Allergen reducing agent, allergen reducing aqueous solution, allergen reducing coating material, and method for producing allergen reduced substrate
Patent Information
- Application Number
- JP2024098088
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-09-04
- Filing Date
- 2024-06-18
- Publication Date
- 2025-03-14
AI Technical Summary
【0017】 本発明のアレルゲン低減化剤は、25℃の水に対する溶解度が300g/L以上であり且つカルボキシ基を有する重合体を含むので、優れたアレルゲン低減化効果を奏する。
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Abstract
Description
[Technical field]
[0001] The present invention relates to an allergen-reducing agent, an allergen-reduced aqueous solution, an allergen-reduced paint, and a method for producing an allergen-reduced substrate. [Background technology]
[0002] In recent years, many allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis have become a problem. The main causes of these allergic diseases are mites that live in homes, especially allergens from Dermatophagoides pteronyssinus (Der1, Der2) that are abundant in indoor dust, and cedar pollen allergens (Cry j1, Cry j2) that are airborne in large quantities mainly in spring.
[0003] Therefore, there is a need for technologies to either remove allergens from living spaces or to inactivate them by denaturing them.
[0004] Patent Document 1 discloses a cellulosic fiber having an allergen treating ability, characterized in that it carries an allergen treating agent containing, as an active ingredient, a nitrogen-containing compound having a specific chemical structural formula or a solvate thereof.
[0005] Patent Document 2 discloses particles for removing allergens, which are made of a vinyl polymer having 0.5 to 12 mmol / g H-type carboxyl groups and a crosslinked structure. [Prior art documents] [Patent documents]
[0006] [Patent Document 1] JP 2007-31889 A [Patent Document 2] JP 2009-160563 A Summary of the Invention [Problem to be solved by the invention]
[0007] However, the allergen treatment ability (allergen reduction effect) of the allergen treatment agent disclosed in Patent Document 1 is insufficient, and an allergen reduction agent that exerts an excellent allergen reduction effect has been desired.
[0008] Furthermore, the allergen removal particles disclosed in Patent Document 2 also react with the antibodies present in the antibody-coated plates used in the ELISA method for measuring the amount of allergens, which poses the problem that even if active allergens are present, the allergens will not be detected by the ELISA method, and there is a risk that the allergen reduction effect will be overestimated.
[0009] The present invention provides an allergen-reducing agent, an allergen-reducing aqueous solution, an allergen-reducing paint, and a method for producing an allergen-reduced substrate, which have an excellent allergen-reducing effect and suppressed action on antibodies in antibody-coated plates used in ELISA. [Means for solving the problem]
[0010] The allergen reducing agent of the present invention is characterized in that it contains a polymer having a solubility in water at 25° C. of 300 g / L or more and having a carboxy group.
[0011] The allergen-reducing aqueous solution of the present invention contains water and the allergen-reducing agent, and is characterized in that the entire amount of the polymer contained in the allergen-reducing agent is dissolved in water.
[0012] The method for producing an allergen-reduced substrate of the present invention is characterized by comprising a step of supplying the above-mentioned allergen-reduced aqueous solution to the surface of a substrate.
[0013] The allergen-reducing paint of the present invention is characterized by comprising the above-mentioned allergen-reducing agent and a binder resin.
[0014] The allergen-reduced water-based paint of the present invention contains water, the allergen-reducing agent, and a binder resin, and is characterized in that the entire amount of the polymer contained in the allergen-reducing agent is dissolved in water.
[0015] The allergen-reduced solvent-based paint of the present invention comprises a solvent, the above-mentioned allergen-reducing agent, and a binder resin, and is characterized in that the above-mentioned allergen-reducing agent contains an organic acid.
[0016] The method for producing an allergen-reduced substrate of the present invention is characterized by comprising a step of supplying the above-mentioned allergen-reduced paint to the surface of a substrate. Effect of the Invention
[0017] The allergen reducing agent of the present invention has a solubility in water at 25° C. of 300 g / L or more and contains a polymer having a carboxy group, and therefore exerts an excellent allergen reducing effect.
[0018] Furthermore, the allergen reducing agent of the present invention does not react easily with the antibodies in the antibody-coated plate used in the ELISA method, and hardly inhibits the reaction between the antibodies formed on the antibody-coated plate and the allergen. Therefore, the amount of allergen can be accurately measured by the ELISA method (hereinafter, this may be expressed as "having little effect on the antibody"). Therefore, the user can take appropriate measures based on the accurate amount of allergen. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] The allergen reducing agent of the present invention contains, as an active ingredient, a polymer (A) (hereinafter, sometimes simply referred to as "polymer (A)") having a solubility of 300 g / L or more in water at 25° C. and having a carboxy group. The polymer having a solubility of 300 g / L or more in water at 25° C. and having a carboxy group may be used alone or in combination of two or more kinds.
[0020] The content of polymer (A) in the allergen reducing agent is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and more preferably 100% by mass.
[0021] Since the polymer (A) has a solubility in water at 25° C. of 300 g / L or more and has a carboxy group (—COOH), it exerts an excellent allergen reducing effect and has little effect on antibodies.
[0022] Here, the allergen reducing agent refers to one that has an allergen reducing effect. The allergen reducing effect can be determined by measuring the allergen reducing rate of cedar pollen allergen (Cryj1) or mite allergen (Derf1) as described below, and if the allergen reducing rate is 60% or more for at least either allergen, it can be determined that the allergen reducing effect is present.
[0023] The cedar pollen allergen (Cryj1) may be, for example, a product commercially available from ITEA under the product name "Cedar Pollen Extract, Code 4-CJ-001." The mite allergen (Derf1) may be, for example, a product commercially available from ITEA under the product name "Mite Allergen Extract, Code 4-DF-001."
[0024] The freeze-dried powder of the allergen is dissolved in purified water to prepare an allergen aqueous solution containing 10 μg / mL of the allergen. Then, PBS-T (phosphate buffer containing 0.05% by weight of Tween 20 (Tokyo Chemical Industry Co., Ltd.), pH 7.4) is added to the allergen aqueous solution and mixed uniformly to prepare an allergen solution containing 15 ng / mL of the allergen.
[0025] 0.4 g of the allergen denaturing agent is placed in a zippered plastic bag, 1 mL of the above allergen solution is dropped into it, the bag is sealed and left to stand at 25°C for 2 hours to prepare a test solution.
[0026] Next, the amount of allergen present in the test liquid W 1 (ng / mL) is measured using an ELISA measurement kit.
[0027] The cedar pollen allergen measurement kit may be, for example, a commercially available measurement kit under the product name "Cedar Pollen Allergen (Cryj1) ELISA Kit, Code 1-CJ1-001" from ITEA, Inc. The mite allergen measurement kit may be, for example, a commercially available measurement kit under the product name "Mite Allergen (Derf1) ELISA Kit, Code 1-DF1-001" from ITEA, Inc.
