WO2013118853A1 - Allergen inhibitor, allergen-inhibiting product, allergen inhibition method, and use as allergen inhibitor - Google Patents

Abstract

The present invention provides an allergen inhibitor that: effectively prevents allergens from reacting with specific antibodies, enabling allergy symptoms to be mitigated or the manifestation of said allergy symptoms to be prevented; is less likely to undergo unpredictable discoloration and discoloration under conditions of everyday use; and has excellent contamination resistance and durability. This allergen inhibitor is characterized by containing a styrene-based polymer containing more than 70 wt% but not more than 98 wt% of a monomeric component with a structural formula represented by general formula (1), and therefore effectively prevents allergens from reacting with specific antibodies, enabling allergy symptoms to be mitigated or the manifestation of said allergy symptoms to be prevented; is less likely to undergo unpredictable discoloration and discoloration under conditions of everyday use; and has excellent contamination resistance and durability.

Description

Allergen inhibitor, allergen inhibitor product, allergen suppression method and use as allergen inhibitor

The present invention can suppress the reaction of allergens such as pollen of vegetation such as cedar, mites, and indoor dust with specific antibodies, and is unlikely to cause unexpected discoloration or discoloration under daily use conditions. The present invention relates to an allergen inhibitor that hardly causes color transfer and has excellent stain resistance and durability, and an allergen-suppressed product obtained by treating the allergen inhibitor with an allergen object.

In recent years, many allergic diseases such as atopic dermatitis, bronchial asthma and allergic rhinitis have become a problem. The main causes of this allergic disease are mites living in the house, especially leopard mite allergens (Der1, Der2), which are abundant in indoor dust, and cedar pollen floating in the air mainly in spring. This is because allergens such as allergens (Cry j1, Cry j2) are increasing in the living space.

ア Leopard mite allergens are not leopard mites themselves, but the dead bodies and feces of leopard mites become allergens, so even if you remove the leopard mites, it will not be a fundamental solution to allergic diseases.

The cedar pollen allergens Cry j1 and Cry j2 are glycoproteins having a molecular weight of about 40 kDa and a molecular weight of about 37 kDa, respectively. These cedar pollen allergens are in vitro as foreign substances when attached to the nasal mucosa. It is recognized and causes an inflammatory response.

Therefore, in order to reduce the symptoms of allergic diseases or prevent new allergic symptoms, it is necessary to completely remove allergens from the living space or to inactivate allergens.

Since allergen is a protein, it is considered that allergen loses allergenicity when it is denatured with heat, strong acid or strong alkali. However, allergens are very stable and are not easily denatured by oxidizing agents, reducing agents, heat, alkalis, acids, etc. that can be used safely at home (see Non-Patent Document 1).

Further, when allergens present in an object that is contaminated with allergens are to be denatured, the objects that are contaminated with allergens, such as tatami mats, carpets, floors, furniture (sofas, cloth chairs, tables), bedding ( Beds, futons, sheets), interior items (seats, child seats), interior materials (ceiling materials, etc.), kitchen items, baby items, curtains, wallpaper, towels, clothing, plush toys, other textiles, air purifiers ( The main body and filter) may be damaged depending on conditions.

For this reason, a method has been considered in which the molecular surface of the allergen is chemically denatured under relatively mild conditions. For example, a method for suppressing allergen using tannic acid used for tanning of rawhide (Patent Document 1), a method for suppressing allergen using tea extract or the like (Patent Document 2), etc. are proposed. In addition, the allergen suppressing effect has been confirmed.

However, most of the compounds used in these methods are colored because they are a kind of polyphenol, which causes the problem of coloring the object.

Patent Document 3 proposes an allergen inhibitor containing an aromatic hydroxy compound as an active ingredient, which has improved the problem of coloring the object, but when processed into a light-colored object such as white. Coloration may occur and was not sufficient.

Patent Document 4 proposes an allergen inhibitor containing an allergen inhibitor compound, in which the allergen inhibitor compound is a sodium sulfonate salt of a p-styrenesulfonic acid homopolymer. When applied to products having a lot of contact with water in daily life, for example, textile products such as clothing, there is a problem that the sustainability of the allergen suppressing effect is deteriorated.

Patent Document 5 proposes an allergen deactivator composed of a polymer compound having a styrene sulfonic acid unit. In the paragraph [0021], in the case of a copolymer, the constituent ratio of styrene sulfonic acid is a constituent unit. It is described that the content is preferably 20% by weight or more, more preferably 50% by weight or more, and still more preferably 70% by weight or more.

However, only examples in which the polymer compound has a styrene sulfonic acid content of 50% by weight or 70% by weight in the copolymer are disclosed, and in the copolymer, the styrene sulfonic acid content exceeds 70% by weight. It is not disclosed whether or not the effect of allergen inactivation is exhibited.

JP 61-44821 A JP-A-6-279273 JP 2003-81727 A Japanese Patent No. 4619452 JP 2009-155453 A

The present invention effectively suppresses allergens from reacting with specific antibodies, can reduce allergy symptoms or prevent their occurrence, and is unlikely to cause unexpected discoloration or discoloration under daily use conditions. Furthermore, the present invention provides an allergen inhibitor having excellent stain resistance and durability. The present invention provides an allergen-suppressed product obtained by treating the allergen inhibitor with an allergen object. The present invention provides an allergen suppression method using an allergen inhibitor. In the present invention, contamination resistance means that the allergen object treated with the allergen inhibitor is easily cleaned. In the present invention, the term “durability” means that color transfer hardly occurs from an allergen object treated with an allergen inhibitor to other products.

The allergen inhibitor of the present invention contains, as an active ingredient, a styrene polymer containing a monomer component of the structural formula represented by the general formula (1) in an amount of more than 70% by weight and 98% by weight or less. Features.

(R ¹ to R ⁵ are each hydrogen, a sulfonic acid group or a sulfonic acid group salt, and at least one of R ¹ to R ⁵ is a sulfonic acid group or a sulfonic acid group salt. is there.)

Here, the allergen inhibitor refers to those having an allergen inhibitory effect, and the “allergen inhibitory effect” refers to leopard mite allergens (Der1, Der2), cedar pollen allergens (Cryj1, Cryj2) floating in the air The allergens such as allergens (Can f1, Fel d1) caused by dogs and cats are denatured or adsorbed to suppress the reactivity of allergens to specific antibodies. As a method for confirming such an allergen inhibitory effect, for example, a method for measuring the amount of allergen by ELISA using an ELISA kit commercially available from Nitinichi Pharmaceutical Co., Ltd., an allergen measuring instrument (commercially available from Sumika Enviro Science Co., Ltd.) And a method for evaluating allergenicity using the name “Mighty Checker”).

A method for producing a styrenic polymer containing the monomer component of the structural formula represented by the general formula (1) exceeding 70 wt% and 98 wt% or less is, for example, (1) represented by the general formula (1) A method of copolymerizing a monomer of the structural formula and another monomer polymerizable with this monomer, (2) a method of sulfonating a part of the benzene ring of polystyrene, and (3) a benzene of polystyrene A method in which a part of the ring is sulfonated and the introduced sulfonic acid group (—SO ₃ H) is neutralized with an aqueous alkali solution to form a sulfonic acid group as a salt; (4) a structural formula represented by the general formula (1) A part of the benzene ring of a copolymer of a monomer and another monomer that can be polymerized with this monomer is sulfonated, and the introduced sulfonic acid group (—SO ₃ H) is neutralized with an aqueous alkaline solution. To make a sulfonic acid group into a salt, (5) polystyrene sulfonic acid, In the copolymer, or salts of these sulfonic acids with Nsuruhon acid and copolymerizable therewith other monomer, a method of desulfonation part of the sulfonic acid group. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, magnesium hydroxide, and ammonium hydroxide.

