JP2009160563A - Allergen removing particle and product comprising the particle for removing allergen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an allergen removing particle and a product comprising the particle for removing an allergen since the need for allergen removal is raised in recent years, an allergen removing material is developed, a vinyl polymer particle having a carboxyl group and a cross-linked structure has been examined and known to exhibit functions such as high moisture absorbing/desorbing properties and pH buffering properties up to now but it is not known at all that the vinyl polymer particle has a function of removing the allergen. <P>SOLUTION: The allergen removing particle consists of a vinyl polymer which has H-type carboxyl groups by 0.5-12 mmol/g and the cross-linked structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to particles having an allergen removing function and products obtained by applying the particles.

In recent years, allergic diseases such as hay fever, atopic dermatitis, bronchial asthma have been increasing, and it is generally known that the causes of these diseases are allergens generated from pollen, mites, etc. . For this reason, the need for the removal of allergen is increasing, and development of the allergen removal material is advanced.

On the other hand, vinyl polymer particles having a carboxyl group and a cross-linked structure have been studied, and functions such as high moisture absorption / release (Patent Document 1) and pH buffering property (Patent Document 2) are developed. It is known that things can be done. However, it has not been known at all that such polymer particles have a function of removing allergens.
JP 2001-11320 A Japanese Patent Laid-Open No. 10-237126

The present invention has been made in view of the above-described situation, and an object thereof is to provide particles having an allergen removing function and an allergen removing product containing the particles.

As a result of diligent studies to achieve the above-mentioned object, the present inventor has found that a vinyl polymer having a carboxyl group and a crosslinked structure, which is known to have functions such as high moisture absorption and desorption and pH buffering property. The inventors have found that the particles have a function of removing allergens, and have reached the present invention.

That is, the present invention is achieved by the following means.
(1) Allergen-removing particles comprising a vinyl polymer having an H-type carboxyl group of 0.5 to 12 mmol / g and a crosslinked structure.
(2) The allergen removal according to (1), wherein the vinyl polymer has a crosslinked structure introduced by copolymerization using a compound having two or more vinyl groups as a copolymerization component. Particles.
(3) A vinyl polymer is a crosslinked structure obtained by copolymerizing a monomer having a nitrile group as a copolymerization component and reacting the nitrile group with a nitrogen-containing compound having 2 or more nitrogen atoms in one molecule. The allergen-removing particles according to (1), wherein the allergen-removing particles are introduced.
(4) An allergen-removing product, wherein the allergen-removing particles according to any one of (1) to (3) are fixed.

The allergen-removing particles of the present invention can efficiently remove allergens generated from pollen and mites. Moreover, since it can take forms such as a dry powder form, an aqueous dispersion emulsion form, and an organic solvent dispersion form, it can be easily applied to products in various applications and fields, and can be provided with an allergen removing function.

The allergen-removing particles of the present invention are made of a vinyl polymer, and the vinyl polymer needs to have an H-type carboxyl group and a crosslinked structure. In the present invention, the H-type carboxyl group is considered to be a factor for developing the function of removing allergen. As the type of the carboxyl group, it is important that it is H type, but a metal salt type carboxyl group may coexist. The crosslinked structure is effective for suppressing the hydrophilicity of the polymer due to the carboxyl group. If the hydrophilicity of the polymer is increased, it will swell due to water absorption or elution, and the shape cannot be maintained, which can be a major hindrance in developing applications.

The method for introducing an H-type carboxyl group into a vinyl polymer is not particularly limited. For example, a monomer having an H-type carboxyl group may be homopolymerized or copolymerized with another monomer that can be copolymerized. And a method of introducing an H-type carboxyl group by chemical modification, a method of introducing an H-type carboxyl group by graft polymerization, and the like.

Examples of a method for introducing an H-type carboxyl group by polymerizing a monomer having an H-type carboxyl group include, for example, vinyl series containing a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinylpropionic acid, and the like. A method of obtaining a copolymer by homopolymerization of monomers, copolymerization of two or more of the monomers, or copolymerization with other monomers copolymerizable with these monomers Is mentioned.

