Emulsion composition, spray product, and aerosol product

Abstract

To provide an emulsion composition which is excellent in both emulsion stability and spray characteristics, forms an oil-in-water emulsion, and does not substantially contain a surfactant.SOLUTION: The emulsion composition contains mechanically fibrillated fine fibrous cellulose, a water-soluble polymer, an oily component, and water. The emulsion composition forms an oil-in-water emulsion in which an oil phase containing the oily component is dispersed in an aqueous phase containing the water. The emulsion composition does not substantially contain a surfactant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to emulsion compositions that are substantially free of surfactants, and spray and aerosol products using the emulsion compositions. [Background technology]

[0002] Emulsions are widely used in foods, cosmetics, medicines, household goods, industrial goods, etc., and it is widely known that surfactants are used as emulsifiers to stabilize the dispersion of emulsions. On the other hand, in recent years, with the growing trend toward natural products, there is an increasing demand for products that do not contain alcohol or surfactants in order to reduce the burden on the human body caused by irritation caused by alcohol and surfactants, and also to conserve resources.

[0003] Here, as a method for uniformly applying an appropriate amount of oily component to a target surface, an oil-in-water (O / W) emulsion using water as a dispersion medium is known. For example, a method for preparing an emulsion using an oily component, an aqueous dispersion medium, an emulsifier (surfactant), and cellulose nanofiber is known (for example, Patent Document 1). In order to meet the above demand, development of an oil-in-water emulsion that does not contain a surfactant is being carried out.

[0004] For the emulsion stability of oil-in-water emulsions, a method of using a water-soluble polymer instead of a surfactant is known. For example, in the preparation of oil-in-water emulsions, a method of emulsifying by mechanical force such as a homogenizer using polyvinyl alcohol or polyvinylpyrrolidone without using a surfactant is known (e.g., Patent Document 2). Furthermore, a method is known in which a gel is formed in water by association of hydrophobic groups using a water-soluble amphiphilic polymer (HHM-HEC) in which a stearyl group as a hydrophobic group and a sulfonate group as a hydrophilic group are introduced into the main chain of hydroxyethyl cellulose (HEC), and an association thickening mechanism is used to stabilize oil-in-water emulsions (e.g., Non-Patent Document 1). In addition, it is known that hydrophobized hydroxypropyl methylcellulose, which is hydrophobized by introducing a stearoyl group into hydroxypropyl methylcellulose, stabilizes oil-in-water (O / W) emulsions with silicone oil as a dispersoid (e.g., Non-Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-59502 [Patent Document 2] Patent Publication No. 2022-126615 [Non-patent literature]

[0006] [Non-Patent Document 1] Eri Akiyama, "Emulsification using amphiphilic polymers", Oleoscience, Japan Oil Chemists' Society, 2012, Vol. 12, No. 8, pp. 333-338 [Non-Patent Document 2] Masami Kawaguchi, “Silicone oil emulsions aabilized by polymers and solid particles”, Adv.Colloid Interfase Sci., 233 (2016) p.186-199 Summary of the Invention [Problem to be solved by the invention]

[0007] When an oil-in-water emulsion is applied to a mist spray product or an aerosol product, it is necessary to have not only good emulsion stability of the oil-in-water emulsion, but also good spray properties such as sufficiently small spray particle size, sufficiently large spray range (spray pattern), and no dripping of the formulation after spraying. On the other hand, when an oil-in-water emulsion using a water-soluble polymer instead of a surfactant is applied to a spray product or an aerosol product, the viscosity of the emulsion increases, making it difficult to form a mist, leaving room for improvement in the spray characteristics. Thus, there is a problem in that it is difficult to achieve both emulsion stability and spray characteristics in spray products or aerosol products using surfactant-free oil-in-water emulsions.

[0008] In view of such problems, the present disclosure provides an emulsion composition that forms an oil-in-water emulsion that is excellent in both emulsion stability and spray properties even when it is substantially free of a surfactant. [Means for solving the problem]

[0009] As a result of investigations aimed at solving the above-mentioned problems, the inventors found that the above-mentioned problems could be solved by blending mechanically defibrated fine fibrous cellulose and a water-soluble polymer in an emulsion composition, and thus completed the present invention.

[0010] That is, the present invention includes the following aspects. [1] An emulsion composition containing mechanically defibrated fine fibrous cellulose, a water-soluble polymer, an oily component, and water, The emulsion composition forms an oil-in-water emulsion in which an oil phase containing the oily component is dispersed in an aqueous phase containing water, An emulsion composition, characterized in that the emulsion composition is substantially free of a surfactant. [2] The emulsion composition according to [1], wherein the content of the mechanically defibrated fine fibrous cellulose in the emulsion composition is 0.005% by mass to 10.00% by mass. [3] The emulsion composition according to [1] or [2], wherein the content of the water-soluble polymer in the emulsion composition is 0.001% by mass to 1.00% by mass. [4] The emulsion composition according to any one of [1] to [3], wherein the water-soluble polymer comprises at least one selected from the group consisting of carboxyvinyl polymer, acrylates / alkyl acrylate crosspolymer, polyvinyl alcohol, and cellulose-based polymer. [5] The emulsion composition according to any one of [1] to [4], wherein the oily component is liquid at 20°C. [6] The emulsion composition according to any one of [1] to [5], wherein the amount of hydrophilic substituent introduced into the mechanically defibrated fine fibrous cellulose is 0 mmol / g to 0.1 mmol / g. [7] The emulsion composition according to any one of [1] to [6], which is a spray composition. [8] A spray product in which the emulsion composition is filled in a spray container, A spray product, wherein the emulsion composition is the emulsion composition according to any one of [1] to [7]. [9] An aerosol product in which an emulsion composition and a propellant are filled in an aerosol container, An aerosol product, wherein the emulsion composition is the emulsion composition according to any one of [1] to [7]. Effect of the Invention

