JP2022061453A - Anti-pollution agent - Google Patents

Abstract

To provide an anti-pollution agent that alleviates damage of skin or hair caused by air pollutant, and has excellent use feeling.SOLUTION: An anti-pollution agent containing polyurethane (C) which includes a polyol component (A) and polyisocyanate (B) as constituent monomer, in which the polyol component (A) essentially includes cationic polyol (a1).SELECTED DRAWING: None

Description

The present invention relates to anti-pollution agents.

Skin and hair are exposed to external stimuli such as atmospheric pollutants and ultraviolet rays, and are subject to various damages. Conventionally, research has been conducted on the fact that ultraviolet rays have an adverse effect on the skin, and many developments have been made on compositions that mitigate damage caused by ultraviolet rays. On the other hand, in recent years, attention has also been focused on damage to the skin and hair caused by air pollutants such as pollen, PM2.5, yellow sand, soot and smoke, and volatile organic compounds (VOCs), and it has an anti-pollution effect in the market. Proposals for cosmetics have been made. For example, Patent Document 1 discloses a cosmetic having an anti-pollution effect, which contains magnesium aluminometasilicate and an ultraviolet protective agent as active ingredients. Further, in Patent Documents 2 and 3, a method of physically protecting the skin by forming a coating film of an organic compound on the skin is known. However, since magnesium aluminometasilicate is a component that is sparingly soluble in water, there are problems that the products that can be blended are limited and that the effect of preventing air pollutants from adhering to the skin is poor.

Japanese Unexamined Patent Publication No. 2017-105825 Japanese Unexamined Patent Publication No. 2016-88866 Japanese Unexamined Patent Publication No. 2018-52819

The present invention has been made in view of the above problems, and an object of the present invention is to have an excellent effect of preventing air pollutants from adhering to the skin, alleviate irritation to the skin by air pollutants, and provide a feeling of use. Aims to provide a good anti-pollution agent.

The present inventors have reached the present invention as a result of diligent studies to achieve the above object. That is, the present invention is an antipollution agent containing a polyurethane (C) containing a polyol component (A) and a polyisocyanate (B) as constituent monomers, and the polyol component (A) is a cationic polyol (a1). Is essential, and the cationic polyol (a1) is a tertiary amine compound (a11) represented by the following general formula (1), a salt (a12) of a tertiary amine compound (a11), and a tertiary amine compound ( It is an antipolyurethane agent which is at least one compound selected from the group consisting of the quaternary compound (a13) of a11).

［式中、Ｒ^１はヒドロキシ基を有する炭素数１～６のアルキル基であり、Ｒ^２はヒドロキシ基を有する炭素数１～６のアルキル基であり、Ｒ^３は、炭素数１～２４の炭化水素基又はヒドロキシ基を有する炭素数１～６のアルキル基である。］

[In the formula, R ¹ is an alkyl group having a hydroxy group and having 1 to 6 carbon atoms, R ² is an alkyl group having a hydroxy group and having 1 to 6 carbon atoms, and R ³ is an alkyl group having 1 to 24 carbon atoms. It is an alkyl group having 1 to 6 carbon atoms and having a hydrocarbon group or a hydroxy group. ]

The anti-pollution agent of the present invention has a good usability, is excellent in the effect of preventing air pollutants from adhering to the skin, and can alleviate irritation to the skin caused by air pollutants.

Schematic diagram of an evaluation device for the effect of preventing harmful substances from adhering to cigarette smoke and the effect of removing harmful substances. Schematic diagram of an oxidative stress evaluation device for stratum corneum cells caused by harmful substances derived from cigarette smoke.

In the present invention, the antipollution agent is an agent showing an effect of alleviating the irritation to the skin caused by air pollutants. It is an effective drug.
The anti-pollution agent of the present invention suppresses the adhesion and permeation of air pollutants to the skin, thereby alleviating the irritation to the skin caused by the air pollutants. By doing so, it is considered that the irritation to the skin can be alleviated by comprehensively suppressing the abnormal metabolism, inflammation, oxidation, etc. of cells caused by air pollutants.

The air pollutant targeted by the anti-pollution agent of the present invention refers to a harmful substance or a group of harmful substances existing in the atmosphere. For example, suspended particulate matter (SPM, PM10, PM2.5) derived from smoke exhaust from automobiles, incinerators, etc., soaring soil particles, sulfur oxides, nitrogen oxides, etc. emitted by dust, combustion, etc. Examples thereof include volatile organic compounds (VOCs, aldehydes, dioxin, polycyclic aromatic hydrocarbons (PAH), etc.) derived from carbon oxide and volatilization from petroleum products.

The anti-pollution agent of the present invention contains a polyurethane (C) containing a polyol component (A) essential for the following cationic polyol (a1) and a polyisocyanate (B) as constituent monomers.
Polyurethane (C) forms a smooth and flexible thin film on the skin and hair, plays a role of blocking air pollutants, and suppresses the adhesion and penetration of air pollutants to the skin.

The polyol component (A) requires a cationic polyol (a1) and may be one kind of compound or a mixture of two or more kinds of compounds.
The cationic polyol (a1) acts as a protective film that repels cationic air pollutants and adsorbs to anionic air pollutants to prevent permeation.

［式中、Ｒ^１はヒドロキシ基を有する炭素数１～６のアルキル基であり、Ｒ^２はヒドロキシ基を有する炭素数１～６のアルキル基であり、Ｒ^３は、炭素数１～２４の炭化水素基又はヒドロキシ基を有する炭素数１～６のアルキル基である。］ The cationic polyol (a1) is a tertiary amine compound (a11) represented by the following general formula (1), a salt (a12) of a tertiary amine compound (a11), and a tertiary amine compound (a11). It is at least one compound selected from the group consisting of the quaternary compound (a13).

[In the formula, R ¹ is an alkyl group having a hydroxy group and having 1 to 6 carbon atoms, R ² is an alkyl group having a hydroxy group and having 1 to 6 carbon atoms, and R ³ is an alkyl group having 1 to 24 carbon atoms. It is an alkyl group having 1 to 6 carbon atoms and having a hydrocarbon group or a hydroxy group. ]

In the general formula (1), examples of the alkyl group having 1 to 6 carbon atoms having a hydroxy group represented by R ¹ , R ² and R ³ include a hydroxymethyl group, a hydroxyethyl group, a hydroxy-n-propyl group, and hydroxy. Examples thereof include -n-butyl group and hydroxy-n-hexyl group.
Of these, from the viewpoint of the flexibility of the film formed on the skin or hair, a hydroxymethyl group and a hydroxyethyl group are preferable, and a hydroxyethyl group is more preferable.

In the general formula (1), the hydrocarbon group having 1 to 24 carbon atoms represented by R ³ includes a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a dodecyl group, a hexadecyl group and a 9-octadecenyl group. , Icosyl group, docosyl group, tetracosyl group and the like.
Of these, from the viewpoint of smoothness when applied to the skin or hair, a hydrocarbon group having 1 to 6 carbon atoms is preferable, and a hydrocarbon group having 1 to 3 carbon atoms is more preferable, and most preferably. , Methyl group and ethyl group.

As the tertiary amine compound (a11) represented by the general formula (1), a tertiary hydroxyamine having at least one hydroxy group in the molecule is preferable, and a specific example of the preferable compound is N-. Examples thereof include methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-dodecyldiethanolamine, N-methylethanolpropanolamine and triethanolamine.
Of these, N-methyldiethanolamine, triethanolamine and N-methyldipropanolamine are more preferable, and N-methyldiethanolamine is particularly preferable, from the viewpoint of the flexibility and smoothness of the film formed on the skin and hair. And triethanolamine.

The salt (a12) of the tertiary amine compound (a11) is an acid neutralized product obtained by neutralizing the tertiary amine compound (a11) with the acid (D).
Examples of the acid (D) include inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, etc.), organic acids (galic acid, acetic acid, oxalic acid, citric acid, tartaric acid, lactic acid, itaconic acid, stearic acid, lauric acid, etc.) and the like. ..
The acid (D) is preferably hydrochloric acid, sulfuric acid, citric acid and lactic acid, more preferably lactic acid, from the viewpoint of anti-pollution effect.

