JP2009240965A - Hazardous substance removing material and method for removing hazardous substance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hazardous substance removing material whose collection efficiency is high and whose pressure drop is low and that can efficiently utilize an antibody and a method for removing hazardous substances. <P>SOLUTION: The hazardous substance removing material is composed of a carrier where an antibody is supported prepared by supporting the antibody after electret treatment is performed on a compound object where fine fiber aggregates of fiber diameter of 1 μm or less are laminated on a fiber aggregate of fiber diameter of 10 μm or more, wherein the fiber aggregate of the fiber diameter of 10 μm or more is composed of an apolar polymer substance and the mass/surface area of the fine fiber aggregate of the fiber diameter of 1 μm or less is 0.5 g/m<SP>2</SP>or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a harmful substance removing material capable of selectively inactivating bacteria and viruses and a method for removing the harmful substance.

  In recent years, infectious diseases caused by bacteria, molds, viruses, and the like have become a social problem. For example, there are concerns about mass infection in hospitals and places where a large number of unspecified people gather such as public facilities. In particular, infection in hospitals may cause the occurrence of MRSA (methicillin-resistant Staphylococcus aureus) and the like due to the abuse of antibiotics.

  In this regard, in recent buildings, ducts are provided in all rooms, and air is circulated through these ducts to adjust the room temperature etc. of the entire building, so that the inside of the facility floats through this air conditioner. Bacteria, molds, viruses, and the like often diffuse throughout the facility, and it has been considered that it is particularly effective to block infection routes using such air as a medium. In other words, bacteria, mold, viruses, or fine suspended matters in the air (dust, etc.) are adsorbed on fine filters as air media such as air conditioners and air purifiers, and titanium oxide or strong acidity. The sterilization zone is provided to inactivate and remove bacteria, molds, viruses, and the like that pass through the sterilization zone.

  Patent Document 1 describes a harmful substance removing material that removes a harmful substance in a gas phase atmosphere in which an antibody is supported on a carrier. Although fiber material is mentioned as a support | carrier, there is no mention about a fiber diameter. Inactivation of an antibody filter by an antibody is considered to be effective in the first stage because harmful substances collected in the filter diffuse on the filter and are inactivated by the antibody. Therefore, when the filter used as a substrate does not have sufficient collection efficiency, a sufficient effect is not shown.

  Patent Document 2 describes an antibacterial charging filter characterized in that antibacterial fine particles are attached to fibers constituting a base fabric, and the fibers are electretized. It is obtained by impregnating and drying a base fabric in an antibacterial fine particle dispersion, but it does not show an appropriate binder, has the disadvantage of powdering off during use, and cannot withstand long-term use. When a binder is used, as described in Patent Document 2, since the effect of electret is reduced, the collection rate may be reduced.

JP 2004-313755 A JP-A-11-201559

  An object of the present invention is to provide a hazardous substance removing material and a hazardous substance removing method that have high collection efficiency, low pressure loss, and that can efficiently utilize antibodies.

  As a result of intensive studies to solve the above problems, the present inventors have performed an electret treatment on a composite in which a fine fiber assembly having a fiber diameter of 1 μm or less is laminated on a fiber assembly having a fiber diameter of 10 μm or more. After that, the present inventors have found that by carrying an antibody, it is possible to provide a hazardous substance removing material that has high collection efficiency, low pressure loss, and can efficiently use the antibody, and has completed the present invention.

That is, according to the present invention, the composite comprising a fiber aggregate having a fiber diameter of 10 μm or more laminated with a fine fiber aggregate having a fiber diameter of 1 μm or less is subjected to an electret treatment and then loaded with an antibody. A harmful substance removing material comprising an antibody-supported carrier, wherein the fiber aggregate having a fiber diameter of 10 μm or more is composed of a nonpolar polymer substance, and the fine fiber aggregate having a fiber diameter of 1 μm or less The harmful substance removing material is provided, characterized in that the weight of the body is 0.5 g / m ² or less.

Preferably, the electret process is a charging process by corona discharge.
Preferably, the antibody is a chicken egg antibody.
Furthermore, according to the present invention, there is provided a method for removing harmful substances, comprising removing harmful substances in the gas phase or liquid phase using the above-mentioned hazardous substance removing material of the present invention.

