WO2012050156A1 - Anti-allergen agent - Google Patents

Anti-allergen agent Download PDF

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Publication number
WO2012050156A1
WO2012050156A1 PCT/JP2011/073508 JP2011073508W WO2012050156A1 WO 2012050156 A1 WO2012050156 A1 WO 2012050156A1 JP 2011073508 W JP2011073508 W JP 2011073508W WO 2012050156 A1 WO2012050156 A1 WO 2012050156A1
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WO
WIPO (PCT)
Prior art keywords
allergen
acid
resin
agent
pka
Prior art date
Application number
PCT/JP2011/073508
Other languages
French (fr)
Japanese (ja)
Inventor
喜直 山田
Original Assignee
東亞合成株式会社
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Filing date
Publication date
Application filed by 東亞合成株式会社 filed Critical 東亞合成株式会社
Priority to KR1020137011896A priority Critical patent/KR101893232B1/en
Priority to US13/879,264 priority patent/US20130273798A1/en
Priority to CN201180049385.5A priority patent/CN103261357B/en
Priority to JP2012538710A priority patent/JP5594367B2/en
Publication of WO2012050156A1 publication Critical patent/WO2012050156A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00Coating compositions based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1606Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612Non-macromolecular compounds
    • C09D5/1618Non-macromolecular compounds inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/66Additives characterised by particle size
    • C09D7/67Particle size smaller than 100 nm
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/66Additives characterised by particle size
    • C09D7/69Particle size larger than 1000 nm
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71Salts of phosphoric acids
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2525Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]

Definitions

  • the present invention relates to an anti-allergen agent comprising an inorganic powder having a specific acid point concentration, an anti-allergen composition containing the anti-allergen agent, and a product.
  • Anti-allergens are sprayed and painted on textile products such as clothing, bedding, and masks, interior products such as filters, curtains, carpets, and furniture used in air cleaners and air conditioners, and automotive interior materials.
  • textile products such as clothing, bedding, and masks
  • interior products such as filters, curtains, carpets, and furniture used in air cleaners and air conditioners, and automotive interior materials.
  • acaricides are generally used to control mites in house dust. Even after death, the allergens are gradually released as the worms decompose, so killing the mites does not inactivate the allergens. Also, the mask is used to prevent inhalation of pollen such as cedar, but the pollen adhering to the mask does not lose allergen activity, so there is a risk of inhalation by scattering again. .
  • allergens that cause allergic symptoms are removed from the living space before being aspirated into the human body or denatured. It is necessary to make them harmless.
  • ⁇ As a method for removing allergens without using chemicals
  • a method of reducing allergens by physically removing floor accumulated dust and airborne dust with a vacuum cleaner or air cleaner there is a method of reducing allergens by physically removing floor accumulated dust and airborne dust with a vacuum cleaner or air cleaner.
  • a large amount of allergen sucked by the electric vacuum cleaner is only stored in the dust bag, and there is a risk that the allergen is scattered again when the dust bag is discarded.
  • it is difficult to completely remove the fine particulate matter by removal with an air cleaner and there is a risk of re-entrainment.
  • Patent Documents 1 and 2 disclose methods using tannic acid which are similar compounds of tannic acid.
  • Patent Document 3 discloses polyphenols such as tea extract and gallic acid which are similar compounds of tannic acid. Is disclosed.
  • organic allergen reducing agents such as tannic acid are chemically unstable, and when attached to fibers and textiles, they may be colored or discolored over time, or the environment may be caused by moisture, oil, solvent or washing. The problem is that it spills into the skin and soils clothes and causes skin irritation.
  • Patent Document 1 discloses that tannic acid can be removed with distilled water, it is clear that tannic acid is lost if fibers treated with tannic acid are washed repeatedly. Therefore, it is problematic to use it as an anti-allergen for textiles and textile products that may be washed or touched directly, and it can be used for textile products that are exposed to human eyes due to problems such as color tone, heat resistance, and durability. There was a drawback that the target was limited. In order to improve such a defect, an antiallergen agent composed of an inorganic substance has been proposed. Patent Document 4 discloses that an allergen is adsorbed using an inorganic substance such as activated carbon.
  • Patent Document 5 discloses that among inorganic substances, those having high solid acid strength are excellent in antiallergen activity. However, even if the substance exhibits the same solid acid strength, there may be a significant difference in allergen inactivation performance, and the higher the solid acid strength is, the higher the anti-allergen activity is not always. There wasn't. Furthermore, it has become clear that when a solid acid having a very high solid acid strength is used to perform fiber processing in an aqueous system, the metal part of the processing apparatus may corrode.
  • JP-A 61-44821 Japanese Patent Publication No. 2-16731 JP-A-6-279273 JP 2002-167332 A WO2009 / 044648 International pamphlet
  • the present invention is an anti-allergen agent composed of an inorganic substance having high anti-allergen performance, excellent heat resistance and processability, little coloration and not flowing out with water, preferably a coating composition It is an object of the present invention to provide an anti-allergen agent that hardly causes corrosion or discoloration of a mechanical device even when used as a product or a resin composition, and an anti-allergen composition and an anti-allergen product using the same.
  • the present invention is an anti-allergen agent comprising an inorganic powder having a pKa of 4.8 or less and an acid point concentration of 0.001 mmol / g or more, an anti-allergen composition using the anti-allergen agent, and an anti-allergen product.
  • the anti-allergen agent of the present invention not only exhibits a high anti-allergen activity compared to existing anti-allergen agents, but also is an inorganic substance, so it has excellent heat resistance and little coloration or discoloration, and will flow out with water. It is durable because there is no. Excellent antiallergenicity can be imparted to various products by a simple processing method.
  • the acid point concentration used in the anti-allergen agent of the present invention is the number of acid points or acidic centers on the surface of the solid, and can usually be expressed as the number per unit weight or unit surface area of the solid or the number of moles.
  • the acid strength of the acid point that is included in the quantity of the acid point concentration can be expressed by pKa.
  • the acid strength indicates the strength of the property that the acid point on the solid surface gives a proton to the base, or the property of receiving an electron pair from the base, and the property that gives a proton to the base as the pKa of the acid point is smaller, or The strength of accepting electron pairs from the base is increased, and the ability to adsorb and inactivate allergen proteins is increased.
  • the acid strength at the acid point is small, that is, when the pKa is large, the property of giving a proton to the base or the property of receiving an electron pair from the base is weakened.
  • the ability of the acid sites to adsorb and inactivate allergen proteins decreases, so that it becomes difficult to sufficiently adsorb allergen proteins no matter how large the number of acid sites, that is, the acid site concentration.
  • This balance is also related to the structure of the allergen protein and the compatibility between the basicity and the acid point.
  • the pKa of the acid point of the inorganic substance having an acid point is 4.8.
  • the effect of inactivation was shown for any allergen protein, and the quantity of acid sites, that is, the acid site concentration and the anti-allergen effect were correlated regardless of the type of allergen protein. That is, it has been found that if an acid point concentration of a solid acid having an acid point pKa of 4.8 or less is measured, it can be used as an index of the antiallergen performance of the substance.
  • the number of acid points of an inorganic substance powder having an acid point pKa of 4.8 or less is defined as the “acid point concentration” in the present invention, The larger this value, the higher the anti-allergen performance, which is a preferable anti-allergen agent. Specifically, those having an acid point concentration of 0.001 mmol / g or more are preferable. Although there is no upper limit that should not exceed the acid point concentration, since a powder of an inorganic substance exceeding 10 mmol / g is not generally known as a specific material, the usual upper limit is 10 mmol / g or less.
  • Measurement of the number of acid points with a pKa of 4.8 or less is obtained by applying a titration method using an indicator corresponding to a pKa of 4.8 to measure the total of all acid points with a pKa of 4.8 or less.
  • the value is defined as the acid point concentration having a pKa of 4.8 or less.
  • the acid point concentration is more preferably 0.01 mmol / g or more, and more preferably the acid point concentration is 0.05 mmol / g or more.
  • an inorganic substance having an acid point concentration of 0.05 mmol / g or more has an excellent anti-allergen effect and exhibits a high effect on various allergen substances.
  • the acid point concentration can be determined by measuring the amount of base that reacts with the powder.
  • the measurement in the liquid phase is a titration method
  • the measurement in the gas phase is a gas chemical adsorption method
  • the adsorption / desorption amount of He or hydrogen gas is a gas chemical adsorption method
  • the reaction between the anti-allergen agent and the allergen in the present invention is a liquid-mediated reaction
  • measurement by a titration method in a liquid phase is suitable.
  • the method for measuring the acid point concentration of the inorganic powder by the titration method in the liquid phase is as follows.
  • the inorganic powder dispersed in the nonpolar solvent is titrated with n-butylamine, and the end point of the titration is confirmed by the discoloration of the indicator.
  • the indicator before the reaction exhibits a base type color, but when adsorbed on the inorganic powder, exhibits a conjugate acid type color.
  • the acid point concentration is determined from the titration amount of n-butylamine required to return from the conjugate acid type color to the base type color.
  • One solid acid point corresponds to one n-butylamine molecule.
  • the titrating base must replace the indicator bound to the solid acid point, its basicity must be stronger than the basicity of the indicator.
  • the indicator shows an acidic color due to solid acidity, but it is preferable to allow sufficient time until the reaction is completed.
  • n-butylamine is dropped, and the acid point concentration is calculated from the amount of n-butylamine when the indicator color returns to the basic color.
  • n-butylamine added in the system with the largest amount of n-butylamine in which no discoloration of the indicator is confirmed is defined as the amount of base reacted with the acid point and expressed as the acid point concentration (mmol / g).
  • An inorganic substance having a high acid point concentration is an individual having many acid points on its surface.
  • Specific examples of the inorganic substance having a high acid point concentration include, but are not limited to, amorphous magnesium silicate, ⁇ -type zirconium phosphate, layered titanium phosphate, activated alumina, activated titania, and the like. .
  • the preferable average particle size is 0.01 to 50 ⁇ m, more preferably 0.02 to 20 ⁇ m.
  • a powder having an average particle size of 0.01 ⁇ m or more has an advantage of being easy to handle because it is difficult to re-aggregate.
  • particles having an average particle size of 50 ⁇ m or less have good dispersibility and do not impair the texture of the fiber. It is preferable because it has advantages such as being difficult to cause.
  • the average value of the average particle diameter can be measured with a laser diffraction particle size distribution meter or the like, and the median diameter analyzed on a volume basis can be used as the representative value of the particle diameter.
  • the color tone of the anti-allergen agent in the present invention is not limited, but white or a light color with high brightness is preferable in order to apply it to various materials and forms.
  • the preferred brightness is 60 or more in terms of L value as measured by a color difference meter.
  • the inorganic substance constituting the anti-allergen agent in the present invention preferably has an acid strength pKa of 1.5 or less. This is because, in addition to the high acid point concentration, the higher the acid strength as a solid acid, the higher the antiallergenicity.
  • the acid strength of the anti-allergen agent in the present invention is the ability of the acid point on the surface of the anti-allergen agent to give a proton to the base or to receive an electron pair from the base.
  • the acid strength can be measured by a method using an indicator. If an appropriate indicator is selected as the base, the acid strength can be measured as the ability to change the base type of the indicator to its conjugate acid type.
  • the acid strength can be measured by using various acid-base conversion indicators with known acid strength (pKa). The more discolored indicator of pKa is, the higher its acid strength is.
  • the method for measuring the acid strength of an inorganic solid acid using the indicator is as follows. Collect 0.1 g of solid acid in a test tube, add 2 mL of benzene and shake gently. Add 2 drops of 0.1% benzene solution of the indicator (however, crystal violet is not a benzene solution but a 0.1% ethanol solution) and shake gently to observe the color change.
  • the acid strength of the solid acid is less than or equal to the strongest acid strength at which indicator discoloration was confirmed (ie, the lowest pKa value), and greater than the weakest acid strength at which indicator discoloration was not confirmed (ie, the highest pKa value).
  • the pKa value of the inorganic solid acid is expressed as (the highest pKa value where no discoloration is confirmed) to (the lowest pKa value where discoloration is confirmed).
  • the value is larger. Is generally written as.
  • the inorganic substance in the present invention has a certain amount of water, so that an anti-allergen effect is easily exhibited.
  • a preferable moisture content in the inorganic substance is preferably 0.5 wt% or more, more preferably 2 wt% or more, and further preferably 10 wt% or more.
  • hygroscopic inorganic substances can be mixed with other materials or the moisture can be kept in the inorganic substance even if the atmospheric humidity changes, and the inorganic substance itself has the moisture necessary for allergen inactivation. Is excellent in terms of
  • the anti-allergen effect in the present invention can be evaluated by an ELISA sandwich method widely used as an antigen detection and quantification method, and can be displayed as the allergen inactivation rate (unit%) shown in ⁇ Formula 1>. is there.
  • the initial allergen amount is the allergen amount used in the ELISA evaluation and evaluated without using the sample, and the residual allergen amount is the allergen amount after contact with the sample.
  • the usage form of the anti-allergen agent of the present invention is not particularly limited, and can be appropriately mixed with other components or combined with other materials depending on the application.
  • it can be used in various forms such as powder, powder-containing dispersion, powder-containing particles, powder-containing paint, powder-containing fiber, powder-containing paper, powder-containing plastic, powder-containing film, and powder-containing aerosol.
  • it can be used in combination with various additives or materials such as deodorants, antibacterial agents, antifungal agents, flameproofing agents, anticorrosives, fertilizers and building materials.
  • allergens in living space can be prevented by adding to materials that may come into contact with humans, such as resin, paper, plastic, rubber, glass, metal, concrete, wood, paint, fiber, leather, and stone. It is possible to activate.
  • the anti-allergen agent of the present invention as a coating composition containing a fixing agent (binder).
  • a fixing agent binder
  • an additive may be added to the coating composition, and the coating composition may be diluted with a solvent or water before being processed into products of various shapes.
  • the larger the weight ratio of the anti-allergen agent / binder solid content the more easily the effect is produced.
  • the larger the weight ratio of the binder solid content the more firmly fixed the anti-allergen agent and There are also favorable aspects.
  • the weight ratio of the antiallergen agent / binder solids in the coating composition containing the antiallergen is preferably 90/10 to 30/70, more preferably 80/20 to 50/50.
  • the concentration of the anti-allergen agent contained in the composition is preferably 0.5 to 50% by mass, more preferably 1 in terms of easy dispersion and good storage stability. ⁇ 30% by mass.
  • the anti-allergen effect is manifested by the contact of the anti-allergen agent and the allergen on the surface of the product of various shapes, so fixing the anti-allergen agent on the surface of the product by the coating composition Since a large effect can be obtained with a smaller amount of the anti-allergen than when used for the entire interior of the product, it is preferable.
  • binder used in the coating composition of the present invention examples include the following. Natural resin, natural resin derivative, phenol resin, xylene resin, urea resin, melamine resin, ketone resin, coumarone / indene resin, petroleum resin, terpene resin, cyclized rubber, chlorinated rubber, alkyd resin, polyamide resin, Polyvinyl chloride, acrylic resin, vinyl chloride / vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl plastic, chlorinated polypropylene, styrene resin, epoxy resin, urethane and cellulose derivatives. .
  • acrylic resins polyvinyl chloride, and vinyl chloride / vinyl acetate copolymer resins are preferable.
  • emulsion type resins are preferable because of low pollution and easy handling.
  • pigments such as zinc oxide and titanium oxide, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact resistance enhancers, glass fibers, metal soaps
  • Lubricants such as lubricants, moisture-proofing agents and extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood powder, antifungal agents, antifouling agents, rust preventives, metal powders, UV absorbers, UV shielding Examples thereof include agents.
  • a method of processing fibers with the coating composition containing the anti-allergen agent of the present invention there is a method of applying, dipping, or spraying a fiber or a fiber product with the coating composition as it is or diluted.
  • the fibers that can be processed for example, natural fibers such as cotton, silk and wool, synthetic fibers such as polyester, nylon and acrylonitrile, semi-synthetic fibers such as triacetate and diacetate, and viscose rayon. Recycled fibers and the like, and composite fibers using two or more of these fibers may be used.
  • it can be used also for the nonwoven fabric using polyethylene, a polypropylene, etc.
  • the method of processing the anti-allergen agent of the present invention into a fiber or a fiber product is not particularly limited, but includes an immersion treatment, a printing treatment, a spraying treatment, etc., and the fiber is processed by drying the fiber containing the composition. Complete.
  • the drying method can be any of natural drying, hot air drying, vacuum drying, etc., but is preferably a method using heat, preferably 40 ° C. to 250 ° C., preferably 50 ° C. to 180 ° C. for 1 minute to 5 hours, preferably
  • the anti-allergen agent can be fixed to the fiber by drying for 5 minutes to 3 hours.
  • the effect can be exhibited when the amount of the anti-allergen agent of the present invention attached to the fiber or fiber product is 0.1 g or more per 1 m 2 of the fiber or fiber product. On the other hand, it is preferably 20 g / m 2 or less, more preferably 1 g to 10 g / m 2 so as not to impair the physical properties and texture of the fiber or fiber product.
  • the coating composition containing the anti-allergen agent of the present invention is too low in pH, it may corrode the metal of the production machine or cause deterioration of the processing solution or decrease in stability. Since the solid acid may be neutralized and the antiallergen effect may be reduced, the pH is preferably 3 or more and 9 or less when the coating composition is capable of pH measurement such as an aqueous system.
  • the factor that determines the pH of the coating composition is the same as the pH of the aqueous dispersion of the inorganic powder, and is greatly affected by the pKa of the solid acid.
  • the acid point concentration and the solubility of the anti-allergen agent itself are also included.
