WO2013118852A1 - Agent inhibiteur d'allergène, produit inhibiteur d'allergène, procédé d'inhibition d'allergène, et mise en œuvre en tant qu'agent inhibiteur d'allergène - Google Patents
Agent inhibiteur d'allergène, produit inhibiteur d'allergène, procédé d'inhibition d'allergène, et mise en œuvre en tant qu'agent inhibiteur d'allergène Download PDFInfo
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- WO2013118852A1 WO2013118852A1 PCT/JP2013/052971 JP2013052971W WO2013118852A1 WO 2013118852 A1 WO2013118852 A1 WO 2013118852A1 JP 2013052971 W JP2013052971 W JP 2013052971W WO 2013118852 A1 WO2013118852 A1 WO 2013118852A1
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- allergen
- styrene
- sulfonic acid
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- inhibitor
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
- A61P31/08—Antibacterial agents for leprosy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
Definitions
- the present invention can suppress the reaction of allergens such as pollen of vegetation such as cedar, mites, and indoor dust with specific antibodies, and is unlikely to cause unexpected discoloration or discoloration under daily use conditions.
- the present invention relates to an allergen inhibitor that hardly causes color transfer, and an allergen-suppressed product obtained by treating the allergen inhibitor with an allergen object.
- 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.
- 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. These cedar pollen allergens are in vitro as foreign substances when attached to the nasal mucosa. It is recognized and causes an inflammatory response.
- allergen 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).
- 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), vehicle interior materials (ceiling materials, etc.), kitchen items, baby items, curtains, wallpaper, towels, clothing, stuffed animals, other textile products, air purifiers ( The main body and filter) may be damaged depending on conditions.
- Patent Document 3 proposes an allergen inhibitor containing an aromatic hydroxy compound as an active ingredient, which has improved the problem of coloring the object, but when processed into a light-colored object such as white. Coloration may occur and was not sufficient.
- Patent Document 4 proposes an allergen inhibitor containing an allergen inhibitor compound, in which the allergen inhibitor compound is a sodium sulfonate salt of a p-styrenesulfonic acid homopolymer.
- Patent Document 5 proposes an allergen deactivator comprising a polymer compound having a styrene sulfonic acid unit. Specifically, in the examples, only the polymer compound having a styrene sulfonic acid ratio of 50 to 70% by weight is proposed. Is used as an allergen deactivator and its inactivation effect has been measured, but the deactivation effect has not been measured for polymer compounds having a styrenesulfonic acid ratio other than 50 to 70% by weight.
- the allergen inactive agent when the styrene sulfonic acid ratio in the polymer compound is 50 to 70% by weight, when the allergen inactive agent is processed into, for example, a textile product such as clothing, the allergen inactive agent causes the fiber. There is a problem that the color of the product is transferred to another product and contaminates the other product.
- 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. Furthermore, the present invention provides an allergen inhibitor that hardly causes color transfer, and an allergen-suppressed product obtained by treating the allergen inhibitor with an allergen object.
- the allergen inhibitor of the present invention contains a styrene polymer containing 20 to 45% by weight of a monomer component having the structural formula represented by the general formula (1) as an active ingredient.
- R 1 to R 5 are each hydrogen, a sulfonic acid group or a sulfonic acid group salt, and at least one of R 1 to R 5 is a sulfonic acid group or a sulfonic acid group salt. is there.
- the allergen inhibitor refers to those having an allergen inhibitory effect
- 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) caused by dogs and cats are denatured or adsorbed to suppress the reactivity of allergens to specific antibodies.
- 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 (commercially available from Sumika Enviro Science Co., Ltd.) And a method for evaluating allergenicity using the name “Mighty Checker”).
- a method for producing a styrenic polymer containing 20 to 45% by weight of the monomer component having the structural formula represented by the general formula (1) is, for example, (1) a single unit of the structural formula represented by the general formula (1).
- Sulfonated and introduced sulfonic acid group (—SO 3 H) is neutralized with an aqueous alkaline solution to form a sulfonic acid group as a salt; (4) a monomer having the structural formula represented by the general formula (1); A part of the benzene ring in the copolymerization of this monomer with another polymerizable monomer is sulfonated, and the introduced sulfonic acid group (—SO 3 H) is neutralized with an alkaline aqueous solution to remove the sulfonic acid group.
- polystyrene sulfonic acid polystyrene sulfonic acid, styrene sulfonic acid and this In the copolymer, or salts of these sulfonic acids with other copolymerizable monomers, a method of desulfonation part of the sulfonic acid group.
