JP5238200B2 - Allergen inhibitor and allergen inhibitor product - Google Patents

Description

   The present invention can suppress allergens such as pollen of vegetation such as cedar, mites, indoor dust, etc., and react with specific antibodies, and suppress allergens that are unlikely to cause unexpected or discoloration under daily use conditions. The present invention relates to an agent and an allergen-suppressed product obtained by treating the allergen inhibitor with an object.

   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 (Cry j1, Cry j2) are increasing in the living space.

   Leopard mite allergens are not leopard mites themselves, but carcasses and feces of leopard mites become allergens, so even if you remove the leopard mites, it will not be a fundamental solution to allergic diseases.

   The cedar pollen allergens Cry j1 and Cry j2 are glycoproteins having a molecular weight of about 40 kDa and a molecular weight of about 37 kDa, respectively, and these cedar pollen allergens are in vitro as foreign substances when attached to the nasal mucosa. It is recognized and causes an inflammatory response.

   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, acids, etc. that can be used safely at home (see Non-Patent Document 1).

   Further, when allergens present in an object that is contaminated with allergens are to be denatured, the objects that are contaminated with allergens, such as tatami mats, carpets, floors, furniture (sofas, cloth chairs, tables), bedding ( Beds, futons, sheets), interior items (seats, child seats), car interior materials (ceiling materials, etc.), kitchen items, baby items, curtains, wallpaper, towels, clothing, plush toys, other textiles, air purifiers (main unit) And filters) 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, a method for suppressing allergen using tannic acid used for tanning of rawhide (Patent Document 1), a method for suppressing allergen using tea extract or the like (Patent Document 2), hydroxybenzoic acid A method for suppressing allergen using an acid compound or a salt thereof (Patent Document 3) has been proposed, and an allergen suppressing effect has also been confirmed.

   However, most of the compounds used in these methods are colored because they are a kind of polyphenol, and there is a problem in that the object is colored.

   Further, Patent Document 4 proposes a method for suppressing allergens using an aromatic hydroxy compound, and although the problem of coloring an object is improved, it is processed into a light-colored object such as white. In some cases, coloring may occur, which is not sufficient.

The Journal of Immunology Vol.144: 1353-1360 JP-A 61-44821 JP-A-6-279273 JP 11-292714 A JP 2003-81727 A

   The present invention effectively suppresses allergens from reacting with specific antibodies, can reduce allergy symptoms or prevent their occurrence, and is unlikely to cause unexpected discoloration or discoloration under daily use conditions. An allergen inhibitor and an allergen inhibitor product obtained by treating the allergen inhibitor with an object are provided.

Allergen suppression agents of the present invention, 40 to 95 weight of the total amount of the aromatic polyether compound and the aromatic and contains an aromatic hydroxy compound and the aromatic polyether compound polyether compound and the aromatic hydroxy compound % Content .

   In addition, an allergen inhibitor means what has an allergen inhibitory effect, and an "allergen inhibitory effect" is a leopard mite allergen (Der1, Der2), the cedar pollen allergen (Cryj1, Cryj2) which floats in the air The allergens such as allergens (Can f1, Fel d1) derived from dogs and cats are denatured or adsorbed to suppress the reactivity of allergens to specific antibodies. As a method for confirming such an allergen inhibitory effect, for example, a method for measuring the amount of allergen by ELISA using an ELISA kit commercially available from Nitinichi Pharmaceutical Co., Ltd., an allergen measuring instrument (trade name “Mighty” manufactured by Shinto Fine Co., Ltd.). And a method of evaluating allergenicity using a checker ").

Examples of the aromatic polyether compound, for example, epoxy resin, phenoxy resin, polysulfone, polyether sulfone, polyallyl sulfone, polyphenyl sulfo emissions, such as polyphenylene ether and the like, in the allergen suppression products, unexpected discoloration of coloring since it is possible to prevent or aging discoloration more effectively, epoxy resin, phenoxy resin, polysulfone, polyether sulfone, polyallyl sulfone, polyether phenylsulfonyl emissions are preferred, epoxy resin, phenoxy resin, polysulfone, polyether sulfone Polyphenylsulfone is more preferable, and phenoxy resin, polysulfone, polyethersulfone, and polyphenylsulfone are particularly preferable. In particular, polysulfone, polyethersulfone, and polyphenylsulfone are particularly preferable because the compound itself has almost no adhesiveness and is less likely to adhere to a roll or the like during processing and is excellent in productivity. In addition, an aromatic polyether compound may be used independently or 2 or more types may be used together.

   The aromatic polyether compound is preferably water-insoluble. Thus, when the aromatic polyether compound is water-insoluble, the aromatic polyether compound does not flow out by dissolving in water, and has an allergen suppressing effect for a long time. Can last over. 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.

   As said epoxy resin, what is obtained by superposing | polymerizing monomers, such as bisphenol A, tetrachlorobisphenol A, bisphenol F, bisphenol S, and epichlorohydrin by polycondensation or an oxidative coupling reaction, is preferable.

   Moreover, as said phenoxy resin, what is obtained by superposing | polymerizing monomers, such as bisphenol A, tetrachlorobisphenol A, bisphenol F, bisphenol S, by polycondensation or an oxidative coupling reaction, is preferable.

   The polysulfone is not particularly limited. For example, “Ultrazone S series” manufactured by BASF, “Udel P series” manufactured by Solvay Advanced Polymer, etc. are commercially available.