[0028] The amount of allergen present in the test liquid W was measured in the same manner as above, except that no allergen denaturing agent was placed in the zippered plastic bag. 0 (ng / mL) was measured. The allergen reduction rate (%) was calculated based on the following formula. Allergen reduction rate (%) = 100-(W 1 / W 0 ) x 100
[0029] The allergen reduction rate of the allergen reducing agent is preferably 70% or more, more preferably 80% or more, more preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more.
[0030] The allergen reducing agent contains a polymer (A) as an active ingredient. The polymer (A) has a carboxy group (-COOH) in the molecule. The polymer (A) exerts an allergen reducing effect due to the molecular structure of the carboxy group, and the allergen reducing effect is further improved by making the solubility in water at 25°C 300g / L or more.
[0031] The pKa1 of the polymer (A) is preferably 5.5 or less, more preferably 5.0 or less, and even more preferably 4.7 or less. When the pKa1 of the polymer (A) is 5.5 or less, the allergen reducing effect of the allergen reducing agent is improved. When the polymer (A) is a polyvalent acid, the polymer (A) undergoes multi-stage ionization, and the pKa1 refers to the pKa calculated based on the ionization constant of the first stage. Here, when the electrolyte HA is H + and A - When an acid dissociates into and reaches ionization equilibrium (1), the acid dissociation constant Ka is defined by equation (2), and pKa is defined as the common logarithm (3) of the reciprocal of the acid dissociation constant Ka.
[0032]
number
[0033] The pKa1 of the polymer (A) is a value measured by titration. Specifically, the pKa1 can be determined by titrating the polymer (A) with sodium hydroxide at 25°C and measuring the pH at 25°C at the half-equivalent point (the point at which half the amount required for complete neutralization is dropped).
[0034] The weight average molecular weight of the polymer (A) is preferably 1000 or more, more preferably 3000 or more. The weight average molecular weight of the polymer (A) is preferably 1,000,000 or less, more preferably 900,000 or less, more preferably 800,000 or less, more preferably 500,000 or less, more preferably 400,000 or less, more preferably 200,000 or less, more preferably 100,000 or less, more preferably 80,000 or less, more preferably 50,000 or less, more preferably 12,000 or less, more preferably 8,000 or less. When the weight average molecular weight of the polymer (A) is 1000 or more, the allergen reducing effect of the allergen reducing agent is improved. When the weight average molecular weight of the polymer (A) is 1,000,000 or less, the allergen reducing agent has less effect on the antibody.
[0035] In the present invention, the weight average molecular weight of the polymer is a value calculated in terms of polystyrene measured by GPC (gel permeation chromatography).
[0036] For example, the measurement can be performed using the following measurement device and under the following measurement conditions. Gel permeation chromatograph: Waters product name "2690 Separations Model" Column: Resonac product name "GPC KF-806L" Detector: Differential refractometer Sample flow rate: 1mL / min Column temperature: 40℃ Eluent: THF
[0037] The pH of a 0.5% by mass aqueous solution of the polymer (A) is preferably 2 or more, more preferably 3 or more. The pH of a 0.5% by mass aqueous solution of the polymer (A) is preferably 12 or less, more preferably 11 or less, more preferably 10 or less, more preferably 9 or less, more preferably 6 or less, more preferably 5 or less, and more preferably 4.5 or less. When the pH of a 0.5% by mass aqueous solution of the polymer (A) is 2 or more, the allergen reducing agent has less influence on the antibody. When the pH of a 0.5% by mass aqueous solution of the polymer (A) is 12 or less, the allergen reducing effect of the allergen reducing agent is improved. The pH of a 0.5% by mass aqueous solution of the polymer (A) refers to the pH value at 25°C of an aqueous solution obtained by adding 0.5 g of the polymer (A) to 99.5 g of purified water and uniformly mixing the solution.
[0038] The polymer (A) having a carboxy group in the molecule may have a solubility of 300 g / L or more in water at 25° C. and one or more carboxy groups in the molecule. An example of the polymer (A) is a polymer having a carboxy group in the side chain of a linear polymer.
[0039] In the polymer having a carboxy group in the side chain of a linear polymer, the linear polymer is not particularly limited, and for example, vinyl polymers, polyesters, and polyurethanes are preferred, and vinyl polymers are more preferred.
[0040] Examples of the polymer having a carboxy group in the side chain of the linear polymer include a polymer containing a carboxy group-containing monomer as a monomer unit. The polymer containing a carboxy group-containing monomer as a monomer unit may be a homopolymer of the carboxy group-containing monomer, or a copolymer of the carboxy group-containing monomer and a monomer copolymerizable therewith.
[0041] The carboxyl group-containing monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, succinic acid mono (meth)acryloyloxyethyl ester, ω-carboxypolycaprolactone mono (meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, carboxybetaine type monomer, etc., and acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred. The carboxyl group-containing monomer may be used alone or in combination of two or more.
[0042] The monomer copolymerizable with the carboxyl group-containing monomer is not particularly limited, and examples thereof include alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, 2-vinylnaphthalene, styrene, acrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, vinyl toluene, vinyl pyridine, etc. The monomer copolymerizable with the carboxyl group-containing monomer may be used alone or in combination of two or more kinds.
[0043] The polymer (A) may be polymerized using a general-purpose polymerization method. For example, the polymer (A) may be obtained by polymerizing a monomer composition containing a carboxyl group-containing monomer in the presence of a general-purpose radical polymerization initiator. Examples of the radical polymerization initiator include thermal cleavage radical polymerization initiators such as 1-hydroxycyclohexane-1-yl phenyl ketone, t-hexyl peroxypivalate, benzoyl peroxide, and azobisisobutyronitrile.
[0044] It is preferable that the polymer (A) does not contain an aromatic ring in the molecule. If the polymer (A) does not contain an aromatic ring, the allergen reducing agent tends to have less effect on the antibody. Furthermore, if the polymer (A) does not contain an aromatic ring, the bulkiness of the polymer (A) is reduced, so that the molecular structure portion containing a carboxy group can efficiently interact with the allergen, thereby exerting an excellent allergen reducing effect.
[0045] The aromatic ring may be a monocyclic aromatic ring, or may be a condensed monocyclic aromatic ring (condensed aromatic ring). The aromatic ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl, and a phenoxyphenyl. The aromatic ring is a ring in which one or more hydrogen atoms are removed from the aromatic ring and the condensed aromatic ring, and is bonded to other atoms by a covalent bond.
