JP5820096B2 - Aqueous composition - Google Patents

Description

  The present invention relates to water-based compositions, for example, water-based personal care products such as cosmetics, medicated cosmetics, mouthwashes, liquid toothpaste, and other water-based household products such as clothes detergents, clothes softeners, dishwashing agents, and bath washings. The present invention relates to a water-based composition containing a polycation type antibacterial agent and a polyvalent anionic compound, such as an agent, a toilet cleaning agent and an antibacterial spray.

  In the aqueous composition of the present invention, the polycation type antibacterial agent is used as a preservative for preventing deterioration or decay of products caused by microorganisms such as bacteria and fungi in the composition, and imparting antibacterial properties to the composition. Is added to prevent or treat disorders caused by microorganisms such as bacteria and fungi in the skin and oral cavity, remove microorganisms on treated clothing and equipment, and impart antibacterial and deodorant properties to the treated surface.

  Conventionally, polycation type antibacterial agents are used in many fields of water-based products as one of various antibacterial agents.

  For example, as antibacterial agents blended into cosmetics for antiseptic purposes, ingredients that can be blended in Appendix 3 of Cosmetic Standards under the Japanese Pharmaceutical Affairs Law, European Cosmetic Directive Attachment 6 and International Cosmetic Ingredient Dictionary and Handbook by the US Cosmetic Industry CTFA Is listed.

  Antibacterial properties are imparted to the composition by quaternary ammonium salts such as benzalkonium chloride and cetylpyridinium chloride, phenols such as triclosan and isopropylmethylphenol, chlorhexidine gluconate and polyhexamethylene biguanide hydrochloride. Biguanide-based compounds such as those used in hand washing soaps, mouthwashes, acne facial cleansers, fiber softeners that have an antibacterial effect, and are applied in a wide range of fields.

  The water-based composition contains a general-purpose polyvalent anionic compound. For example, gums and polyacrylic acid derivatives are used to adjust the viscosity of the composition, citric acid and salts thereof and EDTA and salts thereof as chelating agents and pH adjusters, glycyrrhizic acid and salts thereof, hyaluronic acid and salts thereof, and polyphosphoric acids and The salt and the like are blended for appealing effects in personal care products.

  However, in the aqueous composition, there is a problem that significant cloudiness or precipitation occurs due to the combination of the components, which impairs the transparent appearance and causes a problem in quality assurance. In the case where a polycation type antibacterial agent is blended with a polyvalent anionic compound in an aqueous composition, the solution is useful because white turbidity or precipitation occurs due to electrostatic action between the two.

（式中、Ｒ^１は飽和または不飽和アルキル基である）

（式中、Ｒ^２は飽和または不飽和アルキル基である）を提供する。 The present inventors blended polyoxyethylene alkyl ether and / or polyethylene glycol fatty acid ester in an aqueous composition, so that even when both a polyvalent anionic compound and a polycation type antibacterial agent were blended, significant cloudiness and precipitation were observed. It was found that the occurrence was prevented. That is, the present invention relates to a polycationic antibacterial agent, a polyoxyethylene alkyl ether represented by the general formula (1) and / or a polyethylene glycol fatty acid ester represented by the general formula (2), a polyvalent anionic compound, and water. An aqueous composition comprising:

(Wherein R ¹ is a saturated or unsaturated alkyl group)

Wherein R ² is a saturated or unsaturated alkyl group.

  The polycationic antibacterial agent used in the present invention is an organic compound that is ionized when dissolved in water and has two or more positive charges. For example, chlorhexidine gluconate, chlorhexidine hydrochloride, polyhexamethyleneguanidine hydrochloride, polyhexamethyleneguanidine phosphorus Acid salt, polyhexamethylene biguanide hydrochloride, polyhexamethylene biguanide stearate, poly [oxyethylene (dimethyliminio) ethylene (dimethyliminio) ethylene dichloride]. In particular, polyhexamethylene biguanide salt is highly suitable for water-based personal care products and water-based household products because it has high water solubility and very low skin irritation.

  Polyhexamethylene biguanide salt is commercially available from Arch Chemicals under the product names of VANTOCIL IB, VANTOCIL TG, VANTOCIL P, and PROXEL IB. Other names for polyhexamethylene biguanide include polyaminopropyl biguanide (INCI name in cosmetics) and polyhexanide (INN name in pharmaceuticals). % Aqueous solution is commercially available. In addition to hydrochloride, stearate is known as polyhexamethylene biguanide.

