Freezing inhibitor

Abstract

To provide technology that suppresses freezing of a composition comprising water.SOLUTION: A freezing inhibitor for water contains diisopropylamine dichloroacetate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a freeze inhibitor. [Background technology]

[0002] Patent Document 1 (JP 2023-9815 A) describes a technology for preventing water from freezing. The document aims to provide an antifreeze agent that can suppress salt damage, is environmentally safe, has low impact, and has excellent antifreeze performance, as well as an antifreeze method using the antifreeze agent (paragraph 0011). The document also describes an antifreeze agent containing an ice-controlling substance with ice recrystallization inhibitory activity and a supercooling promoter (claim 1). It also describes that the ice-controlling substance can be an antifreeze protein or peptide (claim 3), and that the supercooling promoter can be at least one selected from the group consisting of melanoidin, bean paste dregs extract, coffee grounds extract, miso extract, banana peel extract, sake extract, purine bases or polymers containing purine bases, and tyrosine peptides (claim 5). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-9815 Summary of the Invention [Problem to be solved by the invention]

[0004] The technology described in Patent Document 1 leaves room for improvement in terms of simply obtaining an anti-freezing effect.

[0005] The present invention provides a technique for inhibiting freezing of a composition containing water. [Means for solving the problem]

[0006] According to the present invention, the following freeze inhibitor, freeze inhibitor method and composition are provided. [1] A water freeze inhibitor containing diisopropylamine dichloroacetate. [2] The antifreeze agent according to [1], which is added to the water in a mass ratio of 0.01 to 2.0. [3] A method for inhibiting the freezing of water, comprising adding a freezing inhibitor containing diisopropylamine dichloroacetate to a composition containing water. [4] The method for inhibiting freezing described in [3], wherein the content of the diisopropylamine dichloroacetate in the composition is 0.01% by mass or more and 2% by mass or less with respect to the total amount of the composition. [5] The method for suppressing freezing described in [3] or [4], wherein the composition further contains at least one selected from the group consisting of tranexamic acid and salts thereof. [6] The method for inhibiting freezing described in [5], wherein the content of tranexamic acid and its salt in the composition is 0.1% by mass or more and 5% by mass or less relative to the total amount of the composition. [7] The method for inhibiting freezing described in [5] or [6], wherein the mass ratio of the content of diisopropylamine dichloroacetate to the content of tranexamic acid and its salts in the composition is 0.001 or more and 1 or less. [8] The method for inhibiting freezing described in any one of [3] to [7], wherein the content of water in the composition is 50 mass% or more based on the total amount of the composition. [9] A composition comprising water and a freeze inhibitor, A composition wherein the freeze inhibitor comprises diisopropylamine dichloroacetate. [Effects of the Invention]

[0007] According to the present invention, freezing of a composition containing water can be suppressed. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, an embodiment of the present invention will be described. In this embodiment, the composition may contain each component either alone or in combination of two or more. In this specification, the symbol "to" indicating a numerical range means "greater than or equal to" or "less than or equal to," and both of the numerical values at both ends are included.

[0009] (antifreeze agents, antifreeze methods) In this embodiment, the anti-freezing agent inhibits the freezing of water and includes diisopropylamine dichloroacetate (DADA). Furthermore, the method for inhibiting water from freezing in this embodiment includes adding a freezing inhibitor containing DADA to a composition containing water.

[0010] The inventors have found that the combination of DADA and water effectively inhibits the freezing of water, and more specifically, achieves an effect exceeding that of freezing point depression. Although the reason for this is not entirely clear, it is thought that by adding DADA to water, DADA inhibits the alignment of water molecules at low temperatures, thereby inhibiting the precipitation of ice crystals.

[0011] According to this embodiment, by using DADA as a water freezing inhibitor, freezing of a water-containing composition can be easily and suitably inhibited. For example, this embodiment makes it possible to inhibit freezing of a water-containing composition when stored at approximately −5 to 0° C. This also makes it possible to improve the storage stability of a water-containing composition in winter, in cold regions, etc., and to inhibit deterioration of the appearance of the composition over time.

[0012] The freeze inhibitor is composed of, for example, DADA, and may further contain components other than DADA. The DADA content of the antifreeze agent is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass or more, and even more preferably 100% by mass, based on the total mass of the antifreeze agent. This allows for more stable inhibition of water freezing. Specifically, the DADA content in the antifreeze agent is 100% by mass or less.