   Furthermore, the polyether sulfone is not particularly limited, and examples thereof include “Ultra Zone E Series” manufactured by BASF, “Radel A Series” manufactured by Solvay Advanced Polymer, “Sumika Excel Series” manufactured by Sumitomo Chemical, and the like. Is commercially available.

   The polyphenylsulfone is not particularly limited, but for example, “Radel R series” manufactured by Solvay Advanced Polymer Co., Ltd. is commercially available.

Furthermore, since the coloring to the object can be particularly effectively prevented, the aromatic polyether compound contains the structural unit represented by the formula (1) and / or the formula (2) as a repeating unit. Is preferred.

(R ^{1 to} R ¹² are hydrogen or a hydrocarbon group, and may be the same or different from each other. X ¹ is a methylene group, an ethylene group, a propylidene group, a butylidene group or a sulfonyl group. A divalent organic group or a direct bond selected from the group consisting of Z ¹ and Z ² is a divalent group selected from the group consisting of a methylene group, an ethylene group, a propylene group, a hydroxytrimethylene group and a butylene group. An organic group, a divalent organic group having a phenylsulfonyl structure, or a direct bond.)

Here, in Formula (1) (2), R < ¹ > -R < ¹² > 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 given.

Furthermore, in the formula (1), X ¹ is a divalent organic group selected from the group consisting of a methylene group, an ethylene group, a propylidene group, a butylidene group and a sulfonyl group, or a direct bond, a methylene group, a propylidene group, A sulfonyl group is preferred.

In the formulas (1) and (2), 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 (9)-(11) is mentioned.

When the aromatic polyether compound is a compound containing the structural unit represented by the formula (1) and / or the formula (2) as a repeating unit , the structural unit of the formula (1) or the formula (2) is repeated. It may be a unit , or the structural unit of the formula (1) and the formula (2) may be a repeating unit , and may contain other structural units.

As the compound containing the structural unit represented by the above formula (1) as a repeating unit , specifically, polysulfone obtained by polycondensation of bisphenol A and bis (4-chlorophenyl) sulfone; bisphenol A or bisphenol Epoxy resins obtained by polycondensation of F and epichlorohydrin are preferred.

Specific examples of the compound containing the structural unit represented by the formula (2) as a repeating unit include aromatic nucleophilic substitution polymerization of bis (4-chlorophenyl) sulfone and bisphenol, and 4,4-oxy. Polyether sulfone obtained by electrophilic substitution polymerization of benzene sulfonic acid chloride and diphenyl ether, self-polycondensation of sodium p-phenoxybenzene sulfonate, poly polycondensation obtained by polycondensation of 4,4'-biphenyl disulfonyl chloride and diphenyl ether Allyl sulfone and the like are preferable.

   And, if the weight average molecular weight of the aromatic polyether compound is low, the allergen inhibitor obtained and the allergen inhibitor product obtained by treating this may not exhibit an allergen inhibitory effect, preferably 1500 or more, 2500 or more is more preferable. Moreover, when using the allergen inhibitor of this invention shape | molded in a film form etc., from a workability viewpoint, 50000 or more are preferable and, as for the weight average molecular weight of an aromatic polyether compound, 100,000 or more are more preferable. An allergen-suppressed product can be obtained by attaching a film made of an allergen-suppressing agent to an object. On the other hand, when the allergen inhibitor is suspended in water and the weight average molecular weight of the aromatic polyether compound is increased, the handleability may be lowered. Therefore, it is preferably 200000 or less, more preferably 50000 or less. preferable.

Next, the aromatic hydroxy compound will be described. The aromatic hydroxy compound is not particularly limited as long as it has an aromatic hydroxy group and has an allergen suppressing effect. For example, it has an aromatic hydroxy group in the main chain like a phenol resin. Aromatic hydroxy compound; aromatic hydroxy compound having at least one substituent of the following formulas (3) to (8) on the linear polymer; represented by formulas (3) to (8) substituent at least such one containing a monomer polymerization or copolymerization aromatic hydroxy compound formed by the like, may be alone, or two or more may be used alone.

   First, an aromatic hydroxy compound obtained by polymerizing or copolymerizing a monomer containing at least one substituent represented by formulas (3) to (8) will be described. The substituents of this aromatic hydroxy compound are represented by the following formulas (3) to (8).

   In the formulas (3) to (8), 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 (3) to (8) becomes insufficient.

In the plurality of substituents R ¹³ , R ¹³ ... In each formula, each substituent R ¹³ is hydrogen or a hydroxy group. Further, in each formula, at least one of the plurality of substituents R ¹³ , R ¹³ ... Needs to be a hydroxy group in order for the aromatic hydroxy compound to exhibit an allergen suppressing effect. However, if the number of hydroxy 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 hydroxy groups is preferably one. That is, in each formula, it is preferable that only one of a plurality of substituents R ¹³ is a hydroxy group, while all the substituents R ¹³ other than the hydroxy group are hydrogen.

   Furthermore, the position of the hydroxy group is preferably bonded to the position having the least steric hindrance. For example, in Formula (3), the hydroxy group is preferably bonded to the para position.

   The monomer containing at least one substituent represented by the formulas (3) to (8) is not particularly limited as long as it has a substituent represented by the formulas (3) to (8). Examples thereof include monomers having a monovalent phenol group such as vinylphenol, tyrosine, 1,2-di (4-hydroxyphenyl) ethene (formula (12)).