  The polyvalent anionic compound used in the aqueous composition of the present invention is an organic compound or an inorganic compound that is ionized when dissolved in water and has a negative charge of 2 or more. For example, gums and polyacrylic acid derivatives are used in the composition. Citric acid and its salts, EDTA and its salts are used as chelating agents and pH adjusters for viscosity adjustment, and glycyrrhizic acid and its salts, hyaluronic acid and its salts, polyphosphoric acids and its salts are appealing effects in personal care products, etc. Formulated for.

  Glycyrrhizic acid and its salts are blended in cosmetics such as lotion, cosmetic liquid and face wash, medicinal cosmetics, mouthwash and the like because of its anti-inflammatory and anti-allergic effects. It is also added as a sweetener to improve the taste of water-based products for various oral uses.

  The chelating agent is blended as a component for improving the detergency by masking heavy metal ions or stabilizing the foam in the detergent or as a pH adjuster for various aqueous products. For example, citric acid and its salts, ethylenediaminetetraacetic acid and its salts, etidronic acid and its salts, malic acid and its salts, nitrilotriacetic acid and its salts, glutamic acid diacetic acid and its salts, ethylenediaminehydroxyethyl triacetic acid and its salts, Tartaric acid and its salts, polyphosphoric acid and its salts, tripolyphosphoric acid and its salts, metaphosphoric acid and its salts are used. Among these, citric acid and its salts are highly safe, highly water-soluble, and the pH of the composition can be easily adjusted from weak acidity to weak alkalinity by a combination of acids and salts, so a wide range of water-based personal care products and Used in water-based household products.

The polyoxyethylene alkyl ether represented by the general formula (1) used in the aqueous composition of the present invention has low hydrolyzability, and can be used in products having a wide pH range even when the aqueous composition is formulated at a high temperature. It is a feature. Which carbon number of R ¹ has a distribution as a single, one R ¹ is a branch to that of linear, R ¹ is the type such as those ones and unsaturated alkyl, saturated alkyl. The number of ethylene oxide repeats n is generally in the range of 2 to 100, and there are those having a single molecular number distribution with no molecular weight distribution from those having a relatively wide molecular weight distribution. A wide range of HLB values (hydrophilic / lipophilic balance) can be selected depending on the combination of the type of R ^{1 and} the number of ethylene oxide repetitions n. Dispersion of pigments and solubilization of oily components such as perfumes and oils in the aqueous phase It is used for etc. Among these, R ¹ having 12 or more carbon atoms, straight chain, and HLB value of 18.0 or more is more preferable for the aqueous composition of the present invention. R ¹ preferably has 24 or less carbon atoms. The repeating number n of ethylene oxide is preferably 2 to 200.

（Ｒ^１及びｎは上記のとおりである）

(R ¹ and n are as described above)

  For example, the polyoxyethylene alkyl ethers in Table 1 can be used.

The polyethylene glycol fatty acid ester represented by the general formula (2) used in the aqueous composition of the present invention is highly safe and can be used in products having a wide pH range even when the aqueous composition is formulated at a high temperature. Is a feature. The number of ethylene oxide repeats m is generally in the range of 2 to 150, and a wide range of HLB values (hydrophilic / lipophilic balance) can be selected depending on the combination of R ² type and ethylene oxide repeat number m. It is used to disperse pigments and solubilize oily components such as perfumes and oils in the aqueous phase. Among these, those having a carbon number of R ² of 11 or more, linear, and HLB value of 18.0 or more are more suitable for the aqueous composition of the present invention. R ² preferably has 23 or less carbon atoms. The repeating number m of ethylene oxide is preferably 2 to 200.

（Ｒ^２及びｍは上記のとおりである）

(R ² and m are as described above)

  For example, the polyethylene glycol fatty acid esters in Table 2 can be used.

  If necessary, surfactants other than polyoxyethylene alkyl ether and polyethylene glycol fatty acid ester are added to the aqueous composition of the present invention, for example, as a solubilizing agent for fragrances, as a skin feel improver or as a cleaning agent. can do.

  If necessary, the aqueous composition of the present invention includes, for example, a thickener, a fragrance, a sweetener, a dye, a pigment, a UV absorber, a solvent, an oil, an anti-inflammatory agent, an astringent, an antioxidant, a polycation type antibacterial agent. You may add antibacterial agents other than an agent, pH adjusters other than a polyvalent anionic compound, and the like.