The quaternary compound (a13) of the tertiary amine compound (a11) is a salt of a quaternary ammonium cation and an anion in which an alkyl group is further added to the nitrogen atom of the tertiary amine compound (a11). It can be obtained by a quaternization reaction using a tertiary amine compound (a11) and an alkylating agent (E).
Alkylating agents (E) include alkyl halides (methyl chloride, methyl bromide, ethyl chloride, etc.), dialkyl sulfate esters (dimethyl sulfate, diethyl sulfate, etc.) and alkyl halide carboxylic acids (salts) (sodium monochloroacetate, etc.). And so on.
As an example of the quaternization reaction, for example, the reaction is carried out by dropping an alkyl halide in a pressure resistant reaction vessel at 50 to 80 ° C. while stirring the tertiary amine compound (a11) and a solvent as necessary. A method of dropping dialkylsulfate to react while stirring the tertiary amine compound (a11) and a solvent as necessary in a glass reaction vessel at normal pressure of 10 to 50 ° C., glass. A method of stirring and reacting a tertiary amine compound (a11), an alkyl halide and, if necessary, a solvent at normal pressure in a reaction vessel at 50 to 80 ° C. can be applied.

When the polyurethane (C) contains a unit derived from a salt of the tertiary amine compound (a11) and a quaternary compound as a constituent unit, the tertiary amine compound (a11) is used as an acid (D) or an alkylating agent (E). ) And the polyol component (A) containing the salt (a12) and the quaternary compound (a13) obtained by reacting with the polyisocyanate (B) may be reacted with the tertiary amine compound (a11). The containing polyol component (A) may be reacted with the polyisocyanate (B) to carry out a polyurethane-forming reaction, and then reacted with an acid (D) or an alkylating agent (E) to make it cationic.

The polyol component (A) may further contain a nonionic polyol (a2).
By containing the nonionic polyol (a2), smoothness and film feeling when applied to the skin and hair can be obtained.
As the nonionic polyol (a2), a compound having two hydroxy groups is preferable, and specific examples of the preferable compound are ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, polytetramethylene ether glycol, and the like. Examples thereof include polyethylene glycol, polypropylene glycol, polyesterdiol and mixtures thereof.

Examples of the polyester diol include those obtained by condensation polymerization of a small molecule diol and a dicarboxylic acid.
Examples of low molecular weight diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and neopentyl glycol. , Spiroglycol, dioxane glycol, adamantandiol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methyl Examples thereof include propanediol, 1,3,3-methylpentanediol, 1,5-hexamethylene glycol, octylene glycol, 9-nonanediol and 2,4-diethyl-1,5-pentanediol.
Of these, ethylene glycol, 1,3-propanediol, 1,4-butanediol and 3-methyl-1,5-pentanediol are preferable from the viewpoint of smoothness when applied to the skin and hair.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, orthophthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6. -Naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid and the like can be mentioned.
Of these, malonic acid, succinic acid, glutaric acid and adipic acid are preferable from the viewpoint of smoothness when applied to the skin and hair.

The polyester diol is obtained by condensation polymerization of a low molecular weight diol and a dicarboxylic acid. In addition to the polyester diol, it is obtained by condensation polymerization of polyoxyalkylene glycol such as polyethylene adipate and polybutylene adipate and adipic acid. Polyester diols can also be preferably used.

The weight average molecular weight of the polyester diol is preferably 500 to 6,000, and more preferably 1,000 to 3,000.
When it is 500 or more, the film feeling when applied to the skin or hair is good, and when it is 6,000 or less, the handleability of the raw material at the time of synthesis is good.

In the present invention, the weight average molecular weight (hereinafter, may be abbreviated as Mw) can be measured using GPC under the following conditions.
Equipment (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): 2 TSK GEL GMH6 manufactured by Tosoh Corporation
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE) manufactured by Tosoh Corporation 12 points (molecular weight 500, 1,050, 2,800, 5,970, 9,100, 18, 100, 37,900) , 96,400, 190,000, 355,000, 1,090,000, 2,890,000)

In the present invention, the polyisocyanate (B) includes aromatic polyisocyanate (B1), aliphatic polyisocyanate (B2), alicyclic polyisocyanate (B3), aromatic aliphatic polyisocyanate (B4) and the above-mentioned (B1). Examples thereof include the modified product (B5) of (B4).
The polyisocyanate (B) may be used alone or in combination of two or more.

The aromatic polyisocyanate (B1) includes aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon atoms in the NCO group; the same applies to the carbon atoms of the following polyisocyanates) and aromatic triisocyanates having 6 to 20 carbon atoms. , Crude products of these isocyanates, mixtures of these isocyanates, and the like.
Specific examples include 1,3-phenylene diisocyanate or 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate (TDI), crude TDI, 2,4'-diphenylmethane diisocyanate or 4 , 4'-Diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI, or polypeptide MDI), and a mixture of TDI and polypeptide MDI.

Examples of the aliphatic polyisocyanate (B2) include aliphatic diisocyanates having 6 to 10 carbon atoms.
Specific examples include 1,6-hexamethylene diisocyanate (HDI) and lysine diisocyanate.

Examples of the alicyclic polyisocyanate (B3) include an alicyclic diisocyanate having 6 to 16 carbon atoms.
Specific examples include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate and the like.

Examples of the aromatic aliphatic polyisocyanate (B4) include aromatic aliphatic diisocyanates having 8 to 12 carbon atoms.
Specific examples include xylylene diisocyanate and α, α, α', α'-tetramethylxylylene diisocyanate.

The above-mentioned polyisocyanates (B1) to (B4) may be modified, and at least one selected from the group consisting of a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group and an isocyanurate group and an oxazolidone group may be used. It may be a modified product contained.
Specific examples include urethane-modified MDI and carbodiimide-modified MDI.

Of these polyisocyanates (B), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI) and 4,4'-diphenylmethane diisocyanate (MDI) from the viewpoint of flexibility when applied to the skin and hair. It is preferable to use.

In the present invention, the isocyanate index [(equivalent ratio of NCO group / OH group) × 100], which is the ratio of the polyol component (A) to the polyisocyanate (B), can be variously changed, but is preferably 50 to 200. It is more preferably 105 to 150, and particularly preferably 115 to 140.

The method for producing polyurethane of the present invention can be carried out by a known method for producing polyurethane. For example, a method in which the polyol component (A) and the polyisocyanate (B) are divided and reacted in multiple stages (prepolymer method), and a method in which the polyol component (A) and the polyisocyanate (B) are collectively reacted (one). The shot method) and the like can be mentioned, but the prepolymer method is preferable. As an example of the prepolymer method, the polyol component (A) and the polyisocyanate (B) are reacted in advance, the reaction is completed with water, a low molecular weight diamine, or the like, and then the tertiary amine group is partially or completely neutralized. Examples thereof include a method of summing, quaternizing and / or amphoterizing.

In the present invention, the reaction can be carried out using a solvent that is inert to the isocyanate group. As the solvent, an amide solvent (N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.), a ketone solvent (acetone, methylethylketone, methylisobutylketone, cyclohexanone, etc.), an aromatic hydrocarbon solvent (toluene, xylene, etc.), an ether solvent (Dioxane, tetrahydrofuran, etc.), sulfoxide solvent (dimethylsulfoxide, etc.) and a mixed solvent of two or more of these can be considered.
Of these, acetone and methyl ethyl ketone are preferable, and acetone is more preferable, from the viewpoint of reaction efficiency and safety of the residual solvent. Further, the amount of the organic solvent used is preferably in the range of 0.2 to 3 times the total weight of the constituent monomers because the reaction efficiency is good. The reaction temperature is preferably 20 to 150 ° C, more preferably 20 to 110 ° C. The reaction time is preferably 3 to 40 hours. The reaction pressure is also carried out under normal pressure, but may be carried out under pressure. A catalyst may also be used to accelerate the reaction. Examples of the catalyst include amine catalysts (such as triethylrangeamine, N-methylmorpholine and triethylamine), tin catalysts (such as dibutyltin dilaurate) and lead catalysts (such as lead octylate).

The weight average molecular weight of polyurethane (C) is preferably 3,000 to 100,000, more preferably 5,000 to 80,000.
If it is 3,000 or more, the safety is high and the anti-pollution performance is excellent, and if it is 100,000 or less, the dispersibility in water is good.

The content of polyurethane (C) in the anti-pollution agent of the present invention may be any amount as long as the polyurethane (C) can function as an active ingredient, for example, preferably 0.1 to 40% by weight based on the total amount of the anti-pollution agent. %, More preferably 0.3 to 25% by weight.

The anti-pollution agent of the present invention is preferably an aqueous dispersion of polyurethane (C).
Examples of the aqueous medium in which the polyurethane (C) is dispersed include water and a mixed solution of water and an organic solvent (methanol, ethanol, etc.) compatible with water. Of these, water is more preferable from the environmental aspect.

The viscosity of the aqueous dispersion of polyurethane (C) at 25 ° C. is preferably 5 to 3,000 mPa · s, more preferably 8 to 2,000 mPa · s, and most preferably 8 to 2,000 mPa · s, from the viewpoint of handleability. It is 10 to 1,000 mPa · s.
The viscosity can be measured using a BL type viscometer [TVB-10 manufactured by Toki Sangyo Co., Ltd.].