[0046] The polymer (A) has a sulfo group (-SO 3It is preferable that the polymer (A) does not contain a sulfo group or a salt of a sulfo group, and more preferably does not contain a sulfo group or a salt of a sulfo group in the molecule. If the polymer (A) does not contain a sulfo group or a salt of a sulfo group in the molecule, preferably does not contain a sulfo group or a salt of a sulfo group in the molecule, the allergen reducing agent is likely to have less effect on the antibody. Furthermore, if the polymer (A) does not contain a sulfo group or a salt of a sulfo group in the molecule, preferably does not contain a sulfo group or a salt of a sulfo group in the molecule, the number of oxygen atoms with high electronegativity in the molecule is reduced, so that the coagulation tendency of the polymer (A) is reduced, and the molecular structure portion containing a carboxy group can efficiently interact with the allergen, thereby exerting an excellent allergen reducing effect.
[0047] The salt of the sulfo group is not particularly limited, and examples thereof include sodium salt (-SO 3 Na), calcium salt [(-SO 3 - ) 2 Ca 2+ ], ammonium salts (-SO 3 - NH 4 + ), magnesium salt [(-SO 3 - ) 2 Mg 2+ ], barium salts [(-SO 3 - ) 2 Ba 2+ ] etc.
[0048] The content of carboxy groups in the polymer (A) is preferably 13 mmol / g or more, more preferably 13.1 mmol / g or more, more preferably 13.2 mmol / g or more, and more preferably 13.5 mmol / g or more. The content of carboxy groups in the polymer (A) is preferably 20 mmol / g or less, more preferably 18 mmol / g or less, more preferably 17 mmol / g or less, and more preferably 16 mmol / g or less. When the total content of carboxy groups in the polymer (A) is 13 mmol / g or more, the allergen reducing effect of the allergen reducing agent is improved. When the content of carboxy groups in the polymer (A) is 20 mmol / g or less, the coagulation property of the polymer (A) is reduced, and as a result, the polymer (A) and the allergen are easily interacted with each other, and the allergen reducing effect of the allergen reducing agent is improved.
[0049] The content of carboxyl groups in the polymer (A) is a value measured by titration. Specifically, about 1 g (Xg) of the dried polymer (A) is precisely weighed, 200 mL of purified water is added to the polymer (A), and then titration is performed at 25°C using a 0.1 mol / L aqueous sodium hydroxide solution to determine the amount of aqueous sodium hydroxide solution consumed (YmL) up to the half-equivalent point (the point at which half the amount required for complete neutralization is dropped), and the content of carboxyl groups in the polymer (A) (mmol / g) is calculated by the following formula. Carboxylic acid content (mmol / g) = 0.1 × X / Y
[0050] The gel fraction of polymer (A) in ethanol is preferably 5% by mass or less, more preferably 4% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.1% by mass or less. When the gel fraction of polymer (A) in ethanol is 5% by mass or less, the adsorption of the antibody to the antibody-coated plate used in the ELISA method decreases, the effect of the allergen reducing agent on the antibody can be reduced, and the coatability of the allergen reducing agent is improved, improving the appearance of the allergen-reduced substrate.
[0051] The gel fraction of polymer (A) in ethanol is a value measured as follows: 10 g of polymer (A) is weighed out, immersed in 190 g of absolute ethanol at 25° C. for 7 days, the insoluble matter is filtered through a 200-mesh wire screen, the residue on the screen is vacuum-dried, the weight of the dried residue is measured (Xg), and the gel fraction is calculated according to the following formula. Gel fraction of polymer (A) in ethanol (mass%)=(X / 10)×100
[0052] The polymer (A) is preferably not crosslinked (non-crosslinked). If the polymer (A) is crosslinked, the polymer (A) is likely to be adsorbed at multiple points to the antibody of the antibody-coated plate used in the ELISA method, and there is a risk that the polymer (A) may have a large effect on the antibody of the antibody-coated plate used in the ELISA method.
[0053] The solubility of the polymer (A) in water at 25°C is 300 g / L or more, preferably 500 g / L or more, and more preferably 800 g / L or more. The solubility of the polymer (A) in water at 25°C is preferably 990 g / L or less, more preferably 950 g / L or less, and more preferably 900 g / L or less. Since the solubility of the polymer (A) in water at 25°C is 300 g / L or more, the polymer (A) is less likely to be adsorbed at multiple points to the antibody of the antibody-coated plate, and the allergen reducing agent has less effect on the antibody. In particular, since the polymer (A) has a carboxy group in the molecule, and coupled with the solubility being equal to or higher than a predetermined level, it is possible to achieve both an excellent allergen reducing effect and a low effect on the antibody.
[0054] The solubility of polymer (A) in water at 25°C refers to the mass of polymer (A) dissolved in 1 L of water. In other words, the solubility of polymer (A) in water at 25°C refers to the mass of polymer (A) in a saturated aqueous solution (25°C) containing 1 L of water. The solubility of polymer (A) in water at 25°C refers to a value measured at 25°C in accordance with OECD Chemicals Testing Guideline No. 105 (Water Solubility).
[0055] [Organic acid] The allergen reducing agent may contain an organic acid. When the allergen reducing agent contains an organic acid, the allergen reducing effect of the allergen reducing agent is improved by the synergistic effect of the polymer (A) and the organic acid. The organic acid does not include an oligomer or a polymer.
[0056] Organic acids contain a carboxyl group (-COOH) and a sulfo group (-SO 3 H), phosphonic acid group [-P(=O)(OH) 2 ] or a phosphate group [-OPO(OH) 2 It is preferable that the compound has a carboxy group. It may have only one of these functional groups or may have a plurality of functional groups.
[0057] Organic acids contain a carboxyl group (-COOH) and a sulfo group (-SO 3 H), phosphonic acid group [-P(=O)(OH) 2 ] and the phosphate group [-OPO(OH) 2 It is preferable that the organic acid has a plurality of functional groups selected from the group consisting of, and more preferably a plurality of carboxy groups. When the organic acid has a plurality of the above-mentioned functional groups, the allergen-reducing effect of the allergen-reducing agent is improved.
[0058] Organic acids contain a carboxyl group (-COOH) and a sulfo group (-SO 3 H), phosphonic acid group [-P(=O)(OH) 2 ] or a phosphate group [-OPO(OH) 2and examples thereof include citric acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, gluconic acid, formic acid, acetic acid, lactic acid, propionic acid, butyric acid, valeric acid, glycolic acid, malic acid, tartaric acid, salicylic acid, methylenedisalicylic acid, cis-Δ4-tetrahydrophthalic acid, benzoic acid, 4-aminobenzoic acid, benzilic acid, gallic acid, iminodiacetic acid, triglycolaminic acid, 1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetramethylenephosphonic acid, Examples of the organic acid include phenylphosphonic acid, propylene diphosphonic acid, hexylphosphonic acid, phytic acid, 2-aminoethyl dihydrogen phosphate, diethyl phosphate, dibutyl phosphate, monobutyl phosphate, sulfamic acid, formamidinesulfinic acid, 4-aminobenzenesulfonic acid, hydroxybenzenesulfonic acid, m-xylene-4-sulfonic acid, 5-sulfosalicylic acid, 2-amino-3,5-dimethylbenzenesulfonic acid, 1,3-phenylenediamine-4-sulfonic acid, 2-aminoethanesulfonic acid, p-phenolsulfonic acid, 1-aminonaphthalene-5-sulfonic acid, naphthalene-2-sulfonic acid, aminomethanesulfonic acid, and p-toluenesulfonic acid. The organic acid may be used alone or in combination of two or more kinds.
