JP2010031069A - Allergen inhibitor and allergen inhibited product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an allergen inhibitor that effectively inhibits allergens from reacting with specific antibodies and alleviates allergic symptoms or prevents their expressions and that hardly causes unexpected discoloration or discoloration under daily use conditions. <P>SOLUTION: The allergen inhibitor is characterized by containing a sulfonate of a styrene-sulfonic acid homopolymer having a Z average mol.wt. of ≥150,000 as the allergen inhibiting compound. The inhibitor effectively inhibits allergens from reacting with specific antibodies and alleviates allergic symptoms or prevents their expressions, hardly causes unexpected discoloration or discoloration under daily use conditions, and can suitably be used for various daily commodities. <P>COPYRIGHT: (C)2010,JPO&INPIT

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 allergen 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), interior materials (ceiling materials, etc.), kitchen items, baby items, curtains, wallpaper, towels, clothing, plush toys, other textiles, air purifiers ( The 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, 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.

  Patent Document 4 discloses a water-soluble polymer compound such as a homopolymer or copolymer containing 50 to 100 mol% of a structural unit derived from vinyl alcohol, vinyl pyrrolidone, and styrene sulfonic acid or a salt thereof as an allergen suppressing component. Residential environmental improvers have been proposed. In the examples, blending examples using polyvinyl alcohol or polyvinylpyrrolidone as a residential environment improving agent are described, but a homopolymer containing 50 to 100 mol% of a structural unit derived from styrenesulfonic acid or a salt thereof is described. There was no description of the formulation examples used, and furthermore, in all of the examples, there was no evaluation data on the allergen inhibitory effect of the residential environment improving agent, and it was not possible to easily follow up.

  In paragraph [0014], the weight average molecular weight of the water-soluble polymer compound is preferably 1,000 to 6,000,000, more preferably 5,000 to 1,000,000, and particularly preferably 10,000 to 500,000. Yes.

  Therefore, as a sodium styrene sulfonate polymer having a weight average molecular weight in the range of 10,000 to 500,000, a sodium styrene sulfonate polymer having a weight average molecular weight of about 27,000 or about 67,000 in terms of polyethylene oxide is obtained. It was tried to evaluate the allergen inhibitory effect, but the allergen inhibitory effect could not be confirmed.

The Journal of Immunology Vol.144: 1353-1360 JP-A 61-44821 JP-A-6-279273 JP 11-292714 A JP 2004-275605 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 allergen object are provided.

  The allergen inhibitor of the present invention contains a sulfonate of a styrene sulfonic acid homopolymer having a Z average molecular weight of 150,000 or more as an allergen suppressing compound.

  Here, the allergen inhibitor refers to those having an allergen inhibitory effect, and the “allergen inhibitory effect” refers to leopard mite allergens (Der1, Der2), cedar pollen allergens (Cryj1, Cryj2) floating 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 an ELISA method using an ELISA kit commercially available from Nitinichi Pharmaceutical Co., Ltd., an allergen measuring instrument (manufactured by Sumika Enviro Science Co., Ltd.) And a method for evaluating allergenicity using the name “Mighty Checker”).

  And in the sulfonate of the styrene sulfonic acid homopolymer contained as an allergen suppressing compound, the salt is not particularly limited, for example, alkali metal salts such as sodium, potassium and lithium, alkalis such as calcium and magnesium Examples include earth metal salts, ammonium salts, amine salts such as ethanolamine, trimethylamine, and triethylamine, and ester salts such as ethyl polystyrene sulfonate. Alkali metal salts, ammonium salts, and amine salts are preferable, sodium salts, potassium salts, An ammonium salt and a triethylamine salt are more preferable, and a sodium salt is particularly preferable. In addition, the salt contained in the molecule | numerator of the sulfonate salt of a styrenesulfonic acid homopolymer may be single type, or multiple types may be mixed.

  The sulfonate of styrene sulfonic acid homopolymer (polystyrene sulfonic acid sulfonate) contained as an allergen-inhibiting compound is not particularly limited. For example, sodium styrene sulfonate homopolymer, potassium styrene sulfonate alone Polymer, lithium styrenesulfonate homopolymer, calcium styrenesulfonate homopolymer, magnesium styrenesulfonate homopolymer, barium styrenesulfonate homopolymer, aluminum styrenesulfonate homopolymer, ammonium styrenesulfonate homopolymer Styrene ethyl sulfonate homopolymer, sodium styrene sulfonate / potassium polymer, sodium styrene sulfonate / calcium polymer, and the like. Preferable is potassium sulfonate homopolymer, ammonium styrenesulfonate homopolymer, triethylamine styrenesulfonate homopolymer, more preferably sodium styrenesulfonate homopolymer, and less steric hindrance in reactivity with allergen. -Sodium styrenesulfonate homopolymer is more preferred. In addition, the sulfonate of a styrene sulfonic acid homopolymer may be used independently, or 2 or more types may be used together.