  • the coating composition containing the anti-allergen agent of the present invention is non-aqueous, used as a paint containing various paint components, or used as a resin composition containing an anti-allergen agent, the metal part that contacts in the same manner
  • a resin having a pH within a certain range in the aqueous dispersion test is less likely to cause rust and discoloration.
  • the anti-allergen agent may be dispersed in deionized water so as to be 5 wt%, and the pH after stirring for 5 minutes with a stirrer at 25 ° C.
  • the pH at that time is preferably 3 or more and 9 or less.
  • Coating compositions, paints, resins, and the like using such anti-allergen agents are preferable because they hardly cause metal corrosion or discoloration.
  • the paint since the paint is a composition intended for coating, it is a kind of coating composition, but not only for the purpose of fixing functional components such as anti-allergen agents but also for the cured coating film itself of the composition.
  • a coating composition that maintains a certain level of strength and exhibits weather resistance, article surface protection and aesthetics is particularly called a paint.
  • the anti-allergen agent of the present invention can be used in a paint.
  • Various additives may be added to the paint.
  • the resin component of the paint includes oils and fats such as soybean oil, linseed oil, safflower oil and castor oil, natural resins such as rosin, copar and shellac, processed resins such as chroman resin and petroleum resin, alkyd resins and acrylic resins. , Epoxy resin, polyurethane resin, vinyl chloride resin, silicone resin, synthetic resin such as fluororesin, rubber derivatives such as chlorinated rubber and cyclized rubber, cellulose such as nitrified cotton (lacquer), acetyl cellulose, etc. Derivatives and the like.
  • the paint pigments are (white) titanium, (black) carbon, (brown) bengara, (red) chrome vermilion, (blue) bitumen, (yellow) yellow lead, (red) iron oxide, etc. Content, extender pigments such as calcium carbonate, talc and barite powder, rust preventive pigments such as red lead, lead suboxide and cyamido lead, functional pigments such as aluminum powder and zinc sulfide (fluorescent pigment).
  • paint additives include UV curing agents, plasticizers, dispersants, anti-settling agents, emulsifiers, thickeners, antifoaming agents, antifungal agents, antiseptics, anti-skinning agents, drying agents, and anti-sagging agents.
  • Matting agents antistatic agents, conductive agents, flame retardants, graffiti preventing agents and the like.
  • the solvent for the paint include water, alcohol, paint thinner, lacquer thinner, polyurethane resin thinner, and the like. A paint can be prepared by combining these.
  • a brush coating method, a roller method, or a spraying method is applied to a substrate prepared in advance with a liquid as it is or diluted. And iron coating method. Further, the coated paint may be cured by UV irradiation.
  • base materials such as polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, cellophane, etc. , Joint materials such as PVC, modified silicon and urethane, metal, ceramic siding, porcelain, stoneware, pottery, glazed tile, marble, granite, glass and so on.
  • the anti-allergen agent / paint solid content weight ratio in the paint containing the anti-allergen agent of the present invention is preferably 10/90 to 50/50, more preferably 20/80 to 40/60.
  • An anti-allergen resin composition can be easily obtained by blending the anti-allergen agent of the present invention with a resin.
  • a resin There is no restriction
  • Specific resins may be molding resins, fiber resins, and rubber-like resins. For example, polyethylene, polypropylene, vinyl chloride, ABS resin, AS resin, MBS resin, nylon resin, polyester, polychlorinated resin.
  • additives can also be contained.
  • additives include pigments such as zinc oxide and titanium oxide, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact strength enhancers, glass fibers, and metal soaps.
  • any known method can be adopted as a method for producing a resin composition by blending the anti-allergen agent of the present invention into a resin.
  • a resin composition by blending the anti-allergen agent of the present invention into a resin.
  • (1) using an additive for facilitating adhesion between the anti-allergen powder and the resin or a dispersant for improving the dispersibility of the anti-allergen powder, a pellet resin or a powder resin (2) A method of directly mixing with a mixer, (2) A method of mixing as described above, forming into pellets with an extrusion molding machine, and then blending the molded product into a pellet resin, (3) Antiallergen After the agent is molded into a high-concentration pellet using wax, the pellet-shaped product is blended with the pellet-shaped resin.
  • the anti-allergen agent is dispersed and mixed in a high-viscosity liquid such as polyol.
  • all known molding techniques and mechanical devices can be used in accordance with the characteristics of various resins. Mixing and mixing while heating and pressurizing or depressurizing at an appropriate temperature or pressure. Alternatively, they can be easily prepared by a kneading method, and their specific operation may be carried out by a conventional method, such as a lump, sponge, film, sheet, thread or pipe, or a composite thereof. It can be molded into various forms. If the anti-allergen agent / resin solids weight ratio in the resin composition containing the anti-allergen agent of the present invention is 10/90 or more, an obvious effect is easily exhibited.
  • the solid weight ratio of the anti-allergen agent / resin composition in the resin composition containing the anti-allergen agent of the present invention is preferably 10/90 to 50/50, more preferably 20/80 to 40/60.
  • the anti-allergen agent of the present invention can be used in the form of the above composition, resin composition, and resin molded product, as it is or depending on the application where allergen reduction is required, or mixed with other components as appropriate. Or can be used in combination with other materials. For example, it can be used in any form such as powder, liquid dispersion, granular, aerosol, or liquid.
  • the anti-allergen agent of the present invention is used in various fields where allergen reduction is required, that is, indoor products, bedding, filters, furniture, in-car products, textile products, residential building products, paper products, toys, leather products. It can be used as toiletries, cosmetics and other products. For example, carpets, curtains, wall paper, tatami mats, shoji paper, wax for floors, calendars and other indoor products, bedding such as futons, beds, sheets, pillows, pillow covers, air purifiers, air conditioners Filters such as sofas, furniture such as chairs, car seats such as child seats and seat sheets, dust collection bags for vacuum cleaners, clothing, masks, stuffed animals, kitchen utensils, etc. However, the present invention is not limited to this.
  • the average particle diameter of the inorganic powder described in the examples indicates a volume-based median diameter obtained by ultrasonic dispersion in deionized water using a laser diffraction particle size distribution analyzer. Unless otherwise specified,% indicates mass%, but the unit% of the allergen inactivation rate is according to the above ⁇ Formula 1>.
  • To measure the acid point concentration put 0.5 g of inorganic powder in a 20 mL sample bottle, add 10 mL of benzene to it, and shake gently. Add 0.1N n-butylamine, which was added in 20 steps, and stir on a shaker.
  • n-butylamine added in the largest amount of n-butylamine, in which no discoloration of methyl red was confirmed was defined as the amount of base reacted with acid sites, and the acid point concentration (mmol / g).
  • the acid strength is less than or equal to the strongest acid strength (lowest pKa value) at which discoloration of the indicator was confirmed, and is considered to be greater than the weakest acid strength (highest pKa) at which the indicator did not discolor, so the range is defined as the pKa value. As recorded.
  • the moisture content of the inorganic powder was weighed about 5 g in an aluminum cup that had been weighed at 250 ° C. for 1 hour in a dryer (weighed to the nearest 0.1 mg), dried for 2 hours at 250 ° C. in the dryer, and then weighed again. (Weighed to the nearest 0.1 mg), and the water content of the inorganic powder was expressed as a percentage by dividing the drying loss by the mass before drying.
  • the anti-allergen effect was evaluated by the sandwich method of ELISA using a leopard mite allergen (allergen generally referred to as Derf2) and a cedar pollen allergen (allergen generally referred to as Cryj1).
  • Derf2 a leopard mite allergen
  • Cryj1 cedar pollen allergen
  • An antibody coat well was prepared by a conventional method using a persimmon leopard mite allergen (Derf2) -specific antibody (15E11 antibody, manufactured by Asahivir Co., Ltd.). 3 mg of the sample was weighed, and 500 ⁇ L of leopard mite allergen (Derf2) prepared to 40 ng / mL with an antigen diluent was added.
  • the mixture was well stirred to bring the sample into contact with the allergen, and then centrifuged and collected. The supernatant was collected, added to the 15E11 antibody coat well treated with a blocking agent, and allowed to stand at room temperature. One hour later, the sample was discarded, each well was washed with a washing buffer, and horseradish peroxidase-labeled anti-Derf2 monoclonal antibody 13A4PO (Asahivir Co., Ltd.) diluted to 200 ng / mL with the washing buffer was added to each well. It was added to the well and allowed to stand at room temperature.
  • the test procedure by ELISA sandwich method using cedar pollen allergen is as follows.
  • An antibody coat well was prepared by a conventional method using a cedar pollen allergen (Cryj1) specific antibody (Anti-Cryj1mAb013 manufactured by Seikagaku Corporation). 3 mg of the sample was weighed, and 500 ⁇ L of cedar pollen allergen (Cryj1) prepared to 10 ng / mL with the antigen dilution solution was added. The mixture was well agitated to bring the sample into contact with the allergen, and then centrifuged to collect the supernatant. The supernatant was added to the anti-Cryj1 mAb013 antibody coat well treated with a blocking agent and allowed to stand at room temperature.
  • the pH of the aqueous dispersion of inorganic powder was dispersed in ion-exchanged water in a beaker so that the inorganic powder was 5 wt%, and the pH after stirring for 5 minutes with a stirrer at 25 ° C. was measured using a glass electrode pH meter. It measured using-.
  • An iron test piece and an inorganic powder 5 wt% aqueous dispersion were placed in a glass test tube having a diameter of 30 mm, and placed on a heat block adjusted to 60 ° C. After 24 hours, the test piece was taken out, immersed in distilled water, subjected to ultrasonic cleaning for 5 minutes, and then dried for 30 minutes with a 50 ° C. dryer, and the presence or absence of rust on the test piece was visually confirmed.
  • the anti-allergen effect of the processed fiber product is that cedar pollen allergen (Cryj1) is used as the allergen, and 25 cm 2 of fiber is put into a plastic bag with a chuck, and 1 mL of the allergen solution adjusted to 100 ng / mL is brought into contact with the sample for 1 hour. After that, the contact solution is spun down, the supernatant is collected, the absorbance is measured by the same ELISA method evaluation as that of the inorganic powder, and the anti-allergen inactivity according to the above formula 1 is compared with the absorbance when the sample is not used. % Conversion was evaluated.
  • Anti-allergen effect film kneading resins allergens using cedar pollen allergen (Cryj1) to put the film 25 cm 2 into a zippered plastic bag, 1 hour contacting the allergen solution 1mL adjusted to the sample and 10 ng / mL Then, the contact liquid is centrifuged and the supernatant liquid is collected, and the absorbance is measured by the same ELISA method evaluation as that of the inorganic powder. Compared with the absorbance when the sample is not used, anti-allergen resistance is determined by the above formula 1. The activation rate% was evaluated.
  • the anti-allergen effect of the film processed with the acrylic UV curable paint is the allergen solution using cedar pollen allergen (Cryj1) as the allergen, putting the film 25cm 2 into a plastic bag with a chuck, and adjusting the sample to 10ng / mL. After contacting 1 mL for 3 hours, the contact solution is spun down, the supernatant is collected, the absorbance is measured by the same ELISA method as for inorganic powder, and the above formula is compared with the absorbance when no sample is used.
  • the anti-allergen inactivation rate% was evaluated according to 1.
  • Table 1 shows the average particle size, water content, acid strength, and the mite allergen inactivation effect and the cedar pollen allergen inactivation effect measured by the ELISA method for the obtained amorphous magnesium silicate.
  • Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • Example 2 ⁇ -type zirconium phosphate
  • a 15% zirconium oxychloride aqueous solution was added to a 75% phosphoric acid aqueous solution and aged at 120 ° C. for 12 hours, and then the precipitate was filtered, washed with water, dried and crushed to obtain ⁇ -type.
  • a zirconium phosphate powder was obtained.
  • Table 1 shows the average particle size, water content, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect measured by the ELISA method of the obtained ⁇ -type zirconium phosphate.
  • Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • Example 3 A precipitate obtained by using titanyl sulfate and oxalic acid as an active titanium oxide raw material was filtered, dried, calcined at 500 ° C, and pulverized to prepare active titanium oxide.
  • the average particle diameter, water content, acid strength and the mite allergen inactivating effect and the cedar pollen allergen inactivating effect measured by the ELISA method of the obtained titanium oxide are shown in Table 1.
  • Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • Example 4 The average particle diameter, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect of activated white clay (Galeon Ace SH manufactured by Mizusawa Chemical Industry) were measured. The results are shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • Table 1 shows the average particle diameter, water content, acid strength, and the mite allergen inactivating effect and the cedar pollen allergen inactivating effect measured by the ELISA method of the obtained crystalline magnesium silicate.
  • Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • a zirconium carbonate aqueous solution was added to a 75% phosphoric acid aqueous solution, heated and refluxed at 98 ° C. for 24 hours, and then the precipitate was filtered, washed with water, dried and crushed to obtain ⁇ -type phosphoric acid.
  • Zirconium was obtained.
  • Table 1 shows the average particle diameter, water content, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect measured by ELISA method for the obtained ⁇ -type zirconium phosphate.
  • Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • Titanium oxide Commercially available titanium oxide (MC-50 manufactured by Ishihara Sangyo Co., Ltd.) The average particle diameter, acid strength, and the results of measuring the mite allergen inactivation effect and the cedar pollen allergen inactivation effect by ELISA method It is shown in Table 1.
  • Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • Activated Alumina Results of measuring the mean particle diameter, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect of commercially available activated alumina (Mizusawa Chemical Industry GNDY-2) by ELISA method Is shown in Table 1.
  • Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
  • Example 9 Anti-allergen activity evaluation in the case where Example 1 is not fixed to the fiber
  • a comparative fabric was prepared by the same processing method as Example 7 without using amorphous magnesium silicate which is an inorganic substance of Example 1. did.
  • Table 3 shows the results of measuring the cedar pollen allergen inactivating effect of the comparative cloth.
  • Example 9 Evaluation of heat resistance of Example 1 fixed to fiber After producing anti-allergen cloth in the same manner as in Example 7 and applying heat at 120 ° C. for 100 hours, the anti-allergen cloth was inactivated by cedar pollen allergen and discolored. The results of measuring the properties are shown in Table 4.
  • Example 10 Evaluation of heat resistance of Example 1 fixed to fiber After producing anti-allergen cloth by the same method as in Example 8 and applying heat at 120 ° C. for 100 hours, the inactivation effect and discoloration of cedar pollen allergen of anti-allergen cloth The results of measuring the properties are shown in Table 4.
  • the anti-allergen-processed cloth applied with amorphous magnesium silicate of Example 1 shows a sufficiently high allergen inactivation rate even when heat is applied for a long time, and no discoloration occurs.
  • the anti-allergen product obtained by post-processing the inorganic substance of the present invention into a fiber has excellent heat resistance.
  • Example 11 Water resistance evaluation of Example 1 fixed to fiber An anti-allergen cloth was prepared in the same manner as in Example 7, put into a plastic container, added with ion-exchanged water, and shaken at 25 ° C for 16 hours. Table 5 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen cloth dried at 120 ° C. for 30 minutes.
  • Example 12 Water resistance evaluation of Example 1 fixed to fiber An anti-allergen cloth was prepared in the same manner as in Example 8, put into a plastic container, added with ion-exchanged water, and shaken at 25 ° C for 16 hours. Table 5 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen cloth dried at 120 ° C. for 30 minutes.
  • the anti-allergen-processed cloth impregnated with amorphous magnesium silicate of Example 1 showed a sufficiently high allergen inactivation rate even after water treatment. Therefore, the anti-allergen product obtained by post-processing the inorganic substance of the present invention into a fiber has excellent water resistance.
  • Example 13 Anti-allergen activity evaluation of Example 1 kneaded into resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and powdered polypropylene are mixed so as to have a mass ratio of 10:90 at 220 ° C. Was heated and pressed to produce an antiallergen film having a thickness of 0.2 mm. Table 6 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
  • Example 14 Anti-allergen activity evaluation of Example 1 kneaded into resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and powdered polypropylene were mixed at a solid content mass ratio of 20:80, and 220 ° C. Was heated and pressed to produce an antiallergen film having a thickness of 0.2 mm.
  • Table 6 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
  • Example 10 Anti-allergen activity evaluation when Example 1 was not kneaded into the resin
  • a comparative film was prepared by the same processing method as Example 13 without using amorphous magnesium silicate which is an inorganic substance of Example 1.
  • Table 6 shows the results of measuring the cedar pollen allergen inactivating effect of the comparative film.
  • the anti-allergen-processed film obtained by kneading the amorphous magnesium silicate of Example 1 showed a high allergen inactivation rate by adding 20 wt%. Therefore, the performance of the anti-allergen product obtained by kneading the inorganic substance of the present invention into a resin is excellent.
  • Example 15 Evaluation of anti-allergen activity of Example 1 processed with UV curable resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and acrylic UV curable paint (no solvent) have a solid content mass ratio of 15:85 And then processed to a PET film (Toray Lumira T60-50) to a thickness of 15 ⁇ m using a bar coater, and a conveyor pressure using a high-pressure mercury lamp (strength 60 W / cm) at a distance of 25 cm. The composition was cured by irradiating with ultraviolet rays under a condition of 3.7 m / min to produce an anti-allergen film. Table 7 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
  • Example 16 Anti-allergen activity evaluation of Example 1 processed with UV curable resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and acrylic UV curable paint are mixed so that the solid content mass ratio is 30:70.
  • a PET film Toray Lumilar T60-50
  • a high-pressure mercury lamp strength 60 W / cm
  • Table 7 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
  • Example 11 Evaluation of anti-allergen activity of a film processed with an acrylic UV curable paint when Example 1 is not fixed. Comparison is made by the same processing method as Example 15 without using amorphous magnesium silicate which is an inorganic substance of Example 1. A film was prepared. Table 7 shows the results of measuring the cedar pollen allergen inactivating effect of the comparative film.