The solid content concentration (weight ratio of components other than volatile components) of the aqueous dispersion of polyurethane (C) is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, from the viewpoint of handleability. Most preferably, it is 20 to 30% by weight.
The solid content concentration is such that about 1 g of an aqueous dispersion of polyurethane (C) is thinly spread on a Petri dish, finely weighed, and then heated at 105 ° C. for 90 minutes using a circulating constant temperature dryer, and then weighed. It can be obtained by calculating the ratio (percentage) of the residual weight after heating to the weight before heating.

In addition to the active ingredient polyurethane (C), the antipollution agent of the present invention may contain other raw materials as long as the effects of the present invention are not impaired.
Other raw materials are water, surfactants, waxes, higher alcohols, higher fatty acids, paraffin oils, ester oils, conditioning agents, thickeners, pearlizing agents, UV absorbers / scattering agents, silicones, chelating agents, moisturizers. Examples include agents, pigments and preservatives.

Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, sodium polyoxyethylene lauryl sulfate, sodium polyoxyethylene lauryl sulfosuccinate, sodium 2-hydroxylauryl ether acetate and sodium polyoxyethylene lauryl ether acetate, and coconut oil fatty acid amide. Amphoteric surfactants such as propyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, laurylhydroxysulfobetaine, and β-laurylaminopropyrrate sodium as well as lauryldimethylamine oxide, glycerin monostearate, polyethylene glycol monostearate, distearate. Polyethylene glycol acid acid, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, methyl glucoside polyoxyethylene dioleate, ethylene glycol monostearate, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene polyoxypropylene butyl ether, etc. Examples of nonionic surfactants include cationic surfactants such as stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride and lanolin glycol ethyl sulfate fatty acid aminopropylethyldimethylammonium.

Examples of the wax include natural waxes such as microcrystallin wax, paraffin wax, silicone wax, ceresin, carnauba wax, rice wax and honey wax, and synthetic waxes such as polyethylene wax and sazole wax.

Examples of the higher alcohol include myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol and the like.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like.

Examples of the ester oil include isopropyl myristate, octyl palmitate, diisopropyl adipate, cetyl octanate, tri (caprylic acid / capric acid) glyceryl, glycol dilaurate and diisostearyl malate.

Examples of the conditioning agent include cationized cellulose, cationized guar gum, cationized hydrolyzed wheat protein, cationized hydrolyzed soybean protein and the like.

As the thickener, coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, stearic acid monoethanolamide, coconut oil fatty acid methylethanolamide, propylene glycol laurate, polyethylene glycol distearate, (crosslinked) acrylic acid polymer (Salt), polyethylene glycol methyl glucose dioleate, polyethylene glycol methyl glucose trioleate, polyoxyethylene cetostearyl hydroxymillistyyl ether and the like can be mentioned.

Examples of the pearlizing agent include ethylene glycol distearate.

Examples of the ultraviolet absorber / ultraviolet scattering agent include ethylhexyl methoxycinnamate, octyl methoxycinnamate, ethylhexyltriazone, octyl salicylate, t-butylmethoxydibenzoylmethane, titanium oxide and zinc oxide.

Examples of the silicone include dimethylpolysiloxane, modified silicone in which various organic groups are introduced into a part of the methyl group of dimethylpolysiloxane, and cyclic dimethylsiloxane.

Examples of the chelating agent include ethylenediaminetetraacetic acid and its salt, citric acid and its salt and the like.

Examples of the moisturizer include polyethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, sorbitol, xylitol, maltitol, chondroitin sulfate, hyaluronic acid and pyrrolidone carboxylic acid.

Pigments include inorganic pigments such as red iron oxide, yellow iron oxide and black iron oxide, and red 202, red 228, yellow 4, yellow 5, blue 1, blue 404, orange 201, and green 201. And organic pigments such as Purple No. 201.

Examples of the preservative include methylparaben, propylparaben, butylparaben, phenoxyethanol, benzoic acid (salt), salicylic acid (salt), sorbic acid (salt) and the like.

The anti-pollution agent of the present invention can be used for external skin preparations, and can be preferably used for pharmaceuticals and cosmetics.
The mode of the anti-pollution agent is not limited, and it can be used as a liquid, a gel, granules, or the like.
When the anti-pollution agent of the present invention is used as a cosmetic product, specific cosmetic products include a washing pigment, a cleaning agent (for example, shampoo and body soap, etc.), a lotion (for example, a whitening lotion), and a cream (for example, a vanishing cream). And cold cream), milky lotion, beauty liquid, pack (eg jelly peel-off type, paste wipe type and powder rinse type), face mask, cleansing, foundation, lotion, lip cream, lip gloss, lip liner, cheek red, Examples include cosmetic bases, shaving lotions, sunscreens, after-sun lotions, deodorant lotions, body lotions (including hand care lotions and foot care lotions) and body oils.

Further, by superimposing the anti-pollution agent of the present invention or a cosmetic containing the same (make-up keep mist, etc.) on the make-up cosmetics, not only can the irritation to the skin caused by suspended particulate matter in the air be alleviated. , It is also possible to prevent the makeup cosmetics from collapsing. Therefore, the anti-pollution agent of the present invention can be preferably used as a cosmetic such as make-keeping mist or as a raw material thereof.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates weight% and parts indicate parts by weight.

<Manufacturing example 1>
In a pressure-resistant reaction vessel equipped with a thermometer and a stirrer, a polyester diol consisting of 1,4-butanediol and adipic acid with a molecular weight of approximately 1,000 [Teslac 2464 (manufactured by Showa Denko Materials Co., Ltd.), Tesslac is Hitachi Chemical Co., Ltd. Registered trademark of Co., Ltd.] 150.0 parts, polytetramethylene glycol with a molecular weight of about 2,000 [PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.)] 58.0 parts, N-methyldiethanolamine [amino alcohol MDA (Japan) Emulsifier Co., Ltd.)] 12.0 parts, isophorone diisocyanate [Death Module I (manufactured by Sumika Cobestrourethane Co., Ltd.), Death Module is a registered trademark of Covestro Deutschland Actien Gezel Shaft] 67.0 parts and acetone [Manufactured by KH Neochem Co., Ltd.] 125 parts were charged, the inside of the reaction vessel was replaced with nitrogen gas, and then the reaction was carried out at 90 ° C. for 5 hours under stirring. After cooling the obtained acetone solution to 30 ° C., 12.5 parts of dimethyl sulfate [manufactured by Tsujimoto Chemical Industry Co., Ltd.] was added dropwise, and quaternization was performed at 30 to 40 ° C. 720 parts of ion-exchanged water was added to the obtained quaternary product under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a polyurethane having a solid content concentration of 30% by weight and a viscosity of 420 mPa · s. To obtain 1,000 parts of the aqueous dispersion of (U-1).

<Manufacturing example 2>
In a pressure resistant reaction vessel equipped with a thermometer and a stirrer, 97.0 parts of polytetramethylene glycol [PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.)] with a molecular weight of about 2,000 and 3-methylpentanediol with a molecular weight of about 2,000 Polyester diol [P-2010 (manufactured by Claret Co., Ltd.)] 100.0 parts, 1,4-butanediol [manufactured by Mitsubishi Chemical Co., Ltd.] 7.0 parts, N-methyldiethanolamine [amino alcohol] MDA (manufactured by Nippon Emulsor Co., Ltd.)] 15.0 parts, 1,6-hexamethylene diisocyanate [Desmodule H (manufactured by Sumika Cobestrourethane Co., Ltd.)] 65.0 parts and acetone [KH Neochem Co., Ltd. Manufactured] 125 parts were charged, the inside of the reaction vessel was replaced with nitrogen gas, and then the reaction was carried out at 90 ° C. for 5 hours with stirring. After cooling the obtained acetone solution to 70 ° C., 16.0 parts of sodium monochloroacetic acid [monochromolacetic acid sodium salt (manufactured by Denak Co., Ltd.)] was added, and further amphoterization was performed at 70 ° C. To the obtained amphoteric product, 720 parts of ion-exchanged water was added under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a polyurethane having a solid content concentration of 30% by weight and a viscosity of 600 mPa · s. 1,000 parts of an aqueous dispersion was obtained (U-2).

