WO2012050156A1 - Anti-allergen agent - Google Patents
Anti-allergen agent Download PDFInfo
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- 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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- allergen
- acid
- resin
- agent
- pka
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating 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
- D06M11/32—Treating 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
- D06M11/36—Treating 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
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating 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
- D06M11/68—Treating 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
- D06M11/70—Treating 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
- D06M11/71—Salts of phosphoric acids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating 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
- D06M11/77—Treating 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
- D06M11/79—Treating 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
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated 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
- Y10T442/2525—Coating 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
Description
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.
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.
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.
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>
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.
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.
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).
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Claims (9)
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
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CN201180049385.5A CN103261357B (en) | 2010-10-14 | 2011-10-13 | Anti-allergen agent |
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JP2017075420A (en) * | 2015-10-14 | 2017-04-20 | 住化エンバイロメンタルサイエンス株式会社 | Allergen-reducing composition for fiber |
WO2017150063A1 (en) * | 2016-03-01 | 2017-09-08 | 東亞合成株式会社 | Antiviral agent, coating composition, resin composition and antiviral product |
WO2020105227A1 (en) * | 2018-11-22 | 2020-05-28 | 日揮ユニバーサル株式会社 | Filtering material for air filters and method for manufacturing filtering material for air filters |
JP2020164604A (en) * | 2019-03-28 | 2020-10-08 | 住化エンバイロメンタルサイエンス株式会社 | Allergen-reducing composition |
WO2021182299A1 (en) * | 2020-03-13 | 2021-09-16 | 東亞合成株式会社 | Zirconium phosphate particles, basic gas deodorant agent using same, and methods respectively for producing said zirconium phosphate particles and said basic gas deodorant agent |
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JPWO2012050156A1 (en) | 2014-02-24 |
CN103261357B (en) | 2014-12-31 |
KR20130118881A (en) | 2013-10-30 |
CN103261357A (en) | 2013-08-21 |
KR101893232B1 (en) | 2018-08-29 |
US20130273798A1 (en) | 2013-10-17 |
JP5594367B2 (en) | 2014-09-24 |
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