  • the anti-allergen film obtained by UV-curing the amorphous magnesium silicate of Example 1 showed a high anti-allergen inactivation rate. Therefore, the performance of the anti-allergen product in which the inorganic substance of the present invention is UV-cured on the surface is excellent.
  • Example 17 In order to evaluate the antiallergenicity in an actual use environment, an amorphous magnesium silicate which is an inorganic substance was converted into an acrylic emulsion binder (NW-7060 manufactured by Toagosei Co., Ltd., solid content concentration 50 wt. %) And the mass ratio of the solid content of 2: 1 are immersed in a bath towel (155 cm ⁇ 70 cm component: cotton) for 5 minutes, and then dried at 120 ° C. for 60 minutes, An anti-allergen cloth (bath towel) having a fixed amount of 2 g / m 2 was prepared.
  • NW-7060 manufactured by Toagosei Co., Ltd., solid content concentration 50 wt. %
  • the cedar pollen floating in the environment was adsorbed on a sunny day with cedar pollen scattered by bathing a bath towel on the outdoor clothes for 6 hours.
  • a vacuum cleaner with a nonwoven fabric set after standing overnight was applied to the entire surface of the bath towel, and the allergen was sucked and collected on the nonwoven fabric.
  • the allergen placed on the nonwoven fabric was extracted with 10 ml of an antigen dilution solution (0.1% BSA + PBS buffer), and the amount of cedar pollen allergen (Cryj1) was measured by ELISA to obtain the allergen recovery amount.
  • Table 8 shows the results of allergen recovery by conducting the same adsorption test three times on another sunny day with more than three days. It was. The meaning of the first, second and third days in Table 8 means that the adsorption test was performed three different days.
  • Comparative Example 12 A bath towel of Comparative Example 12 was prepared in the same manner as in Example 17 except that only a binder containing no amorphous magnesium silicate was used, and it floated in the environment in the same place on the same day as Example 17. To adsorb cedar pollen. The results of the allergen recovery amount are shown in Table 8.
  • the anti-allergen agent of the present invention it is possible to impart a function to inactivate allergens derived from pollen, mites, etc. to materials related to human living space such as textile products and housing building materials, Allergen products can be manufactured.

Abstract

[Problem] Conventional tannic acid and polyphenol anti-allergen agents are known as anti-allergen agents capable of deactivating allergens such as mites and pollen, but these agents have inferior heat resistance and pose problems with coloration, discoloration, and elution. The purpose of the present invention is to provide an anti-allergen agent that has excellent heat resistance, shows no coloration, and has excellent water resistance and workability. [Solution] It was discovered that by using an inorganic substance having a high acid site concentration, with acid site concentration being defined as the number of acid sites having a pKa of 4.8 or less, it is possible to realize an anti-allergen agent that manifests strong anti-allergen effects, has excellent heat resistance and water resistance, shows little coloration, and has excellent workability.

Description

抗アレルゲン剤Antiallergen
 本発明は、特定の酸点濃度を有する無機粉体からなる抗アレルゲン剤およびその抗アレルゲン剤を含有する抗アレルゲン組成物並びに製品に関するものである。抗アレルゲン剤は衣類、寝具、マスクなどの繊維製品、空気清浄機やエアコンなどに用いられるフィルタ-、カ-テン、カ-ペット、家具などのインテリア製品、自動車内装材などに噴霧加工、塗装加工、あるいは壁紙、フロ-リング材などの建築材料の表面層に固定することでダニや花粉などによるアレルギ-原因物質を低減する効果を付与することができる。 The present invention relates to an anti-allergen agent comprising an inorganic powder having a specific acid point concentration, an anti-allergen composition containing the anti-allergen agent, and a product. Anti-allergens are sprayed and painted on textile products such as clothing, bedding, and masks, interior products such as filters, curtains, carpets, and furniture used in air cleaners and air conditioners, and automotive interior materials. Alternatively, by fixing to a surface layer of a building material such as wallpaper or flooring material, an effect of reducing allergen-causing substances due to ticks or pollen can be imparted.
近年、スギ花粉等による花粉症や、ダニ等が原因のハウスダストによる気管支喘息、花粉症、アレルギ-性鼻炎、アトピ-性皮膚炎などのアレルギ-性疾患に悩む人が増加し深刻な問題となっている。これらアレルギ-性疾患の治療法としては、抗アレルギ-剤とよばれる一連の薬剤や吸入用あるいは外用ステロイド剤が開発され大きく前進したが対症療法的な域を出ず根治的な治療法ではない。 In recent years, the number of people suffering from allergic diseases such as hay fever caused by cedar pollen and bronchial asthma, hay fever, allergic rhinitis, and atopic dermatitis due to house dust caused by ticks and the like has increased. It has become. As a treatment for these allergic diseases, a series of drugs called anti-allergic agents and inhalation or topical steroids have been developed and made great progress, but they are not radical treatment because they are not symptomatic. .
 また、ハウスダスト中のダニ駆除には一般的に殺ダニ剤等が用いられるが、ハウスダスト中のコナヒョウヒダニやヤケヒョウヒダニなどは虫体のみならずその糞や死骸までもアレルゲン反応を引き起こすという特徴を持っており、死んだ後も虫体が分解するに従い徐々に微粒子のアレルゲンを放出するため、ダニを殺しただけではアレルゲンを不活性化したことにならない。また、マスクはスギ等の花粉を吸入するのを防ぐために用いられているが、マスクに付着した花粉はアレルゲン活性が消失するわけではないので、再び飛散することによって吸入してしまう危険性がある。 In addition, acaricides are generally used to control mites in house dust. Even after death, the allergens are gradually released as the worms decompose, so killing the mites does not inactivate the allergens. Also, the mask is used to prevent inhalation of pollen such as cedar, but the pollen adhering to the mask does not lose allergen activity, so there is a risk of inhalation by scattering again. .
 このような問題から、アレルギ-疾患の症状軽減あるいは新たな感作を防ぐためには、アレルギ-症状を引き起こす原因物質であるアレルゲンを人体内に吸引される前に生活空間から取り除くか、変性させるなどして無害化させることが必要となる。 To alleviate symptoms of allergic diseases or prevent new sensitization from these problems, allergens that cause allergic symptoms are removed from the living space before being aspirated into the human body or denatured. It is necessary to make them harmless.
 薬剤を使わないアレルゲン除去の方法としては、電気掃除機による吸引や空気清浄機により床面堆積塵や空中浮遊塵を物理的に除去しアレルゲンを減少させる方法がある。しかしながら、電気掃除機により吸引した多量のアレルゲンは集塵袋に貯蔵されるだけであり、集塵袋の廃棄時にアレルゲンが再飛散する危険性が考えられる。また、空気清浄機による除去では微細化された粒子状物質を完全に除去することは困難であり再飛散の危険性がある。 ¡As a method for removing allergens without using chemicals, there is a method of reducing allergens by physically removing floor accumulated dust and airborne dust with a vacuum cleaner or air cleaner. However, a large amount of allergen sucked by the electric vacuum cleaner is only stored in the dust bag, and there is a risk that the allergen is scattered again when the dust bag is discarded. In addition, it is difficult to completely remove the fine particulate matter by removal with an air cleaner, and there is a risk of re-entrainment.
 そこで近年、有害なアレルゲンの抗体との反応部位を吸着や被覆などの効果で不活性化し無害化する抗アレルゲン剤が提案されている。例えば、タンニン酸を用いた方法が特許文献1および2、非特許文献1等に開示されており、特許文献3にはタンニン酸の類似化合物である茶抽出物、没食子酸等のポリフェノ-ル類が開示されている。しかしながらタンニン酸などの有機のアレルゲン低減化剤は化学的に不安定であり、繊維や繊維製品に付着させた場合、着色あるいは経時的に変色を起こしたり、あるいは水分、油分、溶剤や洗濯によって環境に流れ出し、衣服を汚したり皮膚に炎症を起こしたりするという問題がある。例えば特許文献1には、蒸留水によってタンニン酸が除去できることが開示されているから、タンニン酸で処理された繊維は繰り返し洗濯すればタンニン酸が失われてしまうことは明らかである。したがって、洗濯したり直接肌に触れる可能性のある繊維や繊維製品に抗アレルゲン剤として使用するのは問題があり、色調や耐熱性、耐久性といった問題からも人目にさらされる繊維製品では使用できる対象が限定されるという欠点があった。このような欠点を改善するものとして、無機物質からなる抗アレルゲン剤が提案されている。特許文献4には、活性炭のような無機物質を用いてアレルゲンを吸着させることが開示されているが、活性炭のように、多孔質比表面積が大きいことにより物理吸着の原理で吸着を示すような物質は、一般的に抗アレルゲン吸着性能が低いうえ、黒色であるために用途が限定される問題がある。また、特許文献5には無機物質の中でも固体酸強度が高いものが抗アレルゲン活性に優れることが開示されている。しかし、同等の固体酸強度を示す物質であっても、実際にはアレルゲン不活性化性能に著しく差が生じることがあり、必ずしも固体酸強度のみが高いほど優れた抗アレルゲン活性を示すとは限らなかった。さらに、固体酸強度が非常に大きい固体酸を用いて、水系で繊維加工などをする場合には、加工装置の金属部分が腐食する問題が起きる場合があることも明らかになってきた。 Therefore, in recent years, antiallergen agents have been proposed that inactivate and detoxify reactive sites of harmful allergens with antibodies by effects such as adsorption and coating. For example, methods using tannic acid are disclosed in Patent Documents 1 and 2, Non-Patent Document 1, and the like. Patent Document 3 discloses polyphenols such as tea extract and gallic acid which are similar compounds of tannic acid. Is disclosed. However, organic allergen reducing agents such as tannic acid are chemically unstable, and when attached to fibers and textiles, they may be colored or discolored over time, or the environment may be caused by moisture, oil, solvent or washing. The problem is that it spills into the skin and soils clothes and causes skin irritation. For example, since Patent Document 1 discloses that tannic acid can be removed with distilled water, it is clear that tannic acid is lost if fibers treated with tannic acid are washed repeatedly. Therefore, it is problematic to use it as an anti-allergen for textiles and textile products that may be washed or touched directly, and it can be used for textile products that are exposed to human eyes due to problems such as color tone, heat resistance, and durability. There was a drawback that the target was limited. In order to improve such a defect, an antiallergen agent composed of an inorganic substance has been proposed. Patent Document 4 discloses that an allergen is adsorbed using an inorganic substance such as activated carbon. However, like activated carbon, adsorption is performed on the principle of physical adsorption due to a large porous specific surface area. In general, the substance has a low anti-allergen adsorption performance and has a problem that its use is limited because it is black. Patent Document 5 discloses that among inorganic substances, those having high solid acid strength are excellent in antiallergen activity. However, even if the substance exhibits the same solid acid strength, there may be a significant difference in allergen inactivation performance, and the higher the solid acid strength is, the higher the anti-allergen activity is not always. There wasn't. Furthermore, it has become clear that when a solid acid having a very high solid acid strength is used to perform fiber processing in an aqueous system, the metal part of the processing apparatus may corrode.
特開昭61-44821号公報JP-A 61-44821 特公平2-16731号公報Japanese Patent Publication No. 2-16731 特開平6-279273号公報JP-A-6-279273 特開2002-167332号公報JP 2002-167332 A WO2009/044648号国際公開パンフレットWO2009 / 044648 International pamphlet
 本発明は上記事情に鑑み、抗アレルゲン性能が高く、かつ、耐熱性と加工性に優れ、着色性が少なく水で流出することのない無機物質からなる抗アレルゲン剤であり、好ましくは、コーティング組成物や樹脂組成物として用いるときにも機械装置の腐食や変色を起こしにくい抗アレルゲン剤、およびそれ用いた抗アレルゲン組成物ならびに抗アレルゲン製品を提供することを目的とする。 In view of the above circumstances, the present invention is an anti-allergen agent composed of an inorganic substance having high anti-allergen performance, excellent heat resistance and processability, little coloration and not flowing out with water, preferably a coating composition It is an object of the present invention to provide an anti-allergen agent that hardly causes corrosion or discoloration of a mechanical device even when used as a product or a resin composition, and an anti-allergen composition and an anti-allergen product using the same.
 本発明者は上記課題を解決すべく鋭意検討した結果、pKaが4.8以下の酸点濃度が0.001mmol/g以上である無機粉体が、高い抗アレルゲン活性を発現させることを見出し、本発明を完成した。本発明はpKaが4.8以下の酸点濃度が0.001mmol/g以上である無機粉体からなる抗アレルゲン剤およびその抗アレルゲン剤を用いた抗アレルゲン組成物ならびに抗アレルゲン製品である。 As a result of intensive studies to solve the above problems, the present inventor has found that an inorganic powder having a pKa of 4.8 or less and an acid point concentration of 0.001 mmol / g or more exhibits high antiallergen activity, The present invention has been completed. The present invention is an anti-allergen agent comprising an inorganic powder having a pKa of 4.8 or less and an acid point concentration of 0.001 mmol / g or more, an anti-allergen composition using the anti-allergen agent, and an anti-allergen product.
 本発明の抗アレルゲン剤は、既存の抗アレルゲン剤と比較し、高い抗アレルゲン活性を示すだけでなく、無機物質であるため耐熱性に優れるうえ着色性や変色性も少なく、水で流出することがないため耐久性のあるものである。様々な製品に対し簡便な加工方法により、優れた抗アレルゲン性を付与することができる。 The anti-allergen agent of the present invention not only exhibits a high anti-allergen activity compared to existing anti-allergen agents, but also is an inorganic substance, so it has excellent heat resistance and little coloration or discoloration, and will flow out with water. It is durable because there is no. Excellent antiallergenicity can be imparted to various products by a simple processing method.
 以下本発明について説明する。
 本発明の抗アレルゲン剤に用いる、酸点濃度とは、固体表面の酸点あるいは酸性中心の数量であり、通常は固体の単位重量あたりあるいは単位表面積あたりの数あるいはモル数として表わすことができる。酸点濃度の数量に算入する酸点の酸強度は、pKaで表すことができる。酸強度は、固体表面の酸点が塩基にプロトンを与える性質、または、塩基から電子対を受け取る性質の強さを示しており、酸点のpKaが小さいほど塩基にプロトンを与える性質、または、塩基から電子対を受け取る性質の強さが強くなり、アレルゲンタンパク質を吸着し、不活性化する能力が高くなる。
The present invention will be described below.
The acid point concentration used in the anti-allergen agent of the present invention is the number of acid points or acidic centers on the surface of the solid, and can usually be expressed as the number per unit weight or unit surface area of the solid or the number of moles. The acid strength of the acid point that is included in the quantity of the acid point concentration can be expressed by pKa. The acid strength indicates the strength of the property that the acid point on the solid surface gives a proton to the base, or the property of receiving an electron pair from the base, and the property that gives a proton to the base as the pKa of the acid point is smaller, or The strength of accepting electron pairs from the base is increased, and the ability to adsorb and inactivate allergen proteins is increased.
 しかしながら、通常1つの酸点は1つのアレルゲンタンパク質を吸着している間は、他のアレルゲンタンパク質を吸着することはできないので、たとえ個々の酸点の酸強度が高くても酸点の数量すなわち酸点濃度が低ければ、すぐに飽和吸着に達して十分な抗アレルゲン効果を示すことができない。アレルゲンタンパク質が多量に存在する場合、吸着する数量、即ち酸点濃度が高ければ、高い抗アレルゲン効果を示す。 However, since one acid point normally cannot adsorb other allergen proteins while adsorbing one allergen protein, even if the acid strength of each acid point is high, the quantity of acid points, ie, acid If the point concentration is low, saturation adsorption is reached immediately and sufficient antiallergen effect cannot be shown. When allergen protein is present in a large amount, a higher anti-allergen effect is exhibited if the quantity to be adsorbed, that is, the acid point concentration is high.
 一方、酸点の酸強度が小さい、すなわちpKaが大きい場合には塩基にプロトンを与える性質、または、塩基から電子対を受け取る性質の強さが弱くなるので、あまりpKaが大きい場合には、個々の酸点がアレルゲンタンパク質を吸着し、不活性化する能力が小さくなるため、いくら酸点の数量すなわち酸点濃度が大きくても、アレルゲンタンパク質を十分に吸着することが難しくなる。このバランスはアレルゲンタンパク質の構造や塩基性と酸点の相性にもかかわるが、本発明において代表的なアレルゲンタンパク質について調べた結果では、酸点を有する無機物質の、酸点のpKaが4.8以下のとき、いずれのアレルゲンタンパク質に対しても不活性化の効果を示し、酸点の数量すなわち酸点濃度と抗アレルゲン効果とがアレルゲンタンパク質の種類にかかわらず相関した。すなわち、酸点のpKaが4.8以下の固体酸の酸点濃度を測定すれば物質の抗アレルゲン性能の指標として用いることができることを見出した。 On the other hand, when the acid strength at the acid point is small, that is, when the pKa is large, the property of giving a proton to the base or the property of receiving an electron pair from the base is weakened. The ability of the acid sites to adsorb and inactivate allergen proteins decreases, so that it becomes difficult to sufficiently adsorb allergen proteins no matter how large the number of acid sites, that is, the acid site concentration. This balance is also related to the structure of the allergen protein and the compatibility between the basicity and the acid point. However, according to the result of examining the representative allergen protein in the present invention, the pKa of the acid point of the inorganic substance having an acid point is 4.8. In the following cases, the effect of inactivation was shown for any allergen protein, and the quantity of acid sites, that is, the acid site concentration and the anti-allergen effect were correlated regardless of the type of allergen protein. That is, it has been found that if an acid point concentration of a solid acid having an acid point pKa of 4.8 or less is measured, it can be used as an index of the antiallergen performance of the substance.