[0011] According to the present disclosure, it is possible to provide an emulsion composition that forms an oil-in-water emulsion that is excellent in both emulsion stability and spray properties even when it does not substantially contain a surfactant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The description of a numerical range such as "XX to YY" or "XX to YY" means a numerical range including the lower and upper limits, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined.

[0013] (Emulsified composition) An emulsion composition according to one embodiment of the present invention (hereinafter, also simply referred to as "emulsion composition") is an emulsion composition containing mechanically defibrated fine fibrous cellulose, a water-soluble polymer, an oily component, and water, and the emulsion composition forms an oil-in-water emulsion in which an oil phase containing the oily component is dispersed in an aqueous phase containing water, and does not substantially contain a surfactant. Even if the emulsion composition does not substantially contain a surfactant, it has excellent emulsion stability and spray properties.

[0014] In the present disclosure, a surfactant refers to an amphipathic substance that has a hydrophilic portion in its molecule that is compatible with water and a hydrophobic portion that is compatible with hydrophobic substances (i.e., a clearly defined hydrophilic head group and a hydrophobic tail group), and that adsorbs to the water-hydrophobic substance interface by interacting with the hydrophilic portion and the hydrophobic portion interacting with the hydrophobic substance, thereby significantly reducing the interfacial tension at the water-hydrophobic substance interface and improving the emulsion stability of emulsions and suspensions.

[0015] For example, sodium lauryl sulfate, stearyl trimethylammonium chloride, glyceryl stearate, polyglyceryl-10 diisostearate, polyoxyethylene coconut oil fatty acid glyceryl, sorbitan laurate, polysorbate 80, polyoxyethylene hydrogenated castor oil, polyoxyethylene lauryl ether, PEG 45 stearate, sodium coconut oil fatty acid methyl taurate, and lauryl dimethylaminoacetate betaine.

[0016] Other examples of surfactants include the following: Anionic surfactants include fatty acid salts, alkyl phosphates, polyoxyethylene alkyl ether phosphates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl ether carboxylates, alkyl sulfosuccinates, N-acyl amino acid salts, N-acyl methyl amino acid salts, acyl lactates, α-olefin sulfonates, α-sulfofatty acid methyl ester salts, alkyl sulfosuccinates, alkanesulfonates, alkene sulfonates, acyl isethionates, alkyl sulfates, alkyl benzene sulfonates, fatty acid alkanolamide sulfates, monoacyl glycerin sulfates, alkyl phosphates, and polyoxyethylene alkyl phenyl ether phosphates. Cationic surfactants include fatty acid amide amine salts, ester-containing tertiary amine salts, Arcobal-type tertiary amine salts, monoalkyl quaternary ammonium salts, dialkyl quaternary ammonium salts, trialkyl quaternary ammonium salts, alkylamine salts, monoalkyl ether-type quaternary ammonium salts, alkylpyridinium salts, alkylisoquinolium salts, benzethonium chloride, and benzalkonium-type quaternary ammonium salts.

[0017] Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene castor oil, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, monoglycerin fatty acid esters, diglycerin fatty acid esters, sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkyl polyglucosides, polyoxyalkylene sterol ethers, polyoxyethylene alkylamines, alkyl alkanolamides, alkyl glyceryl ethers, and Pluronic-type surfactants.

[0018] Amphoteric surfactants include glycine-type amphoteric surfactants, aminopropionic acid-type amphoteric surfactants, acetate betaine-type amphoteric surfactants, imidazoline-type amphoteric surfactants, alkyl betaines, amido betaines, sulfo betaines, alkyl amine oxides, alkyl dimethyl amine oxides, amino acetate betaines, alkyl dimethyl amino acetate betaines, alkyl carbamides, etc. Examples of the alkyl esters include carboxymethyl hydroxyethyl imidazolium betaine, alkyl amidopropyl betaine, alkyl hydroxysulfobetaine, alkyl sulfobetaine, amidosulfobetaine, and fatty acid amidopropyl betaine. Further examples include silicone surfactants such as polyether-modified silicone, amino-modified silicone, and polyglycerin-modified silicone; fluorine-based surfactants; and natural surfactants such as lecithin, saponin, bile acid, surfactin, spiculisporic acid, agaricic acid, long-chain dicarboxylic acids, rhamnolipids, trehalose lipids, succinoyl trehalose lipids, oligosaccharide fatty acid esters, and glycosyl lipids.