[0059] The molecular weight of the organic acid is preferably less than 1000, more preferably less than 500, more preferably less than 450, more preferably less than 400, and more preferably less than 200. When the molecular weight of the organic acid is less than 1000, the bulkiness of the organic acid molecule is reduced, and therefore the carboxy group (-COOH) and sulfo group (-SO 3 H), phosphonic acid group [-P(=O)(OH) 2 ] or a phosphate group [-OP(=O)(OH) 2 The molecular structure portion containing this can efficiently interact with allergens, thereby exerting an excellent allergen reduction effect.
[0060] The organic acid preferably has a pKa1 of 4.6 or less, more preferably 3.8 or less, at 25° C. When the organic acid has a pKa1 of 4.6 or less at 25° C., the synergistic action of the polymer (A) and the organic acid causes protein denaturation of the allergen, improving the allergen-reducing effect of the allergen reducing agent.
[0061] The pKa1 of an organic acid at 25°C is a value measured by titration. Specifically, pKa1 can be calculated by titrating an organic acid with sodium hydroxide at 25°C and measuring the pH at 25°C at the half-equivalent point (the point at which half the amount required for complete neutralization is dropped).
[0062] In the allergen reducing agent, the content of the organic acid is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, relative to 100 parts by mass of the polymer (A). In the allergen reducing agent, the content of the organic acid is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 28 parts by mass or less, and more preferably 26 parts by mass or less, relative to 100 parts by mass of the polymer (A). When the content of the organic acid is 1 part by mass or more, the allergen reducing effect of the allergen reducing agent is improved due to the synergistic action of the polymer (A) and the organic acid. When the content of the organic acid is 50 parts by mass or less, the allergen reducing agent has less effect on the antibody.
[0063] [Allergen reduction agent] The allergen reducing agent contains polymer (A) as an active ingredient, and the method for producing the allergen reducing agent is not particularly limited. The allergen reducing agent can be produced by mixing polymer (A) with compounds such as organic acids, which are added as necessary, in a conventional manner.
[0064] Next, the usage of the allergen reducing agent will be described. The allergen reducing agent exerts an allergen reducing effect on various allergens by the action of the polymer (A). Since the allergen reducing agent has little effect on antibodies, the amount of allergens after treatment with the allergen reducing agent can be accurately measured using the ELISA method, and the allergen can be appropriately reduced using the allergen reducing agent.
[0065] Allergens targeted by allergen reduction agents include animal allergens such as dust mite allergens (Der1, Der2) and allergens caused by dogs and cats (Can f1, Fel d1), airborne cedar pollen allergens (Cryj1, Cryj2), and plant allergens such as pollen. Particularly effective animal allergens include allergens from mites (mites, organisms of the Arthropoda Arachnida order, divided into seven main suborders: dorsal stigmata represented by Long-legged mites, tetrastigmata represented by Hard mites, posterior stigmata represented by Ixodes yamatans and Oriental spp., middle stigmata represented by house mites and sparrow mites, anterior stigmata represented by Lucanidae and Tarsus punctatus, house dust mites such as Dermatophagoides farinae, astigmatism represented by Tyrophagus putrescentiae, and cryptostigmata represented by Ophiopogon and Acanthurus nigricans). However, it is particularly effective against house dust mites, which are abundant in indoor dust, especially in bedding and cause allergic diseases.
[0066] The allergen reducing agent is, for example, contained in a substrate to which an allergen reducing effect is to be imparted, forming an allergen-reduced substrate. The substrate containing the allergen reducing agent exerts an allergen reducing effect as an allergen-reduced substrate. The form in which the allergen reducing agent is contained in the substrate is not particularly limited, and examples thereof include a form in which the allergen reducing agent is attached to the substrate surface, and a form in which the allergen reducing agent is kneaded into the substrate.
[0067] [Allergen-reduced aqueous solution] The allergen-reducing agent is preferably completely dissolved in water (preferably ion-exchanged water) in a known manner to prepare an allergen-reducing aqueous solution, and this allergen-reducing aqueous solution is supplied to a substrate by coating or the like, thereby attaching the allergen-reducing agent to the substrate surface, thereby producing an allergen-reduced substrate. The allergen-reducing aqueous solution may contain additives such as water-soluble solvents and dispersants, if necessary.
[0068] In the allergen-reducing aqueous solution, it is preferable that the entire amount of the polymer (A) contained in the allergen-reducing agent is dissolved in water. If the entire amount of the polymer (A) contained in the allergen-reducing agent is dissolved in water and the polymer (A) is not precipitated in the allergen-reducing aqueous solution, after the allergen-reducing aqueous solution is applied to a substrate by coating or the like, the polymer (A) will precipitate uniformly as the water in the allergen-reducing aqueous solution evaporates, and the allergen-reducing substrate can be uniformly imparted with an excellent allergen-reducing effect. The appearance of the allergen-reduced substrate is also improved.
[0069] The allergen-reducing aqueous solution contains water and an allergen-reducing agent. In the allergen-reducing aqueous solution, the content of the polymer (A) constituting the allergen-reducing agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. In the allergen-reducing aqueous solution, the content of the polymer (A) constituting the allergen-reducing agent is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. When the content of the polymer (A) is 0.01% by mass or more, an excellent allergen-reducing effect can be imparted to the substrate. When the content of the polymer (A) is 40% by mass or less, the viscosity of the allergen-reducing aqueous solution is reduced, and the coatability to the substrate is improved.
[0070] [Allergen-reducing paint] An allergen-reducing paint containing an allergen-reducing agent and a binder resin is prepared, and the allergen-reducing paint is applied to a substrate by coating or the like to adhere the allergen-reducing agent to the substrate surface, thereby producing an allergen-reduced substrate. The allergen-reducing paint can be in the form of a water-based paint, a solvent-based paint, a light-curable paint, an electron beam-curable paint, a powder paint, or the like.
[0071] The binder resin is not particularly limited as long as it can fix the allergen reducing agent to the surface of the substrate. For example, the binder resin may be a synthetic resin binder such as a one-liquid type urethane resin, a two-liquid type urethane resin, etc., a silicone resin, an acrylic resin, a urethane acrylate resin, a polyester resin, an unsaturated polyester resin, an alkyd resin, a vinyl acetate resin, a vinyl chloride resin, an epoxy resin, or an epoxy acrylate resin, with a urethane resin being preferred.
[0072] The binder resin also includes a curable resin that is polymerized by irradiation with radiation such as ultraviolet light or by heating to generate a binder component.