 より具体的に言えば、本発明の抗アレルゲン剤においては、酸点のpKaが4.8以下の無機物質の粉体の酸点の数量を、本発明における「酸点濃度」として定義し、この値が大きいほど抗アレルゲン性能が高く、好ましい抗アレルゲン剤である。具体的には、酸点濃度が0.001mmol/g以上であるものが好ましい。酸点濃度に超えてはならない上限はないが、具体的な材料としては10mmol/gを超える無機物質の粉体は一般的に知られていないので、通常の上限は10mmol/g以下である。 More specifically, in the anti-allergen agent of the present invention, the number of acid points of an inorganic substance powder having an acid point pKa of 4.8 or less is defined as the “acid point concentration” in the present invention, The larger this value, the higher the anti-allergen performance, which is a preferable anti-allergen agent. Specifically, those having an acid point concentration of 0.001 mmol / g or more are preferable. Although there is no upper limit that should not exceed the acid point concentration, since a powder of an inorganic substance exceeding 10 mmol / g is not generally known as a specific material, the usual upper limit is 10 mmol / g or less.
 pKaが4.8以下の酸点の数量の測定は、pKaが4.8に対応した指示薬を用いた滴定法を応用することで、pKaが4.8以下のすべての酸点の合計を測定することができるので、その値をpKaが4.8以下の酸点濃度として定義する。本発明におけるさらに好ましい酸点濃度は0.01mmol/g以上、より好ましくは酸点濃度が0.05mmol/g以上である。特に酸点濃度が0.05mmol/g以上の無機物質の抗アレルゲン効果は優れており、様々なアレルゲン物質に対して高い効果を示す。 Measurement of the number of acid points with a pKa of 4.8 or less is obtained by applying a titration method using an indicator corresponding to a pKa of 4.8 to measure the total of all acid points with a pKa of 4.8 or less. The value is defined as the acid point concentration having a pKa of 4.8 or less. In the present invention, the acid point concentration is more preferably 0.01 mmol / g or more, and more preferably the acid point concentration is 0.05 mmol / g or more. In particular, an inorganic substance having an acid point concentration of 0.05 mmol / g or more has an excellent anti-allergen effect and exhibits a high effect on various allergen substances.
 酸点濃度は、粉体と反応する塩基の量を測定することで求めることが可能である。液相または気相で測定する方法があり、液相での測定は滴定法、気相での測定は気体化学吸着法として、Heや水素ガスの吸脱着量と塩基性ガスの吸脱着量との差を測定する方法が知られているが、本発明における抗アレルゲン剤とアレルゲンの反応は液体を媒介とした反応であるため、液相での滴定法による測定が適している。 The acid point concentration can be determined by measuring the amount of base that reacts with the powder. There is a method of measuring in the liquid phase or gas phase, the measurement in the liquid phase is a titration method, the measurement in the gas phase is a gas chemical adsorption method, the adsorption / desorption amount of He or hydrogen gas and the adsorption / desorption amount of basic gas However, since the reaction between the anti-allergen agent and the allergen in the present invention is a liquid-mediated reaction, measurement by a titration method in a liquid phase is suitable.
 液相での滴定法による無機粉体の酸点濃度の測定方法は以下のとおりである。
無極性溶媒中に分散した無機粉体をn-ブチルアミンで滴定し、滴定の終点を指示薬の変色で確認する。反応前の指示薬は塩基型の色を呈しているが、無機粉体に吸着するとその共役酸型の色を呈する。共役酸型の色から塩基型の色に戻るまでに要したn-ブチルアミンの滴定量よりその酸点濃度を決定する。固体の酸点一個とn-ブチルアミン一分子とが対応する。滴定用塩基は固体の酸点と結合した指示薬を置換しなければならないため、その塩基性は指示薬の塩基性よりも強いものでなければならない。通常の滴定方法として、まず無機粉体/ベンゼン分散液に指示薬を加えると、固体酸性により指示薬は酸性色を示すが、反応が完結するまで十分な時間をおくことが好ましい。次にn-ブチルアミンを滴下していき、指示薬の色がもとの色である塩基性色にもどったときのn-ブチルアミンの量から酸点濃度を計算する。
The method for measuring the acid point concentration of the inorganic powder by the titration method in the liquid phase is as follows.
The inorganic powder dispersed in the nonpolar solvent is titrated with n-butylamine, and the end point of the titration is confirmed by the discoloration of the indicator. The indicator before the reaction exhibits a base type color, but when adsorbed on the inorganic powder, exhibits a conjugate acid type color. The acid point concentration is determined from the titration amount of n-butylamine required to return from the conjugate acid type color to the base type color. One solid acid point corresponds to one n-butylamine molecule. Since the titrating base must replace the indicator bound to the solid acid point, its basicity must be stronger than the basicity of the indicator. As an ordinary titration method, when an indicator is first added to the inorganic powder / benzene dispersion, the indicator shows an acidic color due to solid acidity, but it is preferable to allow sufficient time until the reaction is completed. Next, n-butylamine is dropped, and the acid point concentration is calculated from the amount of n-butylamine when the indicator color returns to the basic color.
 さらに具体的には、無機粉体0.5gを20mLのサンプル瓶に入れ、そこへベンゼン10mLを添加し軽く振り混ぜる。さらに20段階に添加量を振った0.1Nのn-ブチルアミンを加え、振とう機で攪拌する。24時間後に0.1%指示薬メチルレッド溶液を0.5mL加え、指示薬の変色を観察する。指示薬の変色が確認されない最もn-ブチルアミンの添加量が多い系のn-ブチルアミンの添加量を酸点と反応した塩基量とし、酸点濃度(mmol/g)として表す。なお、Nは規定度とも呼ばれ、規定度=モル濃度×1分子の酸価数で定義される当業者の慣用単位である。 More specifically, 0.5 g of inorganic powder is put into a 20 mL sample bottle, and 10 mL of benzene is added thereto and shaken lightly. Further, add 0.1N n-butylamine, which was added in 20 steps, and stir with a shaker. After 24 hours, add 0.5 mL of 0.1% indicator methyl red solution and observe indicator discoloration. The amount of n-butylamine added in the system with the largest amount of n-butylamine in which no discoloration of the indicator is confirmed is defined as the amount of base reacted with the acid point and expressed as the acid point concentration (mmol / g). N is also referred to as normality, and normality is a unit commonly used by those skilled in the art, defined by normality = molar concentration × acid number of one molecule.
 酸点濃度の高い無機物質は、その表面に多くの酸点をもつ個体である。酸点濃度の高い無機物質の具体例には、非晶質ケイ酸マグネシウム、α型リン酸ジルコニウム、層状リン酸チタニウム、活性アルミナ、活性チタニアなどが例示されるが、これらに限定するものではない。 An inorganic substance having a high acid point concentration is an individual having many acid points on its surface. Specific examples of the inorganic substance having a high acid point concentration include, but are not limited to, amorphous magnesium silicate, α-type zirconium phosphate, layered titanium phosphate, activated alumina, activated titania, and the like. .
 本発明における抗アレルゲン剤は、様々な材質や形態への加工に適用させるために、好ましい平均粒径は0.01~50μmであり、より好ましくは0.02μm~20μmである。平均粒径が0.01μm以上の粉体は再凝集し難いため取り扱い易いという長所がある。また、バインダ-等に分散させて繊維に後加工する場合、平均粒径が50μm以下の粒子は、分散性がよくて繊維の風合いを損ねないことや、繊維に練りこんだ場合に糸切れを起こし難いことなどの長所があり好ましい。平均的な粒径の代表値はレーザー回折式粒度分布計などで測定することができ、体積基準で解析したメジアン径を粒径の代表値として用いることができる。 In order to apply the anti-allergen agent in the present invention to various materials and forms, the preferable average particle size is 0.01 to 50 μm, more preferably 0.02 to 20 μm. A powder having an average particle size of 0.01 μm or more has an advantage of being easy to handle because it is difficult to re-aggregate. In addition, when the fiber is post-processed by dispersing in a binder or the like, particles having an average particle size of 50 μm or less have good dispersibility and do not impair the texture of the fiber. It is preferable because it has advantages such as being difficult to cause. The average value of the average particle diameter can be measured with a laser diffraction particle size distribution meter or the like, and the median diameter analyzed on a volume basis can be used as the representative value of the particle diameter.
 本発明における抗アレルゲン剤の色調に限定はないが、様々な材質や形態への加工に適用させるために白色または明度の高い淡色が好ましい。好ましい明度は色彩色差計で測定した際のL値で60以上のものである。 The color tone of the anti-allergen agent in the present invention is not limited, but white or a light color with high brightness is preferable in order to apply it to various materials and forms. The preferred brightness is 60 or more in terms of L value as measured by a color difference meter.
 さらに本発明における抗アレルゲン剤を構成する無機物質は酸強度pKaが1.5以下であることが好ましい。酸点濃度が高い値であることに加え、固体酸としての酸強度も高ければより高い抗アレルゲン性を有するためである。本発明における抗アレルゲン剤の酸強度とは、抗アレルゲン剤表面の酸点が塩基にプロトンを与える能力あるいは塩基から電子対を受け取る能力である。酸強度の測定は指示薬を用いる方法で実施できる。塩基として適当な指示薬を選べば、その指示薬の塩基型をその共役酸型に変える能力として酸強度を測定することが可能となる。 Furthermore, the inorganic substance constituting the anti-allergen agent in the present invention preferably has an acid strength pKa of 1.5 or less. This is because, in addition to the high acid point concentration, the higher the acid strength as a solid acid, the higher the antiallergenicity. The acid strength of the anti-allergen agent in the present invention is the ability of the acid point on the surface of the anti-allergen agent to give a proton to the base or to receive an electron pair from the base. The acid strength can be measured by a method using an indicator. If an appropriate indicator is selected as the base, the acid strength can be measured as the ability to change the base type of the indicator to its conjugate acid type.
 酸強度の測定に用いることができる指示薬および(pKa値)の例としては、メチルレッド(+4.8)、4-フェニルアゾ-1-ナフチルアミン(+4.0)、ジメチルイエロー(+3.3)、2-アミノ-5-アゾトルエン(+2.0)、4-フェニルアゾ-ジフェニルアミン(+1.5)、4-ジメチルアミノアゾ-1-ナフタレン(+1.2)、クリスタルバイオレット(+0.8)、p-ニトロベンゼンアゾ-p’-ニトロ-ジフェニルアミン(+0.43)、ジシンナミルアセトン(-3.0)、ベンザルアセトフェノン(-5.6)、アントラキノン(-8.2)等がある。これら酸強度(pKa)の知られた種々の酸塩基変換指示薬を使うことにより酸強度を測定することができる。pKaの小さい指示薬を変色するものほどその酸強度は大きい。 Examples of indicators and (pKa values) that can be used to measure acid strength include methyl red (+4.8), 4-phenylazo-1-naphthylamine (+4.0), dimethyl yellow (+3.3), 2 -Amino-5-azotoluene (+2.0), 4-phenylazo-diphenylamine (+1.5), 4-dimethylaminoazo-1-naphthalene (+1.2), crystal violet (+0.8), p-nitrobenzeneazo -P'-nitro-diphenylamine (+0.43), dicinnamylacetone (-3.0), benzalacetophenone (-5.6), anthraquinone (-8.2) and the like. The acid strength can be measured by using various acid-base conversion indicators with known acid strength (pKa). The more discolored indicator of pKa is, the higher its acid strength is.
 上記指示薬を用いた無機固体酸の酸強度の測定方法は以下のとおりである。
試験管に固体酸を0.1g採取し、ベンゼン2mLを加え軽く振り混ぜる。そこへ、指示薬の0.1%ベンゼン溶液(ただしクリスタルバイオレットはベンゼン溶液でなく、0.1%エタノ-ル溶液とする)を2滴添加し軽く振り混ぜ、色の変化を観察する。その固体酸の酸強度は指示薬の変色が確認された最も強い酸強度(すなわち最も低いpKa値)以下であり、指示薬の変色が確認されない最も弱い酸強度(すなわち最も高いpKa値)より大きいことになる、このことを当該無機固体酸のpKa値は(変色の確認されない最も高いpKa値)~(変色の確認された最も低いpKa値)として表記する。また、下限を示す適当な指示薬がない場合は(変色の確認された最も低いpKa値)以下、および上限を示す適当な指示薬がない場合は(変色の確認されない最も高いpKa値)より大きい。として表記されるのが一般的である。
The method for measuring the acid strength of an inorganic solid acid using the indicator is as follows.
Collect 0.1 g of solid acid in a test tube, add 2 mL of benzene and shake gently. Add 2 drops of 0.1% benzene solution of the indicator (however, crystal violet is not a benzene solution but a 0.1% ethanol solution) and shake gently to observe the color change. The acid strength of the solid acid is less than or equal to the strongest acid strength at which indicator discoloration was confirmed (ie, the lowest pKa value), and greater than the weakest acid strength at which indicator discoloration was not confirmed (ie, the highest pKa value). That is, the pKa value of the inorganic solid acid is expressed as (the highest pKa value where no discoloration is confirmed) to (the lowest pKa value where discoloration is confirmed). In addition, when there is no appropriate indicator indicating the lower limit (the lowest pKa value in which discoloration is confirmed) or less, and when there is no appropriate indicator indicating the upper limit (the highest pKa value in which discoloration is not confirmed), the value is larger. Is generally written as.
 本発明における無機物質は一定の水分量を持つことで抗アレルゲン効果が発現しやすくなる。無機物質中の好ましい含水率は0.5wt%以上が好ましく、さらに好ましくは2wt%以上で、さらに好ましくは10wt%以上である。また、吸湿性を有する無機物質は他の材料と混合したり、大気の湿度が変化しても水分を無機物質中に保つことができ、アレルゲン不活性化に必要な水分を無機物質自体が有している点で優れている。 The inorganic substance in the present invention has a certain amount of water, so that an anti-allergen effect is easily exhibited. A preferable moisture content in the inorganic substance is preferably 0.5 wt% or more, more preferably 2 wt% or more, and further preferably 10 wt% or more. In addition, hygroscopic inorganic substances can be mixed with other materials or the moisture can be kept in the inorganic substance even if the atmospheric humidity changes, and the inorganic substance itself has the moisture necessary for allergen inactivation. Is excellent in terms of
 本発明における抗アレルゲン効果は抗原の検出、定量法として広く用いられているELISA法のサンドイッチ法により評価し、<式1>に示すアレルゲン不活性化率(単位%)として表示することが可能である。初期アレルゲン量とはELISA評価に用いた、試料を用いずに評価したアレルゲン量を示し、残存アレルゲン量とは試料との接触後のアレルゲン量を示す。また、本発明におけるアレルゲン不活性化とは、アレルゲンの特異抗体との反応を抑えることであり、アレルゲン不活性化率が高いほど好ましい。具体的には、アレルゲン不活性化率90%以上が好ましく、より好ましくはアレルゲン不活性化率99%以上である。

アレルゲン不活性化率
=(1-残存アレルゲン量/初期アレルゲン量)×100(%) <式1>
The anti-allergen effect in the present invention can be evaluated by an ELISA sandwich method widely used as an antigen detection and quantification method, and can be displayed as the allergen inactivation rate (unit%) shown in <Formula 1>. is there. The initial allergen amount is the allergen amount used in the ELISA evaluation and evaluated without using the sample, and the residual allergen amount is the allergen amount after contact with the sample. The allergen inactivation in the present invention is to suppress the reaction of allergen with a specific antibody, and the higher the allergen inactivation rate, the better. Specifically, an allergen inactivation rate of 90% or more is preferable, and an allergen inactivation rate of 99% or more is more preferable.

Allergen inactivation rate = (1-residual allergen amount / initial allergen amount) × 100 (%) <Formula 1>
 本発明の抗アレルゲン剤の使用形態は特に制限がなく、用途に応じて適宜他の成分と混合したり、他の材料と複合することができる。例えば、粉末、粉末含有分散液、粉末含有粒子、粉末含有塗料、粉末含有繊維、粉末含有紙、粉末含有プラスチック、粉末含有フィルム、粉末含有エア-ゾル等の種々の形態で用いることができ、更に必要に応じて、消臭剤、抗菌剤、抗カビ剤、防炎剤、防食、肥料及び建材等の各種の添加剤あるいは材料と併用することもできる。また、人が接触する可能性のある材料、たとえば樹脂、紙、プラスチック、ゴム、ガラス、金属、コンクリ-ト、木材、塗料、繊維、革、石などに添加することによって生活空間におけるアレルゲンを不活性化させることが可能である。 The usage form of the anti-allergen agent of the present invention is not particularly limited, and can be appropriately mixed with other components or combined with other materials depending on the application. For example, it can be used in various forms such as powder, powder-containing dispersion, powder-containing particles, powder-containing paint, powder-containing fiber, powder-containing paper, powder-containing plastic, powder-containing film, and powder-containing aerosol. If necessary, it can be used in combination with various additives or materials such as deodorants, antibacterial agents, antifungal agents, flameproofing agents, anticorrosives, fertilizers and building materials. In addition, allergens in living space can be prevented by adding to materials that may come into contact with humans, such as resin, paper, plastic, rubber, glass, metal, concrete, wood, paint, fiber, leather, and stone. It is possible to activate.