[0013] The antifreeze agent is preferably added to water in a mass ratio of 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and even more preferably 0.2 or more, to more stably inhibit the freezing of water. The antifreeze agent is preferably added to water in a mass ratio of 2 or less, more preferably 1.5 or less, even more preferably 1.2 or less, and even more preferably 1.0 or less, which allows for greater flexibility in the composition of the water-containing composition when the antifreeze agent is used in the composition. Next, specific examples of the composition will be shown.

[0014] (composition) In this embodiment, the composition contains water and a freeze inhibitor, and the freeze inhibitor includes DADA. In such a composition, the freezing of water is suitably inhibited as described above.

[0015] The content of DADA in the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, based on the total mass of the composition, thereby making it possible to more stably suppress water freezing. The content of DADA in the composition is preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.2% by mass or less, and even more preferably 1.0% by mass or less, which allows for greater flexibility in the formulation of the composition.

[0016] The content of water in the composition can be, for example, the remainder after excluding components other than water in the composition. The content of water in the composition is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more, based on the total mass of the composition. This allows each component to be dissolved more stably. Furthermore, the composition can be stably provided with the desired properties. The water content in the composition is less than 100% by mass, preferably 99.99% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less, which allows the composition to have the desired properties more stably.

[0017] The composition may also contain further ingredients other than DADA and water. For example, the composition may further contain at least one selected from the group consisting of tranexamic acid and its salts (hereinafter also referred to as "tranexamic acids"). This makes it possible to prevent freezing at low temperatures, such as temperatures of about -5 to 0°C, even when the composition contains tranexamic acids. This improves the storage stability of the composition containing tranexamic acids, and also makes it possible to prevent deterioration in appearance, for example.

[0018] Tranexamic acids can be produced by known methods, or commercially available products can be used. For example, tranexamic acid is listed in the 18th edition of the Japanese Pharmacopoeia.

[0019] Specific examples of salts of tranexamic acid salts include hydrohalides such as hydrofluoride, hydrochloride, hydrobromide, and hydroiodide; inorganic acid salts such as nitrates, perchlorates, sulfates, and phosphates; Alkanesulfonates having from 1 to 4 carbon atoms, such as methanesulfonates, trifluoromethanesulfonates, and ethanesulfonates; arylsulfonates such as benzenesulfonates and p-toluenesulfonates; organic acid salts such as acetate, malate, fumarate, succinate, citrate, ascorbate, tartrate, oxalate, maleate, etc.; alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; Organic amine salts such as N-methylmorpholine salts, triethylamine salts, tributylamine salts, diisopropylethylamine salts, dicyclohexylamine salts, N-methylpiperidine salts, pyridine salts, 4-pyrrolidinopyridine salts, and picoline salts; and Examples thereof include one or more salts selected from the group consisting of salts with amino acids such as glycine salts, lysine salts, arginine salts, ornithine salts, glutamic acid salts, and aspartic acid salts.

[0020] The tranexamic acids preferably include tranexamic acid, more preferably tranexamic acid, which is expected to have anti-inflammatory and whitening effects.

[0021] The content of tranexamic acids in the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on the total mass of the composition, thereby more reliably achieving the desired effects such as anti-inflammatory activity and melanin production inhibitory activity. The content of tranexamic acids in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of the composition, which can prevent a decrease in the solubility of tranexamic acids in the composition.

[0022] The mass ratio of the DADA content to the tranexamic acids content in the composition is preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.03 or more, and even more preferably 0.1 or more, thereby making it possible to more stably prevent the composition from freezing. Furthermore, the mass ratio of the DADA content to the tranexamic acids content in the composition is preferably not more than 1, more preferably not more than 0.8, even more preferably not more than 0.5, and even more preferably not more than 0.4, which is expected to result in a formulation that is less irritating to the skin.

[0023] The composition may further contain ingredients other than those mentioned above. For example, the composition may further include a polyhydric alcohol. By including a polyhydric alcohol in the composition, the composition can be more stably prevented from freezing.

[0024] Examples of polyhydric alcohols include glycerols such as glycerin, diglycerin, and polyglycerin; sugar derivatives such as sugar alcohols (e.g., one or more selected from the group consisting of sorbitol, erythritol, and xylitol), methyl gluceth, and hydrogenated starch hydrolysates; Examples of the glycol include one or more selected from the group consisting of glycols such as isoprene glycol, 1,2-propylene glycol (PG), dipropylene glycol (DPG), polyethylene glycol (PEG), ethoxydiglycol, 1,3-butylene glycol (BG), and diethylene glycol monoethyl ether.