In the general formula (1), R ¹ to R ⁵ are each hydrogen (—H), a sulfonic acid group (—SO ₃ H), or a salt of a sulfonic acid group, of R ¹ to R ⁵ It is necessary that at least one of these is a sulfonic acid group or a salt of a sulfonic acid group. This is because in the general formula (1), the allergen inhibitor does not exhibit an allergen inhibitory effect unless it has a sulfonic acid group or a salt of a sulfonic acid group as a substituent. The salt of a sulfonic acid group, for _{example, -SO 3 Na, (- SO} 3) 2 Ca, (- SO 3) 2 Mg, -SO 3 - NH 4 + and the like, the freedom of a salt of a sulfonic acid group Is high, the allergen denaturation effect or adsorption effect is high, and the allergen inhibitor has a high allergen inhibitory effect. Therefore, monovalent salts of sulfonic acid groups are preferred, and —SO ₃ Na, —SO ₃ K, —SO ₃ Li, -SO ₃ ^- NH ₄ ⁺ are more ^{_{preferable, -SO 3 Na, -SO 3 -}} NH 4 + is particularly preferred. The monovalent salt of the sulfonic acid group is represented by —SO ₃ M, and M is a monovalent cation. Examples of M include Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ^{+ and the} like.

In the general formula (1), if the total number of sulfonic acid groups and sulfonic acid group salts is large, the allergen suppressing effect is lost, and therefore, 1 to 3 is preferable, and 1 is more preferable.

In the general formula (1), since steric hindrance is small, R ³ is a sulfonic acid group or a salt of a sulfonic acid group, and R ¹ , R ² , R ⁴ and R ⁵ are hydrogen. preferable.

Examples of the monomer represented by the general formula (1) include o-styrene sulfonic acid, o-sodium styrene sulfonate, m-styrene sulfonic acid, sodium m-styrene sulfonate, and p-styrene sulfonic acid. P-sodium styrenesulfonate, calcium styrenesulfonate, calcium styrenesulfonate, potassium o-styrenesulfonate, potassium m-styrenesulfonate, potassium p-styrenesulfonate, lithium o-styrenesulfonate, m-styrenesulfone Lithium sulfonate, lithium p-styrene sulfonate, ammonium o-styrene sulfonate, ammonium m-styrene sulfonate, ammonium p-styrene sulfonate, magnesium styrene sulfonate, etc. Preferred, sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, ammonium styrene sulfonate is more preferred, sodium p- styrenesulfonate are particularly preferable.

Examples of the monomer component other than the monomer component of the structural formula represented by the general formula (1) in the styrenic polymer include alkyl acrylates such as methyl acrylate, ethyl acrylate and 2-hydroxyethyl acrylate, methyl Alkyl methacrylates such as methacrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, vinyl alkyl ethers such as vinyl methyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, 2-vinylnaphthalene, styrene , Acrylonitrile, acrylic acid, sodium acrylate, methacrylic acid, sodium methacrylate, maleic acid, fumaric acid, maleic anhydride, acrylamide, methacrylamide, diacetone Rylamide, vinyltoluene, xylene sulfonic acid, vinyl pyridine, vinyl sulfonic acid, vinyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate, etc. are mentioned, from the point of improving durability of allergen inhibitor and exhibiting high allergen inhibitory effect Styrene is preferred.

In the styrenic polymer, monomer components other than the monomer component of the structural formula represented by the general formula (1) improve the allergen inhibitory effect of the allergen inhibitor, or disappear when contacted with water. Therefore, it is preferable not to have an atomic group containing an oxygen atom or a nitrogen atom having a high electronegativity. Examples of the atomic group containing an oxygen atom or a nitrogen atom having a large electronegativity include —OH,> C═O, —COOH, —NH ₂ , —NO ₂ , —NH ₃ ⁺ , —CN, and the like.

The styrenic polymer is preferably linear because the degree of freedom of the main chain is high, the allergen denaturing effect or adsorption effect is high, and the allergen suppressing effect of the allergen inhibitor is high.

If the content of the monomer component having the structural formula represented by the general formula (1) is small in the styrene polymer of the allergen inhibitor, the following problems are likely to occur. The allergen inhibitory effect of the allergen inhibitor tends to decrease. When the polarity of the remaining components is low, the allergen inhibitor is easy to become familiar with pigments such as pigments and dyes, although the water resistance is improved by reducing the polarity of the allergen inhibitor. As a result, for example, when the allergen object is a dark fiber such as black, the color of the allergen object is transferred to the treatment liquid when the allergen object is immersed in the treatment liquid containing the allergen inhibitor. The color of the allergen object changes (occurrence of liquid color transfer), or the allergen object rubs with clothes in daily life, causing color transfer to light color and contaminating clothes (friction color transfer) Occurrence of sex). That is, the durability of the allergen inhibitor is reduced. Dirt that adheres to clothes is difficult to remove, or when an allergen inhibitor is treated on wallpaper or the like, dirt such as ink is difficult to remove (decrease in stain resistance). If the content of the monomer component having the structural formula represented by the general formula (1) in the styrene polymer of the allergen inhibitor is large, the allergen inhibitory effect of the product treated with the allergen inhibitor is reduced by washing or the like. (A reduction in the durability allergen suppression effect). Accordingly, the content of the monomer component having the structural formula represented by the general formula (1) in the styrene polymer of the allergen inhibitor is limited to more than 70% by weight and 98% by weight or less. % By weight is preferable, and 80 to 90% by weight is more preferable.

Examples of the styrene polymer containing the monomer component having the structural formula represented by the general formula (1) include p-styrene sulfonate-styrene copolymer and o-styrene sulfonate-styrene copolymer. Styrene sulfonate-styrene copolymer such as m-styrene sulfonate-styrene copolymer, styrene sulfonate-styrene sulfonic acid-styrene terpolymer, p-styrene sulfonic acid or a salt thereof A copolymer of at least one monomer and maleic acid, a copolymer of at least one monomer of p-styrenesulfonic acid or a salt thereof and 2-hydroxyethyl methacrylate, p-styrenesulfonic acid Or a copolymer of at least one monomer of its salt and acrylic acid, at least one of p-styrenesulfonic acid or its salt Copolymer of methacrylic acid monomer, copolymer of at least one monomer of p-styrene sulfonic acid or its salt and methyl methacrylate, sulfonated polystyrene, styrene-maleic acid copolymer Examples include polymers in which some or all of the sulfonic acid groups of the polymer sulfonated on the benzene ring are salts, but the durability of the allergen inhibitor is improved and the allergen inhibitor is high. Because of its allergen-inhibiting effect, at least one heavy selected from the group consisting of a styrene sulfonate-styrene copolymer, a styrene sulfonate-styrene sulfonic acid-styrene terpolymer, and a polystyrene sulfonate. It is preferably a coalescence. In addition, the said styrenic polymer may be used independently, or 2 or more types may be used together.

The styrene sulfonate-styrene copolymer is not particularly limited. For example, sodium styrene sulfonate-styrene copolymer, potassium styrene sulfonate-styrene copolymer, lithium styrene sulfonate-styrene copolymer, styrene Examples include calcium sulfonate-styrene copolymer, ammonium styrenesulfonate-styrene copolymer, magnesium styrenesulfonate-styrene copolymer, sodium styrenesulfonate-styrene copolymer, ammonium styrenesulfonate-styrene copolymer. A polymer, potassium styrenesulfonate-styrene copolymer, lithium styrenesulfonate-styrene copolymer is preferable, and p-sodium styrenesulfonate-styrene copolymer is more preferable. The styrene sulfonate-styrene copolymer may be used alone or in combination of two or more.

