Alkenyl group-containing polyoxyalkylene compound, silicone modifier, polyoxyalkylene-modified silicone, and emulsion composition

Abstract

The present invention provides an alkenyl group-containing polyoxyalkylene compound represented by formula (1): R1O-(AO) n-R2 (In formula (1), AO is a C2-4 oxyalkylene group obtained by a dehydration condensation reaction using a phosphinic acid or a phosphinic acid salt; n represents the average addition mole number of AO, and n = 3-90; r1 is alkenyl with the carbon atom number of 3-5, and R2 is alkenyl with the carbon atom number of 3-5 or a hydrogen atom; the ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the alkenyl group-containing polyoxyalkylene compound calculated from a chromatogram obtained by gel permeation chromatography measurement is 1.20-5.00. ).

Description

Technical Field

[0001] The present invention relates to an alkenyl-containing polyoxyalkylene compound, an organosilicon modifier, a polyoxyalkylene-modified organosilicon, and an emulsified composition. Specifically, the present invention relates to an alkenyl-containing polyoxyalkylene compound capable of imparting surface activity to an organopolysiloxane; an organosilicon modifier comprising the compound; a polyoxyalkylene-modified organosilicon that is a reaction product of the organosilicon modifier and the organopolysiloxane; and an emulsified composition comprising the polyoxyalkylene-modified organosilicon, an oil, and water in predetermined amounts. Background Art

[0002] Alkenyl-containing polyoxyalkylene compounds can be obtained by ring-opening addition polymerization of an alkylene oxide, such as ethylene oxide or propylene oxide, to an initiator, such as allyl alcohol, with an active hydrogen, using a base catalyst, or by reacting a halogenated alkenyl group with the polyoxyalkylene compound. These alkenyl-containing polyoxyalkylene compounds possess reactive alkenyl groups and a wide and adjustable range of hydrophilicity. The hydrophilicity of the resulting product can be adjusted by reacting with other substances, making them useful in organosilicon modifiers, polymerizable monomers, and reactive emulsifiers. In particular, organosilicon modifiers can impart surface-active properties to organopolysiloxanes, which exhibit excellent heat resistance, weather resistance, mold release properties, water resistance, and bioinertness.

[0003] For example, modified organopolysiloxanes can be obtained by chemically reacting an organosilicon modifier composed of reactive groups such as alkenyl groups and hydrophilic functional groups such as polyoxyalkylene groups with an organopolysiloxane having reactive functional groups such as silyl groups (hereinafter also referred to as "SiH groups"). The modified organopolysiloxanes obtained by this method, when incorporated as surfactant components in emulsion compositions, can impart excellent emulsion stability and are therefore widely used in a variety of industrial fields, including cosmetics, toiletries, and coatings.

[0004] Emulsified compositions are broadly categorized into oil-in-water and water-in-oil types based on their emulsification state. In the cosmetics industry, they are particularly useful in a variety of applications, including skincare creams, lotions, and sunscreens. Of these, water-in-oil types are superior to oil-in-water types for external skin applications because they allow for efficient distribution of oil-soluble emollient oils, active ingredients, and UV absorbers across the skin.

[0005] However, since the continuous phase of the water-in-oil type is oil, although sufficient moisturizing feeling and the effect of the active ingredient can be obtained, compared with the oil-in-water type, a sticky feeling may be generated during application, resulting in a poorer texture.

[0006] One solution to these problems with water-in-oil emulsions is to increase the water content. This method imparts a moist, soft feel, resulting in a refreshing feel. Furthermore, choosing silicone oil as the lubricant allows for a refreshing, less sticky product with high water resistance. However, conventional emulsifiers, such as polyoxyalkylene fatty acid esters, have been difficult to achieve stable emulsions.

[0007] Against this backdrop, for example, Patent Document 1 discloses a water-in-oil emulsion having high stability by using a polyoxyalkyl-modified silicone having both a polyglyceryl group and a polyoxyalkyl group as an emulsifier.

[0008] Patent Document 2 discloses that the use of branched polyoxyalkylene-modified silicone as an emulsifier can provide excellent emulsification performance for various oils such as silicone oil. Furthermore, the resulting emulsion has a refreshing feel and is excellent in emulsion stability and transparency.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 2012-207078

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 2002-179797 Summary of the Invention

[0013] (1) Technical issues to be resolved

[0014] While the compositions described in Patent Documents 1 and 2 have excellent emulsification stability, they may lack sufficient emulsification power when emulsifying large amounts of oil. Therefore, an excellent emulsifier with high emulsification power and a moist texture is desired. Silicone modifiers are typically those obtained by a polymerization reaction with an alkylene oxide using a base catalyst.

[0015] The following description is not a publicly known matter, but is a matter discovered by the inventors of the present application.

[0016] During the development of the present invention, the inventors of the present application focused on compounds obtained by a dehydration condensation reaction with a diol using a strong acid catalyst. Compounds obtained by this dehydration condensation reaction are known to color, and research on coloration suppression has long been conducted (e.g., see Japanese Patent Application Publication No. 2004-182974). Furthermore, in recent cosmetic development, there has been a strong demand for improved coloration of formulations to enhance their perceived quality. Highly transparent formulations such as lotions are required to be colorless and transparent, while turbid white formulations such as lotions and creams are required to be milky white without a yellowish tint.