  Sulfonate of styrene sulfonic acid homopolymer can be produced in a known manner. For example, radical polymerization of styrene sulfonate, sulfonic acid of styrene sulfonic acid homopolymer is sodium hydroxide, hydroxide The method of neutralizing using alkalis, such as calcium and ammonium chloride, etc. are mentioned.

  Further, not all of the sulfonic acid groups in the sulfonic acid salt molecule of the styrene sulfonic acid homopolymer may be made into a salt, but if the ratio of the sulfonated sulfonic acid group is low, the acidity of the allergen inhibitor is reduced. Is strong, and there is a possibility of damaging the allergen object described later, so 50 mol% or more is preferable, 70 to 100 mol% is more preferable, and 85 to 100 mol% is particularly preferable.

  In addition, the ratio of the sulfonic acid group made into the salt in the molecule | numerator of the sulfonate of a styrenesulfonic acid homopolymer is computed in the following way. When styrene sulfonate is polymerized to obtain a styrene sulfonate homopolymer sulfonate, the total number of moles of the sulfonic acid group and this derivative is calculated in the monomer used for the polymerization. At the same time, the number of moles of the sulfonic acid group converted into a salt is calculated, and the percentage of the number of moles of the sulfonic acid group converted into a salt with respect to the total number of moles may be calculated. Also, when a styrene sulfonic acid homopolymer is polymerized using styrene sulfonic acid as a monomer, and this styrene sulfonic acid homopolymer is neutralized with an alkali to produce a sulfonate salt of the styrene sulfonic acid homopolymer Measure the number of moles of alkali consumed by neutralization titration and measure the number of moles of styrene sulfonic acid used in the polymerization, and the percentage of moles of alkali consumed relative to the number of moles of styrene sulfonic acid. May be calculated.

  If the Z-average molecular weight of the sulfonate salt of the styrene sulfonic acid homopolymer is low, the allergen inhibitory effect of the allergen inhibitor is reduced, so it is limited to 150,000 or more, preferably 200,000 or more, more preferably 500,000 or more. However, if it is too high, the handleability of the allergen inhibitor may decrease, so the upper limit is preferably 5 million.

In the present invention, the weight average molecular weight and the Z average molecular weight of the polymer are those measured by size exclusion chromatography using polyethylene oxide as a standard substance. The weight average molecular weight and the Z average molecular weight of the polymer can be measured, for example, under the following conditions.
Column: (Tosoh TSKgel GMPWXL 7. 8 mm ID x 30 cm x 2)
Eluent: (0.2 M aqueous sodium sulfate solution: acetonitrile = 9: 1)
Flow rate: 1 ml / min Temperature: 40 ° C
Detection: UV (210 nm)
Standard polyethylene oxide: (Tosoh Corporation, SE-2,5,8,15,30,70,150 are used)

  And if the weight average molecular weight of the sulfonate of the styrene sulfonic acid homopolymer is low, the allergen inhibitor compound may not exhibit the allergen inhibitory effect, whereas if high, the handling property of the allergen inhibitor may be reduced. Therefore, 200,000 to 5,000,000 are preferable.

  The sulfonic acid salt of the styrene sulfonic acid homopolymer may be water-soluble or water-insoluble, but the allergen inhibitor is processed into an allergen object that requires washing resistance, such as clothing and bedding. In this case, the sulfonate of the styrene sulfonic acid homopolymer is preferably water-insoluble. 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. Is called water-soluble.

  If the sulfonate of the styrene sulfonic acid homopolymer is water-insoluble, the sulfonate of the styrene sulfonic acid homopolymer dissolves in the water and disappears even when the allergen target is in contact with water. And the allergen suppressing effect of the allergen suppressing product described later can be stably maintained over a long period of time.

  As a method for making the sulfonate of the styrene sulfonic acid homopolymer water-insoluble, the sulfonate of the styrene sulfonic acid homopolymer is prepared by adding a curing agent to the sulfonate of the water-soluble styrene sulfonic acid homopolymer. Crosslinking method, water-soluble styrene sulfonic acid homopolymer sulfonate salt fixed to the carrier, part desulfonating method, partly changing the structure of sulfonate part, poor water solubility For example, a method for forming a salt of a natural salt. Examples of the desulfonation method include a method of reacting an allergen-inhibiting compound and water vapor at a high temperature. As a method for changing the structure of the sulfonate portion, the allergen-inhibiting compound is melted in sodium hydroxide. And then phenolization.