<Manufacturing example 3>
In a pressure-resistant reaction vessel equipped with a thermometer and a stirrer, polytetramethylene glycol having a molecular weight of about 2,000 [PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.)] 48.0 parts, N-methyldiethanolamine [amino alcohol MDA (Japanese emulsifier) 68.0 parts, 1,6-hexamethylene diisocyanate [Desmodule H (manufactured by Sumika Cobestrourethane Co., Ltd.)] 118.0 parts and acetone [manufactured by KH Neochem Co., Ltd.] 125 parts Was charged, the inside of the reaction vessel was replaced with nitrogen gas, and then the reaction was carried out at 90 ° C. for 5 hours with stirring. The obtained acetone solution was cooled to 50 ° C., 30.0 parts of absolute ethanol [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] was added, and the reaction was further carried out at 50 ° C. for 4 hours. 57.0 parts of lactic acid [90% lactic acid (manufactured by Showa Kako Co., Ltd.) was added to the obtained acetone solution, and neutralization was performed at 45 to 55 ° C. To the obtained neutralized product, 720 parts of ion-exchanged water was added under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a solid content concentration of 30% by weight and a viscosity of 2,000 mPa · s. Obtained 1,000 parts of an aqueous dispersion of polyurethane (U-3).

<Manufacturing example 4>
In a pressure-resistant reaction vessel equipped with a thermometer and a stirrer, 170.0 parts of polytetramethylene glycol [PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.)] with a molecular weight of about 2,000, N-methyldiethanolamine [amino alcohol MDA (Japanese emulsifier) (Manufactured by Co., Ltd.)] 23.0 parts, isophorone diisocyanate [Death Module I (manufactured by Sumika Cobestrourethane Co., Ltd.)] 83.0 parts and acetone [manufactured by KH Neochem Co., Ltd.] 125 parts in a reaction vessel. Was replaced with nitrogen gas, and then reacted at 90 ° C. for 5 hours with stirring. After cooling the obtained acetone solution to 30 ° C., 24.0 parts of diethyl sulfate [Koriyama Kasei Co., Ltd.] was added dropwise, and quaternization was performed at 30 to 40 ° C. 720 parts of ion-exchanged water was added to the obtained quaternary product under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a polyurethane having a solid content concentration of 30% by weight and a viscosity of 450 mPa · s. To obtain 1,000 parts of the aqueous dispersion of (U-4).

<Manufacturing example 5>
In a pressure-resistant reaction vessel equipped with a thermometer and a stirrer, polypropylene glycol with a molecular weight of about 2,000 [New Pole PP-2000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.)] 225.0 parts, propylene glycol [Industrial propylene glycol ( ADEKA Corporation] 5.0 parts, N-methyldiethanolamine [Amino alcohol MDA (manufactured by Nippon Emulsifier Co., Ltd.)] 5.0 parts, 4,4'-diphenylmethane diisocyanate [Sumijour 44S92 (Sumika Cobestro) Urethane Co., Ltd.) and Sumijour are registered trademarks of Sumitomo Chemical Co., Ltd.] 63.0 parts and acetone [KH Neochem Co., Ltd.] 125 parts are charged and the inside of the reaction vessel is replaced with nitrogen gas. The reaction was carried out at 90 ° C. for 5 hours with stirring. After cooling the obtained acetone solution to 70 ° C., 2.0 parts of methyl chloride [methyl chloride (manufactured by Shin-Etsu Chemical Co., Ltd.)] was blown into the solution, and quaternization was performed at 65 to 75 ° C. To the obtained quaternary product, 720 parts of ion-exchanged water was added under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a polyurethane having a solid content concentration of 30% by weight and a viscosity of 300 mPa · s. To obtain 1,000 parts of the aqueous dispersion of (U-5).

<Manufacturing example 6>
In a pressure-resistant reaction vessel equipped with a thermometer and a stirrer, a polyester diol consisting of 1,4-butanediol and adipic acid having a molecular weight of about 1,000 [Teslac 2464 (manufactured by Showa Denko Materials Co., Ltd.)] 175.0 parts. , 1,4-Butanediol [manufactured by Mitsubishi Chemical Co., Ltd.] 8.2 parts, N-methyldiethanolamine [Amino alcohol MDA (manufactured by Nippon Emulsifier Co., Ltd.)] 15.2 parts, Isophoron diisocyanate [Death Module I (Sumi) 93.7 parts manufactured by Cobestrolurethane Co., Ltd.] and 125 parts of acetone [manufactured by KH Neochem Co., Ltd.] were charged, the inside of the reaction vessel was replaced with nitrogen gas, and then the reaction was carried out at 90 ° C. for 5 hours under stirring. The obtained acetone solution was cooled to 70 ° C., 7.0 parts of methyl chloride [methyl chloride (manufactured by Shin-Etsu Chemical Co., Ltd.)] was blown into the solution, and quaternization was performed at 65 to 75 ° C. 720 parts of ion-exchanged water was added to the obtained quaternary product under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a polyurethane having a solid content concentration of 30% by weight and a viscosity of 400 mPa · s. To obtain 1,000 parts of the aqueous dispersion of (U-6).

<Manufacturing example 7>
A polyester diol consisting of 1,4-butanediol having a molecular weight of about 1,000 and adipic acid [Teslac 2464 (manufactured by Showa Denko Materials Co., Ltd.)] 180.2 parts in a pressure-resistant reaction vessel equipped with a thermometer and a stirrer. , 1,4-Butanediol [manufactured by Mitsubishi Chemical Co., Ltd.] 6.2 parts, Dimethylol propionic acid [DMPA (GEO Speciality Chemicals)] 19.6 parts, Isophorone diisocyanate [Death Module I (Suika Cobestlorethane) 94.0 parts of acetone [manufactured by KH Neochem Co., Ltd.] and 125 parts of acetone [manufactured by KH Neochem Co., Ltd.] were charged, and the inside of the reaction vessel was replaced with nitrogen gas, and then the reaction was carried out at 90 ° C. for 5 hours under stirring. After cooling the obtained acetone solution to 45 ° C., add 140 parts of a 1N aqueous sodium hydroxide solution [potassium hydroxide [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] diluted to 1N with ultrapure water] and add 45 parts. Neutralization was performed at ~ 55 ° C. To the obtained neutralized product, 588 parts of ion-exchanged water was added under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a polyurethane having a solid content concentration of 30% by weight and a viscosity of 320 mPa · s. To obtain 1,000 parts of the aqueous dispersion of (U'-1).

<Manufacturing example 8>
In a pressure resistant reaction vessel equipped with a thermometer and a stirrer, 91.6 parts of polytetramethylene glycol [PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.)] with a molecular weight of about 2,000 and 3-methylpentanediol with a molecular weight of about 2,000 Polyester diol consisting of adipic acid [P-2010 (manufactured by Claret Co., Ltd.)] 91.6 parts, 1,4-butanediol 6.6 parts, dimethylol propionic acid [DMPA (manufactured by GEO Speciality Chemicals)] 20. 8 parts, isophorone diisocyanate [Death Module I (manufactured by Sumika Cobestrourethane Co., Ltd.)] 78.8 parts and acetone [manufactured by KH Neochem Co., Ltd.] 125 parts were charged, and the reaction system was replaced with nitrogen gas and then stirred. The reaction was carried out at 90 ° C. for 5 hours. The obtained acetone solution was cooled to 50 ° C., 30.0 parts of absolute ethanol [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] was added, and the reaction was further carried out at 50 ° C. for 4 hours. To the obtained polyurethane solution, 13.8 parts of N-methyldiethanolamine [Amino Alcohol MDA (manufactured by Nippon Emulsifying Co., Ltd.)] was added, and neutralization was performed at 45 to 55 ° C. To the obtained neutralized product, 720 parts of ion-exchanged water was added under stirring at 30 to 50 ° C., and acetone was distilled off at 50 to 60 ° C. under reduced pressure to obtain a polyurethane having a solid content concentration of 30% by weight and a viscosity of 380 mPa · s. To obtain 1,000 parts of the aqueous dispersion of (U'-2).

<Manufacturing example 9>
In a pressure-resistant reaction vessel equipped with a thermometer and a stirrer, polytetramethylene glycol with a molecular weight of about 2,000 [PTMG2000 (manufactured by Mitsubishi Chemical Corporation)] 258.4 parts, isophorone diisocyanate [Death Module I (Sumitomo Cobestro) After 41 parts of [manufactured by Urethane Co., Ltd.] and 122 parts of acetone [manufactured by KH Neochem Co., Ltd.] were charged and the inside of the reaction vessel was replaced with nitrogen gas, the reaction was carried out at 90 ° C. for 5 hours under stirring. After cooling the obtained acetone solution to 50 ° C., 720 parts of ion-exchanged water was added under stirring, and acetone was distilled off at 50-60 ° C. under reduced pressure to make a polyurethane having a solid content concentration of 30% by weight and a viscosity of 380 mPa · s. To obtain 1,000 parts of the aqueous dispersion of (U'-3).