[0017] However, when surfactants containing silicone modifiers obtained through dehydration condensation reactions are used as cosmetic ingredients, coloration suppression may be insufficient. Furthermore, since dehydration condensation reactions often occur under high-temperature conditions, silicone modifiers are susceptible to degradation. These modifiers gradually hydrolyze in the presence of moisture and small amounts of acid in the air, generating odorous substances such as propionaldehyde, which can lead to the development of odor in the product over time.

[0018] (2) Technical solution

[0019] To address the above-mentioned technical problems, the inventors of the present application conducted intensive research and, as a result, focused on using a specific polyether obtained by dehydration condensation of a diol as an organosilicon modifier. They discovered that a surfactant, obtained by reacting this organosilicon modifier with an organopolysiloxane containing SiH groups, could suppress coloration. Furthermore, the inventors discovered that an emulsified composition using this surfactant exhibits high emulsifying power, allowing for increased water content. This results in a moist feel during application, and excellent emulsification stability and odor suppression over time.

[0020] The present invention includes the following solutions [1] to [4].

[0021] [1] An alkenyl group-containing polyoxyalkylene compound, which is an alkenyl group-containing polyoxyalkylene compound represented by the following formula (1):

[0022] R 1 O-(AO)nR 2 (1)

[0023] (In formula (1), AO is an oxyalkylene group having 2 to 4 carbon atoms obtained by a dehydration condensation reaction using phosphinic acid or a phosphinic acid salt; n represents the average number of added moles of AO, n = 3 to 90; R 1 is an alkenyl group having 3 to 5 carbon atoms, R 2 is an alkenyl group having 3 to 5 carbon atoms or a hydrogen atom; and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyoxyalkylene compound containing an alkenyl group, as calculated from a chromatogram obtained by gel permeation chromatography, is 1.20 to 5.00.

[0024] [2] An organosilicon modifier comprising the alkenyl group-containing polyoxyalkylene compound described in [1].

[0025] [3] A polyoxyalkylene-modified silicone, which is a reaction product of the silicone modifier described in [2] above and a hydrogenated organopolysiloxane represented by the following formula (2),

[0026] [Chemical Formula 1]

[0027]

[0028] (In formula (2), p is 1~100, q is 0~50, r is 0~100, q / (p+r) is 0~1; R 3 Each independently represents an alkyl group having 1 to 8 carbon atoms; R 4 and R 5 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; when q=0, R 4 and R 5 At least one of them is a hydrogen atom.)

[0029] [4] An emulsified composition comprising 0.1 to 40% by mass of (A) the polyoxyalkylene-modified silicone described in [3] above, 1 to 50% by mass of (B) an oily agent that is liquid at 25°C, and 10 to 98% by mass of (C) water, wherein the mass ratio of component (B) to component (A) ((B) / (A)) is 0.5 to 30.

[0030] (3) Beneficial effects

[0031] Because the polyoxyalkylene-modified silicone of the present invention, obtained by reacting an alkenyl-containing polyoxyalkylene compound with an organopolysiloxane containing SiH groups, exhibits suppressed coloration, it is less likely to cause coloration problems when used in products such as cosmetic raw materials. Furthermore, because emulsified compositions using this polyoxyalkylene-modified silicone as a surfactant possess high emulsifying power, the amount of water added can be increased, resulting in a moist feel during application and excellent emulsification stability and odor suppression over time. DETAILED DESCRIPTION

[0032] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described in this specification, and various modifications can be made without departing from the spirit of the present invention.

[0033] In this specification, a numerical range defined by the symbol "~" includes both ends (upper and lower limits) of the "~." For example, "2 to 5" means 2 or more and 5 or less.

[0034] In this specification, in multiple numerical ranges described in a segmented manner, each upper limit and each lower limit may be the upper limit or lower limit of any combination of numerical ranges. For example, when the content of a certain component is described as "5-20% by mass, 10-15% by mass", the numerical ranges may be "5-15% by mass", "10-20% by mass", "5-10% by mass", and "15-20% by mass".

[0035] In addition, in the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range can be replaced with the value shown in the Examples or the value clearly derived from the Examples.

[0036] Throughout this specification, unless otherwise indicated, all numerical values ​​preceded by the word "about" are to be understood as modified values. Numerical values ​​are subject to the inherent variability of the measurement techniques used to determine such values. Furthermore, numerical values ​​should at least be interpreted as numbers with respect to significant figures and any rounding should be applied.

[0037] <Polyoxyalkylene compounds containing alkenyl groups>

[0038] The alkenyl group-containing polyoxyalkylene compound of the present invention (hereinafter also referred to as "the compound of the present invention") is a polyether represented by the following formula (1).

[0039] R 1 O-(AO)nR 2 (1)

[0040] In formula (1), AO is an oxyalkylene group having 2 to 4 carbon atoms, and the oxyalkylene group may have a branched chain. Examples of AO include oxyethylene, oxypropylene, oxytrimethylene, 1,2-oxybutylene (oxy-1-ethylethylene), and 1,4-oxybutylene (oxytetramethylene). Preferred are oxyethylene, oxypropylene, and oxytrimethylene, and more preferred are oxyethylene. The molecule of formula (1) may contain different oxyalkylene groups, and the different oxyalkylene groups may be bonded in a block or random manner.

[0041] The compound of the present invention is a composition containing two or more polyethers, wherein the two or more polyethers have different numbers of added oxyalkylene groups. Therefore, n in formula (1) represents the average number of added oxyalkylene groups. n = 3 to 90, preferably n = 6 to 70, more preferably n = 6 to 50, particularly preferably n = 7 to 30, and even more preferably n = 8 to 20. Furthermore, when the molecule of formula (1) contains two or more different oxyalkylene groups, the sum of the average number of added oxyalkylene groups of the different groups may be within the above range.