[0019] The emulsion composition does not substantially contain a surfactant. In the present disclosure, "substantially does not contain a surfactant" means that no surfactant is added to the emulsion composition for the purpose of increasing emulsion stability, and may contain a small amount of surfactant that is inevitably mixed in during the production of the emulsion composition, or a surface active substance that is blended for the purpose of improving the functionality of the formulation (such as adding moisturizing effect, anti-inflammatory effect, and antiseptic effect). For example, a surfactant (so-called carry-over component) that is associated with the blended components and is contained in the emulsion composition in an amount smaller than that at which the effect of increasing emulsion stability is exerted (for example, the surfactant content in the emulsion composition is equal to or less than the critical micelle concentration) may be contained. For example, the content of the surfactant in the emulsion composition is less than 0.10% by mass, preferably 0.05% by mass or less, more preferably 0.01% by mass or less, even more preferably 0.001% by mass or less, and particularly preferably 0% by mass.

[0020] Each component used in the emulsion composition will be described below.

[0021] (Mechanically defibrated fine fibrous cellulose) The emulsion composition contains mechanically defibrated fine fibrous cellulose obtained by mechanical defibration. Fine fibrous cellulose can be prepared by finely fibrillating plant-derived cellulose, and can be divided into mechanically defibrated fine fibrous cellulose and chemically treated defibrated fine fibrous cellulose. The mechanically defibrated fine fibrous cellulose contained in the emulsion composition is cellulose that has not been subjected to chemical treatment and has been made into a fine fiber state by mechanical treatment, and is fine fibrous cellulose to which no functional group such as a carboxyl group has been introduced.

[0022] Mechanically defibrated fine fibrous cellulose has a lower viscosity at the same concentration than chemically treated defibrated fine fibrous cellulose obtained by chemical treatment. By containing mechanically defibrated fine fibrous cellulose in an emulsion composition, oil droplets emulsified by a water-soluble polymer can be dispersed well while an excessive increase in the viscosity of the emulsion can be prevented, so that good spray properties can be exhibited and emulsion stability can also be improved.

[0023] The content of the mechanically defibrated fine fibrous cellulose in the emulsion composition is preferably 0.005% by mass to 10.00% by mass, more preferably 0.05% by mass to 7.00% by mass, even more preferably 0.08% by mass to 5.00% by mass, and even more preferably 0.10% by mass to 1.5% by mass. When the content of the mechanically defibrated fine fibrous cellulose is within the above range, the emulsion stability and spray properties of the emulsion composition can be further improved.

[0024] When obtaining chemically treated, defibrated fine fibrous cellulose, a hydrophilic substituent is introduced onto the surface of the fine fibrous cellulose. Examples of the hydrophilic substituent include at least one selected from the group consisting of carboxyalkyl groups such as carboxyl groups and carboxymethyl groups, phosphate groups, phosphite groups, sulfone groups, xanthate groups, and cationic groups such as ammonium groups, but are not limited thereto. Commercially available chemically treated, defibrated fine fibrous cellulose include Cellenpia CS-01C (Nippon Paper Industries Co., Ltd.: carboxymethylated cellulose nanofiber), Leocry Examples include Sta C-2SP (Dai-ichi Kogyo Seiyaku Co., Ltd.: TEMPO oxidized cellulose nanofiber), Auro-Visco CS (Nikko Chemicals Co., Ltd.: phosphate esterified cellulose nanofiber).

[0025] The amount of hydrophilic substituent introduced in the mechanically defibrated fine fibrous cellulose is preferably 0.2 mmol / g or less, more preferably 0.1 mmol / g or less, even more preferably 0.05 mmol / g or less, even more preferably 0.03 mmol / g or less, and particularly preferably 0.01 mmol / g or less. The lower limit of the amount of hydrophilic substituent introduced is not particularly limited, but may be 0 mmol / g. The amount of hydrophilic substituent introduced is, for example, 0 mmol / g to 0.1 mmol / g. When the amount of hydrophilic substituent introduced is within the above range, the emulsion stability and spray properties of the emulsion composition can be further improved. Here, the introduction amount of the hydrophilic substituent can be interpreted as the content. The introduction amount (content) of the hydrophilic substituent can be measured by a known method such as a conductometric titration method.

[0026] The number average fiber diameter of the mechanically defibrated fine fibrous cellulose is 1 to 1000 nm. If the number average fiber diameter is less than 1 nm, the network structure of the nanofibers becomes weak and the structure cannot be maintained, which may cause the emulsion to become unstable. If the number average fiber diameter exceeds 1000 nm, the size may become too large and the stability of the emulsion may be impaired. The number average fiber diameter of the mechanically defibrated fine fibrous cellulose is preferably 10 nm or more, more preferably 20 nm or more. Also, it is preferably 100 nm or less, more preferably 50 nm or less. By having the number average fiber diameter of the mechanically defibrated fine fibrous cellulose within the above range, the emulsion stability and spray properties of the emulsion composition can be further improved.

[0027] The length-weighted average fiber length of the mechanically defibrated fine fibrous cellulose is not particularly limited, but is preferably 0.05 μm to 100 μm, and more preferably 0.1 μm to 50 μm. The length-weighted average fiber length can be determined by a known method such as image analysis using a TEM, SEM, AFM or the like. The length-weighted average fiber length of the mechanically defibrated fine fibrous cellulose is preferably 1000 nm or more, more preferably 2000 nm or more, and is preferably 100 μm or less, more preferably 50 μm or less. The number average fiber diameter and length-weighted average fiber length of the mechanically defibrated fine fibrous cellulose can be determined, for example, by measuring the fiber diameter (fiber width) and length of the fibers by observation with a transmission electron microscope and calculating the average value thereof. The aspect ratio (length-weighted average fiber length / number average fiber diameter) of the mechanically defibrated fine fibrous cellulose is preferably 20-10,000, more preferably 40-5,000, and even more preferably 100-1,000.