  According to the present invention, the electret effect improves the collection efficiency, can eliminate an increase in pressure loss in ultrafine fibers, and provides a harmful substance removal material that can reliably invalidate collected harmful substances. it can. According to the present invention, an air cleaner or a liquid cleaner that can efficiently remove harmful substances in a gas phase or a liquid phase can be produced, which is very useful in the industry.

Hereinafter, the present invention will be described in more detail.
The harmful substance removing material of the present invention carries the composite after a fine fiber assembly having a fiber diameter of 1 μm or less is laminated on a fiber assembly having a fiber diameter of 10 μm or more, and then carries an antibody. A harmful substance removing material comprising an antibody-supported carrier obtained by the above, wherein the fiber aggregate having a fiber diameter of 10 μm or more is composed of a nonpolar polymer substance, and the fine fiber having a fiber diameter of 1 μm or less The basis weight of the aggregate is 0.5 g / m ² or less.

  In the present invention, the collection efficiency can be improved by electret treatment, and the amount of nanofibers per unit area can be reduced by the increase in the collection efficiency, resulting in an increase in pressure loss due to the increase in the amount per unit area. Can be avoided. In the present invention, fine fiber aggregates (nanofibers) having a fiber diameter of 1 μm or less are supported by the nanofibers so as to be embedded in the voids of fiber aggregates (substrate filters) having a fiber diameter of 10 μm or more. A harmful substance removing material capable of selectively inactivating bacteria and viruses captured by the nanofiber itself by the antibody, as well as bacteria and viruses captured electrostatically, is provided.

  The fiber diameter of the fiber aggregate having a fiber diameter of 10 μm or more is not particularly limited as long as it is 10 μm or more, but is generally 10 μm or more and 100 μm or less, preferably 10 μm or more and 50 μm or less.

  A fiber aggregate having a fiber diameter of 10 μm or more is composed of a nonpolar polymer substance. The type of non-polar polymer material is not particularly limited, but polyolefins and polycarbonates such as polypropylene or polyethylene are chemically and mechanically stable, economical, and exhibit excellent electret performance. Because it is preferred. Also, certain types of fluoropolymers such as polytetrafluoroethylene (PTFE) or perfluorinated ethylene / propylene copolymer (PFEP) have excellent electrets, although some have a charge (polarization) retention life of several decades. Can be used to show performance.

The fiber diameter of the fine fiber aggregate having a fiber diameter of 1 μm or less is not particularly limited as long as it is 1 μm or less, but is generally 10 nm or more and 1 μm or less, preferably 100 nm or more and 1 μm or less. Further, the basis weight of the fine fiber aggregate having a fiber diameter of 1 μm or less (weight per unit area. Weight per 1 m ² expressed in g (gram)) is 0.5 g / m ² or less, preferably 0.01 g / m ² or more and 0.5 g / m ² or less, more preferably 0.1 g / m ² or more and 0.5 g / m ² or less, and further preferably 0.1 g / m ² or more and 0.4 g / m ² or less. Particularly preferably, it is 0.2 g / m ² or more and 0.4 g / m ² or less.

  As the main fibers forming the fine fiber aggregate having a fiber diameter of 1 μm or less, fibers mainly composed of at least one of cellulose ester, vinylon, acrylic and polyurethane are preferable.

  The cellulose ester in the present invention refers to a cellulose derivative in which the hydroxyl group of cellulose is esterified with an organic acid. Examples of organic acids used for esterification include fatty carboxylic acids such as acetic acid, propionic acid, and butyric acid, and aromatic carboxylic acids such as benzoic acid and salicylic acid. It may be used alone or in combination. Although there is no restriction | limiting in particular about the ester group substitution rate of the hydroxyl group of a cellulose, It is preferable that it is 60% or more.

  Cellulose acylate fibers are desirable among the group of main materials forming a fine fiber aggregate having a fiber diameter of 1 μm or less in the present invention. Cellulose acylate refers to a cellulose ester in which some or all of the hydrogen atoms constituting the hydroxyl group of cellulose are substituted with acyl groups. Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group. These groups may be constituted by replacing only one kind, or two or more kinds of acyl groups may be mixed and substituted. The total acyl group substitution degree is preferably 2.0 to 3.0, more preferably 2.1 to 2.8, and particularly preferably 2.2 to 2.7. Among these, cellulose acetate, cellulose acetate propionate, or cellulose acetate butyrate that satisfies this degree of substitution is preferable, and cellulose acetate is most preferable. Cellulose acylate is generally known to have different solvents depending on the degree of esterification, but after preparing a fine fiber aggregate with a fiber diameter of 1 μm or less with cellulose acylate with a high esterification rate, alkali hydrolysis treatment Etc. may be performed to make the surface hydrophilic.