[0042] In formula (1), R 1 is an alkenyl group having 3 to 5 carbon atoms, R 2 is an alkenyl group having 3 to 5 carbon atoms or a hydrogen atom. These alkenyl groups may have branches. 2 When it is alkenyl, R 1 With R 2 They may be different alkenyl groups or the same alkenyl groups. 1 and R 2It is an allyl group which is an alkenyl group having 3 carbon atoms, or it is a methallyl group which is an alkenyl group having 4 carbon atoms, and it is more preferably an allyl group.

[0043] The compounds of the present invention are defined by their molecular weight as determined by a chromatogram obtained using a differential refractometer during gel permeation chromatography (GPC). This chromatogram is a graph showing the relationship between refractive index intensity and elution time. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained from the chromatogram is in the range of 1.20 to 5.00.

[0044] If the ratio (Mw / Mn) is too small, there is a high possibility that no emulsion will be obtained, while if the ratio (Mw / Mn) is too large, there is a high possibility that a moist feel during application will not be obtained. It is preferably 1.25 to 3.00, more preferably 1.30 to 2.00, particularly preferably 1.40 to 1.80, and even more preferably 1.50 to 1.70.

[0045] In the present invention, gel permeation chromatography (GPC) for determining Mw and Mn is measured under the following conditions, and a chromatogram represented by refractive index intensity and elution time is obtained by using the BORWIN GPC calculation program.

[0046] System: SHODEX (registered trademark) GPC101 GPC dedicated system

[0047] Differential refractometer: SHODEX (registered trademark) RI-71s

[0048] Guard column: SHODEX (registered trademark) KF-G

[0049] Chromatographic column: SHODEX (registered trademark) 3 KF804L installed in series

[0050] Column temperature: 40°C

[0051] Developing solvent: tetrahydrofuran

[0052] Flow rate: 1ml / min

[0053] [Method for preparing the compound of the present invention]

[0054] The compound of the present invention can be produced by first subjecting a diol represented by the following formula (3) to dehydration condensation to obtain a reaction product, and then alkenylating the product.

[0055] HO-(A'O)mH (3)

[0056] In formula (3), A'O is an oxyalkylene group having 2 to 4 carbon atoms, and the oxyalkylene group may have a branched chain. Examples of A'O include oxyethylene, oxypropylene, oxytrimethylene, 1,2-oxybutylene (oxy-1-ethylethylene), and 1,4-oxybutylene (oxytetramethylene). Preferred are oxyethylene, oxypropylene, and oxytrimethylene, and more preferred are oxyethylene. m is an integer from 1 to 3. When m is 2 or 3, the molecule of formula (3) may contain different oxyalkylene groups.

[0057] Examples of the diol represented by formula (3) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butylene glycol, and 1,4-butylene glycol. One of these diols may be used alone or in combination of two or more. From the perspective of the stability of the resulting emulsion, triethylene glycol and tripropylene glycol are preferred, and triethylene glycol is more preferred.

[0058] The reaction temperature during dehydration condensation is preferably 100-200°C, and more preferably 110-140°C from the perspectives of reactivity and coloration of the resulting organosilicon modifier. Furthermore, the pressure during preparation is below atmospheric pressure, preferably about 10 kPa or less, and more preferably about 3 kPa or less.

[0059] In the dehydration condensation reaction, a dehydration condensation catalyst can generally be used. Examples of the dehydration condensation catalyst include homogeneous catalysts such as Lewis acids, Brønsted acids, super acids, and mixtures of these acids. Examples include inorganic acids, organic sulfonic acids, heteropoly acids, and metal salts of these acids. More specifically, examples include sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid, phosphomolybdic acid, trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, 1,1,1,2,3,3-hexafluoropropanesulfonic acid, bismuth trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, neodymium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, scandium trifluoromethanesulfonate, and zirconium trifluoromethanesulfonate. In addition, heterogeneous catalysts such as zeolite, fluorinated alumina, acid-treated silica, acid-treated silica-alumina, heteropolyacids, heteropolyacids supported on zirconia, titania, alumina, and silica can also be used. The homogeneous catalysts listed above are preferred, and sulfuric acid is more preferred.

[0060] The amount of the dehydration condensation catalyst used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the diol used.

[0061] In the method of the present invention, during the dehydration condensation, AO in formula (1), i.e., an oxyalkylene group having 2 to 4 carbon atoms, can be obtained by the presence of phosphinic acid or phosphinic acid salt.

[0062] The phosphinate is preferably an alkali metal salt of phosphinic acid, and examples thereof include sodium phosphinate and potassium phosphinate.

[0063] From the viewpoint of availability and suppression of coloration, phosphinic acid or sodium phosphinate is preferably used, and phosphinic acid is more preferably used.

[0064] The amount of phosphinic acid or phosphinic acid salt used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the diol used. In addition, phosphinic acid and phosphinic acid salt can be used simultaneously, in which case the total amount of the two is preferably within the above range.

[0065] The hydroxyl value of the reaction product after the dehydration condensation reaction is preferably 25 to 750 mgKOH / g, more preferably 50 to 500 mgKOH / g. The hydroxyl value is measured in accordance with JIS K1557-1.

[0066] The Hazen unit chromaticity (APHA) of the reaction product is preferably 0 to 500, more preferably 0 to 300. The Hazen unit chromaticity (APHA) is measured in accordance with JIS K0071-1.