[0028] The degree of polymerization of the mechanically defibrated fine fibrous cellulose is not particularly limited, but is preferably 100-1,000, and more preferably 150-500. The degree of polymerization is the number of glucose units linked together, which are the minimum structural units of cellulose, and is determined by a viscosity method using a copper ethylenediamine solution.

[0029] The mechanically defibrated fine fibrous cellulose preferably has a cellulose type I crystal structure. The fact that the cellulose fiber has a type I crystal structure can be identified by the presence of typical peaks at two positions, near scanning angles 2θ=14 to 17° and 2θ=22 to 23°, in a diffraction profile (wide-angle X-ray diffraction image) obtained by wide-angle X-ray diffraction image measurement.

[0030] Mechanically defibrated fine fibrous cellulose can be obtained by mechanically defibrating raw cellulose. Examples of the mechanical defibration method include a method in which pulp is cut to a predetermined length using a beater or refiner, and then fibrillated or refined using a high-pressure homogenizer, grinder, impact crusher, bead mill, or the like.

[0031] The mechanically defibrated fine fibrous cellulose is preferably obtained by pulverizing the raw cellulose by a high-pressure injection process of 100 to 245 MPa through an injection nozzle with a diameter of 0.1 to 0.8 mm, by impinging a dispersion fluid of the raw cellulose against a hard body for collision, or by injecting and impinging each other. This defibration method is capable of continuous processing at high pressure using not only a shear force that homogenizes the dispersion fluid when released by passing the dispersion fluid through a narrow flow path at high pressure and low speed, as in a commercially available high-pressure homogenizer, but also a collision force by impinging the dispersion fluid against a hard body for collision, or cavitation. The defibration method using the shear force, collision force, and cavitation of these water jets (WJ) is defined as the WJ method. In addition, one collision process is considered to be one pass, and in order to obtain uniform nanofibers, it is preferable to perform 1 to 30 passes of repeated collision, and more preferably to perform 5 to 20 passes of repeated collision.

[0032] (Water-soluble polymer) The emulsion composition contains a water-soluble polymer. By containing a water-soluble polymer in the emulsion composition, emulsion stability and spray characteristics can be improved.

[0033] Examples of water-soluble polymers include the following: Cellulosic polymers such as cellulose gum, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydrophobized hydroxypropylmethylcellulose, hydroxypropylmethylcellulose stearoxyether, carboxymethylcellulose, sodium cellulose sulfate; Plant-based thickeners such as gum arabic, locust bean gum, tara gum, guar gum, glucomannan, xanthan gum, pectin, agar-agar; Starches such as starch, carboxymethyl starch, methylhydroxypropyl starch; Alginate-based polymers such as sodium alginate and propylene glycol alginate; Synthetic polymers such as polyvinyl alcohol, carboxyvinyl polymer, polyacrylic acid amide, sodium polyacrylate, polyethyleneimine, and highly polymerized polyethylene glycol; Examples of the polymerizable polymer include highly polymerized polyethylene glycol (highly polymerized PEG, preferably with an average degree of polymerization of 2,000 to 150,000), (PEG-240 / decyltetradeceth-20 / HDI) copolymer, polyurethane, and polymerization polymers such as acrylates / alkyl acrylate crosspolymer. These water-soluble polymers can be used alone or in combination of two or more kinds.

[0034] The water-soluble polymer may be produced according to a known production method, or a commercially available product may be used. Examples of commercially available products include "GOHSENOL (trademark) EG-05C" (polyvinyl alcohol) sold by Mitsubishi Chemical Corporation, "SANGELOSE 60L" (hydroxypropyl methylcellulose stearoxy ether) sold by Daido Kasei Kogyo Co., Ltd., "Carbopol ETD 2050 Polymer" (carboxyvinyl polymer) and "Pemulen TR-2" sold by Lubrizol. Polymeric Emulsifier ((Acrylates / C10-30 alkyl acrylate crosspolymer)), "Pemulen EZ-4U Polymeric Emulsifier ((Acrylates / C10-30 alkyl acrylate crosspolymer)) ) crosspolymer), and "Metolose 60SH-06" (hydroxypropyl methylcellulose) sold by Shin-Etsu Chemical Co., Ltd.

[0035] The water-soluble polymer preferably includes one or more selected from the group consisting of carboxyvinyl polymer, acrylates / alkyl acrylate crosspolymer, polyvinyl alcohol, and cellulose-based polymer. By including the water-soluble polymer in the emulsion composition, the emulsion stability and spray properties of the emulsion composition can be further improved.

[0036] The content of the water-soluble polymer in the emulsion composition is preferably 0.001% by mass to 1.00% by mass, more preferably 0.002% by mass to 0.7% by mass, even more preferably 0.003% by mass to 0.5% by mass, and even more preferably 0.005% by mass to 0.3% by mass. By ensuring that the content of the water-soluble polymer is within the above range, the emulsion stability and spray characteristics of the emulsion composition can be further improved.

[0037] (Oily ingredients) The emulsion composition contains an oily component. The emulsion composition forms an oil-in-water (O / W) emulsion in which an oil phase containing the oily component is dispersed in an aqueous phase containing water. The oily component is not particularly limited, and a wide variety of known oily components that are insoluble in water (phase-separated from water) can be used. "Insoluble in water" refers to, for example, a solubility of 1.0 g or less in 100 g of water at 25°C.