If the content of the styrene sulfonate component in the styrene sulfonate-styrene copolymer is small, the following problems are likely to occur. The allergen inhibitory effect of the allergen inhibitor tends to decrease. Allergen inhibitors can be easily blended with pigments such as pigments and dyes. As a result, for example, when the allergen object is a dark fiber such as black, the color of the allergen object is transferred to the treatment liquid when the allergen object is immersed in the treatment liquid containing the allergen inhibitor. The color of the allergen object changes (occurrence of liquid color transfer), or the allergen object rubs against clothes in daily life, causing color transfer to light color and contaminating clothes (friction color transfer) Occurrence of sex). That is, the durability of the allergen inhibitor is reduced. Dirt that adheres to clothes is difficult to remove, or when an allergen inhibitor is treated on wallpaper or the like, dirt such as ink is difficult to remove (decrease in stain resistance). If the content of the styrene sulfonate component in the styrene sulfonate-styrene copolymer is large, the allergen inhibitory effect of the product treated with the allergen inhibitor is likely to be reduced by washing (decrease in the durable allergen inhibitory effect). ). Accordingly, the content of the styrene sulfonate component in the styrene sulfonate-styrene copolymer is preferably more than 70% by weight and 98% by weight or less, more preferably 75 to 95% by weight, and more preferably 80 to 90% by weight. Is particularly preferred.

The styrene sulfonate-styrene sulfonic acid-styrene terpolymer is not particularly limited. For example, sodium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, potassium styrene sulfonate-styrene sulfonic acid- Styrene terpolymer, lithium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, calcium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, ammonium styrene sulfonate-styrene sulfonic acid-styrene ternary Examples include styrene copolymer, magnesium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, and ammonium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, sodium styrene sulfonate-styrene sulfonic acid. Preferred are styrene terpolymer, potassium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, lithium styrene sulfonate-styrene sulfonic acid-styrene terpolymer, sodium styrene sulfonate-styrene sulfonic acid- Styrene terpolymers are more preferred, and p-sodium styrene sulfonate-styrene sulfonic acid-styrene terpolymers are particularly preferred. The styrene sulfonate-styrene sulfonic acid-styrene terpolymer may be used alone or in combination of two or more.

If the content of the styrene sulfonate component in the styrene sulfonate-styrene sulfonic acid-styrene terpolymer is small, the following problems are likely to occur. The allergen inhibitory effect of the allergen inhibitor tends to decrease. Allergen inhibitors can be easily blended with pigments such as pigments and dyes. As a result, for example, when the allergen object is a dark fiber such as black, the color of the allergen object is transferred to the treatment liquid when the allergen object is immersed in the treatment liquid containing the allergen inhibitor. The color of the allergen object changes (occurrence of liquid color transfer), or the allergen object rubs against clothes in daily life, causing color transfer to light color and contaminating clothes (friction color transfer) Occurrence of sex). That is, the durability of the allergen inhibitor is reduced. Dirt that adheres to clothes is difficult to remove, or when an allergen inhibitor is treated on wallpaper or the like, dirt such as ink is difficult to remove (decrease in stain resistance). When the content of the styrene sulfonate component in the styrene sulfonate-styrene sulfonic acid-styrene terpolymer is large, the allergen inhibitory effect of the product treated with the allergen inhibitor is likely to be reduced by washing or the like ( Reduced durability allergen suppression effect). Accordingly, the content of the styrene sulfonate component in the styrene sulfonate-styrene sulfonic acid-styrene terpolymer is more than 70% by weight and preferably less than 98% by weight, more preferably 75 to 95% by weight. 80 to 90% by weight is particularly preferable.

When the content of the styrene sulfonic acid component in the styrene sulfonate-styrene sulfonic acid-styrene terpolymer is large, the acidity of the styrene sulfonate-styrene sulfonic acid-styrene terpolymer becomes strong, Since the allergen target to be treated with the allergen inhibitor may be damaged, it is preferably 10% by weight or less, more preferably 3% by weight or less.

Examples of the sulfonated polystyrene include polymers in which a part or all of the sulfonic acid group of a polymer obtained by sulfonating a part of the polystyrene benzene ring is a salt, and a part of the polystyrene benzene ring is sulfonated. A polymer in which all of the sulfonic acid groups of the obtained polymer are salts is preferred. Examples of the polystyrene sulfonated polymer include a polymer in which all of the sulfonic acid groups of a polymer obtained by sulfonating a part of the polystyrene benzene ring are sodium salts, and a polymer in which a part of the polystyrene benzene ring is sulfonated. A polymer in which a part of the sulfonic acid group is a sodium salt, a polymer in which a part of the polystyrene benzene ring is sulfonated, a polymer in which all of the sulfonic acid group is an ammonium salt, and a part of the polystyrene benzene ring A polymer in which a part of the sulfonic acid group of the sulfonated polymer is an ammonium salt, a polymer in which all of the sulfonic acid group of a polymer in which a part of the benzene ring of polystyrene is sulfonated is a calcium salt, a benzene in polystyrene Examples thereof include a polymer in which a part of the sulfonic acid group of a polymer obtained by sulfonating a part of the ring is a calcium salt.

If the content of the styrene sulfonate component in the sulfonated polystyrene is small, the following problems are likely to occur. The allergen inhibitory effect of the allergen inhibitor tends to decrease. Allergen inhibitors can be easily blended with pigments such as pigments and dyes. As a result, for example, when the allergen object is a dark fiber such as black, the color of the allergen object is transferred to the treatment liquid when the allergen object is immersed in the treatment liquid containing the allergen inhibitor. The color of the allergen object changes (occurrence of liquid color transfer), or the allergen object rubs against clothes in daily life, causing color transfer to light color and contaminating clothes (friction color transfer) Occurrence of sex). That is, the durability of the allergen inhibitor is reduced. Dirt that adheres to clothes is difficult to remove, or when an allergen inhibitor is treated on wallpaper or the like, dirt such as ink is difficult to remove (decrease in stain resistance). If the content of the styrene sulfonate component in the sulfonated polystyrene is large, the allergen inhibitory effect of the product treated with the allergen inhibitor is likely to be reduced by washing or the like (decrease in the durable allergen inhibitory effect). Therefore, the content of the styrene sulfonate component in the sulfonated polystyrene is preferably more than 70% by weight and less than 98% by weight, more preferably 75 to 95% by weight, and particularly preferably 80 to 90% by weight.

The polystyrene sulfonated product preferably contains no styrene sulfonic acid component. When the styrene sulfonic acid component is contained, the content of the styrene sulfonic acid component is preferably 10% by weight or less because the acidity of the sulfonated polystyrene becomes strong and may damage the allergen object to be treated. 3% by weight or less is more preferable.

If the weight average molecular weight (Mw) of the styrenic polymer is low, the allergen inhibitory effect of the allergen inhibitor may decrease, so 2000 or more is preferable, and 20000 or more is more preferable, but if it is too high, the allergen inhibitor. Is less than 1,000,000.