<Examples 1 to 6 and Comparative Examples 1 to 6>
The aqueous dispersions (U-1) to (U-6) of polyurethane produced in Production Examples 1 to 6 were used as they were as the anti-pollution agents of the present invention according to Examples 1 to 6.
Further, the aqueous dispersions (U'-1) to (U'-3) of the polyurethanes produced in Production Examples 7 to 9, polyvinylpyrrolidone [LUVISKOL K30 (manufactured by BASF Japan Co., Ltd.), and LUVISKOL are BAS F-sociator. Aqueous solution (concentration 1% by weight) of [European registered trademark] (U'-4) and cationized cellulose [UCARE Polymer JR-30MP (manufactured by Dow Chemical Japan Co., Ltd.), UCARE is Union Carbide Corporation. An aqueous solution (concentration: 1% by weight) of [registered trademark] (U'-5) was used as a comparative antipolyurethane agent according to Comparative Examples 1 to 5.
Using the anti-pollution agents according to Examples 1 to 6 and Comparative Examples 1 to 5, the harmful substances derived from cigarette smoke were evaluated by the following method.

<Evaluation of toxic substance adhesion prevention effect and toxic substance removal effect of anti-pollution agents>
The harmful substance adhesion prevention effect and the harmful substance removal effect of the antipollution agents according to Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated by the following evaluation methods.
In the evaluation of the harmful substance adhesion prevention effect and the harmful substance removal effect, the effect of preventing the adhesion of coloring components (tar, etc.) contained in the smoke generated from the ignited cigarette smoke (hereinafter, may be abbreviated as cigarette smoke). , And the effect of removing aldehydes (formaldehyde, acetaldehyde, acrolein, etc.) and benzopyrene was confirmed.

<Method of manufacturing evaluation filter>
Omnipore Membrane Filter JCWP02500 [Hydrophilic PTFE filter, pore diameter 10 μm, filter diameter 25 mm (manufactured by Merck), omnipore is Merck Command Gezel Shaft Auf) It is a registered trademark of Akchen] and dried in a constant temperature bath at 55 ° C. for evaluation filters (F-1) to (F-6) and comparative filters (F'-1) to (F'-5). ) Was produced.
Further, an omnipore membrane filter JCWP02500 (F'-6) to which no chemical was applied was prepared as a comparative filter.
Using the evaluation filters (F-1) to (F-6) and the comparison filters (F'-1) to (F'-6), the anti-pollution agent has the effect of preventing harmful substances from adhering and is harmful by the following method. The substance removal effect was confirmed, and the results are shown in Table 1.

<Evaluation method of harmful substance adhesion prevention effect and harmful substance removal effect of anti-pollution agent>
To evaluate the effect of preventing the adhesion of harmful substances derived from cigarette smoke and the effect of removing harmful substances, the effect of preventing the adhesion of harmful substances and the effect of removing harmful substances are evaluated by using phosphate buffered saline D-PBS (-) [Dulbecco's Phosphate-Buffered Salone (Fuji). Film Wako Junyaku Co., Ltd.]] was evaluated by the method described in detail below using the cigarette smoke permeation treatment device shown in FIG. 1, which can be bubbled.
The prepared evaluation filter was set in a filter holder portion (T2) having a diameter of 25 mm, and the filter holder portion (T2) was screwed and fixed. Screw tube [Screw tube No. 6 (manufactured by Maruemu Co., Ltd.)] (T9), 5 mL of phosphate buffered saline D-PBS (-) was added, and a screw tube lid (T10) having two openings (X1, X2) having a diameter of 2 mm was attached. I closed it. A glass tube (T8) is passed through the opening (X1) of the transmission processing device, and a rubber tube [Quin tube (manufactured by Utsunomiya Seisakusho): inner diameter 6 mm, outer diameter 8.4 mm] (T7) is connected to the upper part of the glass tube. Further, the opposite end of the rubber tube (T7) was connected to the hose adapter (T6) at the bottom of the filter holder. The lower part of the glass tube (T8) was immersed in phosphate buffered saline D-PBS (−). The hose adapter part (T5) on the upper part of the filter holder part (T2) is attached to the mouthpiece of the cigarette (T1) through a rubber tube [Quin tube (manufactured by Utsunomiya Seisakusho): inner diameter 6 mm, outer diameter 8.4 mm] (T4). Connected.
The opening (X2) is the intake port of the decompression pump (T12) [desktop diaphragm type vacuum pump (manufactured by KNF)] through the tube [Quin tube (manufactured by Utsunomiya Seisakusho): inner diameter 6 mm, outer diameter 8.4 mm] (T11). Connected with.
After igniting the cigarette smoke (T1), the decompression pump (T12) was started, and the cigarette smoke that had passed through the evaluation filter was drawn into the phosphate buffered saline D-PBS (-) and bubbling. The burning rate of the cigarette was adjusted by a decompression pump (T12) so that one cigarette would burn all in 5 minutes.
Hereinafter, the phosphate buffered saline D-PBS (-) after bubbling with the permeation treatment device for cigarette smoke will be referred to as permeation treatment D-PBS (-).
The appearance of the evaluation filter after burning one cigarette was visually confirmed, and the effect of the antipollution agent on preventing the adhesion of harmful substances was evaluated according to the following evaluation criteria. The less the evaluation filter is dirty, the higher the effect of the anti-pollution agent on preventing the adhesion of harmful substances (colored substances in cigarette smoke).
Further, the amounts of aldehyde and benzopyrene contained in the permeation-treated D-PBS (-) were measured by the following method, and the harmful substance removing effect of the antipollution agent was evaluated. The smaller the amount of aldehyde and benzopyrene contained in the permeation-treated D-PBS (-), the higher the effect of removing harmful substances (aldehyde and benzopyrene) by the antipollution agent in the evaluation filter.

(Evaluation criteria for the effect of anti-pollution agents on preventing the adhesion of harmful substances based on the appearance of the evaluation filter)
◯: More than half of the evaluation filter remains white and less than half is stained brown △: Less than half of the evaluation filter remains white and more than half is stained brown ×: For evaluation The entire filter is dirty brown

(Method for measuring the content of aldehyde contained in permeation-treated D-PBS (-))
Permeation-treated D-PBS (-) and acrolein (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a sample for preparing a calibration curve, are 1 mM, 0.5 mM, 0.25 mM, 0.125 mM, 0.0625 mM, 0.0310 mM in ultrapure water. , 0.0250 mM, 0.0156 mM and 0 mM, and well in 96-well Plate [96 well Rigid Plate, Flat Button, Non-Stile, Polystyrene, Black (manufactured by Thermo Scientific)]. 50 μL was added to each.
NBD-H [4-hydrazino-7-nitro-2,1,3-benzoxadiazole hydrazine (manufactured by Tokyo Chemical Industry Co., Ltd.)] was added to DMF [N, N-dimethylformamide (Nacalai Tesque) to 25 mM. Co., Ltd.)] was dissolved to prepare a DMF solution (concentration 25 mM) of NBD-H.
The prepared NBD-H DMF solution (25 mM) was further diluted with a 0.05% aqueous solution of trifluoroacetic acid [trifluoroacetic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) to 0.05% with ultrapure water. ] To prepare a 250 μM solution of NBD-H.
A 250 μM solution of NBD-H prepared was permeated into each of the permeation-treated D-PBS (-) added to the 96-well Plate and the sample for calibration curve measurement (acrolein aqueous solution), and the prepared D-PBS (-) and calibration curve were prepared. 50 μL was added to the well containing the sample for use.
Subsequently, the 96-well Plate was allowed to stand at 25 ° C. under shading for 30 minutes, and then the fluorescence intensity (excitation wavelength) between the solution containing each permeation-treated D-PBS (-) in the well and the sample for calibration curve measurement was observed. 470 nm / fluorescence wavelength 550 nm) was measured using a plate reader [Infinite 200Pro M Nano + (manufactured by TECAN)].
The content of aldehyde contained in the permeation-treated D-PBS (-) was calculated from the fluorescence intensity of each permeation-treated D-PBS (-) and the calibration curve for measuring the aldehyde content.
For the calibration curve for measuring the aldehyde content, a calibration curve was prepared by the least squares method using the relationship between the fluorescence intensity of the sample for measuring the calibration curve and the concentration of the sample for measuring the calibration curve.

(Method for measuring the content of benzopyrene contained in permeation-treated D-PBS (-))
Permeation-treated D-PBS (-) and benzopyrene (manufactured by Sigma-Aldrich), which is a sample for preparing a calibration curve, with dimethyl sulfoxide (manufactured by Nacalai Tesque) at 40 μM, 20 μM, 10 μM, 5 μM, 2.5 μM, 1.25 μM. , 0.63 μM and 0 μM were adjusted, and 100 μL was added to each well of 96-well Plate.
Subsequently, the fluorescence intensity (excitation wavelength 360 nm / fluorescence intensity 450 nm) of the solution containing each permeation-treated D-PBS (-) in the well and the sample for calibration curve measurement was measured by a plate reader [Infinite 200Pro M Nano + (manufactured by TECAN). ] Was measured.
The content of benzopyrene contained in each permeation-treated D-PBS (-) was calculated from the fluorescence intensity of each permeation-treated D-PBS (-) and the calibration curve for measuring the benzopyrene content.
For the calibration curve for measuring the benzopyrene content, a calibration curve was prepared by the least squares method using the relationship between the fluorescence intensity of the sample for preparing the calibration curve and the concentration of the calibration curve measurement sample.