  The styrene sulfonic acid homopolymer sulfonate curing agent is not particularly limited as long as it can crosslink the styrene sulfonic acid homopolymer sulfonate. For example, the styrene sulfonic acid homopolymer sulfonate is synthesized from an amine compound or an amine compound. Compounds such as polyaminoamide compounds, tertiary amine compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenolic compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization initiators, dicyanamide and its derivatives, divinylbenzene And may be used alone or in combination of two or more.

  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, dodecadic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid. , Polyaminoamide compounds synthesized from carboxylic acid compounds such as tetrahydroisophthalic acid and hexahydroisophthalic acid and derivatives thereof; polyaminoimide compounds synthesized from the above amine compounds and maleimide compounds such as diaminodiphenylmethane bismaleimide and derivatives thereof A ketimine compound synthesized from the amine compound and a ketone compound and derivatives thereof; synthesized from the amine compound and a compound such as an epoxy compound, urea, thiourea, an aldehyde compound, a phenol compound, or an acrylic compound; Such that polyamino compounds and derivatives thereof.

  Further, 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 (dimethyl). Aminomethyl) phenol, 1,8-diazabiscyclo (5,4,0) undecene-1 and derivatives thereof.

  The imidazole compound is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole and derivatives thereof. Can be 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 eicosan Examples thereof include acid dihydrazide, adipic acid dihydrazide and derivatives thereof.

  Furthermore, 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 tris Anhydrotrimellitate, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic 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 Polydodecanedioic acid Anhydride, such as chlorendic anhydride and derivatives thereof.

  Moreover, it does not specifically limit as said phenolic compound, For example, a phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, its derivative (s), etc. are mentioned.

  Further, the thermal latent cationic polymerization catalyst is not particularly limited. For example, benzylsulfonium salt, benzylammonium salt, benzylpyridinium using antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride and the like as a counter anion. Examples thereof include ionic thermal latent cationic polymerization catalysts such as salts and 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, an aromatic diazonium salt, an aromatic halonium salt, and an antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride, and the like as a counter anion. Ionic salts such as aromatic sulfonium salts and ionic photolatent cationic polymerization initiators such as organometallic complexes such as iron-allene complexes, titanocene complexes and arylsilanol-aluminum complexes; nitrobenzyl esters, sulfonic acid derivatives, Nonionic photolatent cationic polymerization initiators such as phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like can be mentioned.

  Further, the support on which the sulfonate of the styrene sulfonic acid homopolymer is fixed is not particularly limited, and examples thereof include inorganic carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermulite, pearlite, and the like. And organic polymer carriers such as polyethylene and polypropylene.

  The form of the organic polymer carrier is not particularly limited, and examples thereof include fine particles, fibers, sheets, films, and foams. When the sulfonate of the styrene sulfonic acid homopolymer is supported on the foam, the sulfonate of the styrene sulfonic acid homopolymer may be supported before foaming of the foamable molded article that becomes the raw material of the foam. You may carry | support the sulfonate of a styrenesulfonic acid homopolymer after foaming.

  The method for fixing the sulfonate of the styrene sulfonic acid homopolymer to the carrier is not particularly limited. For example, a method of adsorbing the sulfonate of the styrene sulfonic acid homopolymer to the carrier, grafting, etc. Examples thereof include a method of fixing a sulfonate of a styrene sulfonic acid homopolymer to a support by chemical bonding or binding by a binder.

  The allergen inhibitor of the present invention may contain formulation adjuvants such as a dispersant, an emulsifier, an antioxidant, an ultraviolet absorber, and a dye transfer inhibitor as long as the effectiveness of the allergen suppressing effect is not impaired. In addition, acaricides, bactericides, fungicides, deodorants and the like may be contained.

  The migration inhibitor is not particularly limited, and examples thereof include salts such as calcium chloride, water-soluble cationic compounds, polyvinyl pyrrolidone, polyvinyl pyridine betaine, and polyamine N-oxide polymers.

  Next, how to use the allergen inhibitor will be described. For the allergen inhibitor, a general use method such as a spray type, an aerosol type, a smoke type, a heat transpiration type, or a mixture in a matrix can be used.

  The allergen inhibitor is dissolved or dispersed in a solvent to form an allergen inhibitor solution, and an allergen inhibitor solution is mixed with an aqueous solvent, oil agent, emulsion, suspension, etc. to make the allergen inhibitor spray type. Can do. In addition, a spray type means the usage method which applies a pressure to the allergen inhibitor solution under normal pressure, and sprays an allergen inhibitor in the shape of a mist.