  Although it is possible to form a sufficiently practical harmful substance removal material using only cellulose acylate fibers, polyester fibers, polyolefin fibers, polyamides are used for the purpose of further improving strength and dimensional stability. A fine fiber aggregate having a fiber diameter of 1 μm or less may be formed by blended fibers with fibers, acrylic fibers, and the like. When blended fiber is used, the mass fraction of the cellulose acylate fiber is preferably 50% or more, and more preferably 70% or more.

  Among the main group of materials forming the fine fiber aggregate having a fiber diameter of 1 μm or less in the present invention, it is also desirable that the fiber is a polyamide fiber.

  The polyamide in the present invention refers to a fiber made of a linear polymer having an amide bond in a chemical structural unit.

  Among polyamides, a linear chain that is a combination of an aliphatic diamine such as ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, and hexamethylenediamine and an aliphatic dicarboxylic acid such as malonic acid, succinic acid, and adipic acid. Type aliphatic polyamides are preferred. Nylon 66 is particularly preferable.

  Fats using lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, para-aminomethylbenzoic acid and the like alone or as a copolymer component in addition to the diamine and dicarboxylic acid. A group polyamide can also be used. In particular, nylon 6 produced by using ε-caprolactam alone is preferable.

  In addition to these, some or all of the aliphatic diamines used as raw materials are alicyclic diamines such as cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis (aminomethyl) cyclohexane. An aliphatic polyamide using an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid or the like may be used as an aromatic polyamide and / or as a dicarboxylic acid. .

  Furthermore, by using aromatic diamines such as aliphatic paraxylylenediamine (PXDA) and metaxylylenediamine (MXDA), and aromatic dicarboxylic acids such as terephthalic acid as partial raw materials, water absorption is reduced and elastic modulus is improved. Also included is a polyamide that achieves the above. Moreover, the polymer which has an amide bond in a side chain like polyacrylic acid amide, poly (N-methylacrylic acid amide), poly (N, N-dimethylacrylic acid amide), etc. may be sufficient.

  Most preferred of the polyamides is nylon 66 or nylon 6. Appropriate hygroscopicity derived from amide bonds, easy to orient the molecular chain consisting of long chain fatty acids of appropriate length, relatively high stretchability, high heat of fusion and large heat capacity It is difficult to melt in terms of kinetics (melt resistance), the flexibility of molecular chains consisting of long-chain fatty chains, and the property that fibrillation and kink bands do not easily occur due to the formation of hydrogen bonds between amide bonds. This is because the properties preferable for the carrier of the present invention such as flexibility can be utilized.

  A polyamide having an amide bond in the chemical structural unit in the side chain instead of the main chain can also be preferably used. Polyacrylamide such as poly (N-isopropylacrylamide), poly (N, N′-dimethylacrylamide), and poly (N-hexylacrylamide) can be used. In general, polymers with amide bonds in the side chains are highly hydrophilic and easily swell and deform, so they are hydrophobized by methods such as forming physical crosslinks or introducing alkyl groups using gelation. It is desirable.

  Similarly, for the purpose of improving strength and dimensional stability, the carrier may be reinforced with other appropriate structural materials such as metal, polymer material, ceramics and the like. These reinforcing materials are desirably used for portions other than the substantially outermost surface of the side surface to which the harmful substance removing material is supplied (for example, used on the opposite surface of the side surface or a core material).

  The vinylon in the present invention refers to a fiber made of a linear polymer containing 65% by mass or more of vinyl alcohol units, and having a moisture content of less than 7% after being left for 1 week or longer in an environment of temperature 20 ° C. and humidity 65%. . It may be a formalized hydroxyl group of vinyl alcohol, but it is a non-formalized fiber that has been subjected to water resistance treatment by a polymer such as a boric acid-crosslinked hydroxyl group or a known alkali spinning method or cooling gel spinning method. It may be. Components other than vinyl alcohol units may include ethylene chains, vinyl acetate chains, etc., but fibers formed from vinyl alcohol alone are preferred. Furthermore, it is most desirable to be a non-formalized fiber by cooling gel spinning in that it is homogeneous and has a high degree of orientation and crystallinity, so that excellent mechanical properties and reliability can be obtained.