[0038] Examples of oily components include the following: vegetable fats such as apricot kernel oil, camellia oil, argan oil, soybean oil, olive oil, castor oil, coconut oil, palm oil, palm kernel oil, sesame oil, jojoba oil, cottonseed oil, rapeseed oil, linseed oil, rosehip oil, sunflower oil, essential oils, avocado oil, almond oil, rice bran oil, safflower oil, corn oil, grapeseed oil, coconut oil, Argania spinosa kernel oil, wheat germ oil, rice germ oil, kukui nut oil, crambe abyssinica seed oil, hemp seed oil, peanut oil, camellia oil, evening primrose oil, pistachio oil, macadamia nut oil, meadowhoo oil, cocoa butter, shea butter, and japan wax; Animal fats and oils, such as emu oil, horse fat, beef tallow, lard, mutton tallow, mink oil, egg yolk fat, carp fat, tuna fat, and menhaden fat; Hydrocarbon oils such as light isoparaffin, squalane, liquid paraffin, petrolatum, dodecane, tetradecane, ozokerite, microcrystalline wax, isoparaffin, ceresin, α-olefin oligomer, polybutene, hydrogenated polyisoparaffin, limonene, and turpentine; Fatty acids (preferably having 6 to 40 carbon atoms, more preferably having 12 to 30 carbon atoms), such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, behenic acid, oxystearic acid, palmitoleic acid, linoleic acid, linolenic acid, ricinoleic acid, and undecylenic acid; Higher alcohols such as caproyl alcohol, caprylyl alcohol, capryl alcohol, lauryl alcohol, isostearyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, arachyl alcohol, behenyl alcohol, oleyl alcohol, hexyldecanol, octyldodecanol, decyltetradecanol, cholesterol, and phytosterols; Esters of straight-chain fatty acids and lower alcohols, such as isopropyl myristate, isopropyl palmitate, and ethyl oleate; Esters of straight-chain fatty acids and straight-chain higher alcohols, such as hexyl laurate, myristyl myristate, decyl oleate, and stearyl stearate; Esters of straight-chain fatty acids with branched alcohols, such as octyldodecyl myristate, isostearyl palmitate, and ethylhexyl stearate; Esters of branched fatty acids and lower alcohols, such as ethyl isostearate and isopropyl isostearate; Esters of branched fatty acids and linear higher alcohols, such as cetyl ethylhexanoate and hexyl isostearate; Esters of fatty acids and polyhydric alcohols, such as PG dicaprylate, triethylhexanoin, and tri(caprylcapric acid)glyceryl; Esters of branched fatty acids and branched alcohols, such as 2-octyldodecyl neopentanoate and isostearyl isostearate; Esters of hydroxycarboxylic acids and alcohols, such as lauryl lactate, tri-2-ethylhexyl citrate, trioctyldodecyl citrate, and diisostearyl malate; ester oils such as esters of dibasic acids, such as diisopropyl adipate, diethyl sebacate, etc.; Wax esters such as jojoba oil, jojoba butter, carnauba wax, candelilla wax, rice bran wax, shellac, lanolin, beeswax, montan wax, spermaceti, orange roughy oil, sugar cane wax, palm wax, insect wax, and wool wax; Ethers of polyhydric alcohols with monohydric alcohols, such as chiral alcohol, batyl alcohol, and selachyl alcohol; Batyl isostearate, batyl stearate; Silicones such as alkyl-modified polysiloxane (dimethylpolysiloxane (dimethicone)), methylphenylpolysiloxane, and fluorine-modified polysiloxane; Examples of active ingredients include oil-based ingredients such as UV absorbers (diethylaminohydroxybenzoylhexyl benzoate, ethylhexyl methoxycinnamate, octocrylene, t-butyl methoxybenzoylmethane, ethylhexyl salicylate, polysilicone-15), DEET, icaridin, and fragrances. These oily components may be used alone or in combination of two or more.

[0039] The oil component is preferably liquid at 20°C from the viewpoints of emulsion stability and ease of handling during preparation. The oily component preferably contains at least one selected from the group consisting of hydrocarbon oils, vegetable oils, esters of branched fatty acids and linear higher alcohols, silicones, and esters of fatty acids and polyhydric alcohols.

[0040] The content of the oily component in the emulsion composition is preferably 0.05% by mass to 50.00% by mass, more preferably 0.10% by mass to 40.00% by mass, even more preferably 0.20% by mass to 20.00% by mass, and even more preferably 0.30% by mass to 10.00% by mass.

[0041] (water) The emulsion composition contains water. The content of water in the emulsion composition is not particularly limited, but is preferably 50.00% by mass to 99.85% by mass, more preferably 60.00% by mass to 99.50% by mass, and even more preferably 70.00% by mass to 99.30% by mass.