   Furthermore, the monomer containing at least one substituent represented by the formulas (3) to (8), preferably at least one monovalent phenol group 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 it does not specifically limit as a linear polymer to which the substituent shown by Formula (3)-(8) has couple | bonded, A vinyl polymer, polyester, polyamide, etc. are mentioned. The chemical bond between the linear polymer and the substituents represented by formulas (3) to (8) 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 formulas (3) to (8) in the linear polymer include (1) formulas (3) to (8). A polymer or copolymer of a monomer containing at least one substituent represented by (2), (2) a monomer containing at least one substituent represented by formulas (3) to (8), Examples thereof include a copolymer of a monomer and a copolymerizable monomer.

   As the aromatic hydroxy compound having at least one of the substituents represented by the formulas (3) to (8) in the linear polymer, specifically, 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.

   And, if the weight average molecular weight of the aromatic hydroxy compound is low, the allergen suppressing agent obtained and the allergen suppressing product obtained by treating the same may not exhibit the allergen suppressing effect, and preferably 1500 or more. The above is more preferable. Moreover, when using the allergen inhibitor of this invention shape | molded into a film form etc., from a workability viewpoint, 50000 or more are preferable and, as for the weight average molecular weight of an aromatic hydroxy compound, 100000 or more are more preferable. An allergen-suppressed product can be obtained by attaching a film made of an allergen-suppressing agent to an object. On the other hand, when the allergen inhibitor is used suspended in water, if the weight average molecular weight of the aromatic hydroxy compound is increased, the handleability may be lowered, so that it is preferably 200000 or less, more preferably 50000 or less. .

   The aromatic hydroxy compound is preferably water-insoluble. When the aromatic hydroxy compound is water-insoluble, it will not dissolve and flow in water, and the allergen-suppressing effect can be maintained for a long time. Can be made. 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.

   And the allergen inhibitor of this invention contains the said aromatic polyether compound and the said aromatic hydroxy compound. Thus, the combined use of the aromatic polyether compound and the aromatic hydroxy compound synergistically improves the allergen suppressing effect and exhibits an excellent allergen suppressing effect.

   When the content of the aromatic polyether compound in the allergen inhibitor is small, the object may be easily discolored by light or the like when the allergen inhibitor is applied to the object. Since the improvement of the allergen suppression effect by using together an aromatic polyether compound and an aromatic hydroxy compound cannot be aimed at, it is limited to 40 to 95 weight%, and 45 to 90 weight% is more preferable.

   And as an allergen which the allergen inhibitor of this invention has an effect, plant allergens, such as animal allergen and pollen, etc. are mentioned. 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 a target for any kind of anatomical gills represented by Kenagakonadani, Jesaradani, and Hidden mosquitoes represented by Kasari chick tick, but it is a common source of allergic diseases in indoor dust, especially bedding. Is particularly effective.

   Furthermore, it is preferable to contain a hydrophilic polymer in the allergen inhibitor. The hydrophilic polymer is preferably one that can form a reaction field that can cause interaction with the allergen inhibitor by collecting water molecules in the air.

By including a hydrophilic polymer in the allergen-suppressing agent, the allergen-suppressing agent further effectively suppresses the allergen even under normal humidity conditions, for example, in an atmosphere having an absolute humidity of 50 g / m ³ or less. be able to.

   The “reaction field that can interact with the allergen inhibitor by collecting water molecules in the air” refers to any chemical in order to suppress the antigenicity of the part (epitope) where the allergen exhibits antigenicity. This is a reaction field for exerting a chemical interaction, for example, by stabilizing the electrochemical transition state such as the ionized state and lowering the barrier energy of the transition state of the chemical reaction, the natural chemical reaction proceeds. A reaction field that can occur.

   And normally, liquid state water is required to lower the transition state energy barrier that must be exceeded to cause a chemical reaction, but as described above, the allergen inhibitor contains a hydrophilic polymer. By doing so, it becomes possible to collect moisture in the air, and the above-mentioned reaction field can be more reliably formed without requiring an operation such as artificially increasing the humidity.

   The hydrophilic polymer is not particularly limited, for example, a polymer having an ether bond and / or an amide bond in the main chain, a polymer having a polar group in the side chain, an ether bond and / or in the main chain. Examples thereof include a polymer having an amide bond and a polar group in the side chain. Examples of the polar group include amine groups such as primary amine, secondary amine, and tertiary amine; cationic groups such as ammonium base; ester groups such as sulfate ester and phosphate ester; carboxyl group and sulfone group Anionic groups such as: nonionic groups such as hydroxy groups and amide groups.

   Examples of the hydrophilic polymer include natural compounds having a hydroxy group such as starch, cellulose, tannin, lignin, alginic acid and gum arabic, as well as polyalcohols such as polyvinyl alcohol and butyral; polyoxymethylene, polyoxyethylene Polyethers such as polyoxypropylene; Polymer acids such as polyacrylic acid; Polymer salts such as sodium polyacrylate; Polyamines such as polyallylamine; Polyacrylamide; Polyvinylpyrrolidone; Polyurethane; Synthetic compounds such as acrylic resins Of these, synthetic polymers are preferred in that they do not exhibit deliquescence under normal indoor conditions, and are not only hygroscopic but also highly water-retaining, so that polyvinyl alcohol, polyoxyethylene, polyacrylic acid are preferred. Sodium polyacrylate, polyacrylamide, polyvinyl pyrrolidone are preferred. The hydrophilic polymers may be used alone or in combination of two or more, but it is preferable to combine two or more hydrophilic polymers having different molecular structures.

