[go: up one dir, main page]

WO2025239041A1 - Composé de polyglycérol, son procédé de production, modificateur de silicone, silicone modifiée par un polyglycérol, et composition en émulsion - Google Patents

Composé de polyglycérol, son procédé de production, modificateur de silicone, silicone modifiée par un polyglycérol, et composition en émulsion

Info

Publication number
WO2025239041A1
WO2025239041A1 PCT/JP2025/013077 JP2025013077W WO2025239041A1 WO 2025239041 A1 WO2025239041 A1 WO 2025239041A1 JP 2025013077 W JP2025013077 W JP 2025013077W WO 2025239041 A1 WO2025239041 A1 WO 2025239041A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
polyglycerol
glycidol
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/013077
Other languages
English (en)
Japanese (ja)
Inventor
美穂 笹田
将紀 村井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NOF Corp
Original Assignee
NOF Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NOF Corp filed Critical NOF Corp
Publication of WO2025239041A1 publication Critical patent/WO2025239041A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a polyglycerin compound having one alkenyl group per molecule, a method for producing the same, a silicone modifier, a polyglycerin-modified silicone, and an emulsion composition.
  • the invention relates to a polyglycerin compound having one alkenyl group per molecule that can impart surfactant properties to organopolysiloxanes, a method for producing a polyglycerin compound having one alkenyl group per molecule with low levels of unreacted glycidol and by-product polyglycerin, a silicone modifier comprising this derivative, a polyglycerin-modified silicone that is the reaction product of this derivative with an organopolysiloxane, and an emulsion composition containing predetermined amounts of this polyglycerin-modified silicone, an oil, and water.
  • Polyglycerin compounds with one alkenyl group per molecule contain both the reactive alkenyl group and a highly hydrophilic polyglycerin group, making them more hydrophilic than polyalkylene compounds with one alkenyl group per molecule. Therefore, they are used as resin modifiers to introduce hydrophilic segments into the resin backbone, and as raw materials for copolymerization with silicone modifiers and polymerizable monomers. Silicone modifiers in particular can impart surfactant properties to organopolysiloxanes, which have excellent heat resistance, weather resistance, mold releasability, water repellency, and physiological inertness.
  • modified organopolysiloxanes can be obtained by chemically reacting a silicone modifier composed of reactive groups such as alkenyl groups and hydrophilic functional groups such as polyglycerin groups with an organopolysiloxane having reactive functional groups such as silylidyne groups (hereinafter also referred to as "SiH groups") (Patent Document 1).
  • a silicone modifier composed of reactive groups such as alkenyl groups and hydrophilic functional groups such as polyglycerin groups
  • organopolysiloxane having reactive functional groups such as silylidyne groups
  • Modified organopolysiloxanes obtained by this method are used in cosmetics because, for example, when used as a surfactant component in an emulsion composition, they exhibit effects such as improved surface tension, dispersing power, foaming power, and emulsion stability. They are also widely used in other applications such as detergents, fiber treatment agents, paint additives, ink additives, plastic additives, anti-fogging agents
  • polyglycerol compounds containing one alkenyl group per molecule which are used as raw materials, can be obtained by a method of ring-opening addition polymerization of allyl glycidyl ether to diglycerol using an alkaline catalyst (e.g., Patent Document 1), or by ring-opening addition polymerization of glycidol to allyl alcohol or glycerol monoallyl ether (e.g., Patent Documents 2 and 3).
  • an alkaline catalyst e.g., Patent Document 1
  • Patent Documents 2 and 3 ring-opening addition polymerization of glycidol to allyl alcohol or glycerol monoallyl ether
  • Patent documents 2 and 3 which involve ring-opening addition polymerization of glycidol, provide a method for producing a high-quality polyglycerol compound containing one alkenyl group per molecule with high yield and extremely low impurity content by controlling the alkali catalyst concentration and reaction temperature.
  • Emulsion compositions can be broadly divided into two types of emulsion states: oil-in-water and water-in-oil.
  • they are used in cosmetics for a variety of purposes, including skin care creams, emulsions, and sunscreens. Consumer needs for these cosmetics include a pleasant feel and moisturizing power under any conditions, as well as the ability to apply the right amount evenly to the right areas of the skin.
  • Emulsion compositions using a modified organopolysiloxane composed of a polyglycerin compound having one alkenyl group per molecule as a surfactant, as described in Patent Documents 2 and 3, have an excellent feel when used as cosmetics and are easy to apply evenly to the skin. However, dripping can occur when the product is taken into the hands, making it difficult to apply the appropriate amount to the appropriate areas of the skin, and the moisturizing power can be insufficient.
  • an emulsion composition is thickened by adding a polymer or the like to prevent dripping, the spreadability may be insufficient, resulting in uneven application, taking a long time to spread evenly, applying excessive pressure to the skin, and even resulting in a poor feel to the touch. Therefore, there is a demand for an emulsion composition that has a good feel, is easy to apply evenly to the skin, and has an appropriate viscosity that does not cause dripping. Furthermore, adding a moisturizing agent such as polyglycerin to an emulsion composition to enhance moisturizing power can cause stickiness and a poor feel to the touch, so there is a demand for emulsion compositions that have a good feel to the touch and high moisturizing power.
  • a moisturizing agent such as polyglycerin
  • the temperature of the truck bed can rise to around 70°C, and they are required to maintain their emulsion state and maintain a good feel even when stored in such high temperatures or for long periods of time.
  • Patent Document 1 One way to solve the above problem is to synthesize a polyglycerol compound with one alkenyl group with a higher degree of polymerization per molecule.
  • Patent Document 1 conventional methods of ring-opening addition polymerization of allyl glycidyl ether with polyglycerol (e.g., Patent Document 1) produce large amounts of self-polymerized products of allyl glycidyl ether and polyglycerols with multiple allyl groups, which, when modified into silicone, have a negative impact on performance.
  • Patent Document 3 the glycidol charging rate is slow and the reaction temperature is low, resulting in low reactivity. Therefore, if a large amount of glycidol is added, production takes a long time, making it industrially inefficient. Furthermore, for example, in Patent Document 3, the amount of alkaline catalyst added is large, and the low reaction temperature reduces stirring efficiency, which can lead to a high polyglycerol production rate.
  • the objective of this invention is to obtain a polyglycerol compound having one alkenyl group per molecule in high yield and in a short time by ring-opening polymerizing glycidol from a raw material compound having two or more hydroxyl groups per molecule in the presence of an alkali catalyst.
  • an object of the present invention is to apply a modified organopolysiloxane using the polyglycerin compound of the present invention as a surfactant to an emulsion composition, which has high emulsifying and moisturizing properties, and exhibits appropriate viscosity and excellent thermal stability, allowing the appropriate amount to be applied evenly to the appropriate areas of the skin.
  • the inventors synthesized a polyglycerol compound having one alkenyl group per molecule with a