[0067] When the compound of the present invention has different oxyalkylene groups, the molar ratio of each oxyalkylene group can be determined using, for example, proton nuclear magnetic resonance (H-NMR). For example, when the compound of the present invention has oxyethylene and oxypropylene groups, the molar ratio of oxyethylene to oxypropylene groups can be calculated using the following formula using the integrated value (P1) of the peak for the oxypropylene methyl group and the integrated value (P2) of the peak for the oxyethylene and oxypropylene methylene groups using proton nuclear magnetic resonance (H-NMR). Furthermore, the total molecular weight can be calculated based on the hydroxyl value, thereby calculating the number of added moles.

[0068] Oxyethylene group: oxypropylene group = {(P2-P1) / 4}: (P1 / 3)

[0069] Then, the reaction product can be reacted with an alkenyl halide to carry out alkenylation.

[0070] The halogenated alkenyl group used is R 1 -X or R 2’ -X represents a halide. 1 -X and R 2’ -X can be the same or different. 1 -X or R 2’ -Any one or both of X. R 1 -R in X 1 and R in formula (1) 1Same meaning, R 2’ -R in X 2’ and R in formula (1) 2 The same meaning applies to alkenyl groups having 3 to 5 carbon atoms. X is a halogen. Examples of the halogen include fluorine, chlorine, bromine, and iodine, and a halogen selected from these can be used.

[0071] The amount of the alkenyl halide used is preferably 4 to 120 parts by mass, more preferably 8 to 75 parts by mass, relative to 100 parts by mass of the reaction product.

[0072] The alkenylation may be carried out under basic conditions, for example in the presence of a strong base.

[0073] The reaction temperature during alkenylation is preferably 60 to 200° C., more preferably 70 to 140° C. The pressure during preparation is below atmospheric pressure, preferably about 10 kPa or less, and more preferably about 3 kPa or less.

[0074] The unsaturation degree of the alkenyl group-containing polyoxyalkylene compound of the present invention obtained as described above is preferably 0.40 to 13.00 meq / g, more preferably 0.90 to 8.90 meq / g. The unsaturation degree can be measured according to JIS K 1557-3.

[0075] The Hazen unit chromaticity (APHA) of the compound of the present invention is preferably 0 to 500, more preferably 0 to 400. The Hazen unit chromaticity (APHA) can be measured in accordance with JIS K 0071-1.

[0076] In summary, the method for preparing the alkenyl-containing polyoxyalkylene compound represented by the above formula (1) includes the following steps: a step of subjecting the diol represented by the above formula (3) to a dehydration condensation reaction in the presence of phosphinic acid or a phosphinate to obtain a reaction product; and a step of reacting the obtained reaction product with R1-X and / or R2'-X.

[0077] Silicone modifiers

[0078] The organosilicon modifier of the present invention is composed of an alkenyl group-containing polyoxyalkylene compound as the compound of the present invention, and the compound of the present invention functions as an organosilicon modifier.

[0079] <Polyoxyalkylene-modified silicone>

[0080] The polyoxyalkylene-modified silicone of the present invention is a reaction product of the compound of the present invention that functions as a silicone modifier and a hydrogenated organopolysiloxane represented by the following formula (2). In other words, the reaction product is a hydrosilylated product of the compound of the present invention based on the hydrogenated organopolysiloxane represented by the following formula (2).

[0081] [Chemical Formula 1]

[0082]

[0083] In formula (2), p is 1 to 100, q is 0 to 50, r is 0 to 100, and q / (p+r) is 0 to 1. From the perspective of the stability of the emulsion composition of the present invention described later, p is preferably 80 or less, more preferably 50 or less, and even more preferably 20 or less. q is preferably 30 or less, more preferably 10 or less, and particularly preferably 0. r is preferably 80 or less, more preferably 50 or less, and particularly preferably 20 or less. q / (p+r) is preferably 0.4 or less, and more preferably 0.

[0084] The multiple R contained in formula (2) 3 Each independently represents an alkyl group having 1 to 8 carbon atoms, and the alkyl group may have a branch. 3 For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group etc. are mentioned, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group are preferable.

[0085] R 4 and R 5 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 4 and R 5 At least one of them is a hydrogen atom.

[0086] The alkyl group having 1 to 8 carbon atoms may have a branch. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, and octyl groups, with methyl and ethyl groups being preferred.

[0087] The hydrogenated organopolysiloxane represented by formula (2) can be prepared by a known method, and a commercially available product can also be used. Examples of such products include "methyl H siloxane-dimethyl siloxane copolymer" manufactured by Gelest, with the product code HMS-082 (in formula (2), R 3 , R4 and R5 are all methyl, p is 75, q is 6.5, and r is 0).

[0088] The reaction of the compound of the present invention and the hydrogenated organopolysiloxane is usually carried out by mixing the two in the presence of a catalyst. Examples of the catalyst used include chloroplatinic acid hexahydrate, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinylsiloxane complexes. The amount of the catalyst used is preferably 500 ppm or less, particularly preferably 200 ppm or less, relative to the total mass of the compound of the present invention and the hydrogenated organopolysiloxane, calculated as platinum.

[0089] The reaction temperature is preferably 50 to 130° C., more preferably 60 to 110° C. The completion of the reaction can be confirmed by FT-IR measurement, and the reaction is carried out until the absorption of 2100 to 2300 cm −1 derived from SiH groups disappears.