In the present invention, the weight average molecular weight of the styrene polymer refers to a peak top value when measured by size exclusion chromatography using sodium polystyrene sulfonate as a standard substance. The weight average molecular weight of the styrene polymer can be measured, for example, under the following conditions.
Column: (Showa Denko Shodex GF-7M HQ 7.6mmI.D. × 30cm 1)
Eluent: (0.05M sodium sulfate aqueous solution: THF = 7: 3)
Flow rate: 0.6 ml / min Temperature: 40 ° C
Detection: UV (210 nm)
Standard sodium polystyrene sulfonate: manufactured by scientific polymer products

The allergen inhibitor can be obtained by preparing a predetermined type and a predetermined amount of monomer according to the constituent components and copolymerizing the monomer in a general manner. Further, the allergen inhibitor can be obtained by sulfonating a part of a benzene ring of a copolymer having a styrene skeleton such as a styrene-maleic acid copolymer or polystyrene, and neutralizing the introduced sulfonic acid group with an alkaline aqueous solution. Can also be obtained. For example, a styrene sulfonate-styrene copolymer can be obtained by sulfonating a part of the benzene ring of polystyrene and neutralizing all sulfonic acid groups bonded to the benzene ring with an alkaline aqueous solution. Part of the benzene ring of polystyrene is sulfonated, and part of the sulfonic acid group bonded to the benzene ring is neutralized with an alkaline aqueous solution to obtain a styrenesulfonate-styrenesulfonic acid-styrene copolymer. . Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, magnesium hydroxide, and ammonium hydroxide.

The sulfonation of polystyrene can be carried out in a known manner, and examples thereof include a method using sulfur trioxide or concentrated sulfuric acid.

The average particle size of the styrenic polymer is not particularly limited, but is preferably from 0.01 to 30 μm from the viewpoint of design of an allergen-suppressed product obtained by treating an allergen object with an allergen inhibitor. A thickness of 05 to 10 μm is more preferable. The average particle size of the styrenic polymer is a value measured by a particle size distribution measuring device. As the particle size distribution measuring apparatus, an apparatus commercially available from HORIBA Ltd. under the trade name “LA-950V2” can be used.

In addition, if the allergen inhibitor is water-insoluble, the allergen may be present or an allergen may be present in the future, such as a household article, that is, an object for which allergen is desired to be suppressed (hereinafter, “ Even when the "allergen object" is in contact with water, the allergen inhibitor can be prevented from dissolving and disappearing in water, and the allergen inhibitory effect of the allergen inhibitor product described below can be maintained over a long period of time. It can be sustained stably. Therefore, the allergen inhibitor is preferably water-insoluble. Human bodies and animals are excluded from allergen objects. Further, when the allergen inhibitor is water-soluble, it is preferable to make it water-insoluble. Here, water-insoluble means that the number of grams that can be dissolved in 100 g of water having a pH of 5 to 9 at 20 ° C. (hereinafter referred to as “solubility”) is 1 or less. Is called water-soluble.

As a method for making an allergen inhibitor water-insoluble, a method for crosslinking a styrene polymer by containing a curing agent in a water-soluble styrene polymer, a method for fixing a water-soluble styrene polymer to a carrier Etc.

The curing agent for the styrenic polymer is not particularly limited as long as the styrenic polymer can be crosslinked. For example, amine compounds, compounds such as polyaminoamide compounds synthesized from amine compounds, tertiary amine compounds, Examples include imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenolic compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization initiators, dicyanamide and derivatives thereof, and divinylbenzene. More than one species may be used in combination.

The amine compound is not particularly limited. For example, aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, and derivatives thereof; mensendiamine, isophorone Diamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10 Alicyclic amines such as tetraoxaspiro (5,5) undecane and derivatives thereof; m-xylenediamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine, m-phenylenedia And aromatic amines such as amine, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p-diisopropylbenzene, and derivatives thereof.

The compound synthesized from the amine compound is not particularly limited. For example, the amine compound and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid. , Polyaminoamide compounds synthesized from carboxylic acid compounds such as tetrahydroisophthalic acid and hexahydroisophthalic acid and derivatives thereof; polyaminoimide compounds synthesized from the above amine compounds and maleimide compounds such as diaminodiphenylmethane bismaleimide and derivatives thereof A ketimine compound synthesized from the amine compound and a ketone compound and a derivative thereof; synthesized from the amine compound and a compound such as an epoxy compound, urea, thiourea, an aldehyde compound, a phenol compound, or an acrylic compound. Polyamino compounds and derivatives thereof are exemplified.

Further, the tertiary amine compound is not particularly limited. For example, N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethyl) Aminomethyl) phenol, 1,8-diazabiscyclo (5,4,0) undecene-1 and derivatives thereof.

The imidazole compound is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole and derivatives thereof. Can be mentioned.

Further, the hydrazide compound is not particularly limited, and for example, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosan Examples thereof include acid dihydrazide, adipic acid dihydrazide and derivatives thereof.

Furthermore, the melamine compound is not particularly limited, and examples thereof include 2,4-diamino-6-vinyl-1,3,5-triazine and derivatives thereof.

The acid anhydride is not particularly limited. For example, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris Anhydrotrimellitate, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazeline acid anhydride Polydodecane Anhydrides, such as chlorendic anhydride and derivatives thereof.

The phenol compound is not particularly limited, and examples thereof include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol and derivatives thereof.

Further, the thermal latent cationic polymerization catalyst is not particularly limited. For example, benzylsulfonium salt, benzylammonium salt, benzylpyridinium using antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride and the like as a counter anion. Examples include ionic thermal latent cationic polymerization catalysts such as salts and benzylphosphonium salts; nonionic thermal latent cationic polymerization catalysts such as N-benzylphthalimide and aromatic sulfonic acid esters.

The photolatent cationic polymerization initiator is not particularly limited. For example, an aromatic diazonium salt, an aromatic halonium salt, and an antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride, and the like as a counter anion. Ionic photolatent cationic polymerization initiators such as onium salts such as aromatic sulfonium salts and organometallic complexes such as iron-allene complexes, titanocene complexes and arylsilanol-aluminum complexes; nitrobenzyl esters, sulfonic acid derivatives, Nonionic photolatent cationic polymerization initiators such as phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like can be mentioned.

The carrier for fixing the styrenic polymer is not particularly limited, and examples thereof include inorganic carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermulite, perlite, and organic carriers such as polyethylene and polypropylene. Examples thereof include a polymer carrier.

The form of the organic polymer carrier is not particularly limited, and examples thereof include fine particles, fibers, sheets, films, and foams. When the styrenic polymer is supported on the foam, the styrenic polymer may be supported before foaming of the foamable molded article that is the raw material of the foam, or the styrenic polymer may be supported after foaming. .

The method for fixing the styrenic polymer to the support is not particularly limited. For example, a method for adsorbing the styrenic polymer to the support, a chemical bond such as grafting, or a bond with a binder may be used. Examples thereof include a method of fixing to a carrier.

The allergen inhibitor of the present invention may contain formulation adjuvants such as a dispersant, an emulsifier, an antioxidant, an ultraviolet absorber, and a dye transfer inhibitor as long as the effectiveness of the allergen suppressing effect is not impaired. In addition, acaricides, bactericides, fungicides, deodorants and the like may be contained.

The dye transfer inhibitor is not particularly limited, and examples thereof include salts such as calcium chloride, water-soluble cationic compounds, polyvinyl pyrrolidone, polyvinyl pyridine betaine, and polyamine N-oxide polymers.

Next, the procedure for using the allergen inhibitor will be described. For the allergen inhibitor, a general use method such as a spray type, an aerosol type, a smoke type, a heat transpiration type, or a mixture in a matrix can be used.

The allergen inhibitor is dissolved or dispersed in a solvent to form an allergen inhibitor solution, and an allergen inhibitor solution is mixed with an aqueous solvent, oil agent, emulsion, suspension, etc. to make the allergen inhibitor spray type. Can do. In addition, a spray type means the usage method which applies a pressure to the allergen inhibitor solution under normal pressure, and sprays an allergen inhibitor in the shape of a mist.

Examples of the solvent include water (preferably ion-exchanged water), alcohols (methyl alcohol, ethyl alcohol, propyl alcohol, etc.), hydrocarbons (toluene, xylene, methylnaphthalene, kerosene, cyclohexane, etc.), Examples include ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), amides (N, N-dimethylformamide, etc.).