(Evaluation of irritation to human epidermal cells)
Using HaCaT cells (immortalized keratinocytes) and Neutral Red, the effects of harmful substances on the irritation of human epidermal cells by the use of antipollution agents were evaluated according to the following procedures (i) to (viii). .. Neutral red is a compound that can be taken up into cells only by living cells. Neutral red is taken up by cells, the neutral red taken up by cells is extracted, and the absorbance of the cells is measured. Survival rate can be evaluated.

(I) Phosphate buffered aqueous solution D-PBS (-) was changed to DMEM (-) [Dulvecco's Modified Eagle Medium (manufactured by Fuji Film Wako Junyaku Co., Ltd.)]. Perform the same operation as the evaluation of the toxic substance removal effect and the toxic substance removal effect, and use the above-mentioned evaluation filters (F-1) to (F-6) and comparative filters (F'-1) to (F) for cigarette smoke. DMEM (−) (G1-1) to (G1-6) and (G1 ′ -1) to (G1 ′ -6), which were subjected to permeation treatment in ′ -6), were obtained.

(Ii) HaCaT cells (immortalized keratinocytes) were seeded in each well of 96-well Plate [96-well polystyrene microplate (transparent) (Corning)] at a cell concentration of 3.5 × 10 ⁴ . Further, 100 μL of DMEM (−) (hereinafter referred to as untreated DMEM (−)) which has not been subjected to permeation treatment was added to each well. Then, this 96-well Plate was cultured at 37 ° C. in a 5% CO ₂ incubator [MCO-18AIC (manufactured by SANYO)] for 24 hours, DMEM (-) in each well was removed with an aspirator, and then phosphate buffered. 100 μL of the aqueous solution D-PBS (−) was added per well, and then the phosphate buffered saline D-PBS (−) was removed with an aspirator.

(Iii) The permeation-treated DMEM (−) prepared in (i) above was diluted 5-fold with untreated DMEM (−) to prepare a solution (G2-1). 100 μL of the solution (G2-1) was added to the well containing HaCaT cells (immortalized keratinized cells) prepared in (ii) after culturing for 24 hours, and the medium was exchanged. Culture samples were obtained by culturing in a CO ₂ incubator for 24 hours and mediating in a solution (G2-1).

(Iv) DMEM (-) (G1-2) to (G1-6) and (G1'-1) to (G1'-6) that have been permeated are also diluted 5-fold in the same manner as the solution (G2-1). A solution (G2-x) [x is a number corresponding to the DMEM (-) number (G1-x) before dilution] is prepared, and DMEM (-) (G2-x) is prepared in the same manner as in (iii). Medium exchange and culture were performed using.

(V) An aqueous solution prepared by dissolving Neutral Red [manufactured by Fuji Film Wako Junyaku Co., Ltd.] in purified water at 3.3 mg / mL is 200-fold with DMEM containing 5% FBS (fetal bovine serum). Diluted to prepare DMEM containing neutral red.

(Vi) After removing DMEM (-) from each well after culturing in (iii) and (iv) above with an aspirator, 100 μL of new phosphate buffered saline D-PBS (-) is added per well. Addition was subsequently made, and the phosphate buffered saline D-PBS (-) in each well was subsequently removed with an aspirator. Then, 100 μL of DMEM containing neutral red prepared in (iv) was added per 1 well, and the cells were further cultured at 37 ° C. in a 5% CO ₂ incubator for 2 hours.

(Vii) After removing the neutral red-containing DMEM from each well cultured in (vi) above with an aspirator, 100 μL of phosphate buffered saline D-PBS (-) was added per well, and then from each well. Phosphate buffered saline D-PBS (-) was removed with an aspirator. Then, 100 μL of the phosphate buffered saline D-PBS (−) was added again per well, and then the phosphate buffered saline D-PBS (−) was removed from each well with an aspirator.
Then, 100 μL of a solvent mixed at a volume ratio of purified water / methanol / acetic acid = 49/50/1 (hereinafter referred to as a mixed solvent) is added per well, and the mixture is shaken and stirred for 3 minutes to cause HaCaT cells (immortal). Neutral red taken up by keratinocytes) was extracted into a mixed solvent in well.

(Viii) Using untreated DMEM (-) instead of DMEM (-) that has been subjected to permeation treatment, the above operations (iii) to (vii) are performed, and DMEM (-) that has not been permeated with cigarette smoke. A neutral red extract (referred to as a neutral red extract that has not been permeated with cigarette smoke) was obtained when the medium was replaced using the medium.

(Ix) Absorbance at 550 nm of the neutral red extract obtained in the above (vii) (referred to as the neutral red extract) and the neutral red extract not permeated with the cigarette smoke obtained in the above (viii). And the absorbance at 650 nm were measured with a plate reader while still in the well.
The subtraction value in each extract sample is calculated by subtracting the absorbance at 650 nm from the absorbance at 550 nm, and the "absorbance of the neutral red extract" with respect to the "subtraction value of the absorbance of the neutral red extract not permeated with cigarette smoke". The ratio (%) of "subtracted value" [(absorbance subtracted value of neutral red extract) / (absorbance subtracted value of neutral red extract not permeated with cigarette smoke) x 100] was calculated.
The ratio of the "absorbance subtraction value of the neutral red extract" to the "absorbance subtraction value of the neutral red extract not permeated with cigarette smoke" is that the higher the survival rate of HaCaT cells (immortalized keratinocytes), the higher the survival rate. Since it is a large value, it can be used as a reference for the number of cells that survive in the culture system. In Table 1, this calculated value is shown as HaCaT cell viability.
The higher the HaCaT cell viability, the more harmful substances derived from cigarette smoke are removed by the anti-pollution agent in the filter. In addition, it can be said that the anti-pollution agent in the filter reduces the skin irritation caused by the harmful substances derived from cigarette smoke because more HaCaT cells are alive.

<Examples 11 to 16 and Comparative Examples 11 to 16>
The aqueous dispersions (U-1) to (U-6) of the polyurethanes produced in Production Examples 1 to 6 diluted to a concentration of 3% were used as the anti-pollution agent of the present invention, and in Production Examples 7 to 9. Polyvinylpyrrolidone [LUVISKOL K30 (manufactured by BASF Japan Co., Ltd.)] (U'-4), which is a dispersion obtained by diluting the produced aqueous dispersions (U'-1) to (U'-3) of polyurethane to a concentration of 3%. Aqueous solution (concentration 3% by weight) and an aqueous solution (concentration 3% by weight) of cationized cellulose [UCARE Polymer JR-30MP (manufactured by Dow Chemical Japan Co., Ltd.)] (U'-5) are used as an anti-pollution agent for comparison. The cosmetics (V-1) to (V-6) according to Examples 11 to 16 and the comparative cosmetics (V'-1) to (V') according to Comparative Examples 11 to 15 including the same. -5) was prepared and the stickiness of the cosmetic was evaluated. As the cosmetic according to Comparative Example 16, a cosmetic (V'-6) using the same amount of water as the D phase was prepared.

<Preparation method of cosmetics>
Each component of the following A phase was heated and dissolved at 80 ° C. to prepare an A phase, the following B phase component was added to the A phase, stirred to make it uniform, and the C phase component was added. After defoaming and cooling this solution, the D phase component is added, and the mixture is further stirred to make it uniform, and the cosmetics (V-1) to (V-6) and (V'-1) to (V'-6). Got For the cosmetics (V'-4) and (V'-5), an aqueous solution of the cationic polymer (U'-4) and (U'-5) was used as the D phase, and the cosmetic (V'-6) was used. ), The same amount of water was used as the D phase.
(Phase A of cosmetics)
Tri (caprylic acid / capric acid) glyceryl: 6.0 parts Dimethicone: 1.5 parts Glyceryl stearate: 0.5 parts Polyglyceryl distearate-2: 1.5 parts (Phase B of cosmetics)
Water: 64.8 parts Maltitol: 5.0 parts 1,3-butylene glycol: 10.0 parts Glycerin: 5.0 parts Carbo-mer 980: 0.1 parts Phenoxyethanol: 0.5 parts (C phase of cosmetics) )
Water: 2.0 parts Arginine: 0.1 parts (D phase of cosmetics)
Aqueous dispersion of polyurethane of Production Examples 1 to 6 (U-1) to (U-6) diluted with ultrapure water to a solid content concentration of 3%, aqueous solution of polyurethane prepared in Production Examples 7 to 9. Aqueous dispersions obtained by diluting dispersed solutions (U'-1) to (U'-3) with ultrapure water to a solid content concentration of 3%, cationic polymers (U'-4) and (U'-5). Aqueous solution (concentration: 3% by weight) or water: 3.0 parts each

<Evaluation of stickiness>
For each of the 10 panelists who evaluate the usability, wash the inside of the forearm with tap water, wipe off the water with a towel, apply 1 g of cosmetics (V) to the inside of the forearm, and dry for another 15 minutes. The stickiness of the skin after being allowed to be sensitized was sensorially evaluated.
The sensory evaluation is performed by scoring the feeling of use on a scale of 1 to 5 with 5 points for those with no stickiness and very good feeling of use, and 1 point for those with strong feeling of stickiness and poor feeling of use. The average score of 10 panelists is shown in Table 2.