[0090] <Emulsified composition>

[0091] The emulsified composition of the present invention contains 0.1 to 40% by mass of (A) the polyoxyalkylene-modified silicone of the present invention, 1 to 50% by mass of (B) an oil agent that is liquid at 25° C., and 10 to 98% by mass of (C) water.

[0092] In the emulsified composition of the present invention, the total amount of component (A), component (B), and component (C) is 100% by mass.

[0093] [Component (A): polyoxyalkylene-modified silicone]

[0094] Component (A) used in the emulsion composition of the present invention is the aforementioned polyoxyalkylene-modified silicone that functions as a surfactant. The content of component (A) in the emulsion composition of the present invention is 0.1 to 40% by mass, preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably 3 to 15% by mass. When the content of component (A) is too low, the surface activity of component (A) becomes too low, and a stable emulsion composition may not be obtained. When the content of component (A) is too high, the surface activity of component (A) becomes too high, and partial gelation may occur, and a stable emulsion composition may not be obtained.

[0095] [Component (B): an oil that is liquid at 25°C]

[0096] The oil of component (B) is at least one oil selected from the group consisting of hydrocarbon oils that are liquid at 25°C, ester oils that are liquid at 25°C, triglycerides that are liquid at 25°C, animal and vegetable oils that are liquid at 25°C, and silicone oils that are liquid at 25°C.

[0097] Examples of hydrocarbon oils include liquid paraffin, hydrogenated polyisobutene, hydrogenated polydecene, squalane, squalene, pristane, light isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, liquid isoparaffin, tetradecene, isohexadecane, isododecane, and α-olefin oligomers. Liquid paraffin and hydrogenated polyisobutene are preferred.

[0098] Examples of the ester oil include ethyl oleate, ethyl linoleate, isopropyl myristate, isopropyl palmitate, isopropyl isostearate, cetyl 2-ethylhexanoate, agaryl palmitate, 2-ethylhexyl palmitate, isostearyl isostearate, myristyl myristate, cetyl myristate, isostearyl myristate, isocetyl myristate, hexyl laurate, decyl oleate, octyldodecyl oleate, isononyl isononanoate, and 2-ethylhexyl isononanoate.

[0099] Triglycerides are esters of glycerol and fatty acids. Examples of the fatty acids include caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, isotridecanoic acid, isopalmitic acid, isostearic acid, eicosanoic acid, and oleic acid.

[0100] Examples of animal and vegetable oils and fats include olive oil, sunflower oil, safflower oil, castor oil, and camellia oil.

[0101] Examples of the silicone oil include dimethicone, cyclomethicone, and phenyldimethicone, with dimethicone and cyclomethicone being preferred.

[0102] The oil agent of component (B) used is preferably silicone oil from the viewpoint of compatibility with the surfactant of component (A).

[0103] The content of component (B) in the emulsified composition of the present invention is 1 to 50% by mass, preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 25% by mass. If the content of component (B) is too low, the site where component (A) functions is too small, and thus a stable emulsified composition may not be obtained. If the content of component (B) is too high, the site where component (A) functions is too large, and thus a stable emulsified composition may not be obtained.

[0104] The total amount of component (A) and component (B) in the emulsified composition of the present invention can be calculated to be 1.1 to 90% by mass, preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass. If the total amount of component (A) and component (B) is too small, the content of component (C) described below becomes too large, and a stable emulsified composition may not be obtained. If the total amount of component (A) and component (B) is too large, the content of component (C) becomes too small, and a stable emulsified composition may not be obtained.

[0105] [Ingredient (C): Water]

[0106] Component (C) used in the emulsified composition of the present invention is water. Water is not particularly limited. For example, purified water such as distilled water or ion-exchanged water, physiological saline, and phosphate buffered water can be used.

[0107] The content of component (C) in the emulsified composition of the present invention is 10 to 98% by mass, preferably 20 to 90% by mass, more preferably 40 to 85% by mass, and particularly preferably 45 to 80% by mass. When the content of component (C) is too low or too high, partial gelation may occur due to excessive viscosity, and thus a stable emulsified composition may not be obtained.

[0108] From the perspective of emulsion stability and a moist feel during application, the ratio of the mass of component (B) to the mass of component (A) ((B) / (A)) is preferably 0.5 to 30, more preferably 1 to 20, particularly preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 6.

[0109] The emulsified composition of the present invention is prepared by blending the aforementioned components (A) and (B) with water as component (C). The emulsified composition of the present invention may be blended with various commonly used ingredients as needed. For example, in the field of cosmetic materials, moisturizers, preservatives, antioxidants, ultraviolet absorbers, cosmetic ingredients, fragrances, water-soluble polymers, colorants, pigments, organic powders, etc. may be blended.

[0110] The emulsified composition of the present invention is not particularly limited in form and can be used in a wide range of applications, such as cosmetic materials and coatings, having excellent emulsion stability. In particular, in the field of cosmetic materials, it is suitable for oil-based cosmetics such as lotions, cleansing oils, and hair oils.

[0111] Example

[0112] Above, for ease of understanding, preferred embodiments have been shown and the present invention has been described. Below, synthesis examples, embodiments and comparative examples are listed to further illustrate the present invention in detail and specifically. The above description and the following synthesis examples, embodiments and comparative examples are provided only for illustration and are not intended to limit the present invention.

[0113] In addition, the intermediates, organosilicon modifiers, and surfactants shown in the following synthesis examples were analyzed according to the methods shown below.