- alkaline aqueous solution include sodium hydroxide, potassium hydroxide, magnesium hydroxide, and ammonium hydroxide.
- R 1 to R 5 are each hydrogen (—H), a sulfonic acid group (—SO 3 H), or a salt of a sulfonic acid group, of R 1 to R 5 It is necessary that at least one of these is a sulfonic acid group or a salt of a sulfonic acid group. This is because in the general formula (1), the allergen inhibitor does not exhibit an allergen inhibitory effect unless it has a sulfonic acid group or a salt of a sulfonic acid group as a substituent.
- the salt of a sulfonic acid group for example, -SO 3 Na, -SO 3 K , -SO 3 Li, (- SO 3) 2 Ca, (- SO 3) 2 Mg, -SO 3 - NH 4 + can be mentioned
- the monovalent salt of a sulfonic acid group is preferred because the degree of freedom of the salt of the sulfonic acid group is high, the allergen denaturing effect or adsorption effect is high, and the allergen inhibitory effect of the allergen inhibitor is high, and —SO 3 Na, -SO 3 K, -SO 3 Li, -SO 3 - NH 4 + are more preferable, -SO 3 Na, -SO 3 - NH 4 + is particularly preferred.
- the monovalent salt of the sulfonic acid group is represented by —SO 3 M, and M is a monovalent cation. Examples of M include Na + , K + , Li + , NH 4 + and the like.
- R 3 is a sulfonic acid group or a salt of a sulfonic acid group
- R 1 , R 2 , R 4 and R 5 are hydrogen. preferable.
- Examples of the monomer represented by the general formula (1) include o-styrene sulfonic acid, o-sodium styrene sulfonate, m-styrene sulfonic acid, sodium m-styrene sulfonate, and p-styrene sulfonic acid.
- sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, ammonium styrene sulfonate is more preferred, sodium p- styrenesulfonate are particularly preferable.
- Examples of the monomer component other than the monomer component of the structural formula represented by the general formula (1) in the styrenic polymer include alkyl acrylates such as methyl acrylate, ethyl acrylate and 2-hydroxyethyl acrylate, methyl Methacrylate, ethyl methacrylate, alkyl methacrylate such as 2-hydroxyethyl methacrylate, vinyl alkyl ether such as vinyl methyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, 2-vinylnaphthalene, styrene, Acrylonitrile, acrylic acid, sodium acrylate, methacrylic acid, sodium methacrylate, maleic acid, fumaric acid, maleic anhydride, acrylamide, methacrylamide, diacetone Rylamide, vinyltoluene, xylene sulfonic acid, vinyl pyridine, vinyl
- Styrenic polymers are preferably linear because they have a high degree of freedom in the main chain and a high allergen-modifying or adsorbing effect.
- the allergen inhibitory effect of the allergen inhibitor is lowered.
- the styrene polymer of the allergen inhibitor if the content of the monomer component of the structural formula represented by the general formula (1) is large, the allergen inhibitor becomes easily compatible with pigments such as pigments and dyes. Is easy to drop off. As a result, for example, when dark fibers such as black are treated with an allergen inhibitor, the fibers will rub against other products in daily life, causing the dark color of the fibers to move to other products and contaminating other products. To do. Therefore, the content of the monomer component of the structural formula represented by the general formula (1) in the styrene polymer of the allergen inhibitor is limited to 20 to 45% by weight, and preferably 25 to 45% by weight.
- Examples of the styrene polymer containing the monomer component having the structural formula represented by the general formula (1) include p-styrene sulfonate-styrene copolymer and o-styrene sulfonate-styrene copolymer.
- Styrene sulfonate-styrene copolymer such as m-styrene sulfonate-styrene copolymer, styrene sulfonate-styrene sulfonic acid-styrene terpolymer, p-styrene sulfonic acid or a salt thereof
- a copolymer of at least one monomer and maleic acid a copolymer of at least one monomer of p-styrenesulfonic acid or a salt thereof and 2-hydroxyethyl methacrylate, p-styrenesulfonic acid Or a copolymer of at least one monomer of its salt and acrylic acid, at least one of p-styrenesulfonic acid or its salt Copolymer of methacrylic acid monomer, copolymer of at least one monomer of p-styrene sulfonic acid or its salt and
- the said styrenic polymer may be used independently, or 2 or more types may be used together.
- the styrene sulfonate-styrene copolymer is not particularly limited.
- examples include calcium sulfonate-styrene copolymer, ammonium styrenesulfonate-styrene copolymer, magnesium styrenesulfonate-styrene copolymer, potassium styrenesulfonate-styrene copolymer, lithium styrenesulfonate-styrene copolymer.