  Examples of the solvent include water (preferably ion-exchanged water), alcohols (methyl alcohol, ethyl alcohol, propyl alcohol, etc.), hydrocarbons (toluene, xylene, methylnaphthalene, kerosene, cyclohexane, etc.), Ethers (diethyl ether, tetrahydrofuran, dioxane etc.), ketones (acetone, methyl ethyl ketone etc.), amides (N, N-dimethylformamide etc.) are mentioned.

  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 can be made into an aerosol type. .

  Here, the aerosol type is a method of using an allergen inhibitor solution enclosed in a container together with a propellant in a compressed state, and spraying the allergen inhibitor in the form of a mist by the pressure of the propellant. Say. Examples of the propellant include nitrogen, carbon dioxide, dimethyl ether, and LPG.

  In addition, the spray-type allergen inhibitors include oxygen supply agents (potassium perchlorate, potassium nitrate, potassium chlorate, etc.), combustion agents (sugars, starches, etc.), and exothermic regulators (guanidine nitrate, nitroguanidine, guanyl phosphate). The allergen inhibitor can be smoked by adding an agent for decomposing oxygen (such as urea) and an auxiliary agent for decomposing oxygen supply agents (potassium chloride, copper oxide, chromium oxide, iron oxide, activated carbon, etc.). The smoke type refers to a method of use in which an allergen inhibitor is finely divided into smoke and dispersed.

  The matrix for mixing the allergen inhibitor 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 the like. Examples include higher fatty acids, paraffins, liquid paraffins, white petrolatum, hydrocarbon gel ointment, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, and various paints.

  Then, the allergen inhibitor, depending on various methods of use, such as daily necessities, allergens present or objects in which the allergens may exist in the future, that is, objects for which allergens are to be suppressed (hereinafter referred to as “allergens”) , "Allergen object") by spraying, dispersing, applying or fixing to an allergen-suppressed product, and the allergen of the allergen object can be suppressed. The above allergen inhibitors may be used alone or in combination of two or more. The allergen inhibitor is excellent in stability when a suspension is added to the above-mentioned allergen inhibitor solution to form a suspension. Spraying is preferred. In addition, as a method of chemically or physically fixing the allergen inhibitor to the allergen object, a method of chemically bonding or physically fixing the allergen inhibitor compound described later to the fiber can be used.

  In addition, examples of the allergen object include daily items that serve as a hotbed for allergens in a living space. Examples of such daily commodities include tatami mats, carpets, furniture (sofas, foam inside sofas, cloth chairs, tables, etc.), bedding (beds, futons, futon batting, duvet feathers, sheets, mattresses, cushions) And foams constituting them), interior parts of vehicles such as cars, airplanes, ships, etc. and interior materials (seats, child seats and foams constituting them), kitchen goods, baby goods, architectural interiors Examples include materials (wallpaper, flooring, etc.), textile products (curtains, towels, clothing, stuffed animals, etc.), screen door filters, screen doors, building interior materials, pharmaceuticals, quasi drugs, cosmetics, and the like.

  In particular, since the allergen inhibitor of the present invention has almost no unexpected coloration or discoloration in the daily living environment, it is subject to fading and discoloration due to light, such as architectural interior materials, in-car accessories, vehicle interiors. Suitable for materials, filters, textile products, etc.

  The above filter refers to a filter having 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, an insect, etc. And screen doors and kayaks that prevent entry.

  The pharmaceuticals, quasi-drugs and cosmetics are not particularly limited, and examples 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 textile product is not particularly limited, and examples thereof include bedding, carpets, curtains, towels, clothes, and stuffed animals.

  There are no particular limitations on the above-mentioned vehicle interior article and vehicle interior material, and examples thereof include a seat, a child seat, a seat belt, a car mat, a seat cover, and a carpet.

  The amount of the allergen inhibitor used in the allergen inhibitor of the present invention may be less if the allergen inhibitory effect of the allergen inhibitor is not expressed. On the other hand, if it is more, the allergen object may be damaged. 0.001-100 weight part is preferable with respect to 100 weight part, 0.01-50 weight part is more preferable, 0.02-30 weight part is especially preferable, and 0.02-20 weight part is the most preferable.

  The allergens targeted by the allergen inhibitor of the present invention include leopard mite allergens (Der1, Der2), animal allergens such as dogs and cats (Can f1, Fel d1), and cedar pollen floating in the air. Examples include allergens (Cryj1, Cryj2) and plant allergens such as 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 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.

  According to the above-mentioned guidelines for the use of an allergen inhibitor, the allergen inhibitor is supplied with an allergen inhibitor as necessary, thereby reacting the allergen object with a specific antibody that may or may be present in the allergen object in the future. Was to suppress.