[0025] The polyhydric alcohol is preferably a polyhydric alcohol having a molecular weight of 2000 or less, more preferably a polyhydric alcohol having a molecular weight of 1000 or less, more preferably a polyhydric alcohol having a molecular weight of 500 or less, even more preferably a polyhydric alcohol having a molecular weight of 200 or less, and even more preferably one or more compounds selected from the group consisting of BG, DPG and glycerin. This makes it possible to more stably prevent the composition from freezing.

[0026] The content of the polyhydric alcohol in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, based on the total mass of the composition, which more effectively suppresses water evaporation and further suppresses precipitation due to drying. The content of the polyhydric alcohol in the composition is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the composition, thereby enabling the production of a formulation that is less irritating to the skin and highly safe.

[0027] In addition to the above-mentioned components, the composition may contain various components used in ordinary cosmetics, quasi-drugs, pharmaceuticals, etc., as appropriate, provided that the effects of the present invention are not impaired. For example, the composition may contain one or more components selected from the group consisting of oily components, UV absorbers, UV scattering agents, moisturizers, surfactants, pH adjusters, water-soluble polymers, thickeners, skin protectants, plant extracts, preservatives, chelating agents (sequestering agents), antioxidants, pearlizing agents, colorants, freshening agents, and fragrances (excluding the above-mentioned tranexamic acids, DADA, and polyhydric alcohols).

[0028] Of these, the oily components specifically include one or more selected from the group consisting of fats and oils (vegetable oils, etc.) such as olive oil, shea butter, grape seed oil, etc.; waxes such as jojoba oil; hydrocarbon oils such as squalane, liquid paraffin, petrolatum, paraffin wax, etc.; ester oils such as octyldodecyl myristate, ethylhexyl palmitate, isopropyl myristate, tri(caprylic / capric acid)glyceryl, etc.; higher alcohols such as cetyl alcohol, stearyl alcohol, etc.; higher fatty acids, and silicone oils. The content of the oily component in the composition may be, for example, 0.01 to 40% by mass, or 1 to 10% by mass, relative to the total mass of the composition.

[0029] Specific examples of surfactants include one or more selected from the group consisting of nonionic surfactants; ionic surfactants such as anionic surfactants and cationic surfactants; and amphoteric surfactants.

[0030] Among these, examples of nonionic surfactants include polyoxyethylene (hereinafter, abbreviated as "POE") sorbitan monolaurate, POE sorbitan monopalmitate, POE sorbitan monostearate (polysorbate-60), POE sorbitan tristearate, POE sorbitan monooleate (polysorbate-80), and POE sorbitan tetraoleate, and other POE sorbitan fatty acid esters; POE sorbitol fatty acid esters such as POE sorbitol monolaurate, POE sorbitol monooleate, POE sorbitol pentaoleate, and POE sorbitol monostearate; POE glycerin fatty acid esters such as POE glyceryl monostearate, POE glyceryl monoisostearate, and POE glyceryl triisostearate; POE fatty acid esters such as POE monooleate, POE monostearate (PEG-75 stearate), POE distearate, and POE monodiolate; POE alkyl ethers such as POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether (e.g., Beheneth-10), POE octyldodecyl ether (e.g., Octyldodeceth-20), and POE cholestanol ether; POE Octylphenyl Ether, POE Nonylphenyl Ether, POE Dinonylphenyl Ether, POE Alkylphenyl Ether; POE polyoxypropylene (hereinafter, abbreviated as "POP") alkyl ethers such as polyoxyethylene polyoxypropylene decyltetradecyl ether (for example, PPG-6 decyltetradeceth-30, PPG-13 decyltetradeceth-24, PPG-20 decyltetradeceth-10); POE hydrogenated castor oil; Sorbitan fatty acid esters such as sorbitan monooleate, sorbitan monoisostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, and diglycerol sorbitan tetra-2-ethylhexylate; Glycerin fatty acid esters such as glycerin monocottonseed oil fatty acid, glycerin monoerucate, glycerin sesquioleate, glycerin monostearate (e.g., lipophilic glyceryl monostearate), glyceryl oleate pyroglutamate, and glyceryl stearate malate; polyglycerin fatty acid esters such as polyglyceryl monolaurate, polyglyceryl monomyristate (e.g., polyglyceryl-10 myristate), polyglyceryl monooleate, polyglyceryl monostearate, polyglyceryl distearate, and polyglyceryl diisostearate (e.g., polyglyceryl-10 diisostearate); propylene glycol fatty acid esters such as propylene glycol monostearate; glycerin alkyl ethers such as 1-heptyl glyceryl ether, 1-(2-ethylhexyl) glyceryl ether, 1-octyl glyceryl ether, 1-decyl glyceryl ether, and 1-dodecyl glyceryl ether; Sucrose fatty acid esters, such as sucrose stearate; and Examples thereof include one or more selected from the group consisting of alkyl glucosides such as cetostearyl glucoside.