[0114] (Analysis Method)

[0115] Hydroxyl value: JIS K 1557-1

[0116] Unsaturation: JIS K 1557-3

[0117] Hazen unit chromaticity (APHA): JIS K 0071-1

[0118] [Synthesis Example A-1]

[0119] To a 1-liter four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and cooling tube were added 750 g of triethylene glycol (manufactured by KANTO CHEMICAL CO., INC.), 9.8 g of sulfuric acid (manufactured by KANTO CHEMICAL CO., INC.), and 6 g of phosphinic acid (manufactured by KANTO CHEMICAL CO., INC.). After nitrogen substitution, the temperature was raised to 120°C and the reaction was carried out for 23 hours under a vacuum of 6 ka and nitrogen bubbling. 5 g each of two adsorbents (KYOWAAD #700 and #1000, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and adsorption treatment was carried out at 90°C, below -0.097 MPa (gauge pressure), and nitrogen bubbling for 1 hour. Filtration yielded 525 g of intermediate (A-1). The hydroxyl value was 251 mgKOH / g, the average number of added moles of ethylene oxide groups was 10, and the APHA content was 60.

[0120] To 300 g of the obtained intermediate (A-1), 113 g of potassium hydroxide and 123 g of allyl chloride were added. After nitrogen substitution, the reaction was carried out at 120°C for 3 hours. 450 g of water was added, stirred for 10 minutes, and then allowed to stand at 80°C for 1 hour. The upper layer after stratification was recovered, neutralized, and then the water was removed by nitrogen bubbling at 80°C. Then, the mixture was treated at 80°C, below -0.097 MPa (gauged pressure), and nitrogen bubbling for 2 hours, and the organosilicon modifier (A-1) was obtained by filtration. The unsaturation was 3.36 meq / g, the APHA was 150, and the Mw / Mn=1.45.

[0121] To a 1-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermocouple, and a cooling tube were added 80 g of hydrogendimethylpolysiloxane (HMS-082 (manufactured by Gelest Co., Ltd.), SiH equivalent per 1 g: 1.06 meq / g) (SiH equivalent: 85 meq), 35 g of an organosilicon modifier (A-1) (unsaturated equivalent: 118 meq), and an isopropanol solution of chloroplatinic acid hexahydrate (1 × 10⁻³ mol / L) as a catalyst at 100 ppm (in terms of platinum). The mixture was stirred under a nitrogen atmosphere and reacted at 90°C. A sample was taken and an N / 10 potassium hydroxide solution in isopropanol was added. The reaction was continued until hydrogen gas generation ceased. FT-IR analysis confirmed the disappearance of the absorption at 2100-2300 cm⁻¹ derived from SiH groups, thereby obtaining a surfactant (A-1).

[0122] [Synthesis Example A-2]

[0123] To a 1-liter four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and cooling tube were added 375 g of triethylene glycol (manufactured by KANTO CHEMICAL CO., INC.), 480 g of tripropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.8 g of sulfuric acid (manufactured by KANTO CHEMICAL CO., INC.), and 6 g of phosphinic acid (manufactured by KANTO CHEMICAL CO., INC.). After nitrogen substitution, the temperature was raised to 120°C and the reaction was carried out for 23 hours under a vacuum of 6 ka and nitrogen bubbling. 5 g each of two adsorbents (KYOWA AD #700 and #1000, manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and adsorption treatment was carried out at 90°C, -0.097 MPa (gauge pressure) or less, under nitrogen bubbling for 1 hour. Filtration yielded 550 g of intermediate (A-2). The hydroxyl value was 220 mgKOH / g, the average number of added moles of ethylene oxide was 5, the average number of added moles of propylene oxide was 4, and the APHA was 80.

[0124] To 300 g of the obtained intermediate (A-2), 99 g of potassium hydroxide and 108 g of allyl chloride were added. After nitrogen substitution, the reaction was carried out at 120 ° C for 3 hours. 396 g of water was added, and after stirring for 10 minutes, it was allowed to stand at 80 ° C for 1 hour. The upper layer after stratification was recovered, neutralized, and then the water was removed by nitrogen bubbling at 80 ° C. Then, it was treated at 80 ° C, below -0.097 MPa (gauging pressure), and nitrogen bubbling for 2 hours, and the organosilicon modifier (A-2) was obtained by filtration. The unsaturation degree was 3.11 meq / g, APHA was 200, and Mw / Mn = 1.30.

[0125] To a 1-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermocouple, and a cooling tube were added 80 g of hydrogendimethylpolysiloxane (HMS-082 (manufactured by Gelest Co., Ltd.), SiH equivalent per 1 g: 1.06 meq / g) (SiH equivalent: 85 meq), 38 g of an organosilicon modifier (A-2) (unsaturated equivalent: 118 meq), and an isopropanol solution of chloroplatinic acid hexahydrate (1 × 10⁻³ mol / L) as a catalyst at 100 ppm (in terms of platinum) were added. The mixture was stirred under a nitrogen atmosphere and reacted at 90°C. A sample was taken and an N / 10 potassium hydroxide solution in isopropanol was added. The reaction was continued until hydrogen gas generation ceased. FT-IR analysis confirmed the disappearance of the absorption at 2100-2300 cm⁻¹ derived from SiH groups, thereby obtaining a surfactant (A-2).