 これらの使用方法の中でも好ましいのは本発明の抗アレルゲン剤を、固着剤(バインダ-)を含むコ-ティング組成物として用いることである。このコ-ティング組成物にはバインダ-の他に添加剤を加えても良く、また、コ-ティング組成物を各種形状の製品に加工する前に溶剤や水で希釈することもできる。本発明のコーティング組成物における、抗アレルゲン剤/バインダー固形分の重量比は大きいほど効果を発現し易い一方で、バインダー固形分の重量比が大きいほど抗アレルゲン剤がしっかり固定されて粉落ちし難く好ましい面もある。従って抗アレゲン剤含むコ-ティング組成物における、抗アレルゲン剤/バインダー固形分の重量比は90/10~30/70が好ましく、80/20~50/50がより好ましい。
 コ-ティング組成物を希釈して用いる場合、組成物中に含まれる前記抗アレルゲン剤の濃度は、分散が容易で保存性が良いことから0.5~50質量%が好ましく、さらに好ましくは1~30質量%である。通常、抗アレルゲン効果は、各種形状の製品の表面で抗アレルゲン剤とアレルゲンとが接触することによって発現するので、前記のコ-ティング組成物によって製品の表面に抗アレルゲン剤を固定することは、製品の内部全体に用いるよりも、より少ない量の抗アレルゲン剤で大きな効果を得ることができるので好ましい。
Among these methods of use, it is preferable to use the anti-allergen agent of the present invention as a coating composition containing a fixing agent (binder). In addition to the binder, an additive may be added to the coating composition, and the coating composition may be diluted with a solvent or water before being processed into products of various shapes. In the coating composition of the present invention, the larger the weight ratio of the anti-allergen agent / binder solid content, the more easily the effect is produced. On the other hand, the larger the weight ratio of the binder solid content, the more firmly fixed the anti-allergen agent and There are also favorable aspects. Accordingly, the weight ratio of the antiallergen agent / binder solids in the coating composition containing the antiallergen is preferably 90/10 to 30/70, more preferably 80/20 to 50/50.
When the coating composition is used after being diluted, the concentration of the anti-allergen agent contained in the composition is preferably 0.5 to 50% by mass, more preferably 1 in terms of easy dispersion and good storage stability. ~ 30% by mass. Usually, the anti-allergen effect is manifested by the contact of the anti-allergen agent and the allergen on the surface of the product of various shapes, so fixing the anti-allergen agent on the surface of the product by the coating composition Since a large effect can be obtained with a smaller amount of the anti-allergen than when used for the entire interior of the product, it is preferable.
 本発明のコ-ティング組成物に用いるバインダ-としては、以下のものがある。すなわち、天然樹脂、天然樹脂誘導体、フェノ-ル樹脂、キシレン樹脂、尿素樹脂、メラミン樹脂、ケトン樹脂、クマロン・インデン樹脂、石油樹脂、テルペン樹脂、環化ゴム、塩化ゴム、アルキド樹脂、ポリアミド樹脂、ポリ塩化ビニル、アクリル樹脂、塩化ビニル・酢酸ビニル共重合樹脂、ポリ酢酸ビニル、ポリビニルアルコ-ル、ポリビニルプラチラ-ル、塩素化ポリプロピレン、スチレン樹脂、エポキシ樹脂、ウレタン及びセルロ-ス誘導体等である。このうち、好ましいものはアクリル樹脂、ポリ塩化ビニル、塩化ビニル・酢酸ビニル共重合樹脂であり、中でもエマルション型の樹脂は低公害で取り扱い易いので好ましい。
 また、添加剤として用いることができるものは酸化亜鉛や酸化チタンなどの顔料、染料、酸化防止剤、耐光安定剤、難燃剤、帯電防止剤、発泡剤、耐衝撃強化剤、ガラス繊維、金属石鹸などの滑剤、防湿剤および増量剤、カップリング剤、核剤、流動性改良剤、消臭剤、木粉、防黴剤、防汚剤、防錆剤、金属粉、紫外線吸収剤、紫外線遮蔽剤などが例示される。
Examples of the binder used in the coating composition of the present invention include the following. Natural resin, natural resin derivative, phenol resin, xylene resin, urea resin, melamine resin, ketone resin, coumarone / indene resin, petroleum resin, terpene resin, cyclized rubber, chlorinated rubber, alkyd resin, polyamide resin, Polyvinyl chloride, acrylic resin, vinyl chloride / vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl plastic, chlorinated polypropylene, styrene resin, epoxy resin, urethane and cellulose derivatives. . Of these, acrylic resins, polyvinyl chloride, and vinyl chloride / vinyl acetate copolymer resins are preferable. Among them, emulsion type resins are preferable because of low pollution and easy handling.
Also usable as additives are pigments such as zinc oxide and titanium oxide, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact resistance enhancers, glass fibers, metal soaps Lubricants such as lubricants, moisture-proofing agents and extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood powder, antifungal agents, antifouling agents, rust preventives, metal powders, UV absorbers, UV shielding Examples thereof include agents.
 本発明の抗アレルゲン剤を含むコ-ティング組成物で繊維を加工する方法としては、コ-ティング組成物をそのままあるいは希釈した液体を、繊維または繊維製品に塗布、浸漬又は吹き付ける方法がある。加工できる繊維には制限はなく、たとえば綿、絹、羊毛等の天然繊維、ポリエステル、ナイロン、アクリルニトリル等の合成繊維、トリアセテ-ト、ジアセテ-トなどの半合成繊維、ビスコ-スレ-ヨン等の再生繊維等が挙げられ、これらの繊維を2種類以上使用した複合繊維でもよい。また、ポリエチレンやポリプロピレンなどを用いた不織布にも使用することが可能である。本発明の抗アレルゲン剤の繊維または繊維製品への加工方法は特に限定されるものではないが、浸漬処理、プリント処理、吹き付け処理等があり、組成物を含んだ繊維を乾燥することによって加工を完了する。乾燥方法は自然乾燥、熱風乾燥、真空乾燥などいずれも用いることができるが好ましくは熱による方法で、40℃~250℃、好ましくは50℃~180℃の間で1分~5時間、好ましくは5分から3時間乾燥することによって抗アレルゲン剤を繊維に定着させることができる。 As a method of processing fibers with the coating composition containing the anti-allergen agent of the present invention, there is a method of applying, dipping, or spraying a fiber or a fiber product with the coating composition as it is or diluted. There are no restrictions on the fibers that can be processed, for example, natural fibers such as cotton, silk and wool, synthetic fibers such as polyester, nylon and acrylonitrile, semi-synthetic fibers such as triacetate and diacetate, and viscose rayon. Recycled fibers and the like, and composite fibers using two or more of these fibers may be used. Moreover, it can be used also for the nonwoven fabric using polyethylene, a polypropylene, etc. The method of processing the anti-allergen agent of the present invention into a fiber or a fiber product is not particularly limited, but includes an immersion treatment, a printing treatment, a spraying treatment, etc., and the fiber is processed by drying the fiber containing the composition. Complete. The drying method can be any of natural drying, hot air drying, vacuum drying, etc., but is preferably a method using heat, preferably 40 ° C. to 250 ° C., preferably 50 ° C. to 180 ° C. for 1 minute to 5 hours, preferably The anti-allergen agent can be fixed to the fiber by drying for 5 minutes to 3 hours.
 本発明の抗アレルゲン剤の繊維または繊維製品に対する添着量は、繊維または繊維製品1m2に対して0.1g以上で効果が発現できる。一方、繊維または繊維製品の物性や風合いなどを損なわないためには20g/m2以下が好ましく、より好ましくは1g~10g/m2である。 The effect can be exhibited when the amount of the anti-allergen agent of the present invention attached to the fiber or fiber product is 0.1 g or more per 1 m 2 of the fiber or fiber product. On the other hand, it is preferably 20 g / m 2 or less, more preferably 1 g to 10 g / m 2 so as not to impair the physical properties and texture of the fiber or fiber product.
 本発明の抗アレルゲン剤を含むコ-ティング組成物は、そのpHが低すぎると生産機械の金属を腐食させたり、処理液の劣化や安定性の低下を引き起こす恐れがあり、一方、あまり高いと固体酸が中和されて抗アレルゲン効果が減少する恐れがあるため、コーティング組成物が水系等のpH測定が可能なものである場合には、pHが3以上9以下であることが好ましい。コ-ティング組成物のpHを決める要因は、無機粉体の水分散液のpHと同じであり、固体酸のpKaの影響が大きいが、他にも酸点濃度や抗アレルゲン剤自体の溶解性や親水性、コーティング組成物を構成する抗アレルゲン剤以外の成分もが影響を与えるため予測が難しいが、pHが低くなり過ぎた場合は、コ-ティング組成物を含む分散液自体が酸性になることを意味するので、加工装置などの金属部分に付着すれば錆を生じたりするし、分散剤の効果が減少して分散液が沈殿を生じたりすることにつながる。 If the coating composition containing the anti-allergen agent of the present invention is too low in pH, it may corrode the metal of the production machine or cause deterioration of the processing solution or decrease in stability. Since the solid acid may be neutralized and the antiallergen effect may be reduced, the pH is preferably 3 or more and 9 or less when the coating composition is capable of pH measurement such as an aqueous system. The factor that determines the pH of the coating composition is the same as the pH of the aqueous dispersion of the inorganic powder, and is greatly affected by the pKa of the solid acid. In addition, the acid point concentration and the solubility of the anti-allergen agent itself are also included. It is difficult to predict because components other than the anti-allergen agent constituting the coating composition, hydrophilicity, and the coating composition are affected. However, if the pH is too low, the dispersion itself containing the coating composition becomes acidic. Therefore, if it adheres to a metal part such as a processing apparatus, rust is generated, and the effect of the dispersant is reduced, leading to precipitation of the dispersion.
 また、本発明の抗アレルゲン剤を含むコーティング組成物が非水系である場合や、各種塗料成分を含む塗料として用いる場合、抗アレルゲン剤を含む樹脂組成物として用いる場合も、同様に接触する金属部分を腐食させたり、樹脂に変色を起こしたりすることがあるが、水分散系の試験でpHが一定範囲となるものは、錆や変色を引き起こしにくく好ましいことを見出した。このような水分散系の試験としては、抗アレルゲン剤を水分散してそのpHを測定するのが簡易な方法である。例えば、抗アレルゲン剤が5wt%となるように脱イオン水に分散し、25℃で攪拌機により5分攪拌後のpHを、ガラス電極式pHメ-タ-を用いて測定してみればよく、その時のpHが3以上9以下であることが好ましい。このような抗アレルゲン剤を用いた、コーティング組成物、塗料、樹脂等は金属腐食や変色を起こしにくいので好ましい。なお、塗料はコーティングを目的とする組成物であるから、コーティング組成物の1種であるが、単に抗アレルゲン剤等の機能成分を固着させる目的だけでなく、組成物の硬化した塗膜自体が一定以上の強度を保ち、耐候性や物品表面の保護や審美性を発揮するコーティング組成物のことを特に塗料と呼ぶ。 In addition, when the coating composition containing the anti-allergen agent of the present invention is non-aqueous, used as a paint containing various paint components, or used as a resin composition containing an anti-allergen agent, the metal part that contacts in the same manner However, it has been found that a resin having a pH within a certain range in the aqueous dispersion test is less likely to cause rust and discoloration. As a test of such an aqueous dispersion system, it is a simple method to disperse the antiallergen agent in water and measure the pH. For example, the anti-allergen agent may be dispersed in deionized water so as to be 5 wt%, and the pH after stirring for 5 minutes with a stirrer at 25 ° C. may be measured using a glass electrode type pH meter. The pH at that time is preferably 3 or more and 9 or less. Coating compositions, paints, resins, and the like using such anti-allergen agents are preferable because they hardly cause metal corrosion or discoloration. In addition, since the paint is a composition intended for coating, it is a kind of coating composition, but not only for the purpose of fixing functional components such as anti-allergen agents but also for the cured coating film itself of the composition. A coating composition that maintains a certain level of strength and exhibits weather resistance, article surface protection and aesthetics is particularly called a paint.
 本発明の抗アレルゲン剤は塗料に配合し用いることも可能である。塗料には各種添加剤を加えても良い。塗料の樹脂成分としては大豆油、あまに油、サフラワ-油、ひまし油などの油脂類、ロジン、コパ-ル、セラックなどの天然樹脂、クロマン樹脂、石油樹脂などの加工樹脂、アルキド樹脂、アクリル樹脂、エポキシ樹脂、ポリウレタン樹脂、塩化ビニル樹脂、シリコ-ン樹脂、フッ素樹脂などの合成樹脂、塩化ゴム、環化ゴムなどのゴム誘導体、硝化綿(ラッカ-)、アセチルセルロ-スなどのセルロ-ス誘導体等である。また、塗料の顔料としては(白)チタン、(黒)カ-ボン、(茶)べんがら、(朱)クロムバ-ミリオン、(青)紺青、(黄)黄鉛、(赤)酸化鉄などの着色含量、炭酸カルシウム、タルク、バライト粉などの体質顔料、鉛丹、亜酸化鉛、シアミド鉛などの防錆顔料、アルミニウム粉、硫化亜鉛(蛍光顔料)などの機能性顔料等である。また、塗料の添加剤としてはUV硬化剤、可塑剤、分散剤、沈降防止剤、乳化剤、増粘剤、消泡剤、防カビ剤、防腐剤、皮張り防止剤、乾燥剤、たれ防止剤、つや消し剤、帯電防止剤、導電剤、難燃剤、落書き防止剤等である。また、塗料の溶剤としては水、アルコ-ル、塗料用シンナ-、ラッカ-シンナ-、ポリウレタン樹脂用シンナ-などのシンナ-等であり、これらの組み合わせにより塗料を調製することができる。 The anti-allergen agent of the present invention can be used in a paint. Various additives may be added to the paint. The resin component of the paint includes oils and fats such as soybean oil, linseed oil, safflower oil and castor oil, natural resins such as rosin, copar and shellac, processed resins such as chroman resin and petroleum resin, alkyd resins and acrylic resins. , Epoxy resin, polyurethane resin, vinyl chloride resin, silicone resin, synthetic resin such as fluororesin, rubber derivatives such as chlorinated rubber and cyclized rubber, cellulose such as nitrified cotton (lacquer), acetyl cellulose, etc. Derivatives and the like. The paint pigments are (white) titanium, (black) carbon, (brown) bengara, (red) chrome vermilion, (blue) bitumen, (yellow) yellow lead, (red) iron oxide, etc. Content, extender pigments such as calcium carbonate, talc and barite powder, rust preventive pigments such as red lead, lead suboxide and cyamido lead, functional pigments such as aluminum powder and zinc sulfide (fluorescent pigment). In addition, paint additives include UV curing agents, plasticizers, dispersants, anti-settling agents, emulsifiers, thickeners, antifoaming agents, antifungal agents, antiseptics, anti-skinning agents, drying agents, and anti-sagging agents. Matting agents, antistatic agents, conductive agents, flame retardants, graffiti preventing agents and the like. Examples of the solvent for the paint include water, alcohol, paint thinner, lacquer thinner, polyurethane resin thinner, and the like. A paint can be prepared by combining these.
 本発明の抗アレルゲン剤を含む塗料で基材を加工する方法としては、塗料をそのままあるいは希釈した液体をあらかじめ製造した基材に刷毛塗り工法、ロ-ラ-工法、吹付け(スプレ-)工法、コテ塗り工法などが挙げられる。また、塗工した塗料をUV照射により硬化させてもよい。加工できる基材には種々のものがあるが、たとえばポリエチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコ-ル、ポリプロピレン、ポリエステル、ポリカ-ボネ-ト、ポリスチレン、ポリアクリロニトリル、セロファン等の各種プラスチックや、塩ビシ-ト、変成シリコンやウレタン等の目地剤、金属、窯業サイディング、磁器、石器、陶器、施釉タイル、大理石、御影石、ガラス等である。 As a method of processing a substrate with a paint containing the anti-allergen agent of the present invention, a brush coating method, a roller method, or a spraying method is applied to a substrate prepared in advance with a liquid as it is or diluted. And iron coating method. Further, the coated paint may be cured by UV irradiation. There are various types of base materials that can be processed. For example, various plastics such as polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, cellophane, etc. , Joint materials such as PVC, modified silicon and urethane, metal, ceramic siding, porcelain, stoneware, pottery, glazed tile, marble, granite, glass and so on.
 本発明の抗アレルゲン剤を含む塗料における、抗アレルゲン剤/塗料固形分重量比は10/90以上あると明らかな効果を発現し易い。また、経済的理由や塗工する基材の物性や風合いなどを損なわない点、あるいは、塗料の物性や機能などを著しく損なわない点で50/50以下が好ましい。従って本発明の抗アレルゲン剤を含む塗料における、抗アレルゲン剤/塗料固形分重量比は10/90~50/50が好ましく、20/80~40/60がより好ましい。 In the paint containing the anti-allergen agent of the present invention, if the anti-allergen agent / paint solid content weight ratio is 10/90 or more, an obvious effect is easily exhibited. Moreover, 50/50 or less is preferable at the point which does not impair the physical property, texture, etc. of the base material to apply | coat for economical reasons, or the point which does not impair the physical property, function, etc. of a coating material remarkably. Therefore, the anti-allergen agent / paint solid content weight ratio in the paint containing the anti-allergen agent of the present invention is preferably 10/90 to 50/50, more preferably 20/80 to 40/60.
