terephthalate fiber three times from a distance of 30 cm. The nonwoven fabric was heated at 50 ° C. for 30 minutes to obtain an allergen-suppressed nonwoven fabric.

(Comparative Example 1)
An allergen-suppressed nonwoven fabric was obtained in the same manner as in Example 1 except that sulfonated benzotriazoles were not used.

(Comparative Example 2)
An allergen-suppressed nonwoven fabric was obtained in the same manner as in Example 2 except that sulfonated benzotriazoles were not used.

(Comparative Example 3)
An allergen-suppressed nonwoven fabric was obtained in the same manner as in Example 3 except that sulfonated benzotriazoles were not used.

(Comparative Example 4)
An allergen-suppressed nonwoven fabric was obtained in the same manner as in Example 3 except that 0.09 part by weight of sulfonated benzotriazole was used instead of 1 part by weight.

  The allergen-suppressing and non-coloring properties of the obtained allergen-suppressing nonwoven fabric were measured in the following manner, and the results are shown in Table 1.

(Allergen suppression ability)
Dust allergen-containing dust was produced by sieving the indoor dust with a mesh 200 sieve. This mite allergen-containing dust was uniformly rubbed against one side of the allergen-suppressing nonwoven fabric. This allergen-suppressed nonwoven fabric was left for 8 hours in an atmosphere maintained at a temperature of 20 ° C., a relative humidity of 35%, and an absolute humidity of 6.0 g / m ³ .

  Next, the allergen-suppressing property of the allergen-suppressing nonwoven fabric was measured using an allergenicity measuring device (trade name “Daniscan” manufactured by Asahi Breweries, Ltd.) and evaluated according to the following criteria.

1 ... no mite allergen contamination (test line T = 0)
2 ... Slightly contaminated with mite allergen (T <C control line)
3 ... Contaminated with mite allergen (T = C)
4 ... Very contaminated with mite allergens (T> C)

(Discoloration)
From the allergen-suppressed non-woven fabric obtained in Comparative Example 2, 13 plane rectangular test pieces of 5 cm × 2 cm were cut out, and 12 test pieces excluding one piece were irradiated with an ultraviolet irradiator (trade name “Suga Test Instruments Co., Ltd.” Super xenon weather meter SX-75 "). Then, each test piece was continuously irradiated with ultraviolet rays with a light amount of 10 W / m ² , and the test pieces were taken out from the ultraviolet irradiator one by one each time a day passed.

  And the coloring degree of the test piece which was not arrange | positioned in an ultraviolet irradiator was made into the coloring level 0, and the coloring degree of the test piece taken out from the ultraviolet irradiator after 1 day passed was made into the coloring level 1, and after 2 days passed. In the manner of setting the coloring level of the test piece taken out from the ultraviolet irradiator to the coloring level 2, the coloring level of the test piece after 1 to 12 days was set to 1 to 12, respectively, and the reference coloring levels 0 to 12 were set.

  Next, five test pieces are cut out from the obtained allergen-suppressing nonwoven fabric, and the reference coloring level closest to the coloring level of each test piece is judged by visual observation, and the closest reference coloring level is determined for each test piece. The arithmetic average value of the coloring levels of the five test pieces was defined as the coloring level of the test piece before ultraviolet irradiation.

Subsequently, 5 test pieces were placed in an ultraviolet irradiator (trade name “Super Xenon Weather Meter SX-75” manufactured by Suga Test Instruments Co., Ltd.), and each test piece was irradiated with a light amount of 10 W / m ² for 12 days. Continued to irradiate with UV rays. Then, the coloring level of each test piece after ultraviolet irradiation is measured in the same manner as described above, and the arithmetic average value of the coloring levels of the five test pieces after ultraviolet irradiation is calculated as the coloring level of the test piece after ultraviolet irradiation. It was.

  The absolute value of the difference between the coloring level of the test piece after ultraviolet irradiation thus obtained and the coloring level of the test piece before ultraviolet irradiation was defined as discoloration. The larger the value of the color change property, the greater the degree of coloring of the test piece after the ultraviolet irradiation.

Claims (4)

An allergen inhibitor comprising 100 parts by weight of a water-insoluble allergen-inhibiting organic compound and 1 to 1000 parts by weight of a sulfonated benzotriazole. The allergen inhibitor according to claim 1, wherein the water-insoluble allergen-inhibiting organic compound is an aromatic hydroxy compound. The allergen inhibitor according to claim 2, wherein the aromatic hydroxy compound is a compound having at least one substituent represented by the formulas (1) to (6) in the linear polymer.

The allergen inhibitor according to claim 1, wherein the water-insoluble allergen-inhibiting organic compound is an aromatic polyether compound.