[0031] The number of carbon atoms in the fatty acid or alkyl group in the nonionic surfactant is preferably 6 or more, more preferably 10 or more, even more preferably 12 or more, still more preferably 14 or more, and even more preferably 16 or more, and is preferably 24 or less, more preferably 22 or less. This makes it possible to more stably prevent the composition from freezing. In a similar respect, when the nonionic surfactant has at least one of a POE and a POP structure, the total number of moles of POE and POP added in the nonionic surfactant is preferably 1 or more, more preferably 3 or more, more preferably 5 or more, even more preferably 10 or more, still more preferably 15 or more, and is preferably 120 or less, more preferably 100 or less, even more preferably 60 or less, still more preferably 50 or less, and still more preferably 30 or less.

[0032] In a similar respect, the nonionic surfactant preferably comprises one or more surfactants selected from the group consisting of POE sorbitan fatty acid esters and glycerin fatty acid esters, more preferably a POE sorbitan fatty acid ester and glycerin stearate. The number of moles of POE added in the POE sorbitan fatty acid ester is preferably as described above.

[0033] The content of the nonionic surfactant in the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on the total mass of the composition, which makes it possible to more stably prevent the composition from freezing. The content of the nonionic surfactant in the composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, still more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on the total mass of the composition, thereby further improving the stability of the composition.

[0034] Examples of the ionic surfactant include one or more selected from the group consisting of N-acylamino acid salts, N-acyltaurine salts, alkyl sulfates, alkyl sulfonates, alkyl betaines, and lecithin. The content of the ionic surfactant in the composition can be, for example, 0.05 to 10% by mass with respect to the total mass of the composition.

[0035] Examples of pH adjusters include one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, arginine, lactic acid, aminomethylpropanol, 2-amino-2-methyl-1,3-propanediol, diethanolamine, triethanolamine, malic acid, citric acid and its salts, and phosphoric acid and its salts. The content of the pH adjuster in the composition can be, for example, 0.01 to 5% by mass with respect to the total mass of the composition.

[0036] Examples of thickeners include one or more selected from the group consisting of natural polymers such as guar gum, carrageenan, xanthan gum, sodium hyaluronate, pullulan, agar, and alginates; semi-synthetic polymers such as hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxypropyl methyl cellulose stearoxy ether; and synthetic polymers such as carboxyvinyl polymers, polyacrylates, polyvinyl alcohol, and acrylic acid-alkyl methacrylate copolymers. The content of the thickener in the composition is preferably 0.001 to 5 mass %, more preferably 0.005 to 3 mass %, and even more preferably 0.01 to 2 mass %, based on the total mass of the composition.

[0037] A specific example of a skin protective agent is trehalose. The content of the skin protective agent in the composition can be, for example, 0.01 to 1% by mass based on the total mass of the composition.

[0038] Specific examples of preservatives include one or more selected from the group consisting of phenoxyethanol, benzoic acid and its salts, parahydroxybenzoic acid esters and its salts, salicylic acid and its salts, isopropylmethylphenol, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, chlorhexidine gluconate, zinc pyrithione, piroctone olamine, methylisothiazolinone, and hinokitiol. The content of the preservative in the composition can be, for example, 0.01 to 1% by mass based on the total mass of the composition.

[0039] Examples of the chelating agent include one or more selected from the group consisting of disodium ethylenediaminetetraacetate, calcium disodium ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, sodium gluconate, sodium citrate, pentasodium diethylenetriaminepentaacetate, and phytic acid. The content of the chelating agent in the composition can be, for example, 0.005 to 5% by mass with respect to the total mass of the composition.

[0040] Next, the properties of the composition will be described. The composition is, for example, one selected from the group consisting of aqueous compositions; and emulsion compositions, such as oil-in-water emulsion compositions.

[0041] The composition is preferably fluid at 25°C, and more preferably liquid at 25°C. The Brookfield viscosity of the composition measured at 25°C with a Brookfield viscometer is, for example, about 0.05 to 20,000 mPa·s, preferably 0.05 to 1,000 mPa·s, more preferably 0.1 to 500 mPa·s, even more preferably 0.25 to 200 mPa·s, and still more preferably 0.25 to 100 mPa·s. Specifically, the Brookfield Brookfield viscosity of the composition can be measured using a Brookfield Brookfield viscometer (e.g., DV3T, spindle LV-2) with rotor number 1, a rotation speed of 60 rpm (for viscosity less than 150 mPa s) or 30 rpm (for viscosity of 150 mPa s or more), a measurement time of 1 minute, and an average value of n = 2.