  Vinylon generally has high strength, high elastic modulus, moderate hydrophilicity, weather resistance, chemical resistance, adhesion and the like with respect to other fibers, and utilizes these preferable performances as a carrier of the present invention. be able to.

  The acrylic system in the present invention refers to a fiber containing 40% or more of acrylonitrile group repeating units, for example, a homopolymer of acrylonitrile, a nonionic monomer such as an acrylate ester, a methacrylate ester, or vinyl acetate; Examples include copolymers of acrylonitrile, copolymers of anionic monomers such as vinylbenzene sulfonic acid and allyl sulfonic acid and acrylonitrile, and copolymers of cationic monomers such as vinyl pyridine and methyl vinyl pyridine and acrylonitrile. So-called promix fibers formed from acrylonitrile and milk casein are also included in this category.

In general, acrylic fibers are often produced by an organic wet spinning method. In this method, when the spinning stock solution forms a coagulated yarn in the coagulation bath, water as a coagulant enters the spinning stock solution spun from the nozzle, while the spinning solvent diffuses from the spun stock solution to the outside. At this time, the water and the organic solvent (DMF, DMAc, etc.) are mutually diffused, so that a polymer is precipitated and a coagulated yarn having a structure in which innumerable cavities are connected in a network form is formed. In addition, it is characterized by deformation of the fiber cross section formed by volume shrinkage due to diffusion of the solvent into the coagulation bath during the coagulation process and formation of irregularities by forming a macrofibril structure on the surface. These fine structures are preferable as the structure of the carrier used in the present invention in terms of improving the specific surface area and ease of carrying the antibody.

  The acrylic fiber used in the present invention varies depending on the composition of the raw material polymer, the spinning method, the post-treatment conditions in the production process, etc., but generally, it is easy to obtain a bulky fiber with moderate hydrophilicity and high weather resistance. There are advantages.

  The polyurethane used in the present invention refers to a fiber composed of a linear synthetic polymer in which the bonding portion between monomers or the bonding portion between base polymer materials is mainly urethane bonds. It is desirable that the polyurethane segment contains 85% or more by mass ratio. It is desirable to be a block copolymer of a segmented polyurethane composed of a soft segment having a low melting point and a soft molecular weight of up to several thousand, and a hard segment having a high melting point and rigidity and high cohesion. Polyethers such as polypropylene glycol and polytetramethylene glycol can be used as the soft segment, and urethane groups formed from 4,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, and the like can be used as the hard segment. Polyurethane is generally characterized by high elasticity. It varies depending on the temporary structure of the polymer chain, such as the chemical structure and distribution of both segments, and on the difference in secondary structure resulting from differences in the spinning conditions, but it stretches well. It has characteristics such as high resilience, resistance to aging compared to rubber materials, and thin fibers can be obtained, and these properties can be utilized even when used as a carrier of the present invention.

  Regarding the mechanical properties and dimensional stability of the fibers constituting the carrier, it is desirable that the elongation at drying is 25% or more. Here, the elongation at drying refers to the breaking elongation in a tensile test at 20 ° C. of the fiber dried over a sufficiently long time. In general, it is preferable that the elongation at drying is 10% or more and that it is suitable for processing such as cloth making is 25% or more in order to prevent filter processing and breakage during practical use (leading to a decrease in filtration efficiency). % Or more is more preferable, and 35% or more is most preferable.

  The official moisture content of the fibers constituting the carrier is preferably 1.0% or more and less than 7.0%, more preferably 3.0% or more and less than 6.7%, and more preferably 5.0% or more and 6% or less. Most preferably, it is less than 5%. At the official moisture content in this area, the activity of the supported antibody can be expressed, and the carrier's mechanical strength, rigidity, and dimensional stability with respect to the environment (especially humidity) should be obtained. Can do.

  The moisture content referred to here is the official moisture content, and the official moisture content is the moisture content contained in the fiber when the fiber is left in an environment of 20 ° C. and a relative humidity of 65% for a long time. Point to. In the case of a blended fiber with other fibers, the official moisture content of the entire blended fiber is indicated.