[0073] [Allergen-reduced water-based paint] The allergen-reducing agent, water (preferably ion-exchanged water), and binder resin can be mixed in a known manner, and the allergen-reducing agent can be dissolved, preferably completely dissolved, in the water to prepare an allergen-reduced water-based paint.
[0074] The allergen-reduced water-based paint contains water, an allergen reducing agent, and a binder resin. In the allergen-reduced water-based paint, the content of the polymer (A) constituting the allergen reducing agent is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass or more. In the allergen-reduced water-based paint, the content of the polymer (A) constituting the allergen reducing agent is preferably 10% by mass or less, more preferably 7% by mass or less, and more preferably 5% by mass or less. When the content of the polymer (A) of the allergen reducing agent is 0.5% by mass or more, an excellent allergen reducing effect can be imparted to the substrate. When the content of the polymer (A) of the allergen reducing agent is 10% by mass or less, the viscosity of the allergen-reduced water-based paint is reduced, and the coatability to the substrate is improved.
[0075] In the allergen-reduced water-based paint, it is preferable that the entire amount of the polymer (A) contained in the allergen-reducing agent is dissolved in water. If the entire amount of the polymer (A) contained in the allergen-reducing agent is dissolved in water and the polymer (A) is not precipitated in the allergen-reduced water-based paint, the polymer (A) will be uniformly precipitated with the evaporation of water in the allergen-reduced water-based paint after the allergen-reduced water-based paint is applied to the substrate by coating or the like, and the allergen-reduced substrate can be uniformly imparted with excellent allergen-reducing effect. The appearance of the allergen-reduced substrate is also improved.
[0076] The allergen-reduced water-based paint may contain additives such as pigments and surfactants within limits that do not impair the physical properties of the paint.
[0077] [Allergen-reduced solvent-based paint] The allergen-reducing agent, the solvent, and the binder resin are mixed in a known manner, and the allergen-reducing agent is dissolved, preferably completely dissolved, in the solvent to produce an allergen-reduced solvent-based paint. This allergen-reduced solvent-based paint is then applied to a substrate by coating or the like, thereby adhering the allergen-reducing agent to the surface of the substrate and producing an allergen-reduced substrate.
[0078] The allergen-reduced solvent-based paint contains a solvent, an allergen reducing agent, and a binder resin. In the allergen-reduced solvent-based paint, the content of the polymer (A) constituting the allergen reducing agent is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass or more. In the allergen-reduced solvent-based paint, the content of the polymer (A) constituting the allergen reducing agent is preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 8% by mass or less. When the content of the polymer (A) of the allergen reducing agent is 0.5% by mass or more, an excellent allergen reducing effect can be imparted to the substrate. When the content of the polymer (A) of the allergen reducing agent is 15% by mass or less, the viscosity of the allergen-reduced solvent-based paint is reduced, and the coatability to the substrate is improved.
[0079] Examples of the solvent include organic solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ester compounds, ketone compounds, and glycol ethers.
[0080] In the allergen-reduced solvent-based paint, the allergen reducing agent preferably contains a polymer (A) and an organic acid. In the allergen-reduced solvent-based paint, the polymer (A) and the organic acid are contained, so that the dispersibility of the polymer (A) in the solvent can be improved and aggregation can be reduced. The polymer (A) is more uniformly precipitated in the coating film formed from the allergen-reduced solvent-based paint, and the coating film can be more uniformly imparted with an excellent allergen-reducing effect, while the allergen-reducing effect and appearance of the coating film are also improved. Since the dispersibility of the polymer (A) can be improved in the allergen-reduced solvent-based paint, the coatability of the allergen-reduced solvent-based paint is improved.
[0081] The organic acid may be the same as the organic acid described above. The preferred content of the organic acid relative to the polymer (A) may be in the same range as the preferred content range described above.
[0082] When the allergen reducing agent contains a polymer (A) and an organic acid, the molecular weight of the organic acid is preferably less than 1000. In this case, the dispersibility of the polymer (A) in the solvent is improved, and the allergen reducing effect of the resulting coating film is improved, as well as the appearance.
[0083] The allergen-reduced solvent-based paint may contain additives such as pigments and surfactants, within limits that do not impair the physical properties of the paint.
[0084] The substrate into which the allergen reducing agent is to be incorporated is not particularly limited as long as it is capable of incorporating the allergen reducing agent, and examples include synthetic resin molded bodies, wallpaper, decorative sheets, flooring materials, fibers, textile products (woven fabrics, nonwoven fabrics, knitted fabrics), interior products and materials for vehicles (e.g., cars, airplanes, ships, etc.) (seats, child seats, and the foams that constitute these), kitchen supplies, baby products, architectural interior materials, etc.
[0085] The synthetic resin constituting the synthetic resin molded body is not particularly limited, and examples thereof include thermoplastic resins (e.g., polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, Teflon (registered trademark), acrylonitrile butadiene styrene resin, acrylonitrile styrene resin, acrylic resin, polyvinyl alcohol, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyester, polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyether sulfone, polyarylate, polyether ether ketone, thermoplastic polyimide, polyamide imide, etc.), thermosetting resins (e.g., phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, silicone resins, polyurethanes, thermosetting polyimides, etc.). The synthetic resins may be used alone or in combination of two or more.
[0086] The architectural interior materials are not particularly limited, and examples thereof include flooring materials, wallpaper, ceiling materials, doorknobs, switches, and switch covers.
[0087] The vehicle interior goods and materials are not particularly limited, and examples thereof include seats, child seats, seat belts, car mats, seat covers, doors, ceiling materials, floor mats, door trims, instrument panels, consoles, glove boxes, hanging straps, and handrails. EXAMPLES
[0088] The present invention will be described in more detail using examples, but the present invention is not limited thereto. Specific numerical values of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit value (a numerical value defined as "equal to or less than") or lower limit value (a numerical value defined as "equal to or more than" or "exceeding") of the corresponding blending ratio (content ratio), physical property value, parameter, etc. described in the "Form for carrying out the invention" or "Means for solving the problem".