[0042] The composition is applied in particular to the skin, preferably by spreading it on the skin. The composition is preferably a cosmetic such as a skin cosmetic, or an external preparation such as a skin external preparation, and may be a quasi-drug (medicated cosmetic) or a pharmaceutical, preferably a quasi-drug (medicated cosmetic). This allows for more reliable application to the desired area.

[0043] The dosage form of the external preparation can be, for example, a liquid preparation for external use including a liniment or a lotion; a cream; a spray preparation including an aerosol or a pump spray; or a gel. Here, the liniment is specifically a liquid or muddy external preparation that is rubbed into the skin. Furthermore, the lotion is specifically an external preparation in which the active ingredient is dissolved, emulsified, or finely dispersed in an aqueous liquid.

[0044] Examples of cosmetics include lotions, emulsions, serums, creams, gels, makeup removers, facial cleansers, sunscreens, makeup bases, foundations, lip balms, shampoos, conditioners, body soaps, etc. The cosmetics may be filled in pump spray containers or aerosol containers.

[0045] In this embodiment, the composition can be obtained by a manufacturing method including, for example, a step of mixing DADA, water, and other ingredients as needed. The other ingredients can be selected depending on, for example, the dosage form of the composition. When the composition is an external preparation, it can be prepared according to the usual method described in, for example, the 18th edition of the Japanese Pharmacopoeia.

[0046] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0047] The present embodiment will be specifically described below with reference to examples, but the present embodiment is not limited to these examples.

[0048] (Examples 1 to 10, Comparative Examples 1 and 2) In this example, an aqueous composition was prepared and evaluated.

[0049] (Method of preparing the composition) The components listed in Table 1 were mixed and dissolved at room temperature (25°C) to obtain the compositions of each example. The viscosity of the compositions obtained in each example was measured at 25°C using a Brookfield viscometer and was found to be 100 mPa·s or less.

[0050] (evaluation) The storage stability (freezing prevention) of each composition was evaluated by the following procedure. That is, 30 g of the composition obtained in each example was placed in a glass bottle and allowed to stand at a constant temperature (-5°C) in a closed state. The condition of the composition after 24 hours was visually observed and evaluated according to the following criteria, with A being considered acceptable. The evaluation results are also shown in Table 1. A: No freezing B: Partially frozen C: The whole thing is frozen.

[0051] Table 1 also shows the freezing point depression (K) of each example composition calculated using the following formula: ΔTf=Kf m ΔTf: degree of freezing point depression Kf: Molar freezing point depression (K kg / mol) (constant: specific to the solvent, 1.85 for water) m: molar mass concentration (mol / kg)

[0052] [Table 1]

[0053] Details of the ingredients listed in Table 1 are shown below. Diisopropylamine dichloroacetate: Liverall, manufactured by Qualitech Pharma Tranexamic acid: Tranexamic acid, manufactured by Kyowa Pharma Chemical Co., Ltd.

[0054] As can be seen from Table 1, in each example, freezing of water was effectively prevented even when stored at −5° C., which is below the freezing point.

Claims

1. A water freeze inhibitor, including diisopropylamine dichloroacetate.

2. The antifreeze agent according to claim 1, which is added to the water in a mass ratio of 0.01 to 2.

3. A method for inhibiting the freezing of water, comprising adding a freezing inhibitor comprising diisopropylamine dichloroacetate to a composition containing water.

4. The method for inhibiting freezing according to claim 3, wherein the content of diisopropylamine dichloroacetate in the composition is 0.01% by mass or more and 2% by mass or less based on the total mass of the composition.

5. The method for suppressing freezing according to claim 3 or 4, wherein the composition further comprises at least one member selected from the group consisting of tranexamic acid and salts thereof.

6. The method for suppressing freezing according to claim 5 , wherein the content of tranexamic acid and its salt in the composition is 0.1% by mass or more and 5% by mass or less based on the total mass of the composition.

7. The method for inhibiting freezing according to claim 5 , wherein the mass ratio of the content of diisopropylamine dichloroacetate to the content of tranexamic acid and its salt in the composition is 0.001 or more and 1 or less.

8. The method for inhibiting freezing according to claim 3 or 4, wherein the content of water in the composition is 50 mass % or more based on the total amount of the composition.

9. A composition comprising water and a freeze inhibitor, A composition wherein the freeze inhibitor comprises diisopropylamine dichloroacetate.

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