  The surface of the fiber constituting the carrier preferably has a fine concavo-convex structure on the scale of several tens of nanometers to several micrometers. The shape of the irregularities may be a three-dimensional shape such as a groove or streak formed in a direction parallel to the fiber direction, or a groove or streak formed perpendicular to the fiber direction, that is, concentrically with respect to the axis. Three-dimensional shapes may be used, and these three-dimensional shapes formed at an arbitrary angle from the direction parallel to the fiber direction to the vertical direction may exist at an arbitrary ratio and density. Samples obtained by the known cellulose acetate fiber spinning method are known to form a chrysanthemum shape with an indefinite fiber cross section due to the formation of a skin layer on the surface layer and the depression of the skin layer accompanying solvent drying. This unevenness is also a preferred form in the present invention.

  The fine concavo-convex structure on the nanometer to micrometer scale may be a hole and / or a protrusion. The average diameter is preferably 50 nm to 1 μm of holes or protrusions. These vacancies and protrusions are formed in a spinning process by a method such as using a solution in which cavitation of a solution or a fine dispersoid is dispersed (for example, mixing with a slurry in which barium sulfate particles are dispersed), It can be formed in a subsequent step by a method such as hydrolysis of the group or surface oxidation treatment (for example, the surface of the fiber is celluloseized with an aqueous alkali solution and then the microcrater is expressed on the fiber surface by enzyme treatment).

  The fiber used in the present invention can be produced by a general production method such as melt spinning, wet spinning, dry spinning, wet drying spinning, or physical treatment (for example, strong mechanical shearing treatment using an ultra-high pressure homogenizer). In order to ensure stable quality, it is preferable to use dry spinning or wet dry spinning. In order to produce uniform fibers with an average fiber diameter of 100 nm or less, further processing techniques, 2005, 40, No. 2, 101, and 167; Polymer International, 1995, 36, 195- 201; Polymer Preprints, 2000, 41 (2), 1193; Journal of Macromolecular Science: Physics, 1997, B36, 169, etc. It is preferable to employ the electrospinning method.

  Solvents used for spinning include chlorinated solvents such as methylene chloride, chloroform and dichloroethane, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and ketones such as acetone, ethyl methyl ketone, methyl isopropyl ketone and cyclohexanone. Any solvent that dissolves the resin used for the synthetic resin fiber, such as a solvent, an ether solvent such as THF or diethyl ether, or an alcohol solvent such as methanol, ethanol, or isopropanol can be used. These solvents may be used alone or in combination of two or more.

  When the electrospinning method is employed, a salt such as lithium chloride, lithium bromide, potassium chloride, or sodium chloride may be further added to the resin solution.

  It is desirable that the fibers constituting the carrier of the harmful substance removing material of the present invention have a structure in which a three-dimensional network is formed by partial adhesion. By adopting such a structure, it is possible to improve processing and practical mechanical resistance, and to improve the reliability of the hazardous substance removing material. In addition, the retention characteristics of the antibody of the present invention can be improved. The adhesion between fibers can be observed by a method such as SEM. The density of the bonding points between the fibers is preferably 10 or more per 1 mm square with respect to the projected surface area of the harmful substance removing material, and more preferably 100 or more.

  As a method for forming an adhesion point, it may be formed by an adhesion formed by a dry spinning method or a fusion point formed by a melt spinning method, or after spinning, addition of an adhesive, a plasticizing solvent, etc. You may perform the adhesion point formation process by. From the viewpoint of production cost, it is preferable to form adhesion points by a dry spinning method using an appropriate solution formulation.

  In the present invention, electret treatment is performed on a composite in which a fine fiber aggregate having a fiber diameter of 1 μm or less is laminated on a fiber aggregate having a fiber diameter of 10 μm or more. The method of electret treatment is not particularly limited, but it is preferable to perform charging treatment by corona discharge. As the fiber aggregate having a fiber diameter of 10 μm or more used in the present invention, a nonpolar polymer substance is used so as to be easily charged.

  In the present invention, the antibody is supported on the complex after the electret treatment. That is, since the effect of the antibody is lost by the electret treatment, the antibody is supported after the electret treatment.

  The antibody used in the hazardous substance removing material of the present invention is a protein that specifically reacts (antigen-antibody reaction) with a specific harmful substance (antigen), has a molecular size of 7 to 8 nm, and has a Y-shape. Having the molecular form of Of the Y-shaped molecular structure of an antibody, a pair of branch parts is called Fab and a trunk part is called Fc, and among these, a toxic substance is captured at the Fab part.