Then, by adding a solid carrier (talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermulite, perlite, etc.) to the spray-type allergen inhibitor, the allergen inhibitor can be made into an aerosol type. .

Here, the aerosol type is a method of using an allergen inhibitor solution enclosed in a container together with a propellant in a compressed state, and spraying the allergen inhibitor in the form of a mist by the pressure of the propellant. Say. Examples of the propellant include nitrogen, carbon dioxide, dimethyl ether, and LPG.

In addition, the spray-type allergen inhibitors include oxygen supply agents (potassium perchlorate, potassium nitrate, potassium chlorate, etc.), combustion agents (sugars, starches, etc.), and exothermic regulators (guanidine nitrate, nitroguanidine, guanyl phosphate). The allergen inhibitor can be smoked by adding an agent for decomposing oxygen (such as urea) and an auxiliary agent for decomposing oxygen supply agents (potassium chloride, copper oxide, chromium oxide, iron oxide, activated carbon, etc.). The smoke type refers to a method of use in which an allergen inhibitor is finely divided into smoke and dispersed.

The matrix for mixing the allergen inhibitor is not particularly limited as long as it does not denature the allergen inhibitor. For example, polysaccharides and salts thereof, dextrin, gelatin, higher alcohols, fats and oils, stearic acid and the like. Examples include higher fatty acids, paraffins, liquid paraffins, white petrolatum, hydrocarbon gel ointment, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, and various paints.

And by supplying the allergen inhibitor by spraying, dispersing, applying or fixing to the allergen object according to various methods of use, an allergen inhibitory effect is imparted to the allergen object, and an allergen inhibitor product is obtained. Allergens of the allergen object can be suppressed. An “allergen object” refers to an object in which an allergen already exists, or an object in which no allergen currently exists but an allergen may exist in the future. Human bodies and animals are excluded from allergen objects. When the allergen is already present in the allergen object, the allergen is suppressed by supplying the allergen inhibitor. If the allergen is not present in the allergen object, the allergen inhibitor is applied to the allergen object in advance by providing the allergen inhibitor with an allergen inhibitory effect. Suppress allergens. The allergen inhibitor may be used alone or in combination of two or more. The allergen inhibitor is excellent in stability when a suspension is added to the above-mentioned allergen inhibitor solution to form a suspension. Spraying is preferred. In addition, as a method of chemically or physically fixing the allergen inhibitor to the allergen object, a method of chemically bonding or physically fixing the allergen inhibitor described later to the fiber can be used.

In addition, examples of the allergen target include daily items that serve as a hotbed for allergens in a living space. When the allergen object is a fiber or a fiber product, the allergen inhibitor exhibits its effect more. Living goods include, for example, tatami mats, carpets, furniture (sofas, foam inside sofas, cloth chairs, tables, etc.), bedding (beds, futons, futon batting, duvet feathers, sheets, mattresses, cushions, etc.) Foams that make up these, etc.) Car interior items such as cars, airplanes, ships, and vehicle interior materials (seats, child seats and foams that make up these), kitchen items, baby items, architectural interior materials (Wallpaper, flooring, etc.), textile products (fabrics, curtains, towels, clothing, stuffed animals, etc.), textiles, filters such as screen doors, screen doors, and building interior materials.

In particular, since the allergen inhibitor of the present invention has almost no unexpected coloration or discoloration in the daily living environment, and there is almost no problem of color transfer, it can be applied to other products caused by light fading, discoloration, or rubbing. It is suitable for applications in which contamination due to color transfer is a problem, for example, textile products, building interior materials, vehicle interior products, vehicle interior materials, filters, and the like.

The above filter refers to a filter having the ability to separate, filter, and remove foreign substances. For example, a filter such as an air cleaner, an air conditioner, a vacuum cleaner, a ventilation fan, a mask that prevents entry of dust or pollen, a shoji, an insect, etc. And screen doors and kayaks that prevent entry.

The architectural interior material is not particularly limited, and examples thereof include floor materials, wallpaper, ceiling materials, paints, and waxes.

The fiber product is not particularly limited, and examples thereof include fabrics, bedding, carpets, curtains, towels, clothes, and stuffed animals.

The vehicle interior and vehicle interior materials are not particularly limited, and examples thereof include a seat, a child seat, a seat belt, a car mat, a seat cover, and a carpet.

When the amount of the allergen inhibitor used for the allergen object is small, the allergen inhibitory effect of the allergen inhibitor may not be manifested. On the other hand, when the amount is large, the allergen object may be damaged. Is preferably 0.001 to 100 parts by weight, more preferably 0.01 to 50 parts by weight, particularly preferably 0.02 to 30 parts by weight, and most preferably 0.02 to 20 parts by weight.

The allergens targeted by the allergen inhibitor of the present invention include leopard mite allergens (Der1, Der2), animal allergens such as dogs and cats (Can f1, Fel d1), and cedar pollen floating in the air. Examples include allergens (Cryj1, Cryj2) and plant allergens such as pollen. Animal allergens that are particularly effective include mite allergens (mites, arthropod ginsengs-mite organisms, which are mainly divided into seven subtypes. , Anterospira represented by ticks, mite, posterior genus represented by spider mite, middle antrum represented by house dust mite, spider mite, anterior genus represented by staghorn tick, nymph mite, leopard mites such as mite It can be a target for any kind of anatomical gills represented by Kenagakonadani, Jesaradani, and Hidden mosquitoes represented by Kasari chick tick, but it is a common source of allergic diseases in indoor dust, especially bedding. Is particularly effective.

According to the above-mentioned procedure for using the allergen inhibitor, by supplying an allergen inhibitor as needed to the allergen object, it may be present in the allergen object, or not present but in the future. It suppressed the reactivity of allergens to specific antibodies.

The above-mentioned allergen inhibitor may be contained in a fiber to form an allergen-suppressing fiber, and the allergen suppressing effect may be imparted to the fiber itself. By producing the above-mentioned daily necessities using this allergen-suppressing fiber, the allergen-inhibiting effect can be imparted to the daily necessities in advance.

Examples of the method of incorporating the allergen inhibitor into the fiber include a method of chemically binding or physically fixing the allergen inhibitor to the fiber. The fiber is not particularly limited as long as it can contain an allergen inhibitor. For example, a synthetic fiber such as a polyester fiber, a nylon fiber, an acrylic fiber, or a polyolefin fiber, or a half of an acetate fiber or the like. Examples thereof include synthetic fibers, recycled fibers such as cupra and rayon, natural fibers such as cotton, hemp, wool, and silk, or composite fibers and mixed cottons of these various fibers.

The method for chemically binding the allergen inhibitor to the fiber includes a method of chemically binding the allergen inhibitor to the fiber by a grafting reaction. The grafting reaction is not particularly limited.For example, (1) a graft polymerization method in which a polymerization initiation point is created in a trunk polymer to be a fiber, and an allergen inhibitor is polymerized as a branch polymer; (2) an allergen inhibitor is a polymer Examples thereof include a polymer reaction method in which the fiber is chemically bonded to the fiber by reaction.

Examples of the graft polymerization method include (1) a method in which a chain transfer reaction to a fiber is used to generate radicals and polymerize, and (2) a second cerium salt or silver sulfate salt such as alcohol, thiol, or amine. A method in which a reducing substance is allowed to act to form an oxidation-reduction system (redox system), and free radicals are generated in the fiber for polymerization. (3) A fiber and a monomer that is a raw material for the styrene polymer. A method of irradiating the fiber with γ rays or accelerated electron beams in the coexisting state, (4) Irradiating only the fibers with γ rays or accelerated electron beams, and then adding a monomer as a raw material of the styrenic polymer (5) A method in which a polymer constituting the fiber is oxidized to introduce a peroxy group or a diazo group is introduced from an amino group in a side chain, and this is used as a polymerization initiation point, and (6) ) Depending on the side chain active group such as hydroxyl, amino or carboxyl Examples thereof include a method using a polymerization initiation reaction of epoxy, lactam, polar vinyl monomer and the like.