- the styrene sulfonate-styrene copolymer may be used alone or in combination of two or more.
- the allergen inhibitory effect of the allergen inhibitor may be reduced.
- the allergen inhibitor becomes easily compatible with a pigment such as a pigment or a dye, and the pigment is easily removed.
- a pigment such as a pigment or a dye
- the content of the styrene sulfonate component in the styrene sulfonate-styrene copolymer is limited to 20 to 45% by weight, and preferably 25 to 45% by weight.
- the styrene sulfonate-styrene sulfonic acid-styrene terpolymer is not particularly limited.
- styrene terpolymer potassium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, lithium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, sodium styrene sulfonate-styrene sulfonic acid- Styrene terpolymers are more preferred, and p-sodium styrene sulfonate-styrene sulfonic acid-styrene terpolymers are particularly preferred.
- the styrene sulfonate-styrene sulfonic acid-styrene terpolymer may be used alone or in combination of two or more.
- the allergen inhibitory effect of the allergen inhibitor may be reduced. If the content of the styrene sulfonate component in the styrene sulfonate-styrene sulfonate-styrene terpolymer is small, the allergen inhibitory effect of the allergen inhibitor may be reduced. If the content of the styrene sulfonate component in the styrene sulfonate-styrene sulfonic acid-styrene terpolymer is high, the allergen inhibitor will be easily compatible with pigments such as pigments and dyes, and the pigments will easily fall off. Become.
- the content of the styrene sulfonate component in the styrene sulfonate-styrene sulfonic acid-styrene terpolymer is limited to 20 to 45% by weight, and preferably 25 to 45% by weight.
- the acidity of the styrene sulfonate-styrene sulfonic acid-styrene terpolymer becomes strong, Since the allergen target to be treated with the allergen inhibitor may be damaged, it is preferably 10% by weight or less, more preferably 3% by weight or less.
- sulfonated polystyrene examples include polymers in which a part or all of the sulfonic acid group of a polymer obtained by sulfonating a part of the polystyrene benzene ring is a salt, and a part of the polystyrene benzene ring is sulfonated.
- a polymer in which all of the sulfonic acid groups of the obtained polymer are salts is preferred.
- polystyrene sulfonated polymer examples include a polymer in which all of the sulfonic acid groups of a polymer obtained by sulfonating a part of the polystyrene benzene ring are sodium salts, and a polymer in which a part of the polystyrene benzene ring is sulfonated.
- the allergen inhibitory effect of the allergen inhibitor may be reduced. If the content of the styrene sulfonate component in the polystyrene sulfonated product is large, the allergen inhibitor becomes easily compatible with pigments such as pigments and dyes, and the pigments easily fall off. As a result, for example, when dark fibers such as black are treated with an allergen inhibitor, the fibers will rub against other products in daily life, causing the dark color of the fibers to move to other products and contaminating other products. There are things to do.
- the content of the styrene sulfonate component in the sulfonated polystyrene is limited to 20 to 45% by weight, and preferably 25 to 45% by weight.
- the allergen object to be treated may be damaged, so that it is preferably 10% by weight or less, and more preferably 3% by weight or less.
- the allergen inhibitory effect of the allergen inhibitor may decrease, so 2000 or more is preferable, and 20000 or more is more preferable, but if it is too high, the allergen inhibitor. Is less than 1,000,000.
- the weight average molecular weight of the styrene polymer refers to a peak top value when measured by size exclusion chromatography using sodium polystyrene sulfonate as a standard substance.
- the weight average molecular weight of the styrene polymer can be measured, for example, under the following conditions.
- the allergen inhibitor can be obtained by preparing a predetermined type and a predetermined amount of monomer according to the constituent components and copolymerizing the monomer in a general manner. Further, the allergen inhibitor can be obtained by sulfonating a part of a benzene ring of a copolymer having a styrene skeleton such as a styrene-maleic acid copolymer or polystyrene, and neutralizing the introduced sulfonic acid group with an alkaline aqueous solution. Can also be obtained.
- a styrene sulfonate-styrene copolymer can be obtained by sulfonating a part of the benzene ring of polystyrene and neutralizing all sulfonic acid groups bonded to the benzene ring with an alkaline aqueous solution.
- Part of the benzene ring of polystyrene is sulfonated, and part of the sulfonic acid group bonded to the benzene ring is neutralized with an alkaline aqueous solution to obtain a styrenesulfonate-styrenesulfonic acid-styrene copolymer.