  The type of the antibody corresponds to the type of harmful substance that can be captured. Examples of harmful substances captured by antibodies include bacteria, molds, viruses, allergens, and mycoplasmas. Specifically, examples of bacteria include gram-positive bacteria, Staphylococcus (S. aureus and Staphylococcus epidermidis), micrococcus, anthrax, cereus, Bacillus subtilis, acne, and gram-negative bacteria. And Pseudomonas aeruginosa, Serratia, Sephacia, Streptococcus pneumoniae, Legionella, and Mycobacterium tuberculosis. Examples of molds include Aspergillus, Penicillius, and Cladosporium. Examples of the virus include influenza virus, coronavirus (SARS virus), adenovirus, rhinovirus and the like. Examples of allergens include pollen, mite allergen, cat allergen and the like.

  Examples of the method for producing the antibody include, for example, a method in which an antigen is administered to an animal such as a goat, horse, sheep, or rabbit, and a polyclonal antibody is purified from the blood, and a spleen cell and a cultured cancer cell of the animal to which the antigen is administered. Methods for purifying monoclonal antibodies from cell cultures and body fluids (such as ascites) of animals that have been transplanted with the cultures, purified antibodies from genetically modified bacteria, plant cells, or animal cell cultures into which antibody-producing genes have been introduced And a method of purifying a chicken egg antibody from egg yolk powder obtained by administering an antigen to a chicken to produce an immunized egg and sterilizing and spray-drying the egg yolk liquid. Among these, the method of obtaining an antibody from a chicken egg can easily obtain a large amount of the antibody and can reduce the cost of the harmful substance removing material.

  The antibody used in the hazardous substance removing material of the present invention is preferably a chicken egg antibody.

  The carrier constituting the hazardous substance removing material of the present invention is subjected to antibacterial processing such as coating containing an antibacterial agent and / or antifungal processing such as coating containing a fungicide. desirable. Antibodies are basically proteins, especially chicken egg antibodies are food, and may be accompanied by proteins other than antibodies, which are good food for bacteria and fungi to grow, but antibacterials are used as carriers. If processing and / or anti-mold processing is performed, the growth of such bacteria and molds is suppressed, and long-term storage can be performed.

  Examples of antibacterial / antifungal agents include organic silicon quaternary ammonium salts, organic quaternary ammonium salts, biguanides, polyphenols, chitosan, silver-supporting colloidal silica, and zeolite-supporting silver. The processing method includes impregnating or applying an antibacterial / antifungal agent to a fiber carrier, or a raw yarn raw cotton modified with an antibacterial / antifungal agent in the synthesis stage of the fibers constituting the carrier. There is a quality law.

  As a method for immobilizing an antibody on the carrier, the carrier is silanized using γ-aminopropyltriethoxysilane or the like, and then an aldehyde group is introduced onto the surface of the carrier with glutaraldehyde or the like. A method of covalent bonding, a method of immersing an untreated carrier in an antibody aqueous solution and immobilizing the antibody on the carrier by ionic bonding, an aldehyde group introduced into a carrier having a specific functional group, and the aldehyde group and the antibody A method of covalently bonding, a method of ionically binding an antibody to a carrier having a specific functional group, a method of introducing an aldehyde group after coating the carrier with a polymer having a specific functional group, and a method of covalently binding the aldehyde group and the antibody I can give you.

Here, examples of the specific functional group include an NHR group (R is any alkyl group other than H, methyl, ethyl, propyl, and butyl), NH ₂ group, C ₆ H ₅ NH ₂ group, and CHO group. , COOH group, and OH group.

  Also, there is a method in which the functional group on the surface of the carrier is converted to another functional group using BMPA (N-β-Maleimidopropionic acid) or the like, and then the functional group and the antibody are covalently bonded (SH group in BMPA). Are converted to COOH groups).

  Furthermore, there is a method in which a molecule (Fc receptor, protein A / G, etc.) that selectively binds to the Fc portion of the antibody is introduced onto the surface of the carrier and the antibody Fc is bound thereto. In this case, the Fab that captures the harmful substance faces outward with respect to the carrier, and the probability of contact of the harmful substance with the Fab increases, so that the harmful substance can be efficiently captured.