   As a combination of two or more kinds of hydrophilic polymers having different molecular structures, a combination of a polyether and a polymer salt and a combination of a polyether and a polyalcohol are preferable. Specifically, polyoxyethylene and polyacrylic acid A combination with sodium and a combination of polyoxyethylene and polyvinyl alcohol are more preferable.

   If the melting point of the hydrophilic polymer is low, it may be in a liquid state under the use atmosphere, and the allergen-suppressed product obtained by treating the allergen-suppressing agent on the object may become sticky, and the texture may be impaired. Therefore, it is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher in order to maintain the allergen-suppressing effect when used in an atmosphere with many opportunities to come into contact with water.

   If the content of the hydrophilic polymer is small, water molecules in the air cannot be collected sufficiently, so that a reaction field sufficient to cause interaction with allergens cannot be formed, and allergen suppression is achieved. On the other hand, the agent may not be able to exert a sufficient allergen inhibitory effect, whereas if it is too much, the amount of the allergen inhibitor will be relatively reduced, and the allergen inhibitory effect of the allergen inhibitor may be reduced. Therefore, it is preferably 40 to 1000 parts by weight, more preferably 50 to 800 parts by weight, and particularly preferably 50 to 300 parts by weight with respect to 100 parts by weight of the total amount of the aromatic polyether compound and the aromatic hydroxy compound.

   The allergen inhibitor of the present invention may be blended with adjuvants such as dispersants, emulsifiers, antioxidants, ultraviolet absorbers and the like as long as the allergen inhibitory effect is not inhibited. In addition, bactericides, antifungal agents, deodorants and the like may be contained.

   Moreover, an allergen inhibitor can be used in the form mixed with the matrix suitably according to the use. Such a matrix is not particularly limited as long as it does not denature the allergen inhibitor. For example, polysaccharides and salts thereof, dextrin, gelatin, higher alcohols, fats and oils, stearic acid and other higher fatty acids, paraffin And liquid paraffins, white petrolatum, hydrocarbon gel ointment, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, water and the like.

   Next, a method for treating an allergen inhibitor with an object to produce an allergen-suppressed product will be described. The allergen suppressing agent can be processed into an object such as daily necessities using a general-purpose usage method such as a spray type, an aerosol type, a smoke type, or a heat transpiration type to obtain an allergen suppressed product.

   An allergen inhibitor can be made into a spray type by dissolving or dispersing an allergen inhibitor in a solvent to make an allergen inhibitor solution, and adding an aqueous solvent, oil agent, emulsion, suspension, etc. to this solution. it can. In addition, a spray type means the usage method which applies a pressure to the allergen inhibitor solution under normal pressure, and sprays the allergen inhibitor in a mist form.

   Since the allergen inhibitor is excellent in stability when it is made into a suspension, it is suitable for use in treating objects such as daily necessities in a spray form such as a spray.

   Examples of the solvent include water (preferably ion-exchanged water), alcohols (such as methyl alcohol, ethyl alcohol, and propyl alcohol), hydrocarbons (such as toluene, xylene, methylnaphthalene, kerosene, and cyclohexane), and ethers. (Diethyl ether, tetrahydrofuran, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), amides (N, N-dimethylformamide, etc.) and the like.

   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 is used in which an allergen inhibitor solution is sealed in a container together with a propellant in a compressed state, and the allergen inhibitor is sprayed in the form of a mist by the pressure of the propellant. Say the method. Examples of the propellant include nitrogen, carbon dioxide, dimethyl ether, and LPG.

   In addition, the above spray-type allergen suppressants include oxygen supply agents (potassium perchlorate, potassium nitrate, potassium chlorate, etc.), combustion agents (sugars, starches, etc.), and heat regulators (guanidine nitrate, nitroguanidine, phosphoric acid) An allergen inhibitor can be made into a smoke type by adding an auxiliary agent for decomposition of oxygen supply agent (such as guanylurea) and the like (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.

   And an allergen suppression product which can suppress an allergen is obtained by supplying an allergen inhibitor by spraying, dispersing, applying, or adhering to an object such as daily necessities according to various usage methods. .

   In the allergen-suppressing product, the allergen-suppressing agent contains a curing agent and crosslinks the aromatic polyether compound and the aromatic hydroxy compound, whereby a solvent such as water for the aromatic polyether compound and the aromatic hydroxy compound is used. Therefore, the allergen inhibitory effect of the allergen inhibitor can be maintained for a long period of time.

   For example, even if the allergen-suppressing product is splashed with water or the allergen-suppressing product is washed, the allergen-suppressing agent can be prevented from dissolving in the water and disappearing from the allergen-suppressing product. The allergen inhibitory effect can be maintained over a long period of time.

   The curing agent is not particularly limited as long as an aromatic polyether compound and / or an aromatic hydroxy compound can be cross-linked. For example, compounds such as amine compounds and polyaminoamide compounds synthesized from amine compounds, tertiary Examples include amine compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenolic compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization initiators, dicyanamide and derivatives thereof, and these are used alone. Two or more of them may be used in combination.

   The amine compound is not particularly limited. For example, aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, and derivatives thereof; mensendiamine, isophorone Diamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10 -Alicyclic amines such as tetraoxaspiro (5,5) undecane and derivatives thereof; m-xylenediamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine, m-phenylenediamine And aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, and α, α-bis (4-aminophenyl) -p-diisopropylbenzene, and derivatives thereof.