[0126] [Synthesis Example A-3]

[0127] To 200 g of the intermediate (A-1) of Synthesis Example A-1, 75 g of potassium hydroxide and 112 g of methylallyl chloride were added. After nitrogen substitution, the reaction was carried out at 120°C for 3 hours. 301 g of water was added, and after stirring for 10 minutes, it was allowed to stand at 80°C for 1 hour. The upper layer after stratification was recovered, neutralized, and then the water was removed by nitrogen bubbling at 80°C. Then, the mixture was treated at 80°C, below -0.097 MPa (gauged pressure), and nitrogen bubbling for 2 hours, and the organosilicon modifier (A-3) was obtained by filtration. The unsaturation was 3.20 meq / g, the APHA was 150, and the Mw / Mn=1.45.

[0128] To a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermocouple, and a cooling tube were added 80 g of hydrogendimethylpolysiloxane (HMS-082 (manufactured by Gelest, Inc.), SiH equivalent per 1 g: 1.06 meq / g) (SiH equivalent: 85 meq), 38 g of an organosilicon modifier (A-3) (unsaturated equivalent: 118 meq), and a 100 ppm platinum equivalent solution of chloroplatinic acid hexahydrate in isopropanol (1×10⁻³ mol / L) as a catalyst. The mixture was stirred under a nitrogen atmosphere and reacted at 90°C. A sample was taken and an N / 10 potassium hydroxide solution in isopropanol was added. The reaction was continued until hydrogen gas generation ceased. FT-IR analysis confirmed the disappearance of the absorption at 2100-2300 cm⁻¹ derived from SiH groups, thereby obtaining a surfactant (A-3).

[0129] [Synthesis Example A'-1]

[0130] To a 1-liter four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and cooling tube, 750 g of triethylene glycol (manufactured by KANTO CHEMICAL CO., INC.) and 9.8 g of sulfuric acid (manufactured by KANTO CHEMICAL CO., INC.) were added. After nitrogen replacement, the temperature was raised to 120°C and the reaction was carried out for 25 hours under a vacuum of 6 kJ and nitrogen bubbling. 5 g each of two adsorbents (KYOWAAD #700 and #1000, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and adsorption treatment was carried out at 90°C and a nitrogen bubbling pressure of less than -0.097 MPa for 1 hour. The mixture was filtered to obtain 550 g of the intermediate (A'-1). The hydroxyl value was 260 mgKOH / g, the average number of added moles of ethylene oxide groups was 10, and the APHA content was 500.

[0131] To 300 g of the obtained intermediate (A'-1), 117 g of potassium hydroxide and 128 g of allyl chloride were added. After nitrogen substitution, the reaction was carried out at 120°C for 3 hours. 468 g of water was added, and after stirring for 10 minutes, it was allowed to stand at 80°C for 1 hour. The upper layer after stratification was recovered, neutralized, and then the water was removed by nitrogen bubbling at 80°C. Then, the mixture was treated at 80°C, below -0.097 MPa (gauged pressure), and nitrogen bubbling for 2 hours, and the organosilicon modifier (A'-1) was obtained by filtration. The degree of unsaturation was 3.45 meq / g, the APHA was 500 or more, and Mw / Mn=1.55.

[0132] To a 1-liter four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and cooling tube were added 80 g of hydrogendimethylpolysiloxane (HMS-082 (manufactured by Gelest, SiH equivalent per 1 g: 1.06 meq / g) (SiH equivalent; 85 meq), 34 g of an organosilicon modifier (A'-1) (unsaturated equivalent; 117 meq), and a 100 ppm platinum equivalent solution of chloroplatinic acid hexahydrate in isopropanol (1 x 10-3 mol / L) as a catalyst. The mixture was stirred under a nitrogen atmosphere and reacted at 90°C. A sample was taken and an N / 10 potassium hydroxide solution in isopropanol was added. The reaction was continued until hydrogen gas generation ceased. FT-IR analysis confirmed the disappearance of the SiH group-derived absorption at 2100-2300 cm-1, thus yielding a surfactant (A'-1).

[0133] [Synthesis Example A'-2]

[0134] The organosilicon modifier (A'-2) represented by formula (4) was obtained by a known preparation technique, with an unsaturation degree of 4.00 meq / g, an APHA value of 50, and a Mw / Mn value of 1.05.

[0135] CH2=CH-CH2-O-(EO)9-CH2-CH=CH2(4)

[0136] Into a 1-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermocouple, and a cooling tube, 80 g of hydrogendimethylpolysiloxane (HMS-082 (manufactured by Gelest Co., Ltd.), SiH equivalent per 1 g: 1.06 meq / g) (SiH equivalent: 85 meq), 30 g of an organosilicon modifier (A'-2) (unsaturated equivalent: 120 meq), and an isopropanol solution of chloroplatinic acid hexahydrate as a catalyst (1×10 -3 mol / L), stirred under a nitrogen atmosphere, and reacted at 90°C. A sample was taken, and a 10 / 10 potassium hydroxide solution in isopropanol was added. The reaction was continued until hydrogen gas ceased to be generated. FT-IR analysis confirmed the disappearance of the absorption at 2100-2300 cm-1 derived from SiH groups, thereby obtaining a surfactant (A'-2).

[0137] Table 1 shows the organosilicon modifiers and surfactants prepared in Synthesis Examples A-1 to A'-2.

[0138] [Table 1]

[0139]

[0140] <Examples 1 to 6>

[0141] Emulsified cosmetics were prepared by the following preparation method according to the compositions shown in Table 2. Sensory evaluations were conducted on the moistness during application, emulsion stability, and odor over time of the emulsified cosmetics of each composition, and the results are shown in Table 2.