  The aqueous composition of the present invention can be prepared by a conventional method in the production of cosmetics and household products, but a liquid containing a polyvalent anionic compound and polyoxyethylene alkyl ether and / or polyethylene glycol fatty acid ester is prepared in advance. The procedure of adding a polycation type antibacterial agent to this is more preferable.

  The concentration of the polycationic antibacterial agent in the aqueous composition of the present invention is preferably 0.001 to 0.3% by weight, more preferably 0.005 to 0.1% by weight for the purpose of preserving the composition. Formulated in a concentration by weight. For the purpose of adding antibacterial properties to the composition, it is preferably blended at a concentration of 0.01 wt% to 0.5 wt%, more preferably 0.02 wt% to 0.3 wt%.

  The polyvalent anionic compound in the aqueous composition of the present invention is preferably blended in the range of 0.001 wt% to 0.5 wt%.

  The polyoxyethylene alkyl ether and / or polyethylene glycol fatty acid ester in the aqueous composition of the present invention is preferably blended at a concentration of 2 times or more with respect to the concentration of the polycation type antibacterial agent. More preferably, the concentration of the polyoxyethylene alkyl ether and / or polyethylene glycol fatty acid ester with respect to the concentration of the polycationic antibacterial agent is 4,000 times or less, more preferably 2,000 times or less.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not restrict | limited by these examples. “%” In Examples and Comparative Examples represents “% by weight”.

Example 1
A purified aqueous solution of 10% polyoxyethylene alkyl ether or polyethylene glycol fatty acid ester (surfactant) was prepared. Monopotassium phosphate (KH ₂ PO ₄ ) 0.24%, disodium phosphate (Na ₂ HPO ₄ ) 0.36%, dipotassium glycyrrhizinate 0.05%, polyoxyethylene alkyl ether to a predetermined concentration, or 50 mL of a purified aqueous solution to which a 10% purified aqueous solution of polyethylene glycol fatty acid ester was added was prepared. While stirring with a stirrer, 1.25 g of a 2% aqueous solution of polyhexamethylene biguanide hydrochloride was added dropwise thereto (0.05% polyhexamethylene biguanide hydrochloride). The appearance of the solution after mixing was observed. The results are shown in Table 3.

(Comparative Example 1)
50 mL of the same purified aqueous solution as in Example 1 was prepared except that the surfactant was changed to that shown in Table 4. While stirring with a stirrer, 1.25 g of a 2% aqueous solution of polyhexamethylene biguanide hydrochloride was added dropwise thereto (0.05% polyhexamethylene biguanide hydrochloride). The appearance of the solution after mixing was observed. The results are shown in Table 4.

(Example 2)
50 mL of the same purified aqueous solution as in Example 1 was prepared except that the surfactant was changed to that shown in Table 5. While stirring with a stirrer, 0.5 g of a 2% aqueous solution of polyhexamethylene biguanide hydrochloride was added dropwise thereto (polyhexamethylene biguanide hydrochloride 0.02%). The appearance of the solution after mixing was observed. The results are shown in Table 5.

(Example 3)
50 mL of a purified aqueous solution containing trisodium citrate dihydrate 0.15%, anhydrous citric acid 0.05 g, and the surfactants listed in Table 6 at a predetermined concentration was prepared. While stirring with a stirrer, 0.5 g of a 2% aqueous solution of polyhexamethylene biguanide hydrochloride was added dropwise thereto (polyhexamethylene biguanide hydrochloride 0.02%). The appearance of the solution after mixing was observed. The results are shown in Table 6.

(Comparative Example 2)
50 mL of the same purified aqueous solution as in Example 3 was prepared except that the surfactant was changed to that shown in Table 7. While stirring with a stirrer, 0.5 g of a 2% aqueous solution of polyhexamethylene biguanide hydrochloride was added dropwise thereto (polyhexamethylene biguanide hydrochloride 0.02%). The appearance of the solution after mixing was observed. The results are shown in Table 7.