   The compound synthesized from the amine compound is not particularly limited. For example, the amine compound and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadioic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydro Polyaminoamide compounds synthesized from carboxylic acid compounds such as isophthalic acid and hexahydroisophthalic acid and derivatives thereof; Polyaminoimide compounds synthesized from maleimide compounds such as the above amine compounds and diaminodiphenylmethane bismaleimide; and derivatives thereof; Ketimine compounds synthesized from amine compounds and ketone compounds and derivatives thereof; synthesized from the above amine compounds and compounds such as epoxy compounds, urea, thiourea, aldehyde compounds, phenol compounds, and acrylic compounds. Such Riamino compounds and derivatives thereof.

   The tertiary amine compound is not particularly limited, and examples thereof include N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl). ) Phenol, 1,8-diazabiscyclo (5,4,0) undecene-1, derivatives thereof and the like.

   And as said imidazole compound, it is not specifically limited, For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, these derivatives, etc. Is mentioned.

   The hydrazide compound is not particularly limited, and examples thereof include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, and eicosanedioic acid dihydrazide. , Adipic acid dihydrazide, and derivatives thereof.

   The melamine compound is not particularly limited, and examples thereof include 2,4-diamino-6-vinyl-1,3,5-triazine and derivatives thereof.

   The acid anhydride is not particularly limited. For example, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol trisanhydro Trimellitate, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazeline acid anhydride, polydodecane Dianhydride, Rorendo acid anhydrides, and derivatives thereof.

   The phenol compound is not particularly limited, and examples thereof include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, and derivatives thereof.

   The heat-latent cationic polymerization catalyst is not particularly limited. For example, benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt using antimony hexafluoride, phosphorous hexafluoride, boron tetrafluoride and the like as a counter anion, Examples include ionic thermal latent cationic polymerization catalysts such as benzylphosphonium salts; nonionic thermal latent cationic polymerization catalysts such as N-benzylphthalimide and aromatic sulfonic acid esters.

The photolatent cationic polymerization initiator is not particularly limited. For example, aromatic diazonium salts, aromatic halonium salts, and aromatics having antimony hexafluoride, phosphorous hexafluoride, boron tetrafluoride and the like as a counter anion. Ionic photolatent cationic polymerization initiators such as onium salts such as sulfonium salts and organometallic complexes such as iron-allene complexes, titanocene complexes and arylsilanol-aluminum complexes; nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid Nonionic photolatent cationic polymerization initiators such as esters, phenol sulfonates, diazonaphthoquinones, N-hydroxyimide sulfonates, etc. may be mentioned.
Examples of a method for imparting washing resistance include a method using a binder such as a silicon-based resin in addition to the above.

   The object is not particularly limited, but for example, tatami mats, carpets, furniture (sofas, cloth chairs, tables, etc.), bedding (beds, futons, sheets, etc.), in-car supplies such as cars, airplanes, ships, etc. Car interior materials (seats, child seats, etc.), kitchenware, baby products, building interior materials (wallpapers, flooring, etc.), textile products (curtains, towels, clothing, stuffed animals, etc.), filters, screen doors, building interiors, pharmaceuticals Quasi-drugs, cosmetics and the like.

   In particular, the allergen suppressant has almost no unexpected coloration or discoloration in the daily living environment, so that it is subject to fading and discoloration due to light, such as architectural interior materials, in-car supplies and car interior materials, Suitable for filters such as screen doors and textiles such as clothing.

   The above filter refers to a filter that has the ability to separate, filter, and remove foreign substances, for example, a filter such as an air cleaner, an air conditioner, a vacuum cleaner, a ventilation fan, a mask that prevents entry of dust or pollen, a shoji, or And screen doors and kayaks that prevent insects from entering.

   The cosmetics, pharmaceuticals and quasi drugs are not particularly limited, and examples thereof include skin external preparations, nasal sprays, eye drops, shampoos, bathing agents, hair styling agents, foundations, and facial cleansing agents. .

   The architectural interior material is not particularly limited, and examples thereof include floor materials, wallpaper, ceiling materials, paints, and waxes.

   The fiber product is not particularly limited, and examples thereof include bedding, carpets, curtains, clothes, and stuffed animals.

   The interior goods and the vehicle interior materials are not particularly limited, and examples thereof include a seat, a child seat, a seat belt, a car mat, a seat cover, and a carpet.

   If the treatment amount of the allergen suppressant on the target is small, the allergen suppression effect may not be manifested. Therefore, 0.001 to 100 parts by weight is preferable, 0.01 to 50 parts by weight is more preferable, and 0.05 to 30 parts by weight is particularly preferable.

   In the above description, the case where the allergen inhibitor is treated on the object has been described. However, the allergen inhibitor may be pretreated on the fibers constituting the fiber product. Examples of the method of treating the allergen inhibitor with fibers include a method of chemically binding or physically fixing the allergen inhibitor to the fibers.

   The above fibers include synthetic fibers such as polyester fibers, nylon fibers, acrylic fibers and polyolefin fibers; semi-synthetic fibers such as acetate fibers; recycled fibers such as cupra and rayon; natural fibers such as cotton, hemp, wool and silk. A composite fiber or mixed cotton of these various fibers can be used.