Furthermore, the graft polymerization methods are specifically listed. a) A method of carrying out graft polymerization by generating free radicals by grinding cellulose in a monomer that is a raw material of a styrenic polymer. b) A method of performing graft polymerization using a monomer as a raw material of a styrene polymer and a cellulose derivative (for example, mercaptoethyl cellulose) having a group that is susceptible to chain transfer as a fiber. c) A method in which graft polymerization is performed by oxidizing ozone and peroxide to generate radicals. d) A method of carrying out graft polymerization by introducing a double bond such as allyl ether, vinyl ether or methacrylic acid ester into the side chain of cellulose. e) A method of performing graft polymerization by irradiating a fiber with ultraviolet rays using sodium anthraquinone-2,7-disulfonate as a photosensitizer. f) A method of performing graft polymerization electrochemically by winding fibers around the cathode, adding a monomer as a raw material of the styrene polymer to dilute sulfuric acid, and applying an external voltage.

Considering that the graft polymerization to the fiber, the following method is preferable. g) A method in which a fiber coated with glycidyl methacrylate (GMA) and benzoyl peroxide is graft polymerized by heating in a monomer solution that is a raw material for the styrenic polymer. h) To the dispersion liquid in which benzoyl peroxide, a surfactant (nonionic surfactant or anionic surfactant) and monochlorobenzene are dispersed in water, a monomer which is a raw material for the styrene polymer is added to the fiber. As a method, for example, a polyester fiber is immersed and heated to perform graft polymerization.

As the polymer reaction method, a general-purpose method can be used, for example, (1) chain transfer reaction, oxidation reaction, substitution reaction for C—H, (2) addition reaction for double bond, oxidation reaction, (3) Hydroxyl esterification, etherification, acetalization, substitution reaction for ester group and amide group, addition reaction, hydrolysis reaction, substitution reaction for halogen group, elimination reaction, (4) substitution reaction for aromatic ring (halogenation, nitro , Sulfonation, chloromethylation) and the like.

Next, a method for physically fixing the allergen inhibitor to the fiber will be described. As a method of physically fixing the allergen inhibitor to the fiber, for example, (1) An allergen inhibitor solution is prepared by dissolving or dispersing the allergen inhibitor in a solvent, and the allergen inhibitor solution is impregnated with the fiber. A method of impregnating the fiber with an allergen inhibitor solution, (2) a method of applying the allergen inhibitor solution to the fiber surface, and (3) immersing the fiber in a binder obtained by dissolving or dispersing the allergen inhibitor. A method of fixing the allergen inhibitor to the fiber with a binder, (4) a method of applying a binder obtained by dissolving or dispersing the allergen inhibitor on the fiber surface, and fixing the allergen inhibitor to the fiber with a binder, etc. Can be mentioned. In the methods (1) and (2), the allergen inhibitor solution may contain the following binder.

The solvent is not particularly limited. For example, water; alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol; hydrocarbons such as toluene, xylene, methylnaphthalene, kerosene, and cyclohexane; diethyl ether, tetrahydrofuran, dioxane, and the like Ethers; ketones such as acetone and methyl ethyl ketone; amides such as N, N-dimethylformamide and the like.

The binder is not particularly limited as long as it can fix the allergen inhibitor to the fiber surface. For example, the binder made of a synthetic resin may be a urethane resin such as a one-component urethane resin or a two-component urethane resin. Acrylic resin, urethane acrylate resin, polyester resin, unsaturated polyester resin, alkyd resin, vinyl acetate resin, vinyl chloride resin, epoxy resin, epoxy acrylate resin, and the like, and urethane resin is preferable.

In the above description, the allergen inhibitor is chemically bonded to a separately manufactured fiber, or physically fixed, so that the allergen inhibitor is contained in the fiber. Fibers may be produced by spinning the combined fiber raw material.

The production method of the fiber raw material in which the allergen inhibitor is chemically bonded is not particularly limited. For example, the monomer having the structural formula represented by the general formula (1) and the monomer to be a general fiber raw material In which the monomer of the structural formula represented by the general formula (1) is copolymerized so as to contain more than 70 wt% and 98 wt% or less.

The allergen inhibitor of the present invention contains a styrene polymer containing a monomer component of the structural formula represented by the general formula (1) in an amount of more than 70% by weight and 98% by weight or less. It is possible to effectively suppress the reaction with the antibody, reduce allergic symptoms or prevent their expression. Furthermore, the allergen inhibitor of the present invention is less susceptible to unexpected discoloration or discoloration under daily use conditions, and can be suitably used for various daily necessities.

The allergen inhibitor of the present invention can be applied to an allergen object to impart an excellent allergen inhibitory effect to the allergen object. Even when an allergen target that has been treated with an allergen inhibitor is colored with pigments or dyes such as dyes, the allergen target does not rub against other products, causing color transfer to other products. The color of the allergen object is not transferred to other products and the other products are not contaminated. The color of the allergen object treated with the allergen inhibitor is transferred to another product, and the color of the allergen object is not lost.

Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
A 2-liter separable flask equipped with a stirrer, a cooler, and a thermometer, 211 parts by weight of sodium p-styrenesulfonate (trade name “Spinomer NaSS” manufactured by Tosoh Corporation, purity: 88.2 wt%), deionized 312 parts by weight of water, 57.4 parts by weight of styrene monomer (trade name “styrene, monomer” manufactured by Wako Pure Chemical Industries, Ltd.) and 407 parts by weight of modified ethanol (trade name “86% ethanol-ME, modified” manufactured by Wako Pure Chemical Industries, Ltd.) Was added and replaced with nitrogen gas while stirring, and then heated and maintained at 78 ° C.

A polymerization initiator solution prepared by dissolving 2.11 parts by weight of potassium peroxodisulfate (manufactured by Wako Pure Chemical Industries, Ltd.) in 95 parts by weight of deionized water was added to the separable flask over 15 minutes, and then over 5 hours. Styrene monomer and sodium p-styrene sulfonate were polymerized.

Thereafter, the reaction solution was dried to obtain a polymer. 50 parts by weight of the obtained polymer is dispersed in 500 parts by weight of ion-exchanged water to prepare a dispersion, and sodium hydroxide is added so that the pH of the dispersion becomes 8.5 while stirring the dispersion with a stirrer. After adding to the dispersion and stirring the dispersion for 5 hours, the polymer was separated from the dispersion, filtered and dried to obtain a p-sodium styrenesulfonate-styrene random copolymer. In the p-sodium styrenesulfonate-styrene random copolymer, the sodium p-styrenesulfonate component was 76% by weight and the styrene component was 24% by weight. The weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 190,000.

Black fabric A (solid twill fabric (cotton 100% by weight)), black fabric B (T / C broad fabric (polyester: 65% by weight, cotton: 35% by weight)) and dark blue fabric C (T / C broad fabric (polyester: 65% by weight, cotton: 35% by weight)) was cut into a flat rectangular shape measuring 5 cm in length and 20 cm in width.

Treatment aqueous solution obtained by dispersing 1% by weight of p-sodium styrenesulfonate-styrene random copolymer obtained above and 1% by weight of an acrylic binder (trade name “Boncoat AC-501” manufactured by DIC) in water. In addition, after the flat rectangular doughs A to C were soaked for 5 minutes each, excess water was removed from the doughs A to C, and the doughs A to C were dried at 150 ° C. for 3 minutes for testing. Pieces A to C were obtained. Each of 100 parts by weight of the fabrics A to C was impregnated with 1 part by weight of a p-sodium styrenesulfonate-styrene random copolymer.