（＊２０％ポリアミノプロピルビグアナイド（アーチ・ケミカルズ社製））
（製法）Ａ、Ｂを５０℃で混合、Ｃを常温で混合する。撹拌しながらＢをＡに徐々に加える。更にＣを滴下し撹拌を続けながら放冷し３０〜３５℃で撹拌を停止する。 (Example 4 lotion)

(* 20% polyaminopropyl biguanide (manufactured by Arch Chemicals))
(Manufacturing method) A and B are mixed at 50 degreeC, and C is mixed at normal temperature. Gradually add B to A with stirring. Further, C is added dropwise and the mixture is allowed to cool while stirring, and stirring is stopped at 30 to 35 ° C.

（＊２０％ポリアミノプロピルビグアナイド（アーチ・ケミカルズ社製））
（製法）Ａ、Ｂを５０℃で混合、Ｃを常温で混合する。撹拌しながらＢをＡに徐々に加える。更にＣを滴下し撹拌を続けながら放冷し３０〜３５℃で撹拌を停止する。 (Comparative Example 3 lotion)

(* 20% polyaminopropyl biguanide (manufactured by Arch Chemicals))
(Manufacturing method) A and B are mixed at 50 degreeC, and C is mixed at normal temperature. Gradually add B to A with stirring. Further, C is added dropwise and the mixture is allowed to cool while stirring, and stirring is stopped at 30 to 35 ° C.

（＊２０％ポリアミノプロピルビグアナイド（アーチ・ケミカルズ社製））
（製法）Ａを６０℃で混合、Ｂ、Ｃは常温で混合する。撹拌しながらＢをＡに徐々に加える。更にＣを滴下し撹拌を続けながら放冷し３０〜３５℃で撹拌を停止する。 (Example 5 mouthwash)

(* 20% polyaminopropyl biguanide (manufactured by Arch Chemicals))
(Manufacturing method) A is mixed at 60 ° C., and B and C are mixed at room temperature. Gradually add B to A with stirring. Further, C is added dropwise and the mixture is allowed to cool while stirring, and stirring is stopped at 30 to 35 ° C.

（＊２０％ポリアミノプロピルビグアナイド（アーチ・ケミカルズ社製））
（製法）Ａを６０℃で混合、Ｂ、Ｃは常温で混合する。撹拌しながらＢをＡに徐々に加える。更にＣを滴下し撹拌を続けながら放冷し３０〜３５℃で撹拌を停止する。 (Comparative Example 4 Mouthwash)

(* 20% polyaminopropyl biguanide (manufactured by Arch Chemicals))
(Manufacturing method) A is mixed at 60 ° C., and B and C are mixed at room temperature. Gradually add B to A with stirring. Further, C is added dropwise and the mixture is allowed to cool while stirring, and stirring is stopped at 30 to 35 ° C.

  The appearance of the preparations of Examples 4 and 5 and Comparative Examples 3 and 4 and the stability of the preparations when stored at -3 ° C for 1 day were observed. The results are shown in Table 8.

  The aqueous composition of the present invention provides an aqueous composition in which significant cloudiness and precipitation are prevented even when a polyvalent anionic compound and a polycationic antibacterial agent are blended as components.

Claims (4)

A polycationic antibacterial agent which is a polyhexamethylene biguanide salt, a polyoxyethylene alkyl ether represented by the general formula (1) and / or a polyethylene glycol fatty acid ester represented by the general formula (2), a polyvalent anionic compound, and Contains water,
The HLB value of the polyoxyethylene alkyl ether represented by the general formula (1) and / or the polyethylene glycol fatty acid ester represented by the general formula (2) is 18.0 or more, and the concentration in the composition is 0.125- 1.0 wt% der is, the amount is 2 times or more than one polycationic antibacterial agent (based on weight percent), wherein der Rukoto, cosmetics, medicated cosmetics, mouthwash, liquid dentifrice, clothing Detergent, clothing softener, dishwashing agent, bath cleaner, toilet cleaner, or antibacterial spray aqueous composition,

(Wherein, ^{R 1} is a number 11 or more 24 or less carbon atoms, Ri saturated or unsaturated alkyl group Der linear, n represents Ru 2 to 200 der.)

(Wherein, ^{R 2} is a number 11 or more 23 or less carbon atoms, Ri saturated or unsaturated alkyl group der linear, m is Ru 2-200 der.).   The aqueous composition according to claim 1, wherein the polyvalent anionic compound is glycyrrhizic acid and / or a salt thereof.   The aqueous composition according to claim 1, wherein the polyvalent anionic compound is a chelating agent.   4. The aqueous composition according to claim 3, wherein the chelating agent is citric acid and / or a salt thereof.