  The allergen inhibitor may be contained in a fiber to form an allergen-suppressing fiber, and an allergen suppressing effect may 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 of incorporating the allergen inhibitor into the fiber include a method of chemically binding or physically fixing the allergen inhibitor compound to the fiber. The fiber is not particularly limited as long as it can contain an allergen-inhibiting compound. For example, a synthetic fiber such as a polyester fiber, a nylon fiber, an acrylic fiber, or a polyolefin fiber, or a half of an acetate fiber or the like. Examples thereof include synthetic fibers, recycled 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 for chemically bonding the sulfonate of the styrene sulfonic acid homopolymer to the fiber include a method of chemically bonding the sulfonate of the styrene sulfonic acid homopolymer to the fiber by a 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 to be a fiber, and a sulfonate of a styrene sulfonic acid homopolymer is polymerized as a branch polymer, (2 And a polymer reaction method in which a sulfonate of a styrene sulfonic acid homopolymer 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 radicals and polymerize, 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, and free radicals are generated in the fiber to perform polymerization. (3) A fiber and a sulfonate salt of a styrene sulfonic acid homopolymer (4) Irradiating the fiber only with γ rays or accelerated electron beams, and then irradiating the fibers with the styrene sulfonic acid homopolymer. (5) Oxidizing the polymer constituting the fiber to introduce a peroxy group or introducing a diazo group from the side chain amino group, A method of polymerizing using this as a polymerization initiation point, (6) hydroxyl group And a method using polymerization initiation reaction of epoxy, lactam, polar vinyl monomer and the like by an active group of a side chain such as amino group and carboxyl group.

  Furthermore, the graft polymerization methods are specifically listed. a) A method of carrying out graft polymerization by generating free radicals by grinding cellulose in a monomer that is a raw material of a sulfonate salt of a styrene sulfonic acid homopolymer. b) A method of performing graft polymerization using a monomer that is a raw material of a sulfonate of a styrene sulfonic acid homopolymer and a cellulose derivative (for example, mercaptoethyl cellulose) having a group that is susceptible to chain transfer as a fiber. c) A method in which graft polymerization is performed by oxidizing ozone and peroxide to generate radicals. d) A method of carrying out graft polymerization by introducing a double bond such as allyl ether, vinyl ether or methacrylic acid ester into the side chain of cellulose. e) A method in which an anthraquinone-2,7-disulfonate sodium salt or the like is used as a photosensitizer and the fiber is irradiated with ultraviolet rays to carry out graft polymerization. f) Method of performing graft polymerization electrochemically by winding fibers around the cathode, adding a monomer as a raw material for the sulfonate salt of styrenesulfonic acid homopolymer to dilute sulfuric acid, and applying an external voltage .

  Considering that it is graft polymerization to fiber, the following method is preferable. g) A method of graft polymerization by heating a fiber coated with glycidyl methacrylate (GMA) and benzoyl peroxide in a monomer solution that is a raw material of a sulfonate of a styrene sulfonic acid homopolymer. h) In a dispersion in which benzoyl peroxide, a surfactant (nonionic surfactant or anionic surfactant) and monochlorobenzene are dispersed in water, a styrene sulfonic acid homopolymer sulfonate salt as a raw material A method in which a polymer is added and, as a fiber, for example, polyester fiber is immersed and heated to perform graft polymerization.

  As the polymer reaction method, a general-purpose method can be used, for example, (1) chain transfer reaction to C—H, oxidation reaction, substitution reaction, (2) addition reaction to double bond, oxidation reaction, (3) Hydroxyl esterification, etherification, acetalization, substitution reaction for ester group and amide group, addition reaction, hydrolysis reaction, substitution reaction for halogen group, elimination reaction, (4) substitution reaction for aromatic ring (halogenation, nitro , Sulfonation, chloromethylation) and the like.

  Next, a method for physically fixing the allergen-inhibiting compound to the fiber 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 is impregnated with the fiber. A method of impregnating the fiber with an allergen inhibitor solution, (2) a method of applying the allergen inhibitor solution to the fiber surface, and (3) immersing the fiber in a binder obtained by dissolving or dispersing the allergen inhibitor. A method of fixing the allergen inhibitor to the fiber with a binder, (4) a method of applying a binder obtained by dissolving or dispersing the allergen inhibitor on the fiber surface, and fixing the allergen inhibitor to the fiber with a binder, etc. Can be mentioned. In the 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 it can fix the allergen inhibitor to the fiber surface. For example, the binder made of a synthetic resin may be a urethane resin such as a one-component urethane resin or a two-component urethane resin. Acrylic resin, urethane acrylate resin, polyester resin, unsaturated polyester resin, alkyd resin, vinyl acetate resin, vinyl chloride resin, epoxy resin, epoxy acrylate resin, and the like, and urethane resin is preferable.