[0089] The compounds used in the production of the allergen reducing agents of the Examples and Comparative Examples are shown below. [Polymer] Polyacrylic acid 1 (Polymer (A), homopolymer of acrylic acid, weight average molecular weight: 800,000, manufactured by Nippon Shokubai Co., Ltd., product name "AS-58") Polyacrylic acid 2 (Polymer (A), homopolymer of acrylic acid, weight average molecular weight: 250,000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Polyacrylic acid 250,000") Polyacrylic acid 3 (Polymer (A), homopolymer of acrylic acid, weight average molecular weight: 10,000, Nippon Shokubai Co., Ltd., product name "HL-415") Polyacrylic acid 4 (Polymer (A), homopolymer of acrylic acid, weight average molecular weight: 50,000, manufactured by Toa Gosei Co., Ltd., product name "AC-10P") Cross-linked polyacrylic acid 1 (cross-linked polyacrylic acid, weight average molecular weight: cannot be measured due to cross-linking, manufactured by Sumitomo Seika Chemicals Co., Ltd., product name "SW-705E") · Crosslinked polyacrylic acid 2 (crosslinked product of polyacrylic acid, weight average molecular weight: unable to be measured due to crosslinking, prepared by the following method) · Crosslinked polyacrylic acid 3 (crosslinked product of polyacrylic acid, weight average molecular weight: unable to be measured due to crosslinking, prepared by the following method)
[0090] [Preparation of crosslinked polyacrylic acids 2 and 3] An epoxy crosslinking agent (sorbitol polyglycidyl ether, trade name "Denacol EX-614B" manufactured by Nagase ChemteX Corporation) was supplied to an aqueous solution of polyacrylic acid (trade name "HL-415" manufactured by Nippon Shokubai Co., Ltd.) and uniformly mixed to prepare a polyacrylic acid solution. The contents (parts by mass) of polyacrylic acid and the epoxy crosslinking agent in the polyacrylic acid solution are shown in Table 1.
[0091] The polyacrylic acid solution was heated at 120 °C for 90 minutes to crosslink the polyacrylic acid and then dried to obtain crosslinked polyacrylic acid.
[0092] [Table 1]
[0093] For each polymer, the solubility in water at 25 °C, the gel fraction in ethanol, the carboxyl group content, pKa1 at 25 °C, and the pH of a 0.5 mass% aqueous solution at 25 °C are shown in Table 2. Note that the solubility in water at 25 °C, the gel fraction in ethanol, the carboxyl group content, pKa1 at 25 °C, and the pH of a 0.5 mass% aqueous solution at 25 °C are described in the columns of "Water solubility", "Gel fraction", "Amount of carboxyl groups", "pKa1", and "pH", respectively. In the table, "<Q" (Q is a numerical value) means less than Q.
[0094] [Organic acid] · Citric acid (molecular weight: 192, having 3 carboxyl groups in the molecule, pKa1 at 25 °C: 3.09) Diethylenetriaminepentaacetic acid (molecular weight: 393, 5 carboxy groups in the molecule, pKa1 at 25°C: 2.55) Iminodiacetic acid (molecular weight: 133, two carboxy groups in the molecule, pKa at 25°C: 1.87) Phenylphosphonic acid (molecular weight: 158, one phosphonic acid group in the molecule, pKa1 at 25°C: 1.83) Sulfanilic acid (molecular weight: 173, one sulfo group in the molecule, pKa1 at 25°C: 3.23)
[0095] (Examples 1 to 5 and Comparative Examples 1 to 3) An allergen-reducing agent was prepared by uniformly mixing the polymer and organic acid in the specified amounts shown in Table 2. A specified amount of purified water shown in Table 2 was added to this allergen-reducing agent and mixed uniformly to prepare an allergen-reducing aqueous solution.
[0096] The allergen-reduced aqueous solutions of Examples 1 to 5 were examined for the presence or absence of polymer precipitation. As a result, no precipitation of polymer (A) was confirmed in any of the allergen-reduced aqueous solutions of Examples 1 to 5, and the entire amount of polymer (A) was dissolved in water.
[0097] On the other hand, in all of the allergen-reduced aqueous solutions of Comparative Examples 1 to 3, precipitation of the polymer was confirmed, and the polymer precipitated in the water.
[0098] [Table 2]
[0099] Next, the products processed using the allergen-reducing aqueous solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were subjected to measurement of the allergen reduction rate, effect on antibodies, coatability, and antiviral activity value in the manner described below, and the results are shown in Tables 3 and 4.
[0100] [Anti-allergen test (fiber-kit A)] [Measurement of the allergen reduction rate of cedar pollen allergen (Cryj1) (Fiber-Kit A)] Purified water was added to 1 g of the allergen-reducing aqueous solution obtained in the Examples and Comparative Examples and mixed uniformly to prepare an allergen-reducing aqueous solution containing 1% by mass of the allergen-reducing agent.
[0101] Next, as the base material, polyester fiber (woven fabric, manufactured by Shikisen Co., Ltd., product name "Polyester Tropical Toray", basis weight 120g / m 2 ) was prepared. The above fiber was immersed in 100 g of the above allergen-reducing aqueous solution for 2 minutes. The immersed polyester fiber was squeezed with a manual mangle and dried at 120°C for 10 minutes to produce an allergen-reducing fiber in which the allergen-reducing agent was fixed to the polyester fiber. In the allergen-reducing fiber, the allergen-reducing agent was fixed at 1 g / m 2 It was contained.
[0102] A freeze-dried powder of cedar pollen allergen (Cryj1) (ITEA Corporation, product name "Cedar pollen extract, code 4-CJ-001") was dissolved in purified water to prepare an allergen aqueous solution containing 10 μg / mL of cedar pollen allergen (Cryj1). Then, PBS-T (phosphate buffer containing 0.05% by mass of Tween 20 (Tokyo Chemical Industry Co., Ltd.), pH 7.4) was added to the allergen aqueous solution and mixed uniformly to prepare an allergen solution containing 15 ng / mL of cedar pollen allergen (Cryj1).
[0103] 0.4 g of the allergen-reduced fiber was placed in a zippered plastic bag, 1 mL of the above allergen solution was dropped into it, and the bag was then sealed and left to stand at 25° C. for 2 hours to prepare a test solution.
[0104] Next, the amount of cedar pollen allergen (Cryj1) present in the test solution W 1 (ng / mL) was measured by ELISA using cedar pollen allergen measurement kit A (ITEA, product name "Cedar Pollen Allergen (Cryj1) ELISA Kit, code 1-CJ1-001").
[0105] The amount of cedar pollen allergen (Cryj1) present in the test solution was measured in the same manner as above, except that no allergen-reduced fiber was placed in the zippered plastic bag. 0 The allergen reduction rate (%) was calculated based on the following formula and shown in the "Reduction rate (%)" column of Table 3. Allergen reduction rate (%) = 100-(W 1 / W 0 ) x 100
[0106] [Measurement of the effect of cedar pollen allergen (Cryj1) on antibodies (Fiber Kit A)] 0.4 g of the allergen-reduced fiber was placed in a plastic bag with a zipper, and 1 mL of PBS-T (phosphate buffer containing 0.05% by mass of Tween 20 (Tokyo Chemical Industry Co., Ltd.), pH 7.4) was dropped into the bag to allow contact, and the bag was then sealed and left to stand at 25°C for 30 seconds to prepare a test solution.
[0107] 100 μL of the test solution was dropped into wells of the antibody-immobilized 96-well plate included in the cedar pollen allergen measurement kit A, and the plate was left for 1 hour at 25° C. Next, the wells were washed three times with PBS-T using a plate washer (manufactured by Tecan, product name "HydroFlexPlus").