<Effect of cosmetics to reduce oxidative stress derived from air pollutants in stratum corneum cells>
Using the cosmetic prepared for the evaluation of usability, the carbonylated protein of the stratum corneum cells after exposure to cigarette smoke was fluorescently labeled and the carbonylated protein level was measured by the method described in detail below to measure the cosmetic protein level. The effect of reducing oxidative stress by the protein was evaluated.
The carbonylated protein means a protein in which amino acid residues of a protein existing in stratum corneum cells are carbonylated by an aldehyde contained in an air pollutant or the like. It is known that when a protein is carbonylated, changes in the higher-order structure of the protein induce the disappearance or deterioration of the original function of the protein, which causes wrinkles and rough skin.

<Preparation of stratum corneum cell sample for confirmation of oxidative stress reduction effect>
After washing the inside of the forearm of 10 panelists with tap water, wiping the water with a towel and drying for 15 minutes, adhesive tape (T1) [Cerotape (manufactured by Nichiban Co., Ltd.), Cerrotape is made by Nichiban Co., Ltd. The outermost layer of the stratum corneum cells on the skin surface was peeled off (tape stripping) by [registered trademark] to obtain an adhesive tape (T2) with stratum corneum cells.
This tape with stratum corneum cells (T2) is attached to another adhesive tape (T3) [High Craft Tape (manufactured by Nichiban Co., Ltd.) on the non-adhesive surface, and the adhesive tape with stratum corneum cells (T2) and the adhesive tape (T3). ) Was prepared. The laminated body (T4) of the adhesive tape (T2) with stratum corneum cells and the adhesive tape (T3) was cut into a size of 5 mm square, and then the above-mentioned laminated body (T4) was prepared. The adhesive tape (T3) was peeled off from T4), and a 5 mm square adhesive tape with stratum corneum cells (T2) was pressed against the slide glass and attached to the slide glass. By immersing it overnight, only the adhesive tape (T1) was peeled off from the slide glass, and the mixture was air-dried at 25 ° C. for 3 hours to obtain a slide glass (corner cell transfer slide glass) to which the stratum corneum cells were transferred.

<Confirmation of oxidative stress reduction effect of stratum corneum cell sample>
0.05 g of the cosmetic (V) was uniformly applied to the stratum corneum cell portion on the stratum corneum cell transfer slide glass and dried for 30 minutes or more. Then, it was placed in the box (S2) of the oxidative stress evaluation device for the stratum corneum cells shown in FIG. 2 and sealed with the lid (S3) of the box.
The oxidative stress evaluation device for stratum corneum cells is provided with two openings (Y1 and Y2) in the box (S2), and the openings Y1 are tubes (S4) [Quintube (manufactured by Utsunomiya Seisakusho): inner diameter 6 mm, Outer diameter 8.4 mm] was connected to the mouthpiece of the cigarette (S1). The horny layer transfer slide glass is installed so that the horny layer cell part is located 3 cm from the opening (Y1), and the tube (S6) [Quin tube (manufactured by Utsunomiya Seisakusho): inner diameter 6 mm, in the opening (Y2). An outer diameter of 8.4 mm] was connected to the decompression pump (S7). After igniting the cigarette smoke (S1), the decompression pump (S7) is started to draw the cigarette smoke into the box (S2), and the stratum corneum cells of the stratum corneum transfer slide glass (S5) are exposed to the cigarette smoke. I let you.
Each cigarette is burned at a rate of 5 minutes, and after exposing the stratum corneum cell transfer slide glass (S5) to the cigarette smoke equivalent to one cigarette, the stratum corneum cell transfer slide glass (S5) is placed. It was left in the box (S2) for 1 hour. After leaving for 1 hour, take out the stratum corneum cell transfer slide glass (S5) and wash it with running water for 30 minutes or more until the cosmetic (V) is exhausted so that the stratum corneum cells on the stratum corneum cell transfer slide glass (S5) do not come off. After draining the water, it was immersed in xylene overnight. After soaking in xylene, the stratum corneum cell transfer slide glass was taken out, the xylene was cut, washed with running water for 30 minutes so that the stratum corneum cells did not come off, and then air-dried at 25 ° C. for 3 hours.
After immersing the air-dried horny cell transfer slide glass in 0.1 M 2-morpholinoethane sulphonic acid buffer solution (pH 5.5, hereinafter MES buffer solution) for 3 minutes, remove the horny layer cell transfer slide glass and drain the solution. rice field. Then, the stratum corneum cell transfer slide glass was immersed in a MES buffer solution containing 20 μM Fluorescein-5-thiosemicalbazide [manufactured by Adipogen Life Sciences] for 1 hour under shading, the stratum corneum cell transfer slide glass was taken out, and then 30 under running water. After washing for a minute, the carbonylated protein of the stratum corneum cells was fluorescently labeled by air-drying at 25 ° C. for 30 minutes.
Five arbitrary locations on the stratum corneum cells of the stratum corneum cell transfer slide glass after fluorescent labeling of the carbonylated protein were observed with a fluorescence microscope [All-in-one fluorescence microscope BZ-X800 (manufactured by Keyence Co., Ltd.)]. A fluorescence image was obtained.
For each of the five obtained fluorescent images, the brightness per one pixel in the image [(total brightness of stratum corneum cells) ÷ (total number of pixels of stratum corneum cells)] was calculated, and further, per five fluorescent images. By calculating the average value of, the fluorescence intensity per stratum corneum cell area of the stratum corneum cell sample exposed to cigarette smoke was obtained.
Fluorescence intensity was measured in the same manner for the stratum corneum cell transfer slide glass that had undergone the same operation except that it was not exposed to cigarette smoke.
Calculate the "fluorescence intensity of the stratum corneum cell sample exposed to cigarette smoke" for the "fluorescence intensity of the stratum corneum cell sample not exposed to cigarette smoke", and calculate the carbonylation protein of each stratum corneum cell. The levels are listed in Table 2.
If the carbonylated protein level of the stratum corneum cells is 1.7 or higher, it indicates that the stratum corneum cells are under oxidative stress.

In Table 1, the harmful substance adhesion prevention effect and the harmful substance removal effect in Comparative Example 6 were obtained when a cigarette smoke permeation test was carried out using an omnipore membrane filter JCWP02500 (F'-6) to which no chemical substance was applied. The result.
As shown in Table 1, in Comparative Examples 1, 2 and 4, the same amount of harmful substances as in Comparative Example 6 was detected in the permeation test of cigarette smoke, and HaCaT cells (immortalized keratinized cells) in the skin irritation test. ) Was also low in survival rate.
In Comparative Examples 3 and 5, the effect of removing harmful substances in the cigarette smoke permeation test and the survival rate of HaCaT cells (immortalized keratinocytes) in the skin irritation test were improved, but when cosmetics (V) were used. The feeling of stickiness was strong and the feeling of use was bad.
On the other hand, in Examples 1 to 6, compared with Comparative Example 3, in the permeation test of cigarette smoke, the effect of preventing the adhesion of colored substances in the cigarette smoke and the effect of removing harmful substances (aldehyde and benzopyrene) in the cigarette smoke were obtained. It was excellent, and the survival rate of HaCaT cells (immortalized keratinized cells) in the evaluation of irritation to human epidermal cells was also high.

In Table 2, Comparative Example 16 is an evaluation result when a cosmetic (V-6) containing no anti-pollution agent, in which the D phase of the cosmetic was completely replaced with water, was used. In Examples 11 to 16 using the cosmetic containing the anti-pollution agent of the present invention, the increase in the carbonylated protein level when the stratum corneum cells were exposed to cigarette smoke was also significantly suppressed, and thus air pollution. It can be seen that the oxidative stress of the stratum corneum cells caused by the substance can be reduced.