The antibody may be supported on a carrier via a linker. In this case, the degree of freedom of the antibody on the carrier is increased and access to harmful substances is facilitated, so that high removal performance can be obtained. Examples of the linker include bi- or higher-valent cross-linking reagents, specifically maleimide, NHS (N-Hydroxysuccinimidyl) ester, imide ester, EDC (1-Ethyl-3- [3-dimethylaminopropyl] carbodiimido), There is PMPI (N- [p-Maleimidophenyl] isocyanate), which is selective to target functional groups (SH group, NH ₂ group, COOH group, OH group) and non-selective. Moreover, the distance (space arm) between crosslinks also changes for every crosslink reagent, and it can select in the range of about 0.1 nm-3.5 nm according to the target antibody. From the viewpoint of efficiently capturing harmful substances, those that bind to the Fc of the antibody as a linker are preferred.

  As a method for introducing a linker, either a method in which a linker is bound to an antibody and then further bound to the antibody, or a method in which a linker is bound to a carrier and the antibody is bound to the linker on the carrier is possible. is there.

The hazardous substance removing material of the present invention can be used for filters, masks, wipes and the like for air cleaners.
When used as a filter for an air purifier, any known filter such as a prefilter for removing coarse dust, a dust removal filter, a photocatalytic filter exhibiting a deodorizing effect, an antibacterial filter for removing other harmful substances, a VOC adsorption filter, etc. It may be used in combination with a filter.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1: Preparation of filter (Filter 1)
A nonwoven fabric made of polyolefin having a basis weight of 10 g / m ² , which is 15 μm as measured by an SEM (scanning electron microscope).

(Filter 2)
A non-woven fabric made of acetate having a basis weight of 10 g / m 2, which is 12 μm when the average fiber diameter is measured by SEM.

(Filter 3)
Using a filter 1 as a substrate, an acetone: water (97: 3) solution (10% by mass) of cellulose acetate (manufactured by Aldrich, total substitution degree 2.4, number average molecular weight 30,000), nanofiber production apparatus (manufactured by Kato Tech) ), Electrospinning at a syringe feed rate of 0.05 mm / min and an applied voltage of 15 kV, and further drying in a vacuum at 80 ° C. for 8 hours to produce a nonwoven fabric having a basis weight of 0.2 g / m ² to prepare a composite filter did. When the average fiber diameter of the nanofiber part was measured by SEM, it was 450 nm.

(Filter 4)
Using a filter 1 as a substrate, an acetone: water (97: 3) solution (10% by mass) of cellulose acetate (manufactured by Aldrich, total substitution degree 2.4, number average molecular weight 30,000), nanofiber production apparatus (manufactured by Kato Tech) ), Electrospinning was performed at a syringe feed rate of 0.05 mm / min and an applied voltage of 15 kV, and further dried in a vacuum at 80 ° C. for 8 hours to prepare a nonwoven fabric having a basis weight of 0.6 g / m 2 to prepare a composite filter. . When the average fiber diameter of the nanofiber part was measured by SEM, it was 450 nm.

(Filter 5)
Using a filter 2 as a substrate, an acetone: water (97: 3) solution (10% by mass) of cellulose acetate (manufactured by Aldrich, total substitution degree 2.4, number average molecular weight 30,000) is used, and a nanofiber production apparatus (manufactured by Kato Tech) ), Electrospinning was performed at a syringe feed rate of 0.05 mm / min and an applied voltage of 15 kV, and further dried in a vacuum at 80 ° C. for 8 hours to prepare a nonwoven fabric having a basis weight of 0.2 g / m 2 to prepare a composite filter. . When the average fiber diameter of the nanofiber part was measured by SEM, it was 450 nm.

(Filter 6)
The filter 1 was charged by corona discharge according to a conventional method.
(Filter 7)
The filter 2 was charged by corona discharge according to a conventional method.
(Filter 8)
The filter 3 was charged by corona discharge according to a conventional method.
(Filter 9)
The filter 4 was charged by corona discharge according to a conventional method.
(Filter 10)
The filter 5 was charged by corona discharge according to a conventional method.
(Filter 11)
It was prepared in the same manner as the filter 3 except that a non-woven fabric having a nanofiber weight per unit area of 0.4 g / m ² was prepared, and charged by corona discharge according to a conventional method.

(Filter 12)
Using a filter 1 as a base, an acetone: water (97: 3) solution (25% by mass) of cellulose acetate (manufactured by Aldrich, total substitution degree 2.4, number average molecular weight 30,000) is heated to 60 ° C., and a melt blow method is performed. A non-woven fabric having a basis weight of 0.2 g / m ² was produced and a composite filter was produced. When the average fiber diameter of the fine fiber part was measured by SEM, it was 2 μm.

(Filter 13)
Using filter 1 as a base, an acetone: water (97: 3) solution (25% by mass) of cellulose acetate (manufactured by Aldrich, total substitution degree 2.4, number average molecular weight 30,000) is heated to 60 ° C., and a melt blow method is performed. A non-woven fabric having a basis weight of 0.6 g / m ² was produced to produce a composite filter. When the average fiber diameter of the fine fiber part was measured by SEM, it was 2 μm.

(Filter 14)
The filter 12 was charged by corona discharge according to a standard method.
(Filter 15)
The filter 13 was charged by corona discharge according to a conventional method.

Example 2: Immobilization of antibody An influenza virus antibody (IgY antibody) prepared by purifying an immunized egg produced by a chicken administered with an antigen was dissolved in phosphate buffered saline (PBS) so that the antibody concentration was 100 ppm. Prepared. The prepared liquid was sprayed on the filters 1 to 15 by spraying to give antibodies to the fiber surface, and antibody filters 1 to 15 were produced. Note that. The nanofiber composite was applied to the nanofiber side.

Example 3: Evaluation of virus inactivation efficiency Virus inactivation efficiency was evaluated for antibody filters 1 to 15.
As the test virus solution, purified influenza virus diluted 10 times with PBS was used. Each of the samples was cut into 5 cm squares and attached and fixed in the center of the virus spray test apparatus. The test virus solution was put in a nebulizer installed on the upstream side, and a virus recovery device was attached on the downstream side. Compressed air was sent from an air compressor, and the test virus was sprayed from the nebulizer spray port. A gelatin filter was installed on the downstream side of the mask, and air in the test apparatus was sucked at a suction flow rate of 10 L / min for 5 minutes to collect passing virus mist.

  After the test, the gelatin filter collecting the virus was collected, and the virus infectivity after passing through the sample was determined by the TCID50 method (50% cell infectious dose measurement method) using MDCK cells. From the comparison of the virus infectivity value of the gelatin filter with and without the sample, the transient removal rate of the virus of each sample was calculated. The measurement results are shown in Table 1.

Example 4: Measurement of collection efficiency The antibody filters 1 to 15 were punched into a 150 mm square, set in a sample holder, and installed in a test duct having the same diameter. The particle capture efficiency test described in the dust mask standard established based on Article 42 of the Occupational Safety and Health Act was conducted to determine the collection efficiency. The measurement results are shown in Table 1.

Example 5: Pressure loss measurement The antibody filters 1 to 15 were punched out to a diameter of 120 mm, set in a sample holder, and the pressure difference before and after flowing air at a flow rate of 1 m / s was measured. The measurement results are shown in Table 1.

  As is clear from Table 1, according to the hazardous substance removing material of the present invention, when a polyolefin substrate which is a nonpolar substrate is used, the collection efficiency is improved by the electret effect, and the pressure loss of the nanofibers is small. It was found that the virus removal rate is high and can be used as an effective removal material in a low region. A filter having a fine fiber of 2 μm does not increase the collection efficiency and has little charging effect.

Claims (4)

A carrier carrying an antibody obtained by carrying an electret treatment on a composite in which a fine fiber assembly having a fiber diameter of 1 μm or less is laminated on a fiber assembly having a fiber diameter of 10 μm or more. A material for removing harmful substances, wherein the fiber aggregate having a fiber diameter of 10 μm or more is made of a nonpolar polymer substance, and the basis weight of the fine fiber aggregate having a fiber diameter of 1 μm or less is 0.5 g / m ^The hazardous substance removing material, characterized in that it is ² or less. The hazardous substance removing material according to claim 1, wherein the electret treatment is a charging treatment by corona discharge. The harmful substance removing material according to claim 1 or 2, wherein the antibody is a chicken egg antibody. A method for removing harmful substances, comprising removing harmful substances in a gas phase or a liquid phase using the hazardous substance removing material according to any one of claims 1 to 3.