[0108] Next, ELISA measurement was performed using the above wells to measure the amount Z (ng / mL) of cedar pollen allergen (Cryj1) present in the allergen solution containing 15 ng / mL of cedar pollen allergen (Cryj1). The effect (%) on antibodies was calculated based on the following formula and is shown in the "Effect (%) on antibodies" column in Table 3. It can be said that the smaller the effect (%) on antibodies, the less the allergen reducing agent affects antibodies. Effect on antibody (%) = 100-(Z / 15) x 100
[0109] [Measurement of allergen reduction rate of mite allergen (Derf1) (Fiber Kit A) and effect on antibodies (Fiber Kit A)] The allergen reduction rate (%) and effect on antibodies (%) of mite allergen (Derf1) were calculated in the same manner as for the measurement of the reduction rate (%) of cedar pollen allergen (Cryj1) and the effect on antibodies (%), except that freeze-dried powder of mite allergen (Derf1) (ITEA, product name "Mite Allergen Extract, code 4-DF-001") was used instead of freeze-dried powder of cedar pollen allergen (Cryj1), and mite allergen measurement kit A (ITEA, product name "Mite Allergen (Derf1) ELISA Kit, code 1-DF1-001") was used instead of cedar pollen allergen measurement kit A, and the results are shown in the "Reduction rate (%)" and "Effect on antibodies (%)" columns in Table 3, respectively.
[0110] [Anti-allergen test (coating film - kit A)] [Measurement of the allergen reduction rate of cedar pollen allergen (Cryj1) (coating film - kit A)] To the allergen-reduced aqueous solutions obtained in the Examples and Comparative Examples, a binder resin (Resonac Corporation, product name "Polysol AM-200", solvent: water, solid content: 40% by mass) was added to 10 parts by mass of the polymer to give a solid content of 90 parts by mass, to prepare an allergen-reduced water-based paint. Next, a polyester film was prepared as a substrate. The allergen-reduced water-based paint was applied to one side of the substrate so that the film thickness after drying was 10 μm, and then dried in an oven at 120° C. for 1 hour, to prepare an allergen-reduced substrate with a coating film formed on one side.
[0111] A freeze-dried powder of cedar pollen allergen (Cryj1) (ITEA Corporation, product name "Cedar pollen extract, code 4-CJ-001") was dissolved in purified water to prepare an allergen solution containing 10 μg / mL of cedar pollen allergen (Cryj1). Then, PBS-T (phosphate buffer containing 0.05 wt% Tween 20 (Tokyo Chemical Industry Co., Ltd.), pH 7.4) was added to the allergen solution and mixed uniformly to prepare an allergen solution containing 15 ng / mL of cedar pollen allergen (Cryj1).
[0112] The allergen-reduced substrate was cut into a flat square shape with sides measuring 5 cm, and 0.4 mL of the allergen solution was dropped onto the coating. The substrate was then covered with a flat square polyethylene film with sides measuring 4 cm and left at 25°C for 24 hours to prepare a test solution.
[0113] Next, the amount of cedar pollen allergen (Cryj1) present in the test solution W 1 (ng / mL) was measured by ELISA using the above-mentioned cedar pollen allergen measurement kit A.
[0114] A blank substrate with a coating film formed on one side was prepared in the same manner as above, except that a blank water-based paint containing 30 parts by weight of water and 225 parts by weight of binder resin was used instead of the allergen-reduced water-based paint. The amount of cedar pollen allergen present in the test solution W was measured in the same manner as above, except that a blank substrate was used instead of the allergen-reduced substrate. 0 The allergen reduction rate (%) was calculated based on the following formula and is shown in the "Reduction rate (%)" column of Table 3. Allergen reduction rate (%) = 100-(W 1 / W 0 ) x 100
[0115] [Measurement of the effect of cedar pollen allergen (Cryj1) on antibodies (coating film - Kit A)] An allergen-reduced substrate was prepared in the same manner as in the measurement of the reduction rate of cedar pollen allergen (Cryj1). 0.4 mL of PBS-T (phosphate buffer containing 0.05 wt% Tween 20 (Tokyo Chemical Industry Co., Ltd.), pH 7.4) was dropped onto the coating film of the allergen-reduced substrate, and the coating was then covered with a flat square polyethylene film with one side measuring 4 cm, and left at 25°C for 24 hours to prepare a test solution.
[0116] 100 μL of the test solution was dropped onto wells of the antibody-immobilized 96-well plate included in the cedar pollen allergen measurement kit A, and the plate was left for 1 hour at 25° C. Next, the wells were washed three times with PBS-T using a plate washer (manufactured by Tecan, product name "HydroFlexPlus").
[0117] Next, ELISA was performed using the wells to measure the amount Z (ng / mL) of cedar pollen allergen (Cryj1) present in the allergen solution containing 15 ng / mL of cedar pollen allergen (Cryj1). The effect on antibodies (%) was calculated based on the following formula and is shown in the "Effect on antibodies (%)" column in Table 3. Effect on antibody (%) = 100-(Z / 15) x 100
[0118] [Measurement of the reduction rate of mite allergen (Derf1) (film-kit A) and the effect on antibodies (film-kit A)] The allergen reduction rate (%) of mite allergen (Derf1) and the effect on antibodies (%) were calculated in the same manner as for the measurement of the cedar pollen allergen reduction rate (%) and the effect on antibodies (%), except that freeze-dried powder of mite allergen (Derf1) (ITEA, product name ``Mite Allergen Extract, code 4-DF-001'') was used instead of freeze-dried powder of cedar pollen allergen (Cryj1) and that the above-mentioned mite allergen measurement kit A was used instead of cedar pollen allergen measurement kit A, and the results are shown in the ``Reduction rate (%)'' and ``Effect on antibodies (%)'' columns in Table 3, respectively.
[0119] (Coatability) For the obtained allergen-reduced water-based paint, the depth at which streaks appeared was measured using a grind gauge in accordance with JIS K5600-2-5, and the maximum streak depth was recorded in the "Coatability" column in Table 3. The smaller the maximum streak depth, the higher the dispersibility of the allergen-reduced agent in the allergen-reduced water-based paint, and the higher the coatability of the allergen-reduced water-based paint can be determined to be.
[0120] (Antiviral activity value) A flat square nonwoven fabric (trade name "Kimwipe S-200" manufactured by Nippon Paper Crecia Co., Ltd.) with a side of 10 cm was prepared. The nonwoven fabric was reciprocated 10 times over the surface of the coating film of the allergen-reduced substrate to wipe it off, to prepare a test coating film.
[0121] The obtained test coating film was subjected to antiviral tests against influenza virus and feline calicivirus in accordance with ISO 21702. After the reaction, the virus suspension was subjected to the plaque method to measure the virus infectivity (common logarithm) (PFU / cm 2 ) was calculated.
[0122] For the coating of the blank substrate, the virus infectivity (common logarithm value) (PFU / cm 2 The virus infectivity (common logarithm) of the blank coating was 6.5 PFU / cm 2 It was.