As a method of introducing an H-type carboxyl group by chemical modification, for example, after obtaining a polymer comprising a monomer having a functional group that can be obtained by chemical modification treatment, a salt form or H Examples of the method include modification to a type carboxyl group and conversion to an H type carboxyl group using an ion exchange resin or the like in the case of a salt type carboxyl group. Monomers that can take such a method include monomers having a nitrile group such as acrylonitrile and methacrylonitrile; derivatives such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and vinyl propionic acid. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, normal propyl (meth) acrylate, isopropyl (meth) acrylate, normal butyl (meth) acrylate, and normal (meth) acrylate. Octyl, ester compounds such as (meth) acrylic acid-2-ethylhexyl, hydroxylethyl (meth) acrylate, anhydrides such as maleic anhydride and itaconic anhydride, (meth) acrylamide, dimethyl (meth) acrylamide, monoethyl (meth) Acrylamide, normal-t-butyl (meta ) Amide compounds such as acrylamide can be exemplified.

In addition, a method in which an H-type carboxyl group is introduced into a polymer having an oxidizable polar group such as a double bond, a halogen group, a hydroxyl group, and an aldehyde group by an oxidation reaction can also be used. For this oxidation reaction, a commonly used oxidation reaction can be used.

As described above, an H-type carboxyl group can be introduced into the vinyl polymer. In the vinyl polymer, not only the above monomers but also other monomers copolymerizable therewith are used. It may be copolymerized. For example, vinyl halide compounds such as vinyl chloride, vinyl bromide, vinyl fluoride; vinylidene chloride monomers such as vinylidene chloride, vinylidene bromide, vinylidene fluoride; acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc. Unsaturated carboxylic acids and salts thereof; acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methoxyethyl acrylate, phenyl acrylate, cyclohexyl acrylate; methyl methacrylate, methacrylic acid Methacrylic acid esters such as ethyl, butyl methacrylate, octyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate; methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, methyl isobutenyl ketone, methyl isopropenyl Unsaturated ketones such as ketones; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl monochloroacetate, vinyl dichloroacetate, vinyl trichloroacetate, vinyl monofluoroacetate, vinyl difluoroacetate, vinyl trifluoroacetate Vinyl esters such as methyl vinyl ether and ethyl vinyl ether; acrylamide and alkyl-substituted products thereof; vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid , Sulfopropyl methacrylate, vinyl stearic acid, vinyl sulfinic acid and other vinyl group-containing acid compounds, or salts, anhydrides and derivatives thereof; styrene, methyl styrene, chlorostyrene, etc. And allyl alcohol and esters or ethers thereof; vinylimides such as N-vinylphthalimide and N-vinylsuccinimide; vinylpyridine, vinylimidazole, dimethylaminoethyl methacrylate, N-vinylpyrrolidone, N basic vinyl compounds such as vinylcarbazole and vinylpyridines; unsaturated aldehydes such as acrolein and methacryloleine; glycidyl methacrylate, N-methylolacrylamide, hydroxyethyl methacrylate, triallyl isocyanurate, triallyl cyanurate, divinylbenzene , Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Mention may be made of crosslinkable vinyl compounds such as limethylolpropane tri (meth) acrylate and methylenebisacrylamide.

The amount of the H-type carboxyl group to be introduced is 0.5 mmol / g or more, preferably 1 mmol / g or more with respect to the allergen-removing particles in order to achieve a practically effective level. On the other hand, from the viewpoint of particle swelling and shape maintenance, the H-type carboxyl group content is desirably 12 mmol / g or less, preferably 10 mmol / g or less.

The cross-linked structure employed in the present invention is not particularly limited, and may be any structure such as cross-linking by covalent bond, ionic cross-linking, interaction between polymer molecules or cross-linking by crystal structure. The amount of the crosslinked structure to be introduced may be determined in consideration of the above-described H-type carboxyl group amount and other properties necessary for the finally obtained allergen-removing particles. That is, if high allergen removal performance is required, it is desirable to reduce the cross-linked structure and introduce as many H-type carboxyl groups as possible, and to increase the cross-linked structure if shape stability is required. .

In addition, the method for introducing a crosslinked structure is not particularly limited, and crosslinking with a crosslinkable monomer in the polymerization stage of the polymer to be a skeleton, post-crosslinking after obtaining the polymer, crosslinking with physical energy It is possible to use a generally used method such as introduction of a structure. In particular, in a method using a crosslinkable monomer in the polymerization stage of a polymer to be a skeleton and a method using post-crosslinking after obtaining a polymer, it is possible to introduce strong cross-linking by a covalent bond.

For example, in the method using a crosslinkable monomer, the crosslinkable vinyl compound described above is crosslinked based on a covalent bond by copolymerizing with a monomer having a carboxyl group or a functional group that can be modified to a carboxyl group. A structure can be introduced. In addition, when a monomer having a functional group that can be modified to a carboxyl group is employed, modification to the carboxyl group is performed by hydrolysis treatment after the introduction of the crosslinked structure, so that the treatment is not impaired. It is desirable to employ a crosslinkable monomer that can introduce a crosslinked structure.