 本発明の抗アレルゲン剤を樹脂と配合することにより抗アレルゲン樹脂組成物を容易に得ることができる。用いることができる樹脂の種類に制限はなく、天然樹脂、合成樹脂、半合成樹脂のいずれであってもよく、また熱可塑性樹脂、熱硬化性樹脂のいずれであってもよい。具体的な樹脂としては成形用樹脂、繊維用樹脂、ゴム状樹脂のいずれであってもよく、例えば、ポリエチレン、ポリプロピレン、塩化ビニル、ABS樹脂、AS樹脂、MBS樹脂、ナイロン樹脂、ポリエステル、ポリ塩化ビニリデン、ポリスチレン、ポリアセタ-ル、ポリカ-ボネイト、PBT、アクリル樹脂、フッ素樹脂、ポリウレタンエラストマ-、ポリエステルエラストマ-、メラミン、ユリア樹脂、四フッ化エチレン樹脂、不飽和ポリエステル樹脂、レ-ヨン、アセテ-ト、アクリル、ポリビニルアルコ-ル、キュプラ、トリアセテ-ト、ビニリデンなどの成形用または繊維用樹脂、天然ゴム、シリコ-ンゴム、スチレンブタジエンゴム、エチレンプロピレンゴム、フッ素ゴム、ニトリルゴム、クロルスルホン化ポリエチレンゴム、ブタジエンゴム、合成天然ゴム、ブチルゴム、ウレタンゴムおよびアクリルゴムなどのゴム状樹脂がある。また、樹脂成分に加えて、各種添加剤を含有させることもできる。添加剤として用いることができるものは酸化亜鉛や酸化チタンなどの顔料、染料、酸化防止剤、耐光安定剤、難燃剤、帯電防止剤、発泡剤、耐衝撃強化剤、ガラス繊維、金属石鹸などの滑剤、防湿剤および増量剤、カップリング剤、核剤、流動性改良剤、消臭剤、木粉、防黴剤、防汚剤、防錆剤、金属粉、紫外線吸収剤、紫外線遮蔽剤などがあり、いずれも好ましく用いることができる。 An anti-allergen resin composition can be easily obtained by blending the anti-allergen agent of the present invention with a resin. There is no restriction | limiting in the kind of resin which can be used, Any of a natural resin, a synthetic resin, and a semi-synthetic resin may be sufficient, and any of a thermoplastic resin and a thermosetting resin may be sufficient. Specific resins may be molding resins, fiber resins, and rubber-like resins. For example, polyethylene, polypropylene, vinyl chloride, ABS resin, AS resin, MBS resin, nylon resin, polyester, polychlorinated resin. Vinylidene, polystyrene, polyacetal, polycarbonate, PBT, acrylic resin, fluororesin, polyurethane elastomer, polyester elastomer, melamine, urea resin, tetrafluoroethylene resin, unsaturated polyester resin, rayon, acetate Mold, acrylic, polyvinyl alcohol, cupra, triacetate, vinylidene and other molding or fiber resins, natural rubber, silicone rubber, styrene butadiene rubber, ethylene propylene rubber, fluorine rubber, nitrile rubber, chlorosulfonated polyethylene Rubber, Tajiengomu, synthetic natural rubber, butyl rubber, there is a rubber resin such as urethane rubber and acrylic rubber. In addition to the resin component, various additives can also be contained. Examples of additives that can be used include pigments such as zinc oxide and titanium oxide, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact strength enhancers, glass fibers, and metal soaps. Lubricant, moisture proofing agent and extender, coupling agent, nucleating agent, fluidity improver, deodorant, wood powder, antifungal agent, antifouling agent, rust preventive agent, metal powder, UV absorber, UV shielding agent, etc. Any of these can be preferably used.
 本発明の抗アレルゲン剤を樹脂へ配合し樹脂組成物を製造する方法は、公知の方法がどれも採用できる。例えば、(1)抗アレルゲン剤粉体と樹脂とが付着しやすくするための添着剤や抗アレルゲン剤粉体の分散性を向上させるための分散剤を使用し、ペレット状樹脂またはパウダ-状樹脂をミキサ-で直接混合する方法、(2)前記のようにして混合して、押し出し成形機にてペレット状に成形した後、その成形物をペレット状樹脂に配合する方法、(3)抗アレルゲン剤をワックスを用いて高濃度のペレット状に成形後、そのペレット状成形物をペレット状樹脂に配合する方法、(4)抗アレルゲン剤をポリオ-ルなどの高粘度の液状物に分散混合したペ-スト状組成物を調製後、このペ-ストをペレット状樹脂に配合する方法などがある。 Any known method can be adopted as a method for producing a resin composition by blending the anti-allergen agent of the present invention into a resin. For example, (1) using an additive for facilitating adhesion between the anti-allergen powder and the resin or a dispersant for improving the dispersibility of the anti-allergen powder, a pellet resin or a powder resin (2) A method of directly mixing with a mixer, (2) A method of mixing as described above, forming into pellets with an extrusion molding machine, and then blending the molded product into a pellet resin, (3) Antiallergen After the agent is molded into a high-concentration pellet using wax, the pellet-shaped product is blended with the pellet-shaped resin. (4) The anti-allergen agent is dispersed and mixed in a high-viscosity liquid such as polyol. There is a method of preparing a paste-like composition and then blending the paste into a pellet-like resin.
 上記の樹脂組成物の成形加工には、各種樹脂の特性に合わせてあらゆる公知の成型加工技術と機械装置が使用可能であり、適当な温度または圧力で加熱および加圧または減圧しながら混合、混入または混練りの方法によって容易に調製することができ、それらの具体的操作は常法により行えば良く、塊状、スポンジ状、フィルム状、シ-ト状、糸状またはパイプ状或いはこれらの複合体など、種々の形態に成形加工できる。本発明の抗アレルゲン剤を含む樹脂組成物における、抗アレルゲン剤/樹脂固形分重量比は10/90以上あると明らかな効果を発現し易い。また、経済的理由や樹脂組成物の成形性や、成形物の物性や風合いなどを損なわない点、50/50以下が好ましい。従って本発明の抗アレルゲン剤を含む樹脂組成物における、抗アレルゲン剤/樹脂組成物の固形分重量比は10/90~50/50が好ましく、20/80~40/60がより好ましい。 For the molding process of the above resin composition, all known molding techniques and mechanical devices can be used in accordance with the characteristics of various resins. Mixing and mixing while heating and pressurizing or depressurizing at an appropriate temperature or pressure. Alternatively, they can be easily prepared by a kneading method, and their specific operation may be carried out by a conventional method, such as a lump, sponge, film, sheet, thread or pipe, or a composite thereof. It can be molded into various forms. If the anti-allergen agent / resin solids weight ratio in the resin composition containing the anti-allergen agent of the present invention is 10/90 or more, an obvious effect is easily exhibited. Moreover, the point which does not impair the economical reason, the moldability of a resin composition, the physical property of a molded object, a texture, etc., 50/50 or less is preferable. Therefore, the solid weight ratio of the anti-allergen agent / resin composition in the resin composition containing the anti-allergen agent of the present invention is preferably 10/90 to 50/50, more preferably 20/80 to 40/60.
 本発明の抗アレルゲン剤の使用形態は上記のような組成物や樹脂組成物、樹脂成形品の他に、アレルゲン低減化が必要とされる用途に応じてそのまま、あるいは適宜他の成分と混合したり、他の材料と複合させて用いることができる。例えば、粉末状、粉末分散液状、粒状、エアゾ-ル状、または液状などのあらゆる形態で用いることができる。 The anti-allergen agent of the present invention can be used in the form of the above composition, resin composition, and resin molded product, as it is or depending on the application where allergen reduction is required, or mixed with other components as appropriate. Or can be used in combination with other materials. For example, it can be used in any form such as powder, liquid dispersion, granular, aerosol, or liquid.
 本発明の抗アレルゲン剤は、アレルゲン低減を必要とされる種々の分野、即ち室内用品、寝具類、フィルタ-類、家具類、車内用品、繊維製品、住宅建材製品、紙製品、玩具、皮革製品、トイレタリ-製品、化粧品およびその他の製品などとして利用することができる。例えばカ-ペット、カ-テン、壁紙、畳、障子紙、床用ワックス、カレンダ-などの室内用品、ふとん、ベット、シ-ツ、枕、枕カバ-などの寝具類、空気清浄機、エアコンなどのフィルタ-類、ソファ-、椅子などの家具類、チャイルドシ-ト、座席シ-トなどの車内用品、電気掃除機の集塵袋、衣料品、マスク、ぬいぐるみ、キッチン用品などが挙げられるが、これに限定されるものではない。 The anti-allergen agent of the present invention is used in various fields where allergen reduction is required, that is, indoor products, bedding, filters, furniture, in-car products, textile products, residential building products, paper products, toys, leather products. It can be used as toiletries, cosmetics and other products. For example, carpets, curtains, wall paper, tatami mats, shoji paper, wax for floors, calendars and other indoor products, bedding such as futons, beds, sheets, pillows, pillow covers, air purifiers, air conditioners Filters such as sofas, furniture such as chairs, car seats such as child seats and seat sheets, dust collection bags for vacuum cleaners, clothing, masks, stuffed animals, kitchen utensils, etc. However, the present invention is not limited to this.
 以下に実施例によって、本発明を更に詳細に説明するが、本発明をかかる実施例に限定することを意図したものではない。 Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not intended to be limited to such examples.
 実施例に記載した無機粉体の平均粒径とは、レ-ザ-回折式粒度分布測定器により、脱イオン水に超音波分散して測定して得られた体積基準のメジアン径を示し、特にことわりのない%は質量%を示すが、アレルゲン不活性化率の単位%は上記の<式1>によるものである。
 酸点濃度の測定は、無機粉体0.5gを20mLのサンプル瓶に入れ、そこへベンゼン10mLを添加し軽く振り混ぜる。さらに20段階に添加量を振った0.1Nのn-ブチルアミンを加え、振とう機で攪拌する。24時間後にベンゼンで希釈した0.1%メチルレッド溶液を0.5mL加え、メチルレッドの変色を目視で観察する。メチルレッドの変色が確認されない最もn-ブチルアミンの添加量が多いn-ブチルアミンの添加量を、酸点と反応した塩基量とし、酸点濃度(mmol/g)とした。
The average particle diameter of the inorganic powder described in the examples indicates a volume-based median diameter obtained by ultrasonic dispersion in deionized water using a laser diffraction particle size distribution analyzer. Unless otherwise specified,% indicates mass%, but the unit% of the allergen inactivation rate is according to the above <Formula 1>.
To measure the acid point concentration, put 0.5 g of inorganic powder in a 20 mL sample bottle, add 10 mL of benzene to it, and shake gently. Add 0.1N n-butylamine, which was added in 20 steps, and stir on a shaker. After 24 hours, 0.5 mL of 0.1% methyl red solution diluted with benzene is added, and the color change of methyl red is visually observed. The amount of n-butylamine added in the largest amount of n-butylamine, in which no discoloration of methyl red was confirmed, was defined as the amount of base reacted with acid sites, and the acid point concentration (mmol / g).
 酸強度の測定は、試験管に試料を0.1g採取し、ベンゼン2mLおよび指示薬の0.1%ベンゼン溶液(ただし、クリスタルバイオレットは0.1%エタノ-ル溶液)を2滴添加し、軽く振り混ぜ、色の変化を観察した。酸強度は指示薬の変色が確認された最も強い酸強度(最も低いpKa値)以下であり、指示薬が変色しなかった最も弱い酸強度(最も高いpKa)より大きいと考えられるのでその範囲をpKa値として記録した。なお、使用した指示薬はメチルレッド(pKa=4.8)、4-フェニルアゾ-1-ナフチルアミン(pKa=4)、ジメチルイエロ-(pKa=3.3)、4-フェニルアゾ-ジフェニルアミン(pKa=1.5)、クリスタルバイオレット(pKa=0.8)、ジシンナミルアセトン(pKa=-3)、ベンザルアセトフェノン(pKa=-5.6)、アントラキノン(pKa=-8.2)である。 To measure the acid strength, take 0.1 g of a sample in a test tube, add 2 mL of benzene and 2 drops of 0.1% benzene solution of the indicator (but 0.1% ethanol solution for crystal violet), and lightly Shake and observe color change. The acid strength is less than or equal to the strongest acid strength (lowest pKa value) at which discoloration of the indicator was confirmed, and is considered to be greater than the weakest acid strength (highest pKa) at which the indicator did not discolor, so the range is defined as the pKa value. As recorded. The indicators used were methyl red (pKa = 4.8), 4-phenylazo-1-naphthylamine (pKa = 4), dimethyl yellow (pKa = 3.3), 4-phenylazo-diphenylamine (pKa = 1. 5), crystal violet (pKa = 0.8), dicinnamylacetone (pKa = -3), benzalacetophenone (pKa = -5.6), anthraquinone (pKa = -8.2).
 無機粉体の含水率は、乾燥機中250℃で1時間恒量したアルミカップに試料約5gを秤量し(0.1mg単位まで秤量)、乾燥機中で250℃で2時間乾燥後、再度秤量し(0.1mg単位まで秤量)、乾燥減分を乾燥前の質量で除したものを%表示として無機粉体の含水率とした。 The moisture content of the inorganic powder was weighed about 5 g in an aluminum cup that had been weighed at 250 ° C. for 1 hour in a dryer (weighed to the nearest 0.1 mg), dried for 2 hours at 250 ° C. in the dryer, and then weighed again. (Weighed to the nearest 0.1 mg), and the water content of the inorganic powder was expressed as a percentage by dividing the drying loss by the mass before drying.
 抗アレルゲン効果は、コナヒョウヒダニアレルゲン(一般的にDerf2と呼ばれるアレルゲン)およびスギ花粉アレルゲン(一般的にCryj1と呼ばれるアレルゲン)を用いるELISA法のサンドイッチ法により評価した。コナヒョウヒダニアレルゲンを用いた場合の試験操作は次のようである。コナヒョウヒダニアレルゲン(Derf2)特異的抗体(15E11抗体、アサヒビ-ル株式会社製)を用いて常法により抗体コ-トウェルを作製した。
試料を3mg秤量し、抗原希釈液で40ng/mLに調製したコナヒョウヒダニアレルゲン(Derf2)を500μL添加した。混合物を良く攪拌して、試料とアレルゲンを接触させた後、遠心沈降させ、上澄み液を回収し、ブロッキング剤で処理してある15E11抗体コ-トウェルに添加して室温で静置した。1時間後試料を捨て、各ウェルを洗浄バッファ-で洗浄し、洗浄バッファ-で200ng/mLに希釈した西洋ワサビペルオキシダ-ゼ標識抗Derf2モノクロ-ナル抗体13A4PO(アサヒビ-ル株式会社)を各ウェルへ添加し室温で静置した。1時間後抗体液を捨て、各ウェルを洗浄バッファ-で洗浄し、基質液を各ウェルへ添加して室温で静置した。5分後に2N硫酸を加え反応を停止させ、490nmの吸光度を測定した。結果は、試料を用いずに評価を行うことで吸光度に対するアレルゲン量の関係を求め、各種試料を評価した場合の吸光度から残存アレルゲン量を求め、上記の<式1>から算出することにより各種試料のアレルゲン不活性化率%を表示した。
The anti-allergen effect was evaluated by the sandwich method of ELISA using a leopard mite allergen (allergen generally referred to as Derf2) and a cedar pollen allergen (allergen generally referred to as Cryj1). The test procedure when using leopard mite allergen is as follows. An antibody coat well was prepared by a conventional method using a persimmon leopard mite allergen (Derf2) -specific antibody (15E11 antibody, manufactured by Asahivir Co., Ltd.).
3 mg of the sample was weighed, and 500 μL of leopard mite allergen (Derf2) prepared to 40 ng / mL with an antigen diluent was added. The mixture was well stirred to bring the sample into contact with the allergen, and then centrifuged and collected. The supernatant was collected, added to the 15E11 antibody coat well treated with a blocking agent, and allowed to stand at room temperature. One hour later, the sample was discarded, each well was washed with a washing buffer, and horseradish peroxidase-labeled anti-Derf2 monoclonal antibody 13A4PO (Asahivir Co., Ltd.) diluted to 200 ng / mL with the washing buffer was added to each well. It was added to the well and allowed to stand at room temperature. After 1 hour, the antibody solution was discarded, each well was washed with a washing buffer, a substrate solution was added to each well, and the mixture was allowed to stand at room temperature. After 5 minutes, 2N sulfuric acid was added to stop the reaction, and the absorbance at 490 nm was measured. As a result, the relationship between the allergen amount with respect to the absorbance was obtained by evaluating without using the sample, the residual allergen amount was obtained from the absorbance when the various samples were evaluated, and various samples were obtained by calculating from the above <Formula 1>. % Of allergen inactivation was displayed.
 スギ花粉アレルゲンを用いた場合のELISA法のサンドイッチ法による試験操作は次のようである。スギ花粉アレルゲン(Cryj1)特異的抗体(生化学工業株式会社製Anti-Cryj1mAb013)を用いて常法により抗体コ-トウェルを作製した。
試料を3mg秤量し、抗原希釈液で10ng/mLに調製したスギ花粉アレルゲン(Cryj1)を500μL添加した。混合物を良く攪拌して、サンプルとアレルゲンを接触させた後、遠心沈降させ、上澄み液を回収し、ブロッキング剤で処理してあるAnti-Cryj1mAb013抗体コ-トウェルに添加して室温で静置した。1時間後サンプルを捨て、各ウェルを洗浄バッファ-で洗浄し、洗浄バッファ-で250ng/mLに希釈した西洋ワサビペルオキシダ-ゼ標識抗Cryj1モノクロ-ナル抗体053(生化学工業株式会社製)を各ウェルへ添加し室温で静置した。2時間後抗体液を捨て、各ウェルを洗浄バッファ-で洗浄し、基質液を各ウェルに添加して室温で静置した。5分後に2N硫酸を加え反応を停止させ、490nmの吸光度を測定した。結果は、コナヒョウヒダニアレルゲンと同様の方法で式1から算出することにより各種試料のアレルゲン不活性化率%を表示した。
The test procedure by ELISA sandwich method using cedar pollen allergen is as follows. An antibody coat well was prepared by a conventional method using a cedar pollen allergen (Cryj1) specific antibody (Anti-Cryj1mAb013 manufactured by Seikagaku Corporation).