  In the above description, the allergen inhibitor is chemically bonded to a separately manufactured fiber, or physically fixed, so that the allergen inhibitor is contained in the fiber. Fibers may be produced by spinning the combined fiber raw material.

  The production method of the fiber raw material in which the allergen inhibitor is chemically bonded is not particularly limited. For example, the monomer used as the raw material of the sulfonate of the styrene sulfonic acid homopolymer and the general fiber raw material are used. The method of producing a fiber raw material by copolymerizing a monomer is mentioned.

  The allergen inhibitor of the present invention is characterized by containing a sulfonate salt of a styrene sulfonic acid homopolymer having a Z average molecular weight of 150,000 or more as an allergen inhibitor compound, so that the allergen reacts with a specific antibody. In addition to being able to suppress allergies and prevent the occurrence of allergic symptoms, unexpected discoloration and discoloration under daily use conditions are unlikely to occur, and it can be suitably used for various daily necessities.

  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
A monomer aqueous solution was prepared by dissolving 280 parts by weight of sodium p-styrenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) in 645 parts by weight of water. On the other hand, 0.38 parts by weight of 2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} is dissolved in 60 parts by weight of water and polymerized. An aqueous initiator solution was prepared.

  The inside of the polymerization vessel was previously purged with nitrogen, and 100 parts by weight of water was supplied into the polymerization vessel and the temperature was raised to 85 ° C. while stirring, and then the monomer aqueous solution and the polymerization initiator aqueous solution were placed in the polymerization vessel for 6 hours. Then, polymerization of sodium p-styrenesulfonate was carried out while continuously feeding.

  After the supply of the monomer aqueous solution into the polymerization vessel was completed, the mixture was aged for 2 hours to obtain a sodium p-styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer). The p-sodium styrenesulfonate homopolymer was water-soluble. In addition, the p-sodium styrenesulfonate homopolymer had a weight average molecular weight of 1139000 and a Z average molecular weight of 1902000. The ratio of the sulfonic acid group made into the sodium salt in the p-sodium styrenesulfonate homopolymer was 100 mol%.

  The obtained sodium p-styrenesulfonate homopolymer was dissolved in ion-exchanged water to obtain an allergen-suppressing solution in which the concentration of the sodium p-styrenesulfonate homopolymer was 2% by weight.

(Example 2)
p-Styrenesulfonic acid was obtained by cation exchange of sodium p-styrenesulfonate using a cation exchange resin (trade name “Amberlite IR-120B” manufactured by Organo Corporation). Next, ammonium p-styrenesulfonate was obtained by adding an equimolar aqueous ammonium hydroxide solution to p-styrenesulfonic acid.

  Example 1 except that 925 parts by weight of an aqueous p-styrene sulfonate solution (ammonium p-styrene sulfonate concentration: 26% by weight) obtained as described above was used instead of sodium p-styrene sulfonate. In the same manner as described above, an ammonium p-styrenesulfonate homopolymer (a homopolymer of ammonium p-styrenesulfonate) was obtained. The ammonium p-styrenesulfonate homopolymer was water soluble. The p-styrene ammonium sulfonate homopolymer had a weight average molecular weight of 996000 and a Z average molecular weight of 1604000. The proportion of the sulfonic acid group converted to an ammonium salt in the homopolymer of ammonium p-styrenesulfonate was 100 mol%.

  The obtained ammonium p-styrenesulfonate homopolymer was dissolved in ion-exchanged water to obtain an allergen-suppressing solution in which the concentration of the ammonium p-styrenesulfonate homopolymer was 2% by weight.

(Example 3)
p-Styrenesulfonic acid was obtained by cation exchange of sodium p-styrenesulfonate using a cation exchange resin (trade name “Amberlite IR-120B” manufactured by Organo Corporation). Next, potassium p-styrenesulfonate was obtained by adding an equimolar aqueous potassium hydroxide solution to p-styrenesulfonic acid.

  Example 1 is used except that p-styrene sulfonate aqueous solution (potassium p-styrene sulfonate concentration: 26% by weight) obtained as described above is used in place of sodium p-styrene sulfonate. Similarly, potassium p-styrenesulfonate homopolymer (p-potassium styrenesulfonate homopolymer) was obtained. The potassium p-styrene sulfonate homopolymer was water-soluble. In addition, the weight average molecular weight of the p-styrene potassium sulfonate homopolymer was 892000, and the Z average molecular weight was 1507000. The proportion of sulfonic acid groups converted to potassium salts in the homopolymer of potassium p-styrenesulfonate was 100 mol%.