(Example 2)
Sodium sulfonate salt of a polymer obtained by sulfonation of a part of the benzene ring of a p-styrene-maleic acid copolymer (styrene component: 75% by weight, maleic acid component: 25% by weight) “VERSA TL-3”, sulfonation rate of styrene component: 99 mol% or more, p-styrenesulfonic acid sodium salt component: 74 wt%, styrene component: 1 wt%, maleic acid component: 25 wt%, weight average molecular weight : 20,000).

Except that a sodium sulfonate salt of a polymer obtained by sulfonating a part of the benzene ring of a p-styrene-maleic acid copolymer was used instead of the p-sodium styrenesulfonate-styrene random copolymer. In the same manner as in Example 1, specimens A to C were obtained. Each of 100 parts by weight of the fabrics A to C was impregnated with 1 part by weight of a sodium sulfonate salt of a polymer obtained by sulfonating a p-styrene-maleic acid copolymer at the benzene ring.

(Example 3)
Sodium p-styrenesulfonate in the same manner as in Example 1 except that sodium p-styrenesulfonate was changed to 250 parts by weight, styrene monomer to 30 parts by weight, and potassium peroxodisulfate to 4 parts by weight. -A styrene random copolymer was obtained. In the p-sodium styrenesulfonate-styrene random copolymer, the sodium p-styrenesulfonate component was 88% by weight and the styrene component was 12% by weight. The weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 90,000. Test pieces A to C were obtained in the same manner as in Example 1. Each of 100 parts by weight of the fabrics A to C was impregnated with 1 part by weight of a p-sodium styrenesulfonate-styrene random copolymer.

Example 4
In the same manner as in Example 1, except that sodium p-styrenesulfonate was changed to 148.5 parts by weight, the styrene monomer was changed to 50 parts by weight, and potassium peroxodisulfate was changed to 3.25 parts by weight. A sodium styrenesulfonate-styrene random copolymer was obtained. In the p-sodium styrenesulfonate-styrene random copolymer, the sodium p-styrenesulfonate component was 72% by weight and the styrene component was 28% by weight. The weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 90,000. Test pieces A to C were obtained in the same manner as in Example 1. Each of 100 parts by weight of the fabrics A to C was impregnated with 1 part by weight of a p-sodium styrenesulfonate-styrene random copolymer.

(Example 5)
148.5 parts by weight of p-styrene sulfonate ammonium salt was used instead of sodium p-styrene sulfonate, styrene monomer was changed to 50 parts by weight, and potassium peroxodisulfate was changed to 3.25 parts by weight. A p-styrene sulfonic acid ammonium-styrene random copolymer was obtained in the same manner as in Example 1 except that 25 wt% aqueous ammonia was used instead of sodium hydroxide for pH adjustment. . In the p-ammonium styrenesulfonate-styrene random copolymer, the ammonium p-styrenesulfonate component was 72% by weight and the styrene component was 28% by weight. The weight average molecular weight of the p-ammonium styrenesulfonate-styrene random copolymer was 80,000. Specimens A to C were obtained in the same manner as in Example 1 except that p-ammonium styrenesulfonate-styrene random copolymer was used instead of p-sodium styrenesulfonate-styrene random copolymer. Each of 100 parts by weight of doughs A to C was impregnated with 1 part by weight of p-ammonium styrenesulfonate-styrene random copolymer.

(Example 6)
148.5 parts by weight of sodium p-styrene sulfonate was used in place of sodium p-styrene sulfonate, 50 parts by weight of acrylic acid monomer was used in place of styrene, and 3.25 parts by weight of potassium peroxodisulfate A p-sodium styrenesulfonate-acrylic acid random copolymer was obtained in the same manner as in Example 1 except for changing to In the p-sodium styrenesulfonate-acrylic acid random copolymer, the sodium p-styrenesulfonate component was 72% by weight and the acrylic acid component was 28% by weight. The weight average molecular weight of the p-sodium styrenesulfonate-acrylic acid random copolymer was 120,000. Specimens A to C were obtained in the same manner as in Example 1 except that p-sodium styrenesulfonate-acrylic acid random copolymer was used instead of p-sodium styrenesulfonate-styrene random copolymer. . Each of 100 parts by weight of the fabrics A to C was impregnated with 1 part by weight of a p-styrene ammonium sulfonate-acrylic acid random copolymer.

(Example 7)
50 parts by weight of the polymer before pH adjustment obtained in the same manner as in Example 1 was dispersed in 500 parts by weight of ion-exchanged water to prepare a dispersion, and this dispersion was stirred with a stirrer to adjust the pH of the dispersion. Hydrochloric acid was added to the dispersion so as to be 5.5, and the dispersion was stirred for 5 hours, and then the polymer was separated from the dispersion, filtered, and dried to obtain p-sodium styrenesulfonate-p- A styrene sulfonic acid-styrene random copolymer was obtained. In addition, in the p-sodium styrenesulfonate-p-styrenesulfonic acid-styrene random copolymer, the sodium p-styrenesulfonate component is 73.1% by weight, the p-styrenesulfonic acid component is 2.9% by weight, styrene The component was 24% by weight. The weight average molecular weight of the sodium p-styrenesulfonate-p-styrenesulfonate-styrene random copolymer was 190,000. Specimen A in the same manner as in Example 1 except that p-sodium styrenesulfonate-p-styrenesulfonic acid-styrene random copolymer was used instead of p-sodium styrenesulfonate-styrene random copolymer. ~ C was obtained. Each of 100 parts by weight of doughs A to C was impregnated with 1 part by weight of p-sodium styrenesulfonate-p-styrenesulfonate-styrene random copolymer. The total content of the p-styrene sulfonic acid sodium component and the p-styrene sulfonic acid component is shown in the column of styrene sulfonate content in Table 1 for convenience.

(Example 8)
After dissolving 10 g of polystyrene (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 2000) in 100 ml of 1,1,2,2-tetrachloroethane (manufactured by Wako Pure Chemical Industries, Ltd.), 98% by weight sulfuric acid aqueous solution ( 500 ml of Wako Pure Chemical Industries, Ltd.) was added and the reaction was carried out at 95 ° C. for 8 hours. Thereafter, the reaction solution was cooled to remove excess sulfuric acid, and the reaction solution was adjusted to pH 8.5 using sodium hydroxide, and then the reaction solution was dried to obtain a sulfonated polystyrene product (sulfonated). Rate: 95 mol%). In the sulfonated polystyrene, the sodium p-styrenesulfonate component was 95% by weight and the styrene component was 5% by weight. The weight average molecular weight of the sulfonated polystyrene was 200,000. Test pieces A to C were obtained in the same manner as in Example 1 except that a polystyrene sulfonated product was used instead of the p-sodium styrenesulfonate-styrene random copolymer. Each of 100 parts by weight of the doughs A to C was impregnated with 1 part by weight of a sulfonated polystyrene.

(Comparative Example 1)
Except that sodium p-styrenesulfonate was changed to 59.5 parts by weight, styrene monomer was changed to 30 parts by weight, and potassium peroxodisulfate was changed to 1.56 parts by weight, p- A sodium styrenesulfonate-styrene random copolymer was obtained. In the p-sodium styrenesulfonate-styrene random copolymer, the sodium p-styrenesulfonate component was 64% by weight and the styrene component was 36% by weight. The weight average molecular weight of the p-sodium styrenesulfonate-styrene random copolymer was 80,000. Test pieces A to C were obtained in the same manner as in Example 1. Each of 100 parts by weight of the fabrics A to C was impregnated with 1 part by weight of a p-sodium styrenesulfonate-styrene random copolymer.