[0042] (Other additives) The emulsion composition may contain additives such as active ingredients that are miscible with water (do not undergo phase separation), fragrances, antioxidants, preservatives, etc., to the extent that the above effects are not impaired. For example, alcohol may be contained. Specific examples include the following. Lower alcohols (e.g., aliphatic monohydric alcohols with 1 to 3 carbon atoms, such as ethanol); polyhydric Alcohols (e.g., glycerin, butylene glycols such as propylene glycol (PG), dipropylene glycol (DPG), 1,3-butylene glycol); pH adjusters (e.g., citric acid, lactic acid, triethanolamine, KOH, NaOH); rust inhibitors (e.g., ammonia water, ammonium benzoate, sodium nitrite); preservatives (e.g., parabens, phenoxyethanol, methyl parahydroxybenzoate); urea; minerals such as calcium, iron, sodium; pigments; colorants; anti-inflammatory agents (e.g., dipotassium glycyrrhizinate); UV absorbers (e.g., terephthalidenedicamphorsulfonic acid), etc.

[0043] (Viscosity of emulsion composition) The viscosity of the emulsion composition at 25° C. is preferably 1000 mPa·s to 50000 mPa·s, more preferably 2000 mPa·s to 15000 mPa·s, and even more preferably 2500 mPa·s to 12000 mPa·s. The viscosity here is measured using a Brookfield viscometer (TVB-10: Toki Sangyo Co., Ltd.) with a No. M2 rotor at a rotation speed of 6 rpm for a measurement time of 3 minutes, and when the measured value exceeds the upper measurement limit (5000 mPa·s), the value is measured using a No. M3 rotor at a rotation speed of 6 rpm for a measurement time of 1 minute. When the viscosity of the emulsion composition at 25° C. is within the above range, the emulsion composition is less prone to dripping, and when sprayed, the spray particle size is sufficiently small and the spray range is sufficiently large.

[0044] (Method of producing emulsion composition) The method for producing the emulsion composition is not particularly limited, and any known method can be used. For example, there is a method in which mechanically defibrated fine fibrous cellulose, a water-soluble polymer, an oily component, and water, as well as other components as necessary, are mixed in any ratio, and emulsified using a rotary homogenizer, a high-pressure homogenizer, an ultrasonic emulsifier, or the like to form an oil-in-water (O / W) emulsion.

[0045] The emulsion composition can be used in, but is not particularly limited to, personal care products, household products, industrial products, etc. The emulsion composition is preferably an aerosol composition or a spray composition. The emulsion composition can be filled in a known container and used. Specific examples of known containers include tubes, pumps, and aerosol containers. The form of the composition discharged from the container is not particularly limited, and may be, for example, a lotion, gel, foam, or spray form. The emulsion composition can also be used in the form of a sheet agent in which a sheet such as a nonwoven fabric is impregnated with the emulsion composition.

[0046] (Spray product) The spray product according to one embodiment of the present invention (hereinafter, also simply referred to as "spray product") is a spray product in which the above-mentioned emulsion composition is filled in a spray container. The spray product may be any product that can spray the contents from a discharge port such as a valve in the form of a spray or mist. It may be a product that is sprayed by high pressure gas such as compressed gas, or may be sprayed electrically or manually. The spray container used for the spray product is not particularly limited, and examples thereof include known aerosol containers, pump spray containers, trigger spray containers, pump dispensers, trigger dispensers, etc.

[0047] (Aerosol products) An aerosol product according to one embodiment of the present invention (hereinafter, also simply referred to as "aerosol product") is an aerosol product in which the above-mentioned emulsion composition and a propellant are filled in an aerosol container. The aerosol container used for the aerosol product may be any of various known pressure-resistant containers. In addition, the structure for mounting the valve device may be appropriately selected depending on the type of pressure-resistant container.

[0048] The aerosol product is produced by filling the emulsion composition into an aerosol container, i.e., a pressure-resistant container equipped with an aerosol valve (spray valve). For example, the aerosol product is produced by preparing an emulsion composition, and filling the obtained emulsion composition and a propellant into an aerosol container. A so-called double container may be used in which an inner container is further provided inside the pressure-resistant container, and the propellant and the emulsion composition are separated by the inner container.

[0049] Regarding the mixing ratio of the emulsion composition and the propellant, in the case of a liquefied gas, the content of the liquefied gas is preferably 1 to 30 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the emulsion composition. The compressed gas is preferably filled so that the pressure inside the aerosol container when filled therein (gauge pressure) is 0.1 MPa to 1.0 MPa at 25°C, and more preferably 0.2 MPa to 0.9 MPa.

[0050] The form of ejection of the aerosol product is not particularly limited, but is preferably a mist. The emulsion composition is preferably a spray composition that is sprayed in the form of a mist. The ejection mechanism of the aerosol product is also not particularly limited, and a known actuator that can spray in the form of a mist can be used. For example, an actuator that generates a swirling flow of the emulsion composition by passing the emulsion composition through a flow path inside the actuator and ejects the emulsion composition in the form of a mist can be mentioned.

[0051] The propellant is not particularly limited, and liquefied gas or compressed gas may be used, or a combination of liquefied gas and compressed gas may be used. Aerosol products preferably contain compressed gas. The compressed gas is not particularly limited, and any known gas that can be used in aerosol products can be used. The compressed gas is preferably at least one selected from the group consisting of carbon dioxide gas, nitrogen gas, nitrous oxide gas, argon, helium, compressed air, etc., and more preferably at least one selected from the group consisting of carbon dioxide gas and nitrogen gas. The liquefied gas is not particularly limited, and any known gas that can be used in aerosol products can be used, such as LPG, LNG, hydrocarbons such as isopentane, dimethyl ether, and hydrofluoroolefins such as HFO-1234ze. EXAMPLES

[0052] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the embodiments of the following examples.