[0123] The antiviral activity value was calculated by subtracting the virus infectivity value of the test coating film from the virus infectivity value of the blank coating film, and the calculated values are shown in the "Anti-influenza activity value" and "Anti-feline calicivirus activity value" columns of Table 3, respectively.
[0124] [Table 3]
[0125] Next, in order to investigate the effect on the allergen reduction rate and antibodies when the measurement kit was changed for the allergen-reduced substrates prepared using the allergen-reduced water-based paints obtained in Examples 1 and 4, and Comparative Examples 1 and 2, measurements were carried out as follows, and the results are shown in Table 4.
[0126] [Anti-allergen test (coating film-kit B)] Except for changing the measurement kit to the product below, the allergen reduction rate (%) and effect on antibodies (%) were calculated in the same manner as for the measurement of the allergen reduction rate and effect on antibodies in the anti-allergen test (coating film - kit A), and are shown in the "Reduction rate (%)" and "Effect on antibodies (%)" columns in Table 4, respectively. Cedar pollen allergen measurement kit B: Nichi Nichi Pharmaceutical Co., Ltd. Product name "Cedar pollen antigen (Cry j1) measurement kit", product number "49500-12" Mite allergen measurement kit B: Nichi Nichi Pharmaceutical Co., Ltd. Product name "Mite allergen (Der f1) measurement kit", product number "49500-11"
[0127] [Anti-allergen test (coating film - kit C)] Except for changing the measurement kit to the product below, the allergen reduction rate (%) and effect on antibodies (%) were calculated in the same manner as for the measurement of the allergen reduction rate and effect on antibodies in the anti-allergen test (coating film - kit A), and are shown in the "Reduction rate (%)" and "Effect on antibodies (%)" columns in Table 4, respectively. Cedar pollen allergen measurement kit C: Fujifilm Wako Pure Chemical Industries, Ltd. Product name "Levis Cry j1 ELISA Kit", code "637-14281"
[0128] [Table 4]
[0129] (Examples 6 to 11 and Comparative Examples 4 to 6) An allergen reducing agent was prepared by uniformly mixing the specified amounts of polymer and organic acid shown in Table 5. 10 parts by mass of this allergen reducing agent was added to 200 parts by mass of a solvent-based UV curing paint containing a solvent (manufactured by Coattec Co., Ltd., product name "HG8-Clear (glossy)") and mixed uniformly to prepare an allergen-reduced solvent-based paint.
[0130] Next, the products processed using the allergen-reduced solvent-based paints obtained in Examples 6 to 11 and Comparative Examples 4 to 6 were evaluated for allergen reduction rate, effect on antibodies, coatability, and appearance of the coating film in the manner described below, and the results are shown in Table 6.
[0131] (Allergen reduction rate (%) and effect on antibodies (%)) A polyester film was prepared as a substrate. One side of this substrate was coated with an allergen-reducing solvent-based paint, which was then dried in an oven at 120°C for 1 hour to volatilize the solvent, resulting in a coating layer with a thickness of 18 μm.
[0132] Next, a UV conveyor device (Eye Graphics "ECS301G1") was used to irradiate the coating layer with ultraviolet light of 365 nm at 25°C with an integrated light dose of 500 mJ / cm 2 Thus, an allergen-reduced substrate having a coating film formed on one side was produced.
[0133] Next, a blank substrate having a coating film formed on one side was prepared in the same manner as above, except that the above solvent-based UV-curable coating material was used as is instead of the allergen-reduced solvent-based coating material.
[0134] Except for using the obtained allergen-reduced substrate and blank substrate, the allergen reduction rate (%) and the effect on antibodies (%) were calculated in the same manner as in the above [Anti-allergen test (coating film - kit A)], and are shown in the "Reduction rate (%)" and "Effect on antibodies (%)" columns in Table 6, respectively.
[0135] (Coatability) The depth at which streaks appeared on the obtained allergen-reduced solvent paint was measured using a grind gauge in accordance with JIS K5600-2-5, and the maximum streak depth was recorded in the "Coatability (μm)" column in Table 6. The smaller the maximum streak depth, the higher the dispersibility of the allergen-reducing agent in the allergen-reduced solvent-based paint, and the higher the coatability of the allergen-reduced solvent-based paint can be determined to be.
[0136] (Appearance of the coating) The number of streaks appearing on the coating surface of the obtained allergen-reduced substrate was visually counted and evaluated based on the number according to the following criteria, and the results are recorded in the "Appearance of Coating" column in Table 6. The fewer the number of streaks, the better the appearance of the allergen-reduced substrate can be judged to be. A: The number of streaks was less than 5. B: The number of streaks was 5 or more and less than 10. C: The number of streaks was 10 or more.
[0137] [Table 5]
[0138] [Table 6] [Industrial Applicability]
[0139] The allergen reducing agent of the present invention exhibits an excellent allergen reducing effect and allows accurate measurement of the amount of allergens by ELISA, thus providing an allergen reducing agent that allows users to take appropriate measures based on the accurate amount of allergens.
Claims
1. An allergen reducing agent comprising a polymer having a solubility in water at 25° C. of 300 g / L or more and having a carboxy group.
2. 2. The allergen reducing agent according to claim 1, wherein the polymer has a gel fraction of 5% by mass or less in ethanol.
3. 3. The allergen reducing agent according to claim 1, wherein the polymer has a carboxy group content of 13 mmol / g or more.
4. 3. The allergen reducing agent according to claim 1, wherein the weight average molecular weight of the polymer is 1,000,000 or less.
5. 3. The allergen reducing agent according to claim 1, further comprising an organic acid having a molecular weight of less than 1,000.
6. 3. An allergen-reducing aqueous solution comprising water and the allergen-reducing agent according to claim 1 or 2, wherein the entire amount of the polymer contained in the allergen-reducing agent is dissolved in water.
7. 7. The allergen-reduced aqueous solution according to claim 6, wherein the content of the polymer in the allergen-reduced aqueous solution is 0.01 to 40% by mass.
8. A method for producing an allergen-reduced substrate, comprising the step of supplying the allergen-reduced aqueous solution according to claim 6 onto a surface of a substrate.
9. An allergen-reducing paint comprising the allergen-reducing agent according to claim 1 or 2 and a binder resin.
10. 3. An allergen-reduced water-based paint comprising water, the allergen-reducing agent according to claim 1, and a binder resin, wherein the entire amount of the polymer contained in the allergen-reducing agent is dissolved in water.
11. 3. An allergen-reduced solvent-based paint comprising a solvent, the allergen-reducing agent according to claim 1 or 2, and a binder resin, wherein the allergen-reducing agent contains an organic acid.
12. A method for producing an allergen-reduced substrate, comprising the step of supplying the allergen-reduced coating material according to claim 9 to a surface of a substrate.
Citation Information
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