3 mg of the sample was weighed, and 500 μL of cedar pollen allergen (Cryj1) prepared to 10 ng / mL with the antigen dilution solution was added. The mixture was well agitated to bring the sample into contact with the allergen, and then centrifuged to collect the supernatant. The supernatant was added to the anti-Cryj1 mAb013 antibody coat well treated with a blocking agent and allowed to stand at room temperature. One hour later, the sample was discarded, each well was washed with a washing buffer, and horseradish peroxidase-labeled anti-Cryj1 monoclonal antibody 053 (manufactured by Seikagaku Corporation) diluted to 250 ng / mL with the washing buffer was used. It added to each well and left still at room temperature. After 2 hours, the antibody solution was discarded, each well was washed with a washing buffer, a substrate solution was added to each well, and the mixture was allowed to stand at room temperature. After 5 minutes, 2N sulfuric acid was added to stop the reaction, and the absorbance at 490 nm was measured. As a result, the percentage of allergen inactivation of various samples was displayed by calculating from Equation 1 in the same manner as for the leopard mite allergen.
無機粉体の水分散液のpHは、無機粉体が5wt%となるようにビーカーのイオン交換水に分散し、25℃で攪拌機により5分攪拌後のpHを、ガラス電極式pHメ-タ-を用いて測定した。 The pH of the aqueous dispersion of inorganic powder was dispersed in ion-exchanged water in a beaker so that the inorganic powder was 5 wt%, and the pH after stirring for 5 minutes with a stirrer at 25 ° C. was measured using a glass electrode pH meter. It measured using-.
 樹脂成型変色確認試験は、ポリプロピレンパウダ-へ無機粉体を2wt%混合し、220℃で射出成型機によりプレ-トを成型した。得られたプレ-トの着色度合いを目視で確認した。 In the resin molding discoloration confirmation test, 2 wt% of inorganic powder was mixed with polypropylene powder, and the plate was molded at 220 ° C. with an injection molding machine. The degree of coloring of the obtained plate was confirmed visually.
 金属腐食性試験は、まず、鉄製テストピ-ス(幅/長さ/厚み=20/80/2mm)を準備し、アセトンで表面を洗浄した。直径30mmのガラス試験管に鉄製テストピ-ス及び無機粉体5wt%水分散液を入れ、60℃に調節したヒ-トブロックに仕掛けた。24時間後にテストピ-スを取り出し、蒸留水に浸漬し、5分間超音波洗浄をした後、50℃乾燥機で30分乾燥後させ、テストピ-スの錆の有り無しを目視により確認した。 In the metal corrosion test, first, an iron test piece (width / length / thickness = 20/80/2 mm) was prepared, and the surface was washed with acetone. An iron test piece and an inorganic powder 5 wt% aqueous dispersion were placed in a glass test tube having a diameter of 30 mm, and placed on a heat block adjusted to 60 ° C. After 24 hours, the test piece was taken out, immersed in distilled water, subjected to ultrasonic cleaning for 5 minutes, and then dried for 30 minutes with a 50 ° C. dryer, and the presence or absence of rust on the test piece was visually confirmed.
 繊維加工製品の抗アレルゲン効果は、アレルゲンにはスギ花粉アレルゲン(Cryj1)を用い、繊維25cm2をチャック付きのポリ袋内へ入れ、サンプルと100ng/mLに調整したアレルゲン溶液1mLを1時間接触させた後、接触液を遠心沈降させ、上澄み液を回収し、無機粉体と同様のELISA法評価により吸光度を測定し、試料を用いない場合の吸光度と比較して上記式1により抗アレルゲン不活性化率%を評価した。 The anti-allergen effect of the processed fiber product is that cedar pollen allergen (Cryj1) is used as the allergen, and 25 cm 2 of fiber is put into a plastic bag with a chuck, and 1 mL of the allergen solution adjusted to 100 ng / mL is brought into contact with the sample for 1 hour. After that, the contact solution is spun down, the supernatant is collected, the absorbance is measured by the same ELISA method evaluation as that of the inorganic powder, and the anti-allergen inactivity according to the above formula 1 is compared with the absorbance when the sample is not used. % Conversion was evaluated.
 樹脂練り込みフィルムの抗アレルゲン効果は、アレルゲンにはスギ花粉アレルゲン(Cryj1)を用い、フィルム25cm2をチャック付きのポリ袋内へ入れ、サンプルと10ng/mLに調整したアレルゲン溶液1mLを1時間接触させた後、接触液を遠心沈降させ、上澄み液を回収し、無機粉体と同様のELISA法評価により吸光度を測定し、試料を用いない場合の吸光度と比較して上記式1により抗アレルゲン不活性化率%を評価した。 Anti-allergen effect film kneading resins, allergens using cedar pollen allergen (Cryj1) to put the film 25 cm 2 into a zippered plastic bag, 1 hour contacting the allergen solution 1mL adjusted to the sample and 10 ng / mL Then, the contact liquid is centrifuged and the supernatant liquid is collected, and the absorbance is measured by the same ELISA method evaluation as that of the inorganic powder. Compared with the absorbance when the sample is not used, anti-allergen resistance is determined by the above formula 1. The activation rate% was evaluated.
アクリル系UV硬化塗料により加工したフィルムの抗アレルゲン効果は、アレルゲンにはスギ花粉アレルゲン(Cryj1)を用い、フィルム25cm2をチャック付きのポリ袋内へ入れ、サンプルと10ng/mLに調整したアレルゲン溶液1mLを3時間接触させた後、接触液を遠心沈降させ、上澄み液を回収し、無機粉体と同様のELISA法評価により吸光度を測定し、試料を用いない場合の吸光度と比較して上記式1により抗アレルゲン不活性化率%を評価した。 The anti-allergen effect of the film processed with the acrylic UV curable paint is the allergen solution using cedar pollen allergen (Cryj1) as the allergen, putting the film 25cm 2 into a plastic bag with a chuck, and adjusting the sample to 10ng / mL. After contacting 1 mL for 3 hours, the contact solution is spun down, the supernatant is collected, the absorbance is measured by the same ELISA method as for inorganic powder, and the above formula is compared with the absorbance when no sample is used. The anti-allergen inactivation rate% was evaluated according to 1.
<実施例1>非晶質ケイ酸マグネシウム
 原料に硫酸マグネシウムと水ガラスを用いて得られた沈殿物をろ過、水洗、乾燥、解砕することで非晶質ケイ酸マグネシウム(SiO2/MgO=1.3)を得た。得られた非晶質ケイ酸マグネシウムの平均粒径、含水率、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
Example 1 Amorphous Magnesium Silicate Amorphous magnesium silicate (SiO 2 / MgO =) by filtering, washing, drying and crushing a precipitate obtained using magnesium sulfate and water glass as raw materials. 1.3) was obtained. Table 1 shows the average particle size, water content, acid strength, and the mite allergen inactivation effect and the cedar pollen allergen inactivation effect measured by the ELISA method for the obtained amorphous magnesium silicate. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<実施例2>α型リン酸ジルコニウム
 75%リン酸水溶液に15%オキシ塩化ジルコニウム水溶液を添加し、120℃で12時間熟成後、沈殿物をろ過、水洗、乾燥、解砕することでα型リン酸ジルコニウム粉末を得た。得られたα型リン酸ジルコニウムの平均粒径、含水率、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Example 2> α-type zirconium phosphate A 15% zirconium oxychloride aqueous solution was added to a 75% phosphoric acid aqueous solution and aged at 120 ° C. for 12 hours, and then the precipitate was filtered, washed with water, dried and crushed to obtain α-type. A zirconium phosphate powder was obtained. Table 1 shows the average particle size, water content, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect measured by the ELISA method of the obtained α-type zirconium phosphate. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<実施例3>活性酸化チタン
原料に硫酸チタニルとシュウ酸を用いて得られた沈殿物をろ過、乾燥し、500℃で焼成処理後、粉砕することで活性酸化チタンを調整した。得られた酸化チタンの平均粒径、含水率、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Example 3> A precipitate obtained by using titanyl sulfate and oxalic acid as an active titanium oxide raw material was filtered, dried, calcined at 500 ° C, and pulverized to prepare active titanium oxide. The average particle diameter, water content, acid strength and the mite allergen inactivating effect and the cedar pollen allergen inactivating effect measured by the ELISA method of the obtained titanium oxide are shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<実施例4>活性白土
市販の活性白土(水澤化学工業製 ガレオンア-スSH)の平均粒径、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Example 4> The average particle diameter, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect of activated white clay (Galeon Ace SH manufactured by Mizusawa Chemical Industry) were measured. The results are shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例1>結晶質ケイ酸マグネシウム
 原料に硫酸マグネシウムと水ガラスを用いて得られた沈殿物をろ過、水洗、乾燥、解砕することで非晶質ケイ酸マグネシウム(SiO2/MgO=3.9)を得た。得られた結晶質ケイ酸マグネシウムの平均粒径、含水率、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
Comparative Example 1 Crystalline Magnesium Silicate Amorphous magnesium silicate (SiO 2 / MgO = 3) by filtering, washing, drying, and crushing a precipitate obtained using magnesium sulfate and water glass as raw materials. 9) was obtained. Table 1 shows the average particle diameter, water content, acid strength, and the mite allergen inactivating effect and the cedar pollen allergen inactivating effect measured by the ELISA method of the obtained crystalline magnesium silicate. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例2>γ型リン酸ジルコニウム
 75%リン酸水溶液に炭酸ジルコニウム水溶液を添加し、98℃で24時間加熱還流後、沈殿物をろ過、水洗、乾燥、解砕することでγ型リン酸ジルコニウムを得た。得られたγ型リン酸ジルコニウムの平均粒径、含水率、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Comparative example 2> γ-type zirconium phosphate A zirconium carbonate aqueous solution was added to a 75% phosphoric acid aqueous solution, heated and refluxed at 98 ° C. for 24 hours, and then the precipitate was filtered, washed with water, dried and crushed to obtain γ-type phosphoric acid. Zirconium was obtained. Table 1 shows the average particle diameter, water content, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect measured by ELISA method for the obtained γ-type zirconium phosphate. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例3>NASICON型リン酸ジルコニウム
オキシ塩化ジルコニウム水溶液にシュウ酸および75%リン酸水溶液を添加し、さらに苛性ソ-ダでpHを2.7に調整後、98℃で12時間加熱還流後、沈殿物をろ過、水洗、乾燥、解砕することでNASICON型リン酸ジルコニウムを得た。得られたNASICON型リン酸ジルコニウムの平均粒径、含水率、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Comparative Example 3> After adding oxalic acid and 75% phosphoric acid aqueous solution to NASICON type zirconium phosphate zirconium oxychloride aqueous solution, and adjusting pH to 2.7 with caustic soda, after heating and refluxing at 98 ° C for 12 hours The NASICON type zirconium phosphate was obtained by filtering, washing, drying and crushing the precipitate. Table 1 shows the results of measuring the mite allergen inactivating effect and the cedar pollen allergen inactivating effect by the average particle size, water content, acid strength, and ELISA method of the obtained NASICON-type zirconium phosphate. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例4>酸化チタン
市販の酸化チタン(石原産業製MC-50)の平均粒径、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Comparative Example 4> Titanium oxide Commercially available titanium oxide (MC-50 manufactured by Ishihara Sangyo Co., Ltd.) The average particle diameter, acid strength, and the results of measuring the mite allergen inactivation effect and the cedar pollen allergen inactivation effect by ELISA method It is shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例5>活性アルミナ
 市販の活性アルミナ(水澤化学工業製GNDY-2)の平均粒径、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Comparative Example 5> Activated Alumina Results of measuring the mean particle diameter, acid strength, and mite allergen inactivation effect and cedar pollen allergen inactivation effect of commercially available activated alumina (Mizusawa Chemical Industry GNDY-2) by ELISA method Is shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例6>シリカ-アルミナ
 原料に水ガラスと硝酸アルミニウムを用いて98℃で撹拌し、得られた沈殿物を400℃で焼成処理後、粉砕することでシリカ-アルミナを調整した。得られたシリカ-アルミナの平均粒径、含水率、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Comparative Example 6> Silica-alumina Using silica glass and aluminum nitrate as raw materials, stirring was performed at 98 ° C, and the resulting precipitate was calcined at 400 ° C and then pulverized to prepare silica-alumina. The average particle size, water content, acid strength, and mite allergen inactivating effect and cedar pollen allergen inactivating effect measured by the ELISA method for the obtained silica-alumina are shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例7>リン酸アルミニウム
市販のリン酸アルミニウム(テイカ製 K-WHITE  105)の平均粒径、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Comparative Example 7> Aluminum phosphate The average particle size, acid strength and ELISA method of mite allergen inactivation and cedar pollen allergen inactivation of commercially available aluminum phosphate (Taika K-WHITE 105) were measured. The results are shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
<比較例8>ハイドロタルサイト
 市販のハイドロタルサイト(堺化学工業製HT-P)の平均粒径、酸強度およびELISA法にてダニアレルゲン不活性化効果およびスギ花粉アレルゲン不活性化効果を測定した結果を表1に示した。また、色調、5wt%水分散液のpH、PPプレ-トの着色性、金属腐食性を測定した結果を表2に示した。
<Comparative Example 8> Hydrotalcite The average particle size, acid strength and ELISA method of mite allergen inactivation effect and cedar pollen allergen inactivation effect of commercially available hydrotalcite (HT-P manufactured by Sakai Chemical Industry) The results are shown in Table 1. Table 2 shows the results of measurement of color tone, pH of 5 wt% aqueous dispersion, colorability of PP plate, and metal corrosivity.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表1の結果から、本発明の酸点濃度0.001mmol/g以上の無機粉体は全てダニアレルゲン不活性化率99%以上を示した。特に酸点濃度0.07mmol/gの非晶質ケイ酸マグネシウムはアレルゲン不活性化率が99%より大きい効果を示しており、抗アレルゲン剤として非常に優れている。
 また、スギ花粉アレルゲンの場合もダニアレルゲンの場合と同様に、本発明の抗アレルゲン剤は高いアレルゲン不活性化率を示し抗アレルゲン剤として非常に優れている。これに対して酸点濃度が0.001以下の比較例ではほとんど抗アレルゲン活性を示さなかった。
 また、表2の結果から、実施例4及び比較例4の分散液は、5wt%分散液のpHが3より小さくなり、金属腐食性を示した。
From the results in Table 1, all the inorganic powders having an acid point concentration of 0.001 mmol / g or more according to the present invention showed a mite allergen inactivation rate of 99% or more. In particular, amorphous magnesium silicate having an acid point concentration of 0.07 mmol / g shows an effect of an allergen inactivation rate of more than 99%, and is very excellent as an antiallergen agent.
In the case of cedar pollen allergens, as in the case of mite allergens, the anti-allergen agent of the present invention exhibits a high allergen inactivation rate and is very excellent as an anti-allergen agent. In contrast, the comparative example having an acid point concentration of 0.001 or less showed almost no antiallergen activity.
Moreover, from the results of Table 2, the dispersions of Example 4 and Comparative Example 4 showed a metal corrosivity because the pH of the 5 wt% dispersion was less than 3.
<実施例7>繊維に固定した実施例1の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムとアクリルエマルジョンバインダー(東亞合成株式会社製NW-7060、固形分濃度50wt%)とを固形分質量比で2:1になるように混ぜ合わせ、布(成分:綿/アクリル繊維=1/1)に5分浸漬後、120℃で30分乾燥の加工を行い、非晶質ケイ酸マグネシウムの固定量1g/m2の抗アレルゲン布を作製した。抗アレルゲン布のスギ花粉アレルゲン不活性化効果を測定した結果を表3に示した。
<Example 7> Evaluation of anti-allergen activity of Example 1 fixed to fiber Amorphous magnesium silicate and acrylic emulsion binder (NW-7060 manufactured by Toagosei Co., Ltd., solid content concentration 50 wt%) of Example 1 ) With a solid content mass ratio of 2: 1, soaked in a cloth (component: cotton / acrylic fiber = 1/1) for 5 minutes, dried at 120 ° C. for 30 minutes, and then amorphous. An anti-allergen cloth having a fixed amount of 1 g / m 2 of fine magnesium silicate was prepared. Table 3 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen cloth.
<実施例8>繊維に固定した実施例1の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムを(東亞合成株式会社製NW-7060、固形分濃度50wt%)と固形分の質量比で2:1 とになるように混ぜ合わせ、布(成分:綿/アクリル繊維=1/1)に5分浸漬後、120℃で30分乾燥の加工を行い、固定量2g/m2の抗アレルゲン布を作製した。抗アレルゲン布のスギ花粉アレルゲン不活性化効果を測定した結果を表3に示した。
<Example 8> Antiallergen activity evaluation of Example 1 fixed to fiber Amorphous magnesium silicate (NW-7060, manufactured by Toagosei Co., Ltd., solid content concentration 50 wt%) and solids of Example 1 were solid and solid After mixing for 5 minutes in a cloth (component: cotton / acrylic fiber = 1/1), the mixture was dried at 120 ° C. for 30 minutes, and the fixed amount was 2 g / min. An m 2 anti-allergen fabric was prepared. Table 3 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen cloth.