  The obtained potassium p-styrenesulfonate homopolymer was dissolved in ion-exchanged water to obtain an allergen-suppressing solution in which the concentration of the potassium p-styrenesulfonate homopolymer was 2% by weight.

Example 4
A monomer aqueous solution was prepared by dissolving 280 parts by weight of sodium p-styrenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) in 645 parts by weight of water. On the other hand, 0.50 part by weight of 4,4′-azobis- (4-cyanopentaic sodium) was dissolved in 40 parts by weight of water to prepare a polymerization initiator aqueous solution.

  After the inside of the polymerization vessel was previously purged with nitrogen, 100 parts by weight of water was supplied into the polymerization vessel and the temperature was raised to 90 ° C. while stirring, and then the monomer aqueous solution and the polymerization initiator aqueous solution were placed in the polymerization vessel for 6 hours. Then, polymerization of sodium p-styrenesulfonate was carried out while continuously feeding.

  After the supply of the monomer aqueous solution into the polymerization vessel was completed, the mixture was aged for 2 hours to obtain a sodium p-styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer). The p-sodium styrenesulfonate homopolymer was water-soluble. In addition, the sodium p-styrenesulfonate homopolymer had a weight average molecular weight of 598,000 and a Z average molecular weight of 975,000. The ratio of the sulfonic acid group made into the sodium salt in the p-sodium styrenesulfonate homopolymer was 100 mol%.

  The obtained sodium p-styrenesulfonate homopolymer was dissolved in ion-exchanged water to obtain an allergen-suppressing solution in which the concentration of the sodium p-styrenesulfonate homopolymer was 2% by weight.

(Example 5)
p-Styrenesulfonic acid was obtained by cation exchange of sodium p-styrenesulfonate using a cation exchange resin (trade name “Amberlite IR-120B” manufactured by Organo Corporation). Next, p-styrene sulfonic acid calcium was obtained by adding an equimolar amount of calcium hydroxide aqueous solution to p-styrene sulfonic acid.

  Example 1 was used except that, instead of sodium p-styrenesulfonate, an aqueous p-styrenesulfonate solution obtained as described above (calcium p-styrenesulfonate concentration: 26% by weight) was used. Similarly, a p-calcium styrenesulfonate homopolymer (p-calcium styrenesulfonate homopolymer) was obtained. The p-styrene sulfonate homopolymer was water-soluble. The p-calcium styrenesulfonate homopolymer had a weight average molecular weight of 516,000 and a Z average molecular weight of 898,000. The ratio of the sulfonic acid group made into the calcium salt in the p-styrene sulfonic acid homopolymer was 100 mol%.

  The obtained p-calcium styrenesulfonate homopolymer was dissolved in ion-exchanged water to obtain an allergen-suppressing solution in which the concentration of the p-styrene calcium sulfonate homopolymer was 2% by weight.

(Example 6)
P-sodium styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer) (ALDRICH), which is an allergen-inhibiting compound, is added to ion-exchanged water and uniformly dissolved, and p-sodium styrenesulfonate alone An allergen inhibitor solution having a polymer concentration of 2% by weight was obtained. In addition, the sodium p-styrenesulfonate homopolymer was water-soluble. In addition, the p-sodium styrenesulfonate homopolymer had a weight average molecular weight of 136,000 and a Z average molecular weight of 238,000. The ratio of the sulfonic acid group made into the sodium salt in the p-sodium styrenesulfonate homopolymer was 100 mol%.

(Example 7)
P-sodium styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer) (ALDRICH), which is an allergen-inhibiting compound, is added to ion-exchanged water and uniformly dissolved, and p-sodium styrenesulfonate alone An allergen inhibitor solution having a polymer concentration of 2% by weight was obtained. In addition, the sodium p-styrenesulfonate homopolymer was water-soluble. In addition, the sodium p-styrenesulfonate homopolymer had a weight average molecular weight of 510,000 and a Z average molecular weight of 884000. The ratio of the sulfonic acid group made into the sodium salt in the p-sodium styrenesulfonate homopolymer was 100 mol%.

(Example 8)
As an allergen-inhibiting compound, p-sodium styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer) (trade name “PS-50” manufactured by Tosoh Organic Chemical Co., Ltd.), p-sodium styrenesulfonate homopolymer content: 20% by weight) was added to ion-exchanged water and uniformly dissolved to obtain an allergen inhibitor solution in which the concentration of the homopolymer of sodium p-styrenesulfonate was 2% by weight. In addition, the sodium p-styrenesulfonate homopolymer was water-soluble. The p-sodium styrenesulfonate homopolymer had a weight average molecular weight of 354000 and a Z average molecular weight of 566000. The ratio of the sulfonic acid group made into the sodium salt in the p-sodium styrenesulfonate homopolymer was 100 mol%.