   Next, a method for physically fixing the allergen inhibitor to fibers will be described. As a method of physically fixing the allergen inhibitor to the fiber, for example, (1) An allergen inhibitor solution is prepared by dissolving or dispersing the allergen inhibitor in a solvent, and the allergen inhibitor solution (2) a method of impregnating fibers with an allergen inhibitor, (2) a method of applying an allergen inhibitor solution prepared by dissolving or dispersing the allergen inhibitor in a solvent to the fiber surface, (3 ) A method in which fibers are immersed in a binder in which an allergen inhibitor is dissolved or dispersed, and the allergen inhibitor is fixed to the fibers with the binder, and (4) a binder in which the allergen inhibitor is dissolved or dispersed. Examples include a method of applying to the fiber surface and fixing the allergen inhibitor to the fiber with a binder. In the above methods (1) and (2), the allergen inhibitor solution may contain the following binder.

   The solvent is not particularly limited. For example, water; alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol; hydrocarbons such as toluene, xylene, methylnaphthalene, kerosene, and cyclohexane; diethyl ether, tetrahydrofuran, dioxane, and the like Ethers; ketones such as acetone and methyl ethyl ketone; amides such as N, N-dimethylformamide and the like.

   The binder is not particularly limited as long as the allergen inhibitor can be fixed to the fiber surface. For example, the binder made of a synthetic resin may be a urethane type such as a one-component urethane resin or a two-component urethane resin. Resins, silicone resins, acrylic resins, urethane acrylate resins, polyester resins, unsaturated polyester resins, alkyd resins, vinyl acetate resins, vinyl chloride resins, epoxy resins, epoxy acrylate resins, and the like, and urethane resins are preferred.

   In the above description, the allergen inhibitor is physically fixed to a separately manufactured fiber to explain how to contain the allergen inhibitor in the fiber, but the allergen inhibitor is chemically bonded. Fibers may be produced by spinning fiber raw materials.

   The production method of the fiber raw material in which the allergen inhibitor is chemically bonded is not particularly limited. For example, a polymerizable monomer that is a raw material of the aromatic polyether compound and the aromatic hydroxy compound, and a general fiber Examples thereof include a method of producing a fiber raw material by copolymerizing a polymerizable monomer as a raw material.

   In addition, it has been explained that the allergen inhibitor contains a hydrophilic polymer, but the polymerizable monomer as a raw material for the aromatic polyether compound and the aromatic hydroxy compound, the polymerization having the hydrophilic polymer as a substituent. An allergen-inhibiting agent by producing a fiber raw material in which an aromatic polyether compound, an aromatic hydroxy compound and a hydrophilic polymer are chemically bonded, and spinning the fiber raw material. In addition, a fiber containing a hydrophilic polymer can be produced.

Since the allergen inhibitor of the present invention contains an aromatic polyether compound and an aromatic hydroxy compound and contains 40 to 95 % by weight of the aromatic polyether compound, the allergen inhibitory effect is obtained. Synergistically improves and exhibits excellent allergen suppression effect.

   Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
45 g of a fine powder obtained by pulverizing polyethersulfone (trade name “GAFONE 3600P” manufactured by Solvay Advanced Polymer Co., Ltd., weight average molecular weight: 110000) to an average particle diameter of 15 μm (hereinafter simply referred to as “polyethersulfone fine powder”), Fine powder obtained by pulverizing (4-vinylphenol) (trade name “Marcalinker M” manufactured by Maruzen Petrochemical Co., Ltd., weight average molecular weight: 5500) to an average particle size of 3 μm (hereinafter simply referred to as “poly (4-vinylphenol) fine powder” To a mixture consisting of 5 g of body), ion-exchanged water 134 g and polystyrene sulfonate type polymer surfactant (trade name “POLYTY PS-1900” manufactured by Lion Corporation) 15 g were added, and a stirrer (M Technique Co., Ltd.). Product name “Clear mix CLM-0.8S”) and rotation speed 20000 rpm After repeating stirring for 2 minutes 5 times, 1 g of xanthan gum (trade name “Kelzan” manufactured by Sanki Co., Ltd.) and 50 g of binder (trade name “TF-3500” manufactured by Kitahiro Chemical Co., Ltd.) are added to add an allergen inhibitor solution. Got.

   Then, the obtained allergen inhibitor solution is diluted 5 times with ion-exchanged water to prepare a diluted solution, and a cotton cloth (trade name “Kanakin 3” manufactured by Japan Standards Association, JIS L0803) is added to the diluted solution. (Compliance product) was dipped, stirred for 5 minutes with a stirrer, and allowed to dry at 80 ° C. for 2 hours to obtain an allergen-suppressed cotton fabric. In addition, the adhesion amount of the allergen inhibitor in the obtained allergen suppression cotton cloth was 1.5 g per 100 g of cotton cloth.

(Example 2 )
Allergen suppression was carried out in the same manner as in Example 1 except that the polyethersulfone fine powder was changed to 47.5 g instead of 45 g and the poly (4-vinylphenol) fine powder was changed to 2.5 g instead of 5 g. An agent and an allergen-suppressed cotton fabric were obtained. In addition, the adhesion amount of the allergen inhibitor in the obtained allergen suppression cotton cloth was 1.6 g per 100 g of cotton cloth.

(Example 3 )
Allergen inhibitor and allergen suppression in the same manner as in Example 1 except that the polyethersulfone fine powder was changed to 25 g instead of 45 g, and the poly (4-vinylphenol) fine powder was changed to 25 g instead of 5 g. A cotton cloth was obtained. In addition, the adhesion amount of the allergen inhibitor in the obtained allergen suppression cotton cloth was 1.9g per 100g of cotton cloth.