The crosslinked structure introduced by such a method includes glycidyl methacrylate, N-methylol acrylamide, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, hydroxyethyl methacrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( Examples include those derived from crosslinkable vinyl compounds such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, and methylenebisacrylamide. Among them, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, methylenebis The cross-linked structure with acrylamide is desirable because it is chemically stable during hydrolysis for introducing a carboxyl group.

Specific examples include divinylbenzene as a crosslinkable monomer and acrylonitrile as a monomer having a functional group that can be modified to a carboxyl group. The copolymer composition may be appropriately set in consideration of the allergen removal performance required for the finally obtained allergen-removing particles, that is, the amount of H-type carboxyl groups and the form stability described above. For example, divinyl Examples include using 10% by weight or more of benzene and 50% by weight or more of acrylonitrile.

Further, the method by post-crosslinking is not particularly limited, and examples thereof include a post-crosslinking method in which a nitrile group contained in a nitrile polymer obtained by copolymerizing a vinyl monomer having a nitrile group and a hydrazine compound or formaldehyde are reacted. be able to. Among them, the method using a hydrazine compound is stable to acids and alkalis and can be preferably used. In addition, although the detail is not identified regarding the crosslinked structure obtained by this method, it is estimated that it is based on a triazole ring structure or a tetrazole ring structure.

The vinyl monomer having a nitrile group here is not particularly limited as long as it has a nitrile group, and specifically, acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, cyanide. And vinylidene chloride. Among them, acrylonitrile is most preferable because it is advantageous in terms of cost and has a large amount of nitrile groups per unit weight.

Specific examples of the post-crosslinking method include an example in which a crosslinked structure is introduced by a reaction between an acrylonitrile polymer and a hydrazine compound. In such an example, regarding the copolymer composition of the acrylonitrile-based polymer, the allergen removal performance required for the finally obtained allergen-removing particles, that is, the amount of H-type carboxyl groups and the form stability described above are considered. However, it is desirable to use 50% by weight or more of acrylonitrile. Regarding the reaction conditions with the hydrazine compound related to the introduction amount of the crosslinked structure, the acrylonitrile polymer is treated in an aqueous solution having a hydrazine compound concentration of 5 to 60% by weight at 50 to 150 ° C. within 5 hours. Conditions can be mentioned.

The hydrazine compounds used herein include hydrazine salts such as hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine nitrate, hydrazine bromate, hydrazine carbonate, and ethylenediamine, guanidine sulfate, guanidine hydrochloride, guanidine nitrate, phosphorus Examples include hydrazine derivatives such as acid guanidine and melamine.

Next, known hydrolysis conditions can be used for the method of introducing an H-type carboxyl group by a hydrolysis reaction. For example, a nitrile polymer having a cross-linked structure obtained as described above may be added to an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or sodium carbonate, a basic aqueous solution such as ammonia, or nitric acid, sulfuric acid or hydrochloric acid. And a means for heat treatment by adding a mineral acid such as formic acid or organic acid such as formic acid or acetic acid. In addition, a hydrolysis reaction can also be performed simultaneously with the introduction of the crosslinking.

The form of the allergen-removing particles of the present invention can be arbitrarily selected depending on the use, such as a dry powder form, a water-dispersed emulsion form, or an organic solvent-dispersed form. When the particle size is 5 μm or less, an emulsion in water is advantageous from the viewpoint of handling and stability.

The polymerization method employed in the present invention is not particularly limited, and examples thereof include suspension polymerization and emulsion polymerization. In the case of a nitrile polymer using acrylonitrile as described above, emulsion polymerization may be difficult because the cohesive strength of the polymer itself is strong, but it is preferable to perform emulsion polymerization under a high temperature and high pressure at a polymerization temperature of 100 ° C. or higher. An emulsion can be obtained.

In addition, the allergen-removing particles of the present invention can be used in a wider range by incorporating them into various products. For example, when it is contained in paper, non-woven fabric, woven fabric, knitted fabric, sheet, foam, etc., it has a large contact area with gas and has excellent shape retention, so that it is useful as a product for removing allergens. It is done.

There is no restriction | limiting in particular as a method of containing the particle | grains for allergen removal of this invention, A various method is employable. For example, a method of mixing the particles with paper, non-woven fabric, woven fabric, knitted fabric, sheet, foam or the like in the manufacturing process or a method of applying the binder together with a binder can be mentioned. Is also possible.

