JP5136076B2 - Products with allergen removal performance - Google Patents

Description

The present invention relates to an allergen removing agent and a product having allergen removing performance obtained by applying the allergen removing agent.

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 allergen removal is increasing, and development of products having allergen removal performance is being promoted.

For example, Patent Document 1 discloses an enzyme that uses an enzyme as an allergen remover. However, since the enzyme is a protein, it is easily deactivated, and the cost is high. In addition, Patent Document 2 discloses an example in which tannic acid is used as an allergen remover. However, there is a problem that the tannic acid is easily discolored by chelation with metal ions or oxidation.
JP 2003-210919A JP-A 61-44821

The present invention has been made in view of the above-described present situation, and an object thereof is to provide an allergen removing agent and a product having allergen removing performance provided with the allergen removing agent.

As a result of diligent studies to achieve the above object, the present inventor has found that a water-soluble vinyl polymer having an H-type carboxyl group has a function of removing allergens, and has reached the present invention.

That is, the present invention is achieved by the following means.
(1) A product having an allergen-removing performance obtained by applying an allergen-removing agent comprising a water-soluble vinyl polymer having an H-type carboxyl group together with an epoxy group-containing compound .
(2) The product having allergen removal performance according to (1), wherein the water-soluble vinyl polymer having an H-type carboxyl group is polyacrylic acid.
(3) The product having allergen removal performance according to (2), wherein the polyacrylic acid has a weight average molecular weight of 5000 or more.

The allergen-removing agent of the present invention can efficiently remove allergens generated from pollen, mites, etc., and does not change color. Moreover, since the allergen remover is water-soluble, it can be handled as an aqueous solution. For this reason, it can be easily applied to various products, and a product having allergen removal performance can be obtained.

The allergen removing agent of the present invention is made of a vinyl polymer, and the vinyl polymer needs to have an H-type carboxyl group. 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 vinyl polymer used in the present invention is water-soluble and has a solubility of 0.1% by weight or more with respect to water at 25 ° C. For this reason, the allergen removing agent of the present invention can be made into an aqueous solution, is easy to handle, and is suitable for processing such as application, impregnation and addition to other products.

Examples of the vinyl polymer include polyacrylic acid and polyitaconic acid, but are not limited to these. For example, other monomers capable of homopolymerizing or copolymerizing a monomer having an H-type carboxyl group can be used. Adopting a polymer obtained by copolymerizing with a polymer, a polymer obtained by introducing an H-type carboxyl group by chemical modification, or a polymer obtained by introducing an H-type carboxyl group by graft polymerization Can do.

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 containing 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.

Known hydrolysis conditions can be used for the hydrolysis conditions. For example, the nitrile polymer 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 a mineral acid such as nitric acid, sulfuric acid or hydrochloric acid. Alternatively, a means of adding an organic acid such as formic acid or acetic acid and performing a heat treatment can be used.

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.

Further, in the vinyl polymer employed in the present invention, not only the above-mentioned monomers, but also other monomers copolymerizable with these are copolymerized as long as the resulting polymer is water-soluble. Also good. 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 acid 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, Examples thereof include basic vinyl compounds such as N-vinylcarbazole and vinylpyridines; and vinyl compounds such as unsaturated aldehydes such as acrolein and methacrylolein.

The degree of polymerization of the vinyl polymer employed in the present invention may affect the allergen removal performance described below. For example, in the case of polyacrylic acid, as the degree of polymerization increases, the allergen removal performance tends to improve, and the weight average molecular weight is preferably 5000 or more, more preferably 25000 or more.

As described above, since the allergen removing agent of the present invention is water-soluble, it can be handled as an aqueous solution. For this reason, it can be easily applied to various products, and a product having allergen removal performance can be obtained.

For example, if the allergen-removing agent of the present invention is added to a water-based paint or coating agent, it can be made into a paint or coating agent having allergen-removing performance. By applying these to furniture or walls, the allergen-removing performance can be improved. Can be granted. In addition, the aqueous solution of the allergen-removing agent of the present invention can be added to paper, non-woven fabric, woven fabric, knitted fabric, sheet, foam, etc. by adding, impregnating, or adding during the production process, etc. Since the contact area is large, a product useful as an allergen removal product can be obtained.

Further, in the case where the aqueous solution of the allergen-removing agent of the present invention is applied or impregnated on the above-mentioned paper or nonwoven fabric, it is desirable to use a crosslinkable compound that can introduce a crosslinked structure into the removing agent during application or impregnation. . Although the water-soluble vinyl polymer having an H-type carboxyl group constituting the allergen remover is crosslinked with a crosslinkable compound, the allergen removal performance may be slightly suppressed, but the water resistance and weather resistance are improved. In addition, elution due to moisture of the allergen remover and deterioration over time can be suppressed.

Such a crosslinkable compound is not particularly limited as long as it reacts with a carboxyl group, but an epoxy group-containing compound and a zirconium-based compound are desirable. In particular, a zirconium-based compound is preferable because it has a small influence on the allergen removal performance described above. Specifically, the epoxy group-containing compound includes polyglycidyl ether such as Epiol G-100 (manufactured by NOF Corporation), and the zirconium-based compound includes carbonic acid such as Baycoat 20 (manufactured by Nippon Light Metal Co., Ltd.). Examples include zirconium ammonium and potassium potassium carbonate.