From the results in Tables 1 and 2, the anti-pollution agent of the present invention used in Examples 1 to 6 and Examples 11 to 16 prevented the adhesion of air pollutants, and as a result, skin irritation when exposed to air pollutants. It can be inferred that sexual and oxidative stress can be suppressed low. Further, in the evaluation of the cosmetics of Examples 11 to 16, it can be seen that the sticky feeling at the time of use is low, and the feeling of use is improved by containing the anti-pollution agent of the present invention.

<Examples 21 to 26 and Comparative Examples 21 to 26>
The aqueous dispersions (U-1) to (U-6) of the polyurethanes produced in Production Examples 1 to 6 were diluted to a concentration of 2% to obtain the anti-pollution agent of the present invention, and were produced in Production Examples 7 to 9. Aqueous dispersion of polyurethane (U'-1) to (U'-3) diluted to a concentration of 2%, an aqueous solution of polyvinylpyrrolidone (U'-4) (concentration 2% by weight), and cationized cellulose (U'. -Comparison of Make Keep Mist (W-1) to (W-6) according to Examples 21 to 26 and Comparative Examples 21 to 25 using an aqueous solution (concentration 2% by weight) of (5) as an anti-pollution agent for comparison. Make-keeping mists (W'-1) to (W'-5) for use were prepared by the following adjustment methods, and the effect of preventing makeup from collapsing and the effect of preventing makeup from adhering to the mask were evaluated by the following methods. As the make-keeping mist according to Comparative Example 26, a make-keeping mist (W'-6) using the same amount of water as the A phase was prepared.

<Preparation method of make-up keep mist (W)>
Make-keep mist (W-1) to (W-6) by mixing each component of the B phase and stirring at 25 ° C. to make it uniform, adding the A phase to the B phase, and further stirring to make it uniform. ) And (W'-1) to (W'-6) were obtained. The prepared make-keeping mist (W) was placed in a spray container [PET subdivided bottle spray type 50 mL (manufactured by Ryohin Keikaku Co., Ltd.)].
(Makeup keep mist phase A)
Aqueous dispersion of polyurethane of Production Examples 1 to 6 (U-1) to (U-6) diluted with ultrapure water to a solid content concentration of 2%, aqueous dispersion of polyurethane of Production Examples 7 to 9 An aqueous dispersion in which (U'-1) to (U'-3) are diluted with ultrapure water to a solid content concentration of 2%, an aqueous solution in which polyvinylpyrrolidone (U'-4) is dissolved in a concentration of 2%, and cationized cellulose. Aqueous solution in which (U'-5) is dissolved at a concentration of 2%, or water: 15.0 parts each (B phase of make-keeping mist)
Water: 74.5 parts Ethanol: 5.0 parts 1,3-Butanediol: 3.0 parts Dipropylene glycol: 2.0 parts Phenoxyethanol: 0.5 parts

<Evaluation of makeup collapse prevention effect>
After having 10 panelists who had washed their faces in advance perform make-up with an underwater oil-type liquid foundation, make-up keep mist (W) was sprayed on the entire face three times from a distance of 15 cm from each panelist's face. After spraying, the panelists were allowed to wait for 5 minutes in a room at 25 ° C. and 30% humidity to dry the sprayed make-keeping mist (W).
After that, have the panelists move to a room at 50 ° C and 50% humidity, wait for 5 minutes, then return to the room at 25 ° C and 30% humidity again, and lightly press the face with tissue paper to wipe off the sweat and make up. The state of collapse was visually observed. Table 3 shows the average score of the 10 panelists who scored the state of makeup collapse according to the following scoring criteria.

(Scoring criteria for makeup collapse prevention effect)
Same as the state of makeup before the test: 5 points Makeup before the test is about 10 to 20% off: 4 points Makeup before the test is about 30 to 50% off: 3 points Makeup before the test is 6 points ~ 80% dropped: 2 points Makeup before the test dropped by 90% or more: 1 point

<Evaluation of the effect of preventing makeup from adhering to the non-woven mask>
The effect of the make-up keep mist (W) containing the anti-pollution agent of the present invention on the mask was evaluated.
After having 10 panelists who had washed their faces in advance perform make-up with an underwater oil-type liquid foundation, make-up keep mist (W) was sprayed on the entire face three times from a distance of 15 cm from each panelist's face. After spraying, the panelists were allowed to wait for 5 minutes in a room at 25 ° C. and 30% humidity to dry the make-keeping mist (W).
After that, after spending 3 hours wearing a non-woven fabric mask [Non-woven fabric mask M (manufactured by Ryohin Keikaku Co., Ltd.)] on each panelist, the degree of adhesion of makeup to the non-woven fabric mask was scored according to the following scoring criteria, and the average. The points are shown in Table 3.

(Scoring criteria for the effect of preventing makeup from adhering to the mask)
No foundation adhered to the mask: 5 points Foundation adhered to about 30% of the mask: 4 points Foundation adhered to about half of the mask: 3 points Foundation thinly adhered to the entire mask: 2 points Foundation thickened to the entire mask Adhesion: 1 point

As shown in Table 3, in Comparative Examples 21 to 25, both the makeup collapse prevention effect and the makeup adhesion prevention effect on the mask are low, while in Examples 21 to 26, the makeup collapse prevention effect and the makeup adhesion prevention effect on the mask are both good. The result was obtained.

By applying the anti-pollution agent of the present invention to the skin and hair, it is possible to prevent the adhesion and penetration of harmful air pollutants to the application site. Further, since the same effect is observed in the dried film, the copolymer can be suitably used for cosmetics, and is also used for, for example, in the fields of pharmaceuticals, medical products, and hygienic products. Can be done.

T1: Paper-wrapped cigarette T2: Filter holder T3: Filter holder foot T4: Tube connecting the paper-wrapped cigarette and the filter holder T5: Hose adapter at the top of the filter holder T6: Hose adapter at the bottom of the filter holder T7: Tube connecting the filter holder and the glass tube T8: Glass tube T9: Screw tube T10: Screw tube lid with openings X1 and X2 T11: Tube connecting screw tube and blower pump T12: Decompression pump T13: Evaluation filter

S1: Paper-wrapped cigarette S2: Box with openings Y1 and Y2 S3: Box lid (can be sealed by packing)
S4: Tube connecting the cigarette and the box S5: Slide glass with the stratum corneum cells transferred S6: Tube connecting the decompression pump and the box S7: Decompression pump

Claims (8)

An antipollution agent containing a polyurethane (C) containing a polyol component (A) and a polyisocyanate (B) as constituent monomers, wherein the polyol component (A) requires a cationic polyol (a1). 4 of the tertiary amine compound (a11) represented by the following general formula (1), the salt (a12) of the tertiary amine compound (a11), and the tertiary amine compound (a11), wherein the cationic polyol (a1) is represented by the following general formula (1). An antipolyurethane agent which is at least one compound selected from the group consisting of the graded product (a13).

[In the formula, R ¹ is an alkyl group having a hydroxy group and having 1 to 6 carbon atoms, R ² is an alkyl group having a hydroxy group and having 1 to 6 carbon atoms, and R ³ is an alkyl group having 1 to 24 carbon atoms. It is an alkyl group having 1 to 6 carbon atoms and having a hydrocarbon group or a hydroxy group. ] The anti-pollution agent according to claim 1, wherein the tertiary amine compound (a11) is N-methyldiethanolamine and / or triethanolamine. The salt (a12) of the tertiary amine compound (a11) is the same as that of the tertiary amine compound (a11), hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, citric acid, tartrate acid, lactic acid, itaconic acid, stearer. The anti-pollution agent according to claim 1 or 2, which is a salt with at least one acid (D) selected from the group consisting of an acid and lauric acid. The quaternary compound (a13) of the tertiary amine compound (a11) contains the tertiary amine compound (a11) at least one selected from the group consisting of methyl chloride, dimethyl sulfate, diethyl sulfate, and sodium monochloroacetate. The anti-pollution agent according to any one of claims 1 to 3, which is a quaternized compound quaternized with the alkylating agent (E) of the species. The anti-pollution agent according to any one of claims 1 to 4, further comprising a nonionic polyol (a2) in the polyol component (A). The nonionic polyol (a2) is composed of ethylene glycol, diethylene glycol, 1,4-butanediol, polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, polyethylene adipate, polybutylene adipate, polyester diol, and a mixture thereof. The antipolylution agent according to claim 5, which is at least one selected compound. The anti-pollution agent according to any one of claims 1 to 5, wherein the polyurethane (C) has a weight average molecular weight of 3,000 to 100,000. An anti-pollution agent which is an aqueous dispersion of polyurethane (C) according to any one of claims 1 to 7.

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