Example 9
As an allergen-inhibiting compound, p-sodium styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer) (trade name “PS-5” manufactured by Tosoh Organic Chemical Co., Ltd.), p-sodium styrenesulfonate homopolymer content: 20% by weight) was added to ion-exchanged water and uniformly dissolved to obtain an allergen inhibitor solution in which the concentration of the homopolymer of sodium p-styrenesulfonate was 2% by weight. In addition, the sodium p-styrenesulfonate homopolymer was water-soluble. In addition, the p-sodium styrenesulfonate homopolymer had a weight average molecular weight of 103,000 and a Z average molecular weight of 171,000. The ratio of the sulfonic acid group made into the sodium salt in the p-sodium styrenesulfonate homopolymer was 100 mol%.

(Comparative Example 1)
P-sodium styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer) (ALDRICH), which is an allergen-inhibiting compound, is added to ion-exchanged water and uniformly dissolved, and p-sodium styrenesulfonate alone An allergen inhibitor solution having a polymer concentration of 2% by weight was obtained. In addition, the sodium p-styrenesulfonate homopolymer was water-soluble. In addition, the p-sodium styrenesulfonate homopolymer had a weight average molecular weight of 67,000 and a Z average molecular weight of 132,000.

(Comparative Example 2)
P-sodium styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer) which is an allergen-inhibiting compound (trade name “PS-1” manufactured by Tosoh Organic Chemical Co., Ltd.), sodium p-styrenesulfonate homopolymer content: 20% by weight) was added to ion-exchanged water and uniformly dissolved to obtain an allergen inhibitor solution in which the concentration of the homopolymer of sodium p-styrenesulfonate was 2% by weight. In addition, the sodium p-styrenesulfonate homopolymer was water-soluble. In addition, the p-sodium styrenesulfonate homopolymer had a weight average molecular weight of 27000 and a Z average molecular weight of 45,000.

  Next, the allergen inhibitory ability of the allergen inhibitor solutions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated in the following manner, and the results are shown in Table 1.

(Allergen suppression ability)
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 8 μg / ml.

  On the other hand, the stock solution of the allergen inhibitor solution obtained in Examples 1-9 and Comparative Examples 1 and 2 and the allergen inhibitor solution obtained in Examples 1-9 and Comparative Examples 1 and 2 were replaced with ion-exchanged water. 4-fold diluted allergen inhibitor diluted 10-fold, and 10-fold allergen inhibitor diluted 10-fold with ion-exchanged water in allergen inhibitor solutions obtained in Examples 1-9 and Comparative Examples 1 and 2. The allergen inhibitor solution obtained by diluting the allergen inhibitor solutions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 20 times with ion-exchanged water was prepared.

  Subsequently, a test tube to which 1 ml of the allergen solution was supplied was prepared, and the stock solution of the allergen inhibitor solution, the allergen inhibitor 4 times diluted solution, the allergen inhibitor 10 times diluted solution and the allergen inhibitor 20 times obtained. The diluted solution was added to each test tube in 100 microliters and shaken at 37 ° C. for 1 hour.

  Next, 100 microliters of the liquid in the test tube is added to an allergen measuring device (trade name “Mighty Checker” manufactured by Sumika Enviro Science Co., Ltd.), and the degree of coloration of the allergen measuring device is visually observed, and the allergen is determined according to the following criteria. Inhibitory ability was evaluated. In addition, the darker the color of the allergen measuring device, the more allergen is present in the liquid.

  In Table 1, the evaluation results of allergen inhibitor solution undiluted solution, allergen inhibitor 4-fold diluted solution, allergen inhibitor 10-fold diluted solution, and allergen inhibitor 20-fold diluted solution are the “all solution” “4 times” of allergen inhibitor solution. It was described in each of the columns of “10 times” and “20 times”.

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.

Claims (5)

An allergen inhibitor comprising a sulfonate of a styrenesulfonic acid homopolymer having a Z average molecular weight of 150,000 or more as an allergen inhibitor compound. 2. The allergen inhibitor according to claim 1, wherein the sulfonate of the styrene sulfonic acid homopolymer is a sodium styrene sulfonate homopolymer. 2. The allergen inhibitor according to claim 1, wherein the sulfonate of the styrene sulfonic acid homopolymer is a p-sodium styrene sulfonate homopolymer. An allergen-suppressing product obtained by treating the allergen inhibitor according to any one of claims 1 to 3 with an allergen object. The allergen-suppressing product according to claim 4, wherein the allergen object is a filter, a building interior material, a textile product, a vehicle interior product, or a vehicle interior material.