[0053] <Examples 1 to 16 and Comparative Examples 1 to 14> A total of 100 g of each raw material was collected and mixed in a glass beaker according to the formulation (mass %) shown in Tables 1 to 4, and then emulsified at 25°C and 7000 rpm for 3 minutes using a rotor homogenizer (Homomixer MARK II 2.5 type, manufactured by Primix Corporation) to obtain the emulsion compositions of Examples 1 to 16 and Comparative Examples 1 to 14.

[0054] The emulsion composition and propellant (nitrogen gas) were then filled into a pressure-resistant container to obtain an aerosol product. The amount of nitrogen gas filled was adjusted so that the internal pressure of the product was 0.75 MPa and 0.3 MPa. The discharge mechanism was a "D91W 0381T"4"-A" (manufactured by Sanyo Denki Co., Ltd.). A valley valve was used. Furthermore, the emulsion compositions and aerosol products obtained were used to carry out the evaluations described below. The results are shown in Tables 1 to 4.

[0055] (1) Viscosity measurement of emulsion composition The viscosity (mPa s) of the resulting emulsion composition was measured using a Brookfield viscometer (TVB-10: Toki Sangyo Co., Ltd.) with a rotor No. M2, a rotation speed of 6 rpm, and a measurement time of 3 minutes, or with a rotor No. M3, a rotation speed of 6 rpm, and a measurement time of 1 minute.

[0056] (2) Evaluation of flow resistance of emulsion composition 0.5 mL of the obtained emulsion composition was placed on the artificial skin. The artificial skin was then tilted by 30°, and the time (s) until the original solution flowed 10 cm was evaluated according to the following evaluation criteria.

[0057] [Evaluation Criteria] A: 60 seconds or more B: 40 seconds or more but less than 60 seconds C: 20 seconds or more but less than 40 seconds D: Less than 20 seconds

[0058] (3) Evaluation of emulsion stability of emulsion composition The obtained emulsion composition was stored in a glass bottle at room temperature for 7 days, and the appearance of the emulsion composition was visually observed and evaluated according to the following evaluation criteria.

[0059] [Evaluation Criteria] A: No creaming and stable. B: Slight creaming but remains dispersed. C: The lower layer is transparent or translucent and a creaming layer is observed.

[0060] (4) Spray particle size measurement The obtained aerosol product was sprayed at a distance of 15 cm for a duration of 3 seconds. The particle size of the sprayed particles was measured using a laser diffraction particle size distribution measuring device (Spraytec: Malvarn Co., Ltd.) and evaluated according to the following evaluation criteria.

[0061] [Evaluation criteria - Product internal pressure 0.75MPa] A: The DV(50) value is less than 75 μm. B: DV(50) value is 75 μm or more and less than 85 μm. C: DV(50) value is 85 μm or more and less than 95 μm. D: DV(50) value is 95 μm or more.

[0062] [Evaluation criteria - when product internal pressure is 0.3MPa] A: The DV(50) value is less than 95 μm. B: The DV(50) value is 95 μm or more and less than 105 μm. C: DV(50) value is 105 μm or more and less than 130 μm. D: DV(50) value is 130 μm or more.

[0063] (Spray pattern evaluation) The obtained aerosol product was sprayed onto water-sensitive paper from a distance of 15 cm for 1 second, and the diameter of the spray pattern was measured and evaluated according to the following evaluation criteria.

[0064] [Evaluation criteria (the evaluation criteria are the same regardless of the product internal pressure)] A: 200mm or more B: 150mm or more and less than 200mm. C: 100mm or more but less than 150mm. D: Less than 100mm.

[0065] [Table 1]

[0066] [Table 2]

[0067] [Table 3]

[0068] [Table 4]

[0069] In the table, the raw materials used are as follows: (water) Water: Purified water (Toyo Aerosol Industry Co., Ltd.)

[0070] (Water-soluble polymer) Carboxyvinyl polymer: Carbopol ETD 2050 Polymer (Lubrizol Corporation) (Acrylates / C10-30 Alkyl Acrylate) Crosspolymer (1): Pemulen TR-1 Polymeric Emulsifier (Lubrizol Corporation) (Acrylates / Alkyl Acrylate (C10-30)) Crosspolymer (2): Pemulen EZ-4U Polymeric Emulsifier (Lubrizol Corporation) Hydroxypropyl methylcellulose stearoxy ether: Sangelose 60L (Daido Chemical Industry Co., Ltd.) Polyvinyl alcohol: Gohsenol EG-05C (Mitsubishi Chemical Corporation) Hydroxypropyl methylcellulose: Metolose 60SH-06 (Shin-Etsu Chemical Co., Ltd.)