- the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, magnesium hydroxide, and ammonium hydroxide.
- the sulfonation of polystyrene can be carried out in a known manner, and examples thereof include a method using sulfur trioxide or concentrated sulfuric acid.
- the average particle size of the styrenic polymer is not particularly limited, but is preferably from 0.01 to 30 ⁇ m from the viewpoint of design of an allergen-suppressed product obtained by treating an allergen object with an allergen inhibitor. A thickness of 05 to 10 ⁇ m is more preferable.
- the average particle size of the styrenic polymer is a value measured by a particle size distribution measuring device.
- the particle size distribution measuring apparatus an apparatus commercially available from HORIBA Ltd. under the trade name “LA-950V2” can be used.
- the allergen inhibitor is water-insoluble, the allergen may be present or an allergen may be present in the future, such as a household article, that is, an object for which allergen is desired to be suppressed (hereinafter, “ Even when the "allergen object” is in contact with water, the allergen inhibitor can be prevented from dissolving and disappearing in water, and the allergen inhibitory effect of the allergen inhibitor product described below can be maintained over a long period of time. It can be sustained stably. Therefore, the allergen inhibitor is preferably water-insoluble. Human bodies and animals are excluded from allergen objects. Further, when the allergen inhibitor is water-soluble, it is preferable to make it water-insoluble.
- 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.
- a method for making an allergen inhibitor water-insoluble a method for crosslinking a styrene polymer by containing a curing agent in a water-soluble styrene polymer, a method for fixing a water-soluble styrene polymer to a carrier Etc.
- the curing agent for the styrenic polymer is not particularly limited as long as the styrenic polymer can be crosslinked.
- amine compounds compounds such as polyaminoamide compounds synthesized from amine compounds, tertiary amine compounds, Examples include imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenolic compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization initiators, dicyanamide and derivatives thereof, and divinylbenzene. More than one species may be used in combination.
- the amine compound is not particularly limited.
- 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, ⁇ - (m-aminophenyl) ethylamine, ⁇ - (p-aminophenyl) ethylamine, m-phenylenedia And aromatic amines
- the compound synthesized from the amine compound is not particularly limited.
- a ketimine compound synthesized from the amine compound and a ketone compound and a derivative 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.
- Polyamino compounds and derivatives thereof are exemplified.
- the tertiary amine compound is not particularly limited.
- 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 for example, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosan Examples thereof include 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.
- 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, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazeline acid anhydride Polyd
- 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 thermal latent cationic polymerization catalyst is not particularly limited.
- examples 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.
- Ionic photolatent cationic polymerization initiators such as onium salts such as aromatic sulfonium salts and 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.
- the carrier for fixing the styrenic polymer is not particularly limited, and examples thereof include inorganic carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermulite, perlite, and organic carriers such as polyethylene and polypropylene. Examples thereof include a polymer carrier.
- the form of the organic polymer carrier is not particularly limited, and examples thereof include fine particles, fibers, sheets, films, and foams.
- the styrenic polymer When the styrenic polymer is supported on the foam, the styrenic polymer may be supported before foaming of the foamable molded article that is the raw material of the foam, or the styrenic polymer may be supported after foaming. .
- the method for fixing the styrenic polymer to the support is not particularly limited.
- a method for adsorbing the styrenic polymer to the support, a chemical bond such as grafting, or a bond with a binder may be used.
- Examples thereof include a method of fixing to a carrier.
- 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.
- acaricides, bactericides, fungicides, deodorants and the like may be contained.
- the dye transfer 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.
- the procedure for using the allergen inhibitor will be described.
- 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.
- 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.
- the solvent examples include water (preferably ion-exchanged water), alcohols (methyl alcohol, ethyl alcohol, propyl alcohol, etc.), hydrocarbons (toluene, xylene, methylnaphthalene, kerosene, cyclohexane, etc.), Examples include ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), amides (N, N-dimethylformamide, etc.).
- 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
- the allergen inhibitor can be made into an aerosol type. .
- a solid carrier talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermulite, perlite, etc.
- 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.
- the propellant include nitrogen, carbon dioxide, dimethyl ether, and LPG.
- 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.
- examples include higher fatty acids, paraffins, liquid paraffins, white petrolatum, hydrocarbon gel ointment, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, and various paints.
- an allergen inhibitory effect is imparted to the allergen object, and an allergen inhibitor product is obtained.
- Allergens of the allergen object can be suppressed.