(Example 4 )
40 g of polyethersulfone (trade name “GAFONE 3000P” manufactured by Solvay Advanced Polymer Co., Ltd., weight average molecular weight: 160000) and poly (4-vinylphenol) (trade name “poly (4-vinylphenol)” manufactured by Aldrich Co., Ltd., weight average molecular weight: 8000) 10 g was dissolved in 450 g of N, N-dimethylformamide to prepare an allergen inhibitor solution.

   Then, the obtained allergen inhibitor solution is diluted 10-fold with N, N-dimethylformamide to prepare a diluted solution, and a cotton cloth (trade name “Kanakin No. 3” manufactured by the Japanese Standards Association) is added to this diluted solution. , JIS L0803 compliant product) was dipped, stirred for 5 minutes with a stirrer, and then left to dry at 80 ° C. for 2 hours to obtain an allergen-suppressed cotton fabric. In addition, the adhesion amount of the allergen inhibitor in the obtained allergen suppression cotton cloth was 1.0 g per 100 g of cotton cloth.

(Comparative Example 1)
An allergen inhibitor and an allergen-suppressed cotton fabric were obtained in the same manner as in Example 1 except that poly (4-vinylphenol) was not used and ion-exchanged water was changed to 139 g instead of 134 g.

(Comparative Example 2)
An allergen inhibitor and an allergen-suppressed cotton fabric were obtained in the same manner as in Example 1 except that polyethersulfone was not used and ion-exchanged water was changed to 179 g instead of 134 g.

(Comparative Example 3)
An allergen inhibitor and an allergen-suppressed cotton fabric were obtained in the same manner as in Example 1, except that polyethersulfone was not used and that the fine powder of poly (4-vinylphenol) was changed to 50 g instead of 5 g.

(Comparative Example 4)
An allergen inhibitor and an allergen-suppressed cotton fabric were obtained in the same manner as in Example 1 except that poly (4-vinylphenol) was not used and that the polyethersulfone was changed to 50 g instead of 45 g.

(Comparative Example 5)
The allergen inhibitor and the allergen-suppressed cotton cloth in the same manner as in Example 1 except that the polyethersulfone fine powder was changed to 15 g instead of 45 g, and the poly (4-vinylphenol) fine powder was changed to 35 g instead of 5 g. Got.

(Comparative Example 6)
Allergen suppression was carried out in the same manner as in Example 1, except that the polyethersulfone fine powder was changed to 49.5 g instead of 45 g, and the poly (4-vinylphenol) fine powder was changed to 0.5 g instead of 5 g. An agent and an allergen-suppressed cotton fabric were obtained.

(Comparative Example 7 )
An untreated cotton fabric (trade name “Kanakin 3” manufactured by the Japanese Standards Association, JIS L0803 compliant product) was prepared.

(Comparative Example 8 )
A non-woven fabric (trade name “Borance 4301N” manufactured by Toyobo Co., Ltd.) that had not been subjected to any treatment was prepared.

Next, Examples 1 to 4 and Comparative Examples 1 to allergen suppression factor of allergen suppression agent obtained in 6, Examples 1 to 4 and Comparative Examples 1 to allergen suppression product obtained in 6, Comparative Example 7 The allergen-suppressing ability and light resistance of the non-woven fabric of Comparative Example 8 were evaluated in the following manner, and the results are shown in Table 1.

(Allergen inhibitory ability of allergen inhibitor)
An allergen-cooled dry powder (trade name “Mite Extract-Df” manufactured by Cosmo Bio) was dissolved in a phosphate buffer (pH 7.6) to prepare an allergen solution having a protein amount of 10 μg / ml.

On the other hand, the allergen inhibitor diluted solution obtained by diluting the allergen inhibitor solution obtained in Examples 1 to 3 and Comparative Examples 1 to 6 with ion-exchanged water 5 times, and allergen suppression obtained in Example 4 An allergen inhibitor diluted solution obtained by diluting the agent solution 2.5 times with N, N-dimethylformamide was prepared.

   Subsequently, a test tube to which 1 ml of the allergen solution was supplied was prepared, and 100 microliters of the allergen inhibitor diluted solution was added to each test tube and shaken at 37 ° C. for 16 hours.

Next, the abundance W ₁ (ng / ml) of Der f1 in the liquid in the test tube was measured using an ELISA kit (manufactured by Nichinichi Pharmaceutical Co., Ltd.).

In addition, the presence of Der f1 in the solution in the test tube except that the phosphate buffer (pH 7.6) was supplied instead of the allergen inhibitor diluting solution to the test tube to which the allergen solution was supplied. The quantity W ₀ (ng / milliliter) was measured.

And the allergen suppression rate (%) was computed based on the following formula.
Allergen suppression rate (%) = 100− (W ₁ / W ₀ ) × 100

(Allergen suppression ability of allergen suppression products)
3.5 ml of the allergen solution prepared in the above-mentioned evaluation of “allergen inhibitory ability of allergen inhibitor” was supplied to each test tube.

Next, the allergen-suppressed products prepared in Examples 1 to 4 and Comparative Examples 1 to 6 , the cotton fabric of Comparative Example 7 , and the nonwoven fabric of Comparative Example 8 were cut out to 2 cm ² , and these were separated into separate test tubes. And soaked in an allergen solution and shaken at 37 ° C. for 16 hours.

   Thereafter, 100 microliters of the liquid in the test tube is added to the allergen measuring device (trade name “Mighty Checker” manufactured by Shinto Fine Co., Ltd.), and the degree of color development of the allergen measuring device is visually observed, and the allergen suppressing ability is observed according to the following criteria. evaluated. In addition, the darker the color of the allergen measuring device, the more allergen is present in the liquid.