[0142] Furthermore, by conducting a preliminary evaluation test before the evaluation test, each evaluator is trained so that the evaluation level of each score is substantially the same, thereby preventing differences in evaluation criteria between evaluators.

[0143] Comparative Examples 1 to 4

[0144] Emulsified cosmetics were prepared by the following preparation method according to the compositions shown in Table 3. Sensory evaluations were conducted on the moistness during application, emulsion stability, and odor over time of the emulsified cosmetics of each composition. The results are shown in Table 3.

[0145] Preparation method

[0146] Step I: Components (A) and (B) listed in the tables were placed in a beaker and stirred at room temperature (25° C.) until uniform.

[0147] Step II: Component (C) (water) is gradually added to the composition prepared in Step I while stirring with a homomixer to emulsify the composition to obtain an emulsified cosmetic.

[0148] Component (B) is as follows.

[0149] (B-1): KF-995 (decamethylcyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0150] (B-2): Liquid paraffin (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0151] (B-3): UNISTER MB-816 (ethylhexyl palmitate, manufactured by NOF CORPORATION)

[0152] <Moisture when applying>

[0153] 0.5 g of the emulsified cosmetic was applied to the forearms of five panelists, and sensory evaluation of the wateriness was performed according to the following criteria.

[0154] 3 points: The evaluator felt that the product was quite tender and had almost no sticky feeling.

[0155] 2 points: The evaluator felt a slight tenderness, but a slightly sticky feeling.

[0156] 1 point: The evaluator felt almost no tenderness and a sticky feeling.

[0157] Furthermore, the total score of the evaluations by the five evaluators was determined according to the following criteria.

[0158] ◎: 12 points or more

[0159] ○: 9 points or more and less than 12 points

[0160] △: less than 9 points

[0161] Emulsion stability

[0162] 30 g of the emulsified composition was placed in a 50 ml transparent glass container, sealed, and stored for one month at 0° C., 25° C., and 40° C. After one month, the appearance of the samples stored at each temperature was observed and evaluated according to the following criteria.

[0163] ○: The appearance of the sample after storage did not change at any temperature.

[0164] ×: The appearance of the sample after storage changed from a uniform appearance to separation of the oil layer or the water layer at any temperature.

[0165] <Changes in odor over time>

[0166] 30 g of the emulsified composition was placed in a 50 ml transparent glass container, sealed, and stored at 40° C. for one month. After one month, five panelists conducted a sensory evaluation of the aldehyde odor according to the following criteria.

[0167] 3 points: The evaluator hardly noticed any odor.

[0168] 2 points: The evaluator detected a slight odor.

[0169] 1 point: The evaluator detected a foul odor.

[0170] Furthermore, the total score of the evaluations of the five evaluators was determined according to the following criteria.

[0171] ◎: 12 points or more

[0172] ○: 9 points or more and less than 12 points

[0173] △: less than 9 points

[0174] [Table 2]

[0175]

[0176] [Table 3]

[0177]

[0178] The emulsified cosmetics of Examples 1 to 6 obtained according to the present invention have a moist feel upon application, are excellent in emulsification stability, and suppress the generation of odor over time.

[0179] The emulsified cosmetics of Comparative Examples 1 to 4, which were not obtained according to the present invention, were inferior to the emulsified cosmetics of Examples in terms of moisture during application, emulsion stability, and odor over time.

[0180] (Remark)

[0181] It should be understood that the scope of the present invention should not be interpreted as being limited by the description of this specification, but should be interpreted as being limited only by the description of the claims. In addition, it should be understood that the contents of the patent applications and technical standards referenced in this specification are specifically as described in this specification and are cited in this specification. Furthermore, the disclosure of Japanese Patent Application No. 2023-069682 filed on April 20, 2023 is incorporated in its entirety into this specification by reference.

Claims

1. An alkenyl-containing polyoxyalkylene compound, which is an alkenyl-containing polyoxyalkylene compound represented by the following formula (1): R 1 O-(AO)nR 2 (1) In formula (1), AO is an oxyalkylene group having 2 to 4 carbon atoms obtained by a dehydration condensation reaction using phosphinic acid or a phosphinic acid salt; n represents the average number of added moles of AO, and n=3 to 90; R 1 is an alkenyl group having 3 to 5 carbon atoms, R 2 The polyoxyalkylene compound containing an alkenyl group has a carbon number of 3 to 5 or a hydrogen atom; the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated from a chromatogram obtained by gel permeation chromatography is 1.20 to 5.

00. 2 . An organosilicon modifier comprising the alkenyl-containing polyoxyalkylene compound according to claim 1 .

3. A polyoxyalkylene-modified silicone, which is a reaction product of the silicone modifier according to claim 2 and a hydrogenated organopolysiloxane represented by the following formula (2): [Chemical Formula 1] In formula (2), p is 1~100, q is 0~50, r is 0~100, q / (p+r) is 0~1; R 3 Each independently represents an alkyl group having 1 to 8 carbon atoms; R 4 and R 5 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; when q=0, R 4 and R 5 At least one of them is a hydrogen atom.

4. An emulsified composition comprising 0.1 to 40% by mass of (A) the polyoxyalkylene-modified silicone according to claim 3, 1 to 50% by mass of (B) an oil agent that is liquid at 25° C., and 10 to 98% by mass of (C) water, wherein: The mass ratio of the component (B) to the component (A) ((B) / (A)) is 0.5 to 30.

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