(Comparative Example 2)
Aqueous solution of sodium p-styrenesulfonate homopolymer (p-sodium styrenesulfonate homopolymer) as a styrene polymer (trade name “PS-50” manufactured by Tosoh Organic Chemical Co., Ltd.), sodium p-styrenesulfonate alone Polymer content: 20 wt%, molecular weight: 570,000) was diluted 20 times with tap water to obtain a 1 wt% aqueous solution. Specimens A to C were obtained in the same manner as in Example 1 except that this aqueous solution was used as the treatment aqueous solution. 100 parts by weight of doughs A to C were impregnated with 1 part by weight of sodium p-styrenesulfonate homopolymer.

(Comparative Example 3)
Black fabric A (solid twill fabric (cotton 100% by weight)), black fabric B (T / C broad fabric (polyester: 65% by weight, cotton: 35% by weight)) and dark blue fabric C (T / C broad fabric (polyester: 65% by weight, cotton: 35% by weight)) was cut into a flat rectangular shape measuring 5 cm in length and 20 cm in width.

After dipping the flat rectangular doughs A to C in a treatment aqueous solution in which 1% by weight of an acrylic binder (manufactured by DIC, trade name “Boncoat AC-501”) is dispersed in water for 5 minutes, the dough Excess water was removed from A to C, and the doughs A to C were dried at 150 ° C. for 3 minutes to obtain test pieces A to C.

For the test specimens A to C obtained in Examples and Comparative Examples, the allergen suppressing effect, liquid color transferability and friction color transferability were measured in the following manner, and the results are shown in Table 1.

(Initial allergen suppression effect)
An allergen chilled dry powder (trade name “MiteExtract-Df” manufactured by Cosmo Bio Inc.) was dissolved in a phosphate buffer (pH 7.6) to prepare an allergen aqueous solution having a protein amount of 20 μg / ml.

Evaluation samples A to C each having a rectangular shape of 1 cm in length and 5 cm in width were cut out from each of the test pieces A to C obtained in Examples and Comparative Examples. A test tube to which 3 ml of the allergen aqueous solution was supplied was prepared. Samples A to C for evaluation were added to separate test tubes and shaken at 37 ° C. for 24 hours.

Next, 100 microliters of the allergen aqueous solution in the test tube is added to the allergen measuring device (trade name “Mighty Checker” manufactured by Sumika Enviro Science Co., Ltd.) The initial allergen inhibitory effect was evaluated. The darker the color of the allergen measuring device, the more allergen is present in the liquid. In addition, as an allergen suppression effect, the following 1 to 3 determination was set as the pass.
5 ... A thick, thick and clear line was observed.
4 ... It can be clearly seen that it is a line.
It is coloring faintly in 3 ... line shape.
2 ... The color is faintly colored.
1 ... No color development at all.

(Durable allergen suppression effect)
Evaluation samples A to C were prepared in the same manner as the evaluation of the initial allergen inhibitory effect. Each of these evaluation samples A to C was separately immersed in 200 ml of water kept at 25 ° C. for 1 minute and taken out, and each evaluation sample A to C was dried at 100 ° C. for 10 minutes. did. With respect to the evaluation sample pieces A to C, the allergen suppressing effect was measured in the same manner as described above.

(Liquid color transferability)
The treated aqueous solution used when preparing the test pieces A to C from the fabrics A to C obtained in the examples and comparative examples was visually observed and evaluated based on the following criteria.
○ Coloring was not observed in all the treatment aqueous solutions.
Δ: Slight coloration was observed in at least one treated aqueous solution.
X: Clear coloring was observed in at least one treatment aqueous solution.

(Friction color transfer)
The test pieces obtained in the examples and comparative examples were evaluated in 5 steps from 1 to 5 in terms of color transferability in 100 round trips using a dry cotton cloth in accordance with JIS L0849. The number becomes smaller as 5 is better and the contamination of the cotton cloth becomes more severe.

The allergen inhibitor of the present invention has an excellent allergen inhibitory effect, is unlikely to cause unexpected discoloration and discoloration under daily use conditions, and is applied to allergen objects such as daily necessities. The allergen suppressing effect can be easily given to the object. Since the allergen inhibitor of the present invention has almost no unexpected coloration or discoloration in the daily living environment, and there is almost no problem of color transfer, coloration to other products due to light fading, discoloration, or rubbing. It can also be suitably used for applications in which contamination due to transfer is a problem, for example, textile products, building interior materials, in-car accessories, vehicle interior materials, filters, and the like.

Claims (10)

1. An allergen inhibitor comprising a styrenic polymer containing a monomer component of the structural formula represented by the general formula (1) in an amount of more than 70% by weight and 98% by weight or less.
   

   

   
   (R ¹ to R ⁵ are each hydrogen, a sulfonic acid group or a sulfonic acid group salt, and at least one of R ¹ to R ⁵ is a sulfonic acid group or a sulfonic acid group salt. is there.)
2. The styrenic polymer is at least one polymer selected from the group consisting of a styrene sulfonate-styrene copolymer, a styrene sulfonate-styrene sulfonic acid-styrene terpolymer and a sulfonated polystyrene. The allergen inhibitor according to claim 1, wherein the allergen inhibitor is present.
3. An allergen-suppressing product obtained by treating the allergen inhibitor according to claim 1 or 2 with an allergen target.
4. Supplying an allergen inhibitor containing a styrenic polymer containing a monomer component of the structural formula represented by the general formula (1) in excess of 70% by weight and 98% by weight or less, An allergen-suppressing method characterized by imparting an allergen-suppressing effect to an allergen object.
   

   

   
   (R ¹ to R ⁵ are each hydrogen, a sulfonic acid group or a sulfonic acid group salt, and at least one of R ¹ to R ⁵ is a sulfonic acid group or a sulfonic acid group salt. is there.)
5. The allergen suppression method according to claim 4, wherein the allergen is present in the allergen object, and the allergen is suppressed by an allergen inhibitor.
6. The styrenic polymer is at least one polymer selected from the group consisting of a styrene sulfonate-styrene copolymer, a styrene sulfonate-styrene sulfonic acid-styrene terpolymer and a sulfonated polystyrene. The method for suppressing allergen according to claim 4, wherein
7. Use of a styrene polymer containing a monomer component of the structural formula represented by the general formula (1) in an amount of more than 70% by weight and 98% by weight or less as an allergen inhibitor.
   

   

   
   (R ¹ to R ⁵ are each hydrogen, a sulfonic acid group or a sulfonic acid group salt, and at least one of R ¹ to R ⁵ is a sulfonic acid group or a sulfonic acid group salt. is there.)
8. The styrenic polymer is at least one polymer selected from the group consisting of a styrene sulfonate-styrene copolymer, a styrene sulfonate-styrene sulfonic acid-styrene terpolymer and a sulfonated polystyrene. Use as an allergen inhibitor according to claim 7, characterized in that it is present.
9. Use for modifying or adsorbing an allergen of a styrenic polymer containing a monomer component of the structural formula represented by the general formula (1) in an amount of more than 70% by weight and 98% by weight or less.
   

   

   
   (R ¹ to R ⁵ are each hydrogen, a sulfonic acid group or a sulfonic acid group salt, and at least one of R ¹ to R ⁵ is a sulfonic acid group or a sulfonic acid group salt. is there.)
10. The styrenic polymer is at least one polymer selected from the group consisting of a styrene sulfonate-styrene copolymer, a styrene sulfonate-styrene sulfonic acid-styrene terpolymer and a sulfonated polystyrene. Use according to claim 9, characterized in that it is.