- An “allergen object” refers to an object in which an allergen already exists, or an object in which no allergen currently exists but an allergen may exist in the future. Human bodies and animals are excluded from allergen objects.
- the allergen is suppressed by supplying the allergen inhibitor. If the allergen is not present in the allergen object, the allergen inhibitor is applied to the allergen object in advance by providing the allergen inhibitor with an allergen inhibitory effect.
- the allergen inhibitor 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.
- 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 described later to the fiber can be used.
- examples of the allergen target include daily items that serve as a hotbed for allergens in a living space.
- the allergen object is a fiber or a fiber product
- the allergen inhibitor exhibits its effect more.
- Living items include, for example, tatami mats, carpets, furniture (sofas, foam inside sofas, cloth chairs, tables, etc.), bedding (beds, futons, futon batting, duvet feathers, sheets, mattresses, cushions, etc.
- Car interior items such as cars, airplanes, ships, and vehicle interior materials (seats, child seats and foams that make up these), kitchen items, baby items, architectural interior materials (Wallpaper, flooring, etc.), textile products (fabrics, curtains, towels, clothing, stuffed animals, etc.), textiles, filters such as screen doors, screen doors, and building interior materials.
- the allergen inhibitor of the present invention since the allergen inhibitor of the present invention has almost no unexpected coloration or discoloration in the daily living environment, and there is almost no problem of color transfer, it can be applied to other products caused by light fading, discoloration, or rubbing. It is suitable for applications in which contamination due to color transfer is a problem, for example, textile products, building interior materials, vehicle interior products, vehicle interior materials, filters, and the like.
- the above filter refers to a filter having the ability to separate, filter, and remove foreign substances.
- 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 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 fabrics, bedding, carpets, curtains, towels, clothes, and stuffed animals.
- the vehicle interior and 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.
- the allergen inhibitory effect of the allergen inhibitor may not be manifested.
- the allergen object may be damaged. Is preferably 0.001 to 100 parts by weight, more preferably 0.01 to 50 parts by weight, particularly preferably 0.02 to 30 parts by weight, and most preferably 0.02 to 20 parts by weight.
- 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. Animal allergens that are particularly effective 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 type of anatomical gates such as Kenagakonadani, Jesa Saladani, and Hidden Gates represented by Kasari Mite, but it is often found in indoor dust, especially bedding, and causes allergic diseases. Is particularly effective.
- 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 above-mentioned allergen inhibitor may be contained in a fiber to form an allergen-suppressing fiber, and the allergen suppressing effect may be imparted to the fiber itself.
- 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 to the fiber.
- the fiber is not particularly limited as long as it can contain an allergen inhibitor.
- 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.
- synthetic 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.
- the method for chemically binding the allergen inhibitor to the fiber includes a method of chemically binding the allergen inhibitor 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 an allergen inhibitor is polymerized as a branch polymer; (2) an allergen inhibitor is a polymer Examples thereof include a polymer reaction method in which the fiber is chemically bonded to the fiber by 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 an oxidation-reduction system (redox system), and free radicals are generated in the fiber for polymerization. (3) A fiber and a monomer that is a raw material for the styrene polymer.
- redox system oxidation-reduction system
- a side chain active group such as hydroxyl, amino or carboxyl Examples thereof include a method using a polymerization initiation reaction of epoxy, lactam, polar vinyl monomer and the like.
- 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 styrenic polymer. b) A method of performing graft polymerization using a monomer as a raw material of a styrene polymer 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.
- 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 of performing graft polymerization by irradiating a fiber with ultraviolet rays using sodium anthraquinone-2,7-disulfonate as a photosensitizer. f) A method of performing graft polymerization electrochemically by winding fibers around the cathode, adding a monomer as a raw material of the styrene polymer to dilute sulfuric acid, and applying an external voltage.
- a fiber coated with glycidyl methacrylate (GMA) and benzoyl peroxide is graft polymerized by heating in a monomer solution that is a raw material for the styrenic polymer.
- a surfactant nonionic surfactant or anionic surfactant
- monochlorobenzene is dispersed in water, a monomer which is a raw material for the styrene polymer is added to the fiber.
- a polyester fiber is immersed and heated to perform graft polymerization.
- a general-purpose method can be used, for example, (1) chain transfer reaction, oxidation reaction, substitution reaction for C—H, (2) addition reaction for 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.
- a method for 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.
- the allergen inhibitor solution may contain the following binder.
- the solvent is not particularly limited.
- 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.
- 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.
- 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.