[0071] (Fine fibrous cellulose) Cellulose gum, water (carboxymethyl cellulose nanofiber): Cellenpia C S-01C (Nippon Paper Industries Co., Ltd.) (A fine fibrous cellulose product in powder form. The fine fibrous cellulose is obtained by mechanical defibration of carboxymethylated cellulose.) Crystalline cellulose, water (TEMPO oxidized cellulose nanofiber dispersion): Leocrysta C-2SP (Dai-ichi Kogyo Seiyaku Co., Ltd.) (A product containing 2% by mass of fine fibrous cellulose in water. The fine fibrous cellulose was obtained by mechanical defibration of TEMPO-oxidized cellulose, with the amount of hydrophilic substituents (carboxyl groups) introduced being 1.64 mmol / g and the number-average fiber diameter being 3 nm.) Cellulose, water (phosphated cellulose nanofiber dispersion): Aurovisco CS (Nikko Chemicals Co., Ltd.) (A product containing 2% by mass of fine fibrous cellulose in water. The fine fibrous cellulose is obtained by mechanical defibration of phosphoric acid esterified cellulose.) Cellulose, water (mechanically defibrated cellulose nanofiber dispersion): BiNFi-s AFo (Sugino Machine Co., Ltd.) (a product containing 2% by mass of mechanically defibrated fine fibrous cellulose in water. The mechanically defibrated fine fibrous cellulose is obtained by mechanical defibration of cellulose that has not been subjected to chemical treatment, and the amount of hydrophilic substituents introduced is 0 to 0.1 mmol / g, and the number average fiber diameter is 10 to 50 nm.)

[0072] (Oily ingredients) Liquid paraffin: Carnation (Sonneborn LLC) Apricot kernel oil: NIKKOL Apricot Kernel Oil (Nikko Chemicals Co., Ltd.) Cetyl ethylhexanoate: NIKKOL CIO (Nikko Chemicals Co., Ltd.) Dimethicone: KF-96-2cs (Shin-Etsu Chemical Co., Ltd.) Caprylic / capric triglyceride: NIKKOL Triester F-810 (Nikko Chemicals Co., Ltd.) Jojoba seed oil: NIKKOL Jojoba Oil S (Nikko Chemicals Co., Ltd.)

[0073] (Additives (pH adjusters)) Triethanolamine: Triethanolamine 99 (Dow Chemical Japan Co., Ltd.) 1,3-Butylene glycol: 1,3-Butylene glycol-P (KH Neochem) Methyl parahydroxybenzoate: Methyl parahydroxybenzoate (Ueno Pharmaceuticals)

[0074] <Example 17 and Comparative Example 15> A total of 100 g of each raw material was taken into a glass beaker and mixed according to the formulation (mass%) shown in Table 5, and then emulsified at 25°C and 7000 rpm for 3 minutes using a rotor homogenizer (Homomixer MARK II 2.5 type, manufactured by Primix Corporation) to obtain the emulsion compositions of Example 17 and Comparative Example 15.

[0075] The obtained emulsion composition was then filled into a pump sprayer to obtain a spray product. The obtained emulsion composition was used to carry out the above-mentioned viscosity measurement, run resistance evaluation, and emulsion stability evaluation. In addition, the obtained spray product was used to measure the spray pattern and the spray particle size by the above-mentioned evaluation method. The determination was made.

[0076] <Examples 18 to 19> A total of 100 g of each raw material was taken into a glass beaker and mixed according to the formulation (mass%) shown in Table 5, and then emulsified at 25°C and 7000 rpm for 3 minutes using a rotor homogenizer (Homomixer MARK II 2.5 type, manufactured by Primix Corporation) to obtain the emulsion compositions of Examples 18 to 19.

[0077] A propellant (LPG or DME) was filled into a pressure-resistant container equipped with an injection valve device for 100.00 parts by mass of each of the obtained aerosol compositions, and the discharge mechanism was equipped with "D91W 0381T" Aerosol products of Examples 18 to 19 were obtained using an evaporative nozzle equipped with a viscometer (EIA 1000-4"-A) (Mitani Valve Co., Ltd.). The emulsion compositions were used to carry out the above-mentioned viscosity measurement, flow resistance evaluation, and emulsion stability evaluation. In addition, the resulting aerosol products were used to measure the spray pattern and spray particle size using the above-mentioned evaluation methods.

[0078] [Table 5]

Claims

1. An emulsion composition comprising mechanically defibrated fine fibrous cellulose, a water-soluble polymer, an oil component, and water, The emulsion composition forms an oil-in-water emulsion in which an oil phase containing the oily component is dispersed in an aqueous phase containing water, An emulsion composition, characterized in that the emulsion composition is substantially free of a surfactant.

2. The emulsion composition according to claim 1, wherein the content of the mechanically defibrated fine fibrous cellulose in the emulsion composition is 0.005% by mass to 10.00% by mass.

3. The emulsion composition according to claim 1, wherein the content of the water-soluble polymer in the emulsion composition is 0.001% by mass to 1.00% by mass.

4. 2. The emulsion composition according to claim 1, wherein the water-soluble polymer comprises at least one selected from the group consisting of carboxyvinyl polymers, acrylates / alkyl acrylate crosspolymers, polyvinyl alcohol, and cellulose-based polymers.

5. The emulsion composition according to claim 1 , wherein the oil component is liquid at 20° C.

6. The emulsion composition according to claim 1, wherein the amount of hydrophilic substituent introduced into the mechanically defibrated fine fibrous cellulose is 0 mmol / g to 0.1 mmol / g.

7. The emulsion composition of claim 1 , which is a spray composition.

8. A spray product in which an emulsion composition is filled in a spray container, A spray product, wherein the emulsion composition is the emulsion composition according to any one of claims 1 to 7.

9. An aerosol product in which an emulsion composition and a propellant are filled in an aerosol container, An aerosol product, wherein the emulsion composition is the emulsion composition according to any one of claims 1 to 7.

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