<比較例9>繊維に実施例1を固定しない場合の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムを用いずに実施例7と同様の加工方法により比較布を作製した。比較布のスギ花粉アレルゲン不活性化効果を測定した結果を表3に示した。
<Comparative Example 9> Anti-allergen activity evaluation in the case where Example 1 is not fixed to the fiber A comparative fabric was prepared by the same processing method as Example 7 without using amorphous magnesium silicate which is an inorganic substance of Example 1. did. Table 3 shows the results of measuring the cedar pollen allergen inactivating effect of the comparative cloth.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表3の結果から実施例1の非晶質ケイ酸マグネシウムを添着加工した抗アレルゲン加工布はアレルゲン不活性化率が99%より大きいことを示した。よって本発明の無機物質を繊維に後加工した抗アレルゲン製品の性能は優れている。
From the results in Table 3, it was shown that the anti-allergen-treated cloth with the amorphous magnesium silicate of Example 1 applied thereto had an allergen inactivation rate of more than 99%. Therefore, the performance of the anti-allergen product obtained by post-processing the inorganic substance of the present invention into a fiber is excellent.
<実施例9>
繊維に固定した実施例1の耐熱性評価
 実施例7と同様の方法で抗アレルゲン布を作製し、120℃で100時間熱を加えた後、抗アレルゲン布のスギ花粉アレルゲン不活性化効果及び変色性を測定した結果を表4に示した。
<Example 9>
Evaluation of heat resistance of Example 1 fixed to fiber After producing anti-allergen cloth in the same manner as in Example 7 and applying heat at 120 ° C. for 100 hours, the anti-allergen cloth was inactivated by cedar pollen allergen and discolored. The results of measuring the properties are shown in Table 4.
<実施例10>
繊維に固定した実施例1の耐熱性評価
 実施例8と同様の方法で抗アレルゲン布を作製し、120℃で100時間熱を加えた後、抗アレルゲン布のスギ花粉アレルゲン不活性化効果及び変色性を測定した結果を表4に示した。
<Example 10>
Evaluation of heat resistance of Example 1 fixed to fiber After producing anti-allergen cloth by the same method as in Example 8 and applying heat at 120 ° C. for 100 hours, the inactivation effect and discoloration of cedar pollen allergen of anti-allergen cloth The results of measuring the properties are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表4の結果から実施例1の非晶質ケイ酸マグネシウムを添着加工した抗アレルゲン加工布は長時間熱を加えても十分に高いアレルゲン不活性化率を示し、また、変色もおこらないことから、本発明の無機物質を繊維に後加工した抗アレルゲン製品は耐熱性も優れている。 From the results of Table 4, the anti-allergen-processed cloth applied with amorphous magnesium silicate of Example 1 shows a sufficiently high allergen inactivation rate even when heat is applied for a long time, and no discoloration occurs. The anti-allergen product obtained by post-processing the inorganic substance of the present invention into a fiber has excellent heat resistance.
<実施例11>繊維に固定した実施例1の耐水性評価
 実施例7と同様の方法で抗アレルゲン布を作製し、ポリ容器へ入れ、そこへイオン交換水を加え、25℃で16時間振とうし、120℃で30分乾燥させた抗アレルゲン布のスギ花粉アレルゲン不活性化効果を測定した結果を表5に示した。
<Example 11> Water resistance evaluation of Example 1 fixed to fiber An anti-allergen cloth was prepared in the same manner as in Example 7, put into a plastic container, added with ion-exchanged water, and shaken at 25 ° C for 16 hours. Table 5 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen cloth dried at 120 ° C. for 30 minutes.
<実施例12>繊維に固定した実施例1の耐水性評価
 実施例8と同様の方法で抗アレルゲン布を作製し、ポリ容器へ入れ、そこへイオン交換水を加え、25℃で16時間振とうし、120℃で30分乾燥させた抗アレルゲン布のスギ花粉アレルゲン不活性化効果を測定した結果を表5に示した。
<Example 12> Water resistance evaluation of Example 1 fixed to fiber An anti-allergen cloth was prepared in the same manner as in Example 8, put into a plastic container, added with ion-exchanged water, and shaken at 25 ° C for 16 hours. Table 5 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen cloth dried at 120 ° C. for 30 minutes.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 表5の結果から実施例1の非晶質ケイ酸マグネシウムを添着加工した抗アレルゲン加工布は水処理後も十分に高いアレルゲン不活性化率を示した。よって、本発明の無機物質を繊維に後加工した抗アレルゲン製品は耐水性も優れている。 From the results in Table 5, the anti-allergen-processed cloth impregnated with amorphous magnesium silicate of Example 1 showed a sufficiently high allergen inactivation rate even after water treatment. Therefore, the anti-allergen product obtained by post-processing the inorganic substance of the present invention into a fiber has excellent water resistance.
<実施例13>
樹脂に練り込み加工した実施例1の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムと粉末状ポリプロピレンを固形分質量比で10:90になるように混ぜ合わせ、220℃で加熱プレスし、膜厚0.2mmの抗アレルゲンフィルムを作製した。抗アレルゲンフィルムのスギ花粉アレルゲン不活性化効果を測定した結果を表6に示した。
<Example 13>
Anti-allergen activity evaluation of Example 1 kneaded into resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and powdered polypropylene are mixed so as to have a mass ratio of 10:90 at 220 ° C. Was heated and pressed to produce an antiallergen film having a thickness of 0.2 mm. Table 6 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
<実施例14>
樹脂に練り込み加工した実施例1の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムと粉末状ポリプロピレンを固形分質量比で20:80になるように混ぜ合わせ、220℃で加熱プレスし、膜厚0.2mmの抗アレルゲンフィルムを作製した。抗アレルゲンフィルムのスギ花粉アレルゲン不活性化効果を測定した結果を表6に示した。
<Example 14>
Anti-allergen activity evaluation of Example 1 kneaded into resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and powdered polypropylene were mixed at a solid content mass ratio of 20:80, and 220 ° C. Was heated and pressed to produce an antiallergen film having a thickness of 0.2 mm. Table 6 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
<比較例10>
樹脂に実施例1を練り込まない場合の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムを用いずに実施例13と同様の加工方法により比較フィルムを作製した。比較フィルムのスギ花粉アレルゲン不活性化効果を測定した結果を表6に示した。
<Comparative Example 10>
Anti-allergen activity evaluation when Example 1 was not kneaded into the resin A comparative film was prepared by the same processing method as Example 13 without using amorphous magnesium silicate which is an inorganic substance of Example 1. Table 6 shows the results of measuring the cedar pollen allergen inactivating effect of the comparative film.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
 表6の結果から実施例1の非晶質ケイ酸マグネシウムを練り込み加工した抗アレルゲン加工フィルムは20wt%添加することにより高いアレルゲン不活性化率を示した。よって、本発明の無機物質を樹脂へ練り込み加工した抗アレルゲン製品の性能は優れている。
From the results shown in Table 6, the anti-allergen-processed film obtained by kneading the amorphous magnesium silicate of Example 1 showed a high allergen inactivation rate by adding 20 wt%. Therefore, the performance of the anti-allergen product obtained by kneading the inorganic substance of the present invention into a resin is excellent.
<実施例15>
UV硬化樹脂により加工した実施例1の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムとアクリル系UV硬化塗料(無溶剤)とを固形分質量比で15:85になるように混ぜ合わせ、バ-コ-タ-によりPETフィルム(東レ製 ルミラ-T60-50)へ厚さ15μmに加工し、25cmの距離で高圧水銀ランプ(強度60W/cm)を用いて、コンベアスピ-ド3.7m/minの条件で紫外線を照射して、組成物を硬化させ、抗アレルゲンフィルムを作製した。抗アレルゲンフィルムのスギ花粉アレルゲン不活性化効果を測定した結果を表7に示した。
<Example 15>
Evaluation of anti-allergen activity of Example 1 processed with UV curable resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and acrylic UV curable paint (no solvent) have a solid content mass ratio of 15:85 And then processed to a PET film (Toray Lumira T60-50) to a thickness of 15 μm using a bar coater, and a conveyor pressure using a high-pressure mercury lamp (strength 60 W / cm) at a distance of 25 cm. The composition was cured by irradiating with ultraviolet rays under a condition of 3.7 m / min to produce an anti-allergen film. Table 7 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
<実施例16>
UV硬化樹脂により加工した実施例1の抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムとアクリル系UV硬化塗料とを固形分質量比で30:70になるように混ぜ合わせ、バ-コ-タ-によりPETフィルム(東レ製 ルミラ-T60-50)へ厚さ15μmに加工し、25cmの距離で高圧水銀ランプ(強度60W/cm)を用いて、コンベアスピ-ド3.7m/minの条件で紫外線を照射して、組成物を硬化させ、抗アレルゲンフィルムを作製した。抗アレルゲンフィルムのスギ花粉アレルゲン不活性化効果を測定した結果を表7に示した。
<Example 16>
Anti-allergen activity evaluation of Example 1 processed with UV curable resin Amorphous magnesium silicate, which is an inorganic substance of Example 1, and acrylic UV curable paint are mixed so that the solid content mass ratio is 30:70. , Processed to a PET film (Toray Lumilar T60-50) with a thickness of 15 μm using a bar coater, and a conveyor speed of 3.7 m using a high-pressure mercury lamp (strength 60 W / cm) at a distance of 25 cm. The composition was cured by irradiating with ultraviolet rays under the conditions of / min to produce an anti-allergen film. Table 7 shows the results of measuring the cedar pollen allergen inactivating effect of the anti-allergen film.
<比較例11>
実施例1を固定しない場合のアクリル系UV硬化塗料により加工したフィルムの抗アレルゲン活性評価
 実施例1の無機物質である非晶質ケイ酸マグネシウムを用いずに実施例15と同様の加工方法により比較フィルムを作製した。比較フィルムのスギ花粉アレルゲン不活性化効果を測定した結果を表7に示した。
<Comparative Example 11>
Evaluation of anti-allergen activity of a film processed with an acrylic UV curable paint when Example 1 is not fixed. Comparison is made by the same processing method as Example 15 without using amorphous magnesium silicate which is an inorganic substance of Example 1. A film was prepared. Table 7 shows the results of measuring the cedar pollen allergen inactivating effect of the comparative film.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
 表7の結果から実施例1の非晶質ケイ酸マグネシウムをUV硬化塗工した抗アレルゲンフィルムは高い抗アレルゲン不活性化率を示した。よって本発明の無機物質を表面にUV硬化加工した抗アレルゲン製品の性能は優れている。 From the results shown in Table 7, the anti-allergen film obtained by UV-curing the amorphous magnesium silicate of Example 1 showed a high anti-allergen inactivation rate. Therefore, the performance of the anti-allergen product in which the inorganic substance of the present invention is UV-cured on the surface is excellent.
<実施例17>
 実使用環境における抗アレルゲン性の評価を行うために、実施例8に準ずる方法で、無機物質である非晶質ケイ酸マグネシウムをアクリルエマルジョンバインダー(東亞合成株式会社製NW-7060、固形分濃度50wt%)と固形分の質量比で2:1とになるように混ぜ合わせたものを、バスタオル(155cm×70cm 成分:綿)に5分浸漬後、120℃で60分乾燥の加工を行い、固定量2g/m2の抗アレルゲン布(バスタオル)を作製した。
 スギ花粉の飛散する晴天に、屋外の物干しにバスタオルを6時間天日干しして環境に浮遊するスギ花粉を吸着させた。一晩静置後に不織布をセットした掃除機をバスタオル全面にかけ、アレルゲンを不織布上に吸引回収した。10mlの抗原希釈液(0.1%BSA+PBSバッファー)で不織布上に載ったアレルゲンを抽出し、ELISA法によりスギ花粉アレルゲン(Cryj1)量を測定してアレルゲン回収量とした。天然のスギ花粉の飛散量は、天候や日によって大きく変わるので、3日以上間をあけた別の晴天の日に、同様な吸着試験を3回行ってアレルゲン回収量の結果を表8に示した。表8の1,2,3日目の意味は、3回の異なる日に吸着試験を行ったことを意味する。
<Example 17>
In order to evaluate the antiallergenicity in an actual use environment, an amorphous magnesium silicate which is an inorganic substance was converted into an acrylic emulsion binder (NW-7060 manufactured by Toagosei Co., Ltd., solid content concentration 50 wt. %) And the mass ratio of the solid content of 2: 1 are immersed in a bath towel (155 cm × 70 cm component: cotton) for 5 minutes, and then dried at 120 ° C. for 60 minutes, An anti-allergen cloth (bath towel) having a fixed amount of 2 g / m 2 was prepared.
The cedar pollen floating in the environment was adsorbed on a sunny day with cedar pollen scattered by bathing a bath towel on the outdoor clothes for 6 hours. A vacuum cleaner with a nonwoven fabric set after standing overnight was applied to the entire surface of the bath towel, and the allergen was sucked and collected on the nonwoven fabric. The allergen placed on the nonwoven fabric was extracted with 10 ml of an antigen dilution solution (0.1% BSA + PBS buffer), and the amount of cedar pollen allergen (Cryj1) was measured by ELISA to obtain the allergen recovery amount. Since the amount of natural cedar pollen varies greatly depending on the weather and the day, Table 8 shows the results of allergen recovery by conducting the same adsorption test three times on another sunny day with more than three days. It was. The meaning of the first, second and third days in Table 8 means that the adsorption test was performed three different days.
<比較例12>
 非晶質ケイ酸マグネシウムを含まないバインダ-のみを用いたこと以外は実施例17と同じにして比較例12のバスタオルを作製し、実施例17と同じ日に同じ場所で同様に環境に浮遊するスギ花粉を吸着させた。アレルゲン回収量の結果を表8に示した。
<Comparative Example 12>
A bath towel of Comparative Example 12 was prepared in the same manner as in Example 17 except that only a binder containing no amorphous magnesium silicate was used, and it floated in the environment in the same place on the same day as Example 17. To adsorb cedar pollen. The results of the allergen recovery amount are shown in Table 8.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 同一日の比較では、実施例17のバスタオルと比較例12のバスタオルに付着したスギ花粉量は同程度だったと考えられるので、非晶質ケイ酸マグネシウムを有しない比較例12のバスタオルに比べて、非晶質ケイ酸マグネシウムを固定した実施例17のバスタオルのスギ花粉アレルゲンの回収量が著しく低かったことは、実施例17のバスタオルでは、付着したスギ花粉のアレルゲンが非晶質ケイ酸マグネシウムによって不活性化されたためであると考えられる。 In the comparison on the same day, it is considered that the amount of cedar pollen adhering to the bath towel of Example 17 and the bath towel of Comparative Example 12 was approximately the same, so the bath towel of Comparative Example 12 having no amorphous magnesium silicate was used. In comparison, the amount of cedar pollen allergen recovered from the bath towel of Example 17 in which amorphous magnesium silicate was fixed was remarkably low. In the bath towel of Example 17, the attached cedar pollen allergen was amorphous. This is thought to be due to inactivation by magnesium silicate.
 本発明の抗アレルゲン剤を用いることにより、繊維製品や住宅建材などの人間の生活空間に関係する材料に、花粉やダニなどに由来するアレルゲンを不活性化する機能を付与することができ、抗アレルゲン製品を製造することができる。 By using the anti-allergen agent of the present invention, it is possible to impart a function to inactivate allergens derived from pollen, mites, etc. to materials related to human living space such as textile products and housing building materials, Allergen products can be manufactured.

Claims (9)

  1. pKaが4.8以下の酸点の酸点濃度が、0.001mmol/g以上10mmol/g以下の無機粉体からなる抗アレルゲン剤。 An antiallergen agent comprising an inorganic powder having an acid point concentration of pKa of 4.8 or less and an acid point concentration of 0.001 mmol / g or more and 10 mmol / g or less.
  2. レーザー粒度分布計で測定し、体積基準で算出した無機粉体のメジアン径が0.01μm以上50μm以下である、請求項1に記載の抗アレルゲン剤。 The anti-allergen agent according to claim 1, wherein the median diameter of the inorganic powder measured with a laser particle size distribution meter and calculated on a volume basis is 0.01 μm or more and 50 μm or less.
  3. 無機粉体の5wt%水分散液のpHが3以上9以下である、請求項1または2に記載の抗アレルゲン剤。 The antiallergen agent according to claim 1 or 2, wherein the pH of the 5 wt% aqueous dispersion of the inorganic powder is 3 or more and 9 or less.
  4. 無機粉体が非晶質ケイ酸マグネシウム、α型リン酸ジルコニウム、活性酸化チタンの中から選択される少なくともひとつである、請求項1~3のいずれかに記載の抗アレルゲン剤。 The anti-allergen agent according to any one of claims 1 to 3, wherein the inorganic powder is at least one selected from amorphous magnesium silicate, α-type zirconium phosphate, and active titanium oxide.
  5. 無機粉体が非晶質ケイ酸マグネシウムである、請求項4に記載の抗アレルゲン剤。 The anti-allergen agent according to claim 4, wherein the inorganic powder is amorphous magnesium silicate.
  6. 請求項1~5のいずれかに記載の抗アレルゲン剤とバインダ-または塗料を含むコ-ティング組成物。 A coating composition comprising the anti-allergen agent according to any one of claims 1 to 5 and a binder or paint.
  7. pHが3以上9以下である、請求項6に記載のコ-ティング組成物。 The coating composition according to claim 6, wherein the pH is 3 or more and 9 or less.
  8. 請求項6または7に記載のコ-ティング組成物により加工された抗アレルゲン製品。 An anti-allergen product processed by the coating composition according to claim 6 or 7.
  9. 請求項6または7に記載のコ-ティング組成物により加工された抗アレルゲン布。
                                                                                        
    An anti-allergen fabric processed with the coating composition according to claim 6 or 7.
PCT/JP2011/073508 2010-10-14 2011-10-13 Anti-allergen agent WO2012050156A1 (en)

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