- the monomer having the structural formula represented by the general formula (1) and the monomer to be a general fiber raw material And a method of preparing a fiber raw material by copolymerizing such that the monomer having the structural formula represented by the general formula (1) is contained in an amount of 20 to 45% by weight.
- the allergen inhibitor of the present invention contains a styrene polymer containing 20 to 45% by weight of the monomer component having the structural formula represented by the general formula (1), the allergen reacts with a specific antibody. Can be effectively suppressed, and allergic symptoms can be reduced or the occurrence thereof can be prevented. Furthermore, the allergen inhibitor of the present invention is less susceptible to unexpected discoloration or discoloration under daily use conditions, and can be suitably used for various daily necessities.
- the allergen inhibitor of the present invention can be applied to an allergen object to impart an excellent allergen inhibitory effect to the allergen object. Even if the allergen object is a fiber product or a fiber such as a fabric colored with a pigment such as a pigment or a dye, the allergen object treated with the allergen inhibitor is rubbed with the other product to give a color to the other product. There is no transfer. Therefore, it is possible to prevent the color fading of the allergen object due to the color transfer to another product and the contamination of the other product due to the color transfer from the allergen object.
- Example 1 A 2-liter separable flask equipped with a stirrer, a cooler and a thermometer, 67 parts by weight of sodium p-styrenesulfonate (trade name “Spinomer NaSS” manufactured by Tosoh Corporation, purity: 88.2% by weight), deionized 312 parts by weight of water, 135 parts by weight of styrene monomer (trade name “styrene, monomer” manufactured by Wako Pure Chemical Industries, Ltd.) and 407 parts by weight of modified ethanol (trade name “86% ethanol-ME, modified” manufactured by Wako Pure Chemical Industries, Ltd.) were added. The mixture was replaced with nitrogen gas while stirring, and then heated and maintained at 78 ° C.
- spinomer NaSS sodium p-styrenesulfonate
- deionized 312 parts by weight of water 135 parts by weight of styrene monomer (trade name “styrene, monomer” manufactured by Wako Pure Chemical Industries
- a polymerization initiator solution prepared by dissolving 4.4 parts by weight of potassium peroxodisulfate (manufactured by Wako Pure Chemical Industries, Ltd.) in 95 parts by weight of deionized water was added to the separable flask over 15 minutes, and then over 5 hours. Styrene monomer and sodium p-styrene sulfonate were polymerized.
- reaction solution was dried to obtain a polymer.
- 50 parts by weight of the obtained polymer was dispersed in 500 parts by weight of ion-exchanged water to prepare a dispersion, and sodium hydroxide was added so that the pH of the dispersion became 8.5 while stirring the dispersion with a stirrer.
- the polymer was separated from the dispersion, filtered and dried to obtain a p-sodium styrenesulfonate-styrene random copolymer.
- the sodium p-styrenesulfonate component was 30.4% by weight and the styrene component was 69.6% by weight.
- the weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 90,000.
- the average particle size of the p-sodium styrenesulfonate-styrene random copolymer was 2 ⁇ m.
- black fabric A plain twill fabric (cotton 100% by weight)
- black fabric B T / C broad fabric (polyester: 65% by weight, cotton: 35% by weight)
- Example 2 In the same manner as in Example 1, except that sodium p-styrenesulfonate was changed to 93.2 parts by weight, styrene monomer to 110 parts by weight, and potassium peroxodisulfate to 4.05 parts by weight, p-styrene was used. A sodium sulfonate-styrene random copolymer was obtained. In the p-sodium styrenesulfonate-styrene random copolymer, the sodium p-styrenesulfonate component was 42.8% by weight and the styrene component was 57.2% by weight.
- the weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 80,000.
- the average particle size of the p-sodium styrenesulfonate-styrene random copolymer was 1 ⁇ m.
- Test piece A in the same manner as in Example 1 to obtain a B.
- Example 3 95.2 parts by weight of ammonium p-styrene sulfonate was used instead of sodium p-styrene sulfonate, styrene monomer was changed to 50 parts by weight, and potassium peroxodisulfate was changed to 4.05 parts by weight.
- a p-styrene sulfonic acid ammonium-styrene random copolymer was obtained in the same manner as in Example 1 except that 25 wt% aqueous ammonia was used instead of sodium hydroxide for pH adjustment. .
- the ammonium p-styrene ammonium sulfonate-styrene random copolymer was 43.2% by weight and the styrene component was 56.8% by weight.
- the weight average molecular weight of the p-ammonium styrenesulfonate-styrene random copolymer was 90,000.
- the average particle size of the p-ammonium styrenesulfonate-styrene random copolymer was 2 ⁇ m.