In the present invention, “having allergen removal performance” means that a practically effective allergen removal effect can be obtained. There are various evaluation methods and conditions for whether or not a practically effective allergen removal effect can be obtained, but in the case of the evaluation methods and conditions described later, the product can obtain a practically effective allergen removal effect. It is desirable to have an inactivation rate of 30% or more with respect to at least either mite allergen or cedar pollen allergen.

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 obtained by adding 4 cm ² of a measurement sample piece to 200 μL of a phosphate buffer containing 10 ng of purified mite antigen Der fII (manufactured by Seikagaku Corporation) and a sample to which no measurement sample is added as a control at 30 ° C. × 24 hours After processing, the amount of mite allergen was measured for these supernatants 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 (manufactured by Wako Pure Chemical Industries, Ltd., Tween 20) Washed 3 times with equivalent) solution). 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), 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). In addition, 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. The inactivation rate was determined.

<Example 1>
Polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 1000000) is used as the allergen remover, and epoxy-based epiol G-100 (manufactured by NOF Corporation) is used as the crosslinkable compound. A 1% aqueous solution of 10: 1 compound was prepared. The aqueous solution was applied to a filter paper (Qualitative filter paper No. 101, manufactured by Advantech Toyo Co., Ltd.), heated and dried at 105 ° C. to prepare an allergen-removing paper having a solid content of 3.1 g / m ² . Table 1 shows the results of evaluating the allergen removal performance of this allergen removal paper.

<Example 2>
As an allergen remover, polyitaconic acid-polymethacrylic acid copolymer (Julimer AC-70N, manufactured by Nippon Pure Chemical Co., Ltd.) was adjusted to pH 2.5 with a cation exchange resin to change the counter ion of the carboxyl group from Na to H. An epoxy-based epiol G-100 (manufactured by NOF Corporation) was used as the converted polymer and the crosslinkable compound to prepare a 1% aqueous solution of allergen remover: crosslinkable compound = 10: 1. The aqueous solution was applied to a filter paper (Qualitative filter paper No. 101, manufactured by Advantech Toyo Co., Ltd.), heated and dried at 105 ° C. to prepare an allergen-removing paper having a solid content of 3.3 g / m ² . Table 1 shows the results of evaluating the allergen removal performance of this allergen removal paper.

<Example 3 (reference example) >
Polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 250,000) is used as the allergen remover, and zirconium-based bay coat 20 (manufactured by Nippon Light Metal Co., Ltd.) is used as the crosslinkable compound. = 10: 1 1% aqueous solution was prepared. The aqueous solution was applied to a filter paper (Qualitative filter paper No. 101, manufactured by Advantech Toyo Co., Ltd.), heated at 105 ° C., and dried to prepare an allergen-removal paper having a solid content of 2.4 g / m ² . Table 1 shows the results of evaluating the allergen removal performance of this allergen removal paper.

<Comparative Example 1>
A 1% aqueous solution of epoxy-based crosslinkable compound Epiol G-100 (manufactured by NOF Corporation) is applied to filter paper (Advantech Toyo Co., Ltd., qualitative filter paper No. 101), heated at 105 ° C., dried, and solid. A paper to which only a crosslinkable compound having a partial adhesion amount of 3.1 g / m ² was applied was prepared. Table 1 shows the results of evaluating the allergen removal performance of the prepared paper.

In Examples 1 to 3, good allergen removal performance was exhibited. On the other hand, in Comparative Example 1 to which only the crosslinkable compound was added, the allergen removal performance was hardly expressed. Thus, it turns out that the allergen remover of this invention has the outstanding allergen removal performance.

<Examples 4 to 6>
Using polyacrylic acid having a molecular weight shown in Table 2 as an allergen remover (manufactured by Wako Pure Chemical Industries, Ltd.) and an epoxy-based epiol G-100 (manufactured by NOF Corporation) as a crosslinkable compound, the allergen remover: A 1% aqueous solution of a crosslinkable compound = 10: 1 was prepared. The aqueous solution was applied to filter paper (Qualitative filter paper No. 101, manufactured by Advantech Toyo Co., Ltd.), heated and dried at 105 ° C. to prepare an allergen-removal paper. Table 2 shows the results of evaluating the allergen removal performance of these allergen removal sheets.

Table 2 shows that the allergen removal performance improves as the molecular weight of polyacrylic acid increases.

Claims (3)

A product having an allergen removing performance obtained by applying an allergen removing agent made of a water-soluble vinyl polymer having an H-type carboxyl group together with an epoxy group-containing compound . The product having an allergen removing performance according to claim 1, wherein the water-soluble vinyl polymer having an H-type carboxyl group is polyacrylic acid. The product having allergen removing performance according to claim 2, wherein the polyacrylic acid has a weight average molecular weight of 5000 or more.