The binder that can be used as the binder is not particularly limited, and examples thereof include acrylic resin-based, epoxy resin-based, polymethacrylate resin-based, and polyvinyl alcohol-based binders.

Examples are shown below for facilitating the understanding of the present invention. However, these are merely examples, and the gist of the present invention is not limited thereto. In the examples, parts and percentages are based on weight unless otherwise specified.

<Evaluation of allergen removal performance (1): mite allergen inactivation rate>
A sample to which a measurement sample was added in 200 μL of a phosphate buffer solution containing 10 ng of purified mite antigen Der fII (manufactured by Seikagaku Corporation) and a sample to which no measurement sample was added as a control were treated at 30 ° C. for 24 hours. The amount of mite allergen in the supernatant was measured by enzyme immunoassay (ELISA).

Specifically, first, monoclonal antibody 15E11 (manufactured by Seikagaku Corporation) as a primary antibody was dispensed into each well of a microplate by 50 μL and allowed to stand at room temperature for 3 hours, and then the plate was washed with PBS-T. (PBS (phosphate buffered saline, 0.01 mol / l, pH 7.2 to 7.4) 0.05% polyoxyethylene (20) sorbitan monolaurate (Wako Pure Chemical Industries, Ltd., equivalent to Tween 20) Product) solution) three times. Subsequently, 300 μL of PBS-T containing 1% BSA (manufactured by Nacalai Tesque, Inc., bovine serum albumin (F-V), pH 5.2) was dispensed into each well and allowed to stand at 4 ° C. for 12 hours. And then washed 3 times with PBS-T. Next, 50 μL of the above supernatant was dispensed into each well, allowed to stand at room temperature for 2 hours, and then washed three times with PBS-T. Subsequently, a secondary antibody peroxidase-labeled monoclonal antibody 13A4 (manufactured by Seikagaku Corporation) was dispensed at 50 μL per well, allowed to stand at room temperature for 2 hours, and then washed 4 times with PBS-T. Next, 100 μL of TMB reagent (manufactured by Funakoshi Co., Ltd.) was dispensed into each well and allowed to react for 5 minutes. Then, 100 μL of 1 M hydrochloric acid was dispensed into each well, the reaction was stopped, and the absorbance (measurement wavelength: 490 nm) was measured with a microplate reader (Bio-Rad Laboratories Inc.). The mite allergen concentration in the supernatant was determined from the obtained measured value using a calibration curve, and the inactivation rate was calculated by the following formula.

Inactivation rate (%) = {1- (A / B)} × 100
(A = allergen concentration when sample is added, B = control allergen concentration)

<Evaluation of allergen removal performance (2): Sugi pollen allergen inactivation rate>
In the evaluation of allergen removal performance (1) above, 20 ng of purified cedar pollen antigen Cry J1 (manufactured by Seikagaku Corporation) was used instead of 10 ng of purified mite antigen Der fII (manufactured by Seikagaku Corporation), and Measurement was carried out in the same manner except that monoclonal antibody 013 (manufactured by Seikagaku Corporation) was used as the primary antibody and peroxidase-labeled monoclonal antibody 053 (manufactured by Seikagaku Corporation) was used as the secondary antibody. Asked. In order to obtain a practically effective allergen removal effect, it is desirable to have an inactivation rate of 30% or more for at least either the mite allergen or the cedar pollen allergen in the evaluation of the allergen removal performance.

<Measurement of H-type carboxyl group content>
Add allergen-removing particles (D [g]) in solid form (C [%]) to 100 ml of pure water and stir with a stirrer using a 0.1 mol / l sodium hydroxide aqueous solution according to a conventional method. Asked. The amount of sodium hydroxide aqueous solution consumed (E [ml]) consumed by the H-type carboxyl group was determined from the titration curve, and the carboxyl group amount was calculated by the following formula.

H-type carboxyl group amount [mmol / g] = 0.1 × E / (D × C × 0.01)

<Examples 1-3>
30 parts of a monomer mixture consisting of 58% acrylonitrile, 9% methyl acrylate, 30% divinylbenzene, and 3% sodium p-styrenesulfonate are added to 70 parts of an aqueous solution containing 1.2% ammonium persulfate in monomer ratio. The polymer was charged in a polymerization tank equipped with a stirrer and polymerized at 135 ° C. for 25 minutes. 10 parts of 40% sodium hydroxide aqueous solution was added to 90 parts of the resulting polymer emulsion, and hydrolysis was carried out at 95 ° C. By adjusting the reaction time at this time as shown in Table 1, the amount of carboxyl groups of the allergen-removing particles was adjusted. The obtained emulsion was adjusted to pH 2.5 with a cation exchange resin to change the carboxyl group to H type to obtain emulsion-like allergen-removing particles. Table 1 shows the results of evaluating the allergen removal performance using 10 mg of allergen-removing particles obtained by drying this emulsion with a dryer at 120 ° C. for 3 hours.