- Specimens A and B were obtained in the same manner as in Example 1, except that p-ammonium styrenesulfonate-styrene random copolymer was used instead of p-sodium styrenesulfonate-styrene random copolymer.
- Example 4 50 parts by weight of the polymer before pH adjustment obtained in the same manner as in Example 1 was dispersed in 500 parts by weight of ion-exchanged water to prepare a dispersion, and this dispersion was stirred with a stirrer to adjust the pH of the dispersion. Hydrochloric acid was added to the dispersion so as to be 5.5, and the dispersion was stirred for 5 hours, and then the polymer was separated from the dispersion, filtered, and dried to obtain p-sodium styrenesulfonate-p- A styrene sulfonic acid-styrene random copolymer was obtained.
- the sodium p-styrenesulfonate component was 27.7% by weight
- the p-styrenesulfonate component was 2.7% by weight
- styrene The component was 69.6% by weight.
- the weight average molecular weight of p-sodium styrenesulfonate-p-styrenesulfonate-styrene random copolymer was 90,000.
- the average particle size of the p-sodium styrenesulfonate-p-styrenesulfonate-styrene random copolymer was 2 ⁇ m.
- Specimen A in the same manner as in Example 1 except that p-sodium styrenesulfonate-p-styrenesulfonic acid-styrene random copolymer was used instead of p-sodium styrenesulfonate-styrene random copolymer. , B was obtained.
- the total content of sodium p-styrene sulfonate and p-styrene sulfonic acid in the p-sodium styrene sulfonate-p-styrene sulfonate-styrene random copolymer is shown in Table 1 “Content of p-styrene sulfonate component”. For convenience, it is shown in the column “Amount”.
- Example 1 In the same manner as in Example 1, except that sodium p-styrenesulfonate was changed to 37 parts by weight, the styrene monomer was changed to 155 parts by weight, and potassium peroxodisulfate was changed to 4.5 parts by weight, p-styrenesulfonic acid was used. A sodium-styrene random copolymer was obtained. In the p-sodium styrenesulfonate-styrene random copolymer, the p-sodium styrenesulfonate component was 17.4% by weight and the styrene component was 82.6% by weight.
- the weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 80,000.
- the average particle size of the p-sodium styrenesulfonate-styrene random copolymer was 3 ⁇ m.
- Test piece A in the same manner as in Example 1 to obtain a B.
- Example 2 Sodium p-styrenesulfonate in the same manner as in Example 1 except that sodium p-styrenesulfonate was changed to 100 parts by weight, styrene was changed to 93 parts by weight, and potassium peroxodisulfate was changed to 3.73 parts by weight. -A styrene random copolymer was obtained. In the p-sodium styrenesulfonate-styrene random copolymer, the sodium p-styrenesulfonate component was 48.6% by weight and the styrene component was 51.4% by weight.
- the weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 100,000.
- the average particle size of the p-sodium styrenesulfonate-styrene random copolymer was 1 ⁇ m.
- Test piece A in the same manner as in Example 1 to obtain a B.
- test pieces A and B obtained in the examples and comparative examples were measured for the allergen suppressing effect and color transferability in the following manner, and the results are shown in Table 1.
- An allergen chilled dry powder (trade name “MiteExtract-Df” manufactured by Cosmo Bio Inc.) was dissolved in a phosphate buffer (pH 7.6) to prepare an allergen aqueous solution having a protein amount of 20 ⁇ g / ml.
- Evaluation samples A and B each having a rectangular shape of 1 cm in length and 5 cm in width were cut out from each of the test pieces A and B obtained in Examples and Comparative Examples.
- the allergen measuring device (trade name “Mighty Checker” manufactured by Sumika Enviro Science Co., Ltd.)
- the initial allergen inhibitory effect was evaluated. The darker the color of the allergen measuring device, the more allergen is present in the liquid.
- the following 1 to 3 determination was set as the pass. 5 ... A thick, thick and clear line was observed. 4 ... It can be clearly seen that it is a line. It is coloring faintly in 3 ... line shape. 2 ... The color is faintly colored. 1 ... No color development at all.
- Evaluation samples A and B were prepared in the same manner as the evaluation of the initial allergen inhibitory effect. Each of these evaluation samples A and B was separately immersed in 200 ml of water kept at 25 ° C. for 1 minute and taken out, and each of the evaluation samples A and B was dried at 100 ° C. for 10 minutes. did. For the evaluation sample pieces A and B, the allergen suppressing effect was measured in the same manner as described above.