5 ... A thick, thick and clear line was observed.
4 ... It can be clearly seen that it is a line.
3 ... The color is slightly colored in a line.
2 ... The color is faintly colored.
1 ... No color development at all.

(Light resistance of allergen suppression products)
Examples 1 to 4 and Comparative Examples 1 to 6 For the prepared allergen-suppressed products, the cotton fabric of Comparative Example 7 and the nonwoven fabric of Comparative Example 8 , the dyeing fastness test for ultraviolet carbon (black panel temperature) according to JIS L0842 : 63 ° C, relative humidity: 50% RH, irradiation time: 40 hours), and using gray scale for discoloration (JIS L0804), 1st grade, 1st-2nd grade, 2nd grade, 2nd-3rd grade, 3 Evaluation was performed in 9 grades of grades, grades 3 to 4, grade 4, grade 4 to 5, grade 5. The light resistance is best when the evaluation by the gray scale for color fading is grade 5, and is the worst when it is grade 1.

Claims (8)

Containing an aromatic polyether compound and an aromatic hydroxy compound, and containing the aromatic polyether compound in an amount of 40 to 95% by weight of the total amount of the aromatic polyether compound and the aromatic hydroxy compound. The polyether compound is a compound containing the structural unit represented by formula (1) and / or formula (2) as a repeating unit , and the aromatic hydroxy compound is represented by formula (3) in the side chain of the linear polymer. ) To (8), an allergen inhibitor characterized by being a compound having at least one substituent.

(R ^{1 to} R ¹² are hydrogen or a hydrocarbon group, and may be the same or different from each other. X ¹ is a methylene group, an ethylene group, a propylidene group, a butylidene group or a sulfonyl group. A divalent organic group or a direct bond selected from the group consisting of Z ¹ and Z ² is a divalent group selected from the group consisting of a methylene group, an ethylene group, a propylene group, a hydroxytrimethylene group and a butylene group. An organic group, a divalent organic group having a phenylsulfonyl structure, or a direct bond.)

(N is an integer of 0 to 5. In addition, in each formula, a plurality of R ¹³ , R ¹³ ... Are hydrogen or hydroxy groups, and R ¹³ , R ¹³ . At least one is a hydroxy group.) Containing an aromatic polyether compound and an aromatic hydroxy compound, and containing the aromatic polyether compound in an amount of 40 to 95% by weight of the total amount of the aromatic polyether compound and the aromatic hydroxy compound. The polyether compound is a compound containing the structural unit represented by formula (1) and / or formula (2) as a repeating unit , and the aromatic hydroxy compound is represented by formulas (3) to (8). An allergen inhibitor characterized by being polymerized or copolymerized with a monomer containing at least one substituent.

(R ^{1 to} R ¹² are hydrogen or a hydrocarbon group, and may be the same or different from each other. X ¹ is a methylene group, an ethylene group, a propylidene group, a butylidene group or a sulfonyl group. A divalent organic group or a direct bond selected from the group consisting of Z ¹ and Z ² is a divalent group selected from the group consisting of a methylene group, an ethylene group, a propylene group, a hydroxytrimethylene group and a butylene group. An organic group, a divalent organic group having a phenylsulfonyl structure, or a direct bond.)

(N is an integer of 0 to 5. In addition, in each formula, a plurality of R ¹³ , R ¹³ ... Are hydrogen or hydroxy groups, and R ¹³ , R ¹³ . At least one is a hydroxy group.) Containing an aromatic polyether compound and an aromatic hydroxy compound, and containing the aromatic polyether compound in an amount of 40 to 95% by weight of the total amount of the aromatic polyether compound and the aromatic hydroxy compound. The polyether compound is an epoxy resin, phenoxy resin, polysulfone, polyethersulfone or polyphenylsulfone, and the aromatic hydroxy compound is represented by the formulas (3) to (8) in the side chain of the linear polymer. An allergen inhibitor, which is a compound having at least one substituent.

(N is an integer of 0 to 5. In addition, in each formula, a plurality of R ¹³ , R ¹³ ... Are hydrogen or hydroxy groups, and R ¹³ , R ¹³ . At least one is a hydroxy group.) Containing an aromatic polyether compound and an aromatic hydroxy compound, and containing the aromatic polyether compound in an amount of 40 to 95% by weight of the total amount of the aromatic polyether compound and the aromatic hydroxy compound. The polyether compound is an epoxy resin, a phenoxy resin, a polysulfone, a polyethersulfone, or a polyphenylsulfone, and the aromatic hydroxy compound includes a single group that includes at least one substituent represented by formulas (3) to (8). An allergen inhibitor characterized by polymerizing or copolymerizing a monomer.

(N is an integer of 0 to 5. In addition, in each formula, a plurality of R ¹³ , R ¹³ ... Are hydrogen or hydroxy groups, and R ¹³ , R ¹³ . At least one is a hydroxy group.) The allergen inhibitor according to any one of claims 1 to 4, wherein the aromatic polyether compound is water-insoluble. The allergen inhibitor according to any one of claims 1 to 4, wherein the aromatic hydroxy compound is water-insoluble. An allergen-suppressing product obtained by treating the allergen-suppressing agent according to any one of claims 1 to 6 with an object. 8. The allergen-suppressing product according to claim 7, wherein the object is a filter, a building interior material, a textile product, a vehicle interior product, or a vehicle interior material.