<Comparative Example 1>
30 parts of a monomer mixture consisting of 58% acrylonitrile, 9% methyl acrylate, 30% divinylbenzene, and 3% sodium p-styrenesulfonate are added to 70 parts of an aqueous solution containing 1.2% ammonium persulfate in monomer ratio. The polymer was charged in a polymerization tank equipped with a stirrer and polymerized at 135 ° C. for 25 minutes. Table 1 shows the results of evaluating the allergen removal performance using 10 mg of particles obtained by drying the obtained polymer emulsion for 3 hours with a dryer at 120 ° C.

<Comparative example 2>
30 parts of a monomer mixture consisting of 58% acrylonitrile, 9% methyl acrylate, 30% divinylbenzene, and 3% sodium p-styrenesulfonate are added to 70 parts of an aqueous solution containing 1.2% ammonium persulfate in monomer ratio. The polymer was charged in a polymerization tank equipped with a stirrer and polymerized at 135 ° C. for 25 minutes. 10 parts of 40% aqueous sodium hydroxide solution was added to 90 parts of the resulting polymer emulsion, and hydrolysis was carried out at 95 ° C. for 8 hours. The obtained emulsion was adjusted to pH 9 with a cation exchange resin to remove residual sodium hydroxide, and emulsion-like particles in which most of the carboxyl groups were Na-type were obtained. Table 1 shows the results of evaluating mite allergen removal performance using 10 mg of particles obtained by drying this emulsion with a dryer at 120 ° C. for 3 hours.

In Examples 1 to 3, good mite allergen removal performance was exhibited. Comparative Example 1 did not have a carboxyl group and had a low mite allergen inactivation rate. Further, in Comparative Example 2, the H-type carboxyl group was present but in a small amount, and most of it was a Na-type carboxyl group, so that the mite allergen inactivation rate was low. Moreover, about Example 3 and Comparative Example 2, the cedar pollen allergen removal performance was also evaluated. The inactivation rate was 95% in Example 3 and less than 20% in Comparative Example 2, and the same tendency as in the case of mite allergen was observed.

<Example 4>
The amount of allergen removing particles obtained by mixing 90 parts of emulsion allergen-removing particles (solid content 10%) obtained in Example 3 with 10 parts of Epiol G-100 (manufactured by NOF Corporation) as a binder is 16 g / m ^2. It was applied to a filter paper (Qualitative filter paper No. 101, manufactured by Advantech Toyo Co., Ltd.) to prepare an allergen-removed paper. Table 2 shows the results of evaluating the mite allergen removing performance by cutting the allergen removing paper into 4 cm ² .

<Example 5>
The amount of allergen-removing particles is 14 g / m ² obtained by mixing 90 parts of emulsion-like allergen-removing particles (solid content 10%) obtained in Example 3 with 10 parts of Carbodilite V-02 (Nisshinbo) as a binder. It was applied to a filter paper (Qualitative filter paper No. 101, manufactured by Advantech Toyo Co., Ltd.) to prepare an allergen-removed paper. Table 2 shows the results of evaluating the mite allergen removing performance by cutting the allergen removing paper into 4 cm ² .

In Examples 4 and 5, good allergen removal performance was exhibited. Thus, the allergen removing particles of the present invention can exhibit allergen removing performance even when mixed with a binder.

Claims (4)

Allergen-removing particles comprising a vinyl polymer having 0.5 to 12 mmol / g of an H-type carboxyl group and a crosslinked structure. 2. The allergen-removing particle according to claim 1, wherein the vinyl polymer has a cross-linked structure introduced by copolymerization using a compound having two or more vinyl groups as a copolymer component. A vinyl polymer is introduced with a crosslinked structure by copolymerizing a monomer having a nitrile group as a copolymerization component and reacting the nitrile group with a nitrogen-containing compound having 2 or more nitrogen atoms in one molecule. The allergen-removing particles according to claim 1, wherein A product having allergen removal performance, wherein the allergen removal particles according to claim 1 are fixed with a resin.