- the allergen inhibitor of the present invention has an excellent allergen suppressing effect, is unlikely to cause unexpected discoloration, and hardly causes color transfer. Therefore, the allergen inhibitor of the present invention can easily give an allergen inhibitory effect to an allergen object such as daily necessities. Furthermore, since the allergen inhibitor of the present invention has almost no unexpected coloration or discoloration in the daily living environment, and there is almost no problem of color transfer, it can be used for other products caused by light fading, discoloration, or rubbing. It can be suitably used for applications in which contamination due to color transfer is a problem, such as textile products, building interior materials, in-car accessories, vehicle interior materials, and filters.
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Abstract
L'invention fournit un agent inhibiteur d'allergène avec lequel il est possible d'inhiber efficacement la réaction d'un allergène par rapport à un anticorps spécifique, et d'atténuer des symptômes allergiques ou d'en prévenir l'expression, simultanément un changement de couleur indésirable ou un changement de couleur sous des conditions normales de mise en œuvre est peu susceptible de se produire, et une migration de couleur peut difficilement se produire. L'agent inhibiteur d'allergène de l'invention étant caractéristique en ce qu'il comprend un polymère de styrène comprenant 20 à 45% en masse d'un composant monomérique dont la formule structurelle est représentée par la formule générale (1), la réaction d'un allergène avec un anticorps spécifique est efficacement inhibée, il est possible d'atténuer des symptômes allergiques ou d'en prévenir l'expression, et d'excellents résultats sont obtenus de sorte qu'un changement de couleur indésirable ou un changement de couleur sous des conditions normales de mise en œuvre est peu susceptible de se produire, et une migration de couleur peut difficilement se produire.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012027717A JP2015078249A (ja) | 2012-02-10 | 2012-02-10 | アレルゲン抑制剤及びアレルゲン抑制製品 |
| JP2012-027717 | 2012-02-10 |
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| Publication Number | Publication Date |
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| WO2013118852A1 true WO2013118852A1 (fr) | 2013-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2013/052971 Ceased WO2013118852A1 (fr) | 2012-02-10 | 2013-02-08 | Agent inhibiteur d'allergène, produit inhibiteur d'allergène, procédé d'inhibition d'allergène, et mise en œuvre en tant qu'agent inhibiteur d'allergène |
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| JP (1) | JP2015078249A (fr) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257376A (ja) * | 2005-02-16 | 2006-09-28 | Sekisui Chem Co Ltd | 水系アレルゲン抑制化剤及びアレルゲン抑制化繊維製品 |
| WO2009078449A1 (fr) * | 2007-12-17 | 2009-06-25 | Sekisui Chemical Co., Ltd. | Inhibiteur d'allergène, produit inhibant les allergènes, procédé d'inhibition des allergènes et utilisation en tant qu'inhibiteur d'allergène |
| JP2009155453A (ja) * | 2007-12-26 | 2009-07-16 | Kao Corp | アレルゲン不活化剤 |
| JP2012001631A (ja) * | 2010-06-16 | 2012-01-05 | Sekisui Chem Co Ltd | アレルゲン抑制剤及びアレルゲン抑制製品 |
| JP2012036362A (ja) * | 2010-07-13 | 2012-02-23 | Sekisui Chem Co Ltd | アレルゲン抑制剤、塗料及び化粧シート |
-
2012
- 2012-02-10 JP JP2012027717A patent/JP2015078249A/ja active Pending
-
2013
- 2013-02-08 WO PCT/JP2013/052971 patent/WO2013118852A1/fr not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257376A (ja) * | 2005-02-16 | 2006-09-28 | Sekisui Chem Co Ltd | 水系アレルゲン抑制化剤及びアレルゲン抑制化繊維製品 |
| WO2009078449A1 (fr) * | 2007-12-17 | 2009-06-25 | Sekisui Chemical Co., Ltd. | Inhibiteur d'allergène, produit inhibant les allergènes, procédé d'inhibition des allergènes et utilisation en tant qu'inhibiteur d'allergène |
| JP2009155453A (ja) * | 2007-12-26 | 2009-07-16 | Kao Corp | アレルゲン不活化剤 |
| JP2012001631A (ja) * | 2010-06-16 | 2012-01-05 | Sekisui Chem Co Ltd | アレルゲン抑制剤及びアレルゲン抑制製品 |
| JP2012036362A (ja) * | 2010-07-13 | 2012-02-23 | Sekisui Chem Co Ltd | アレルゲン抑制剤、塗料及び化粧シート |
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| JP2015078249A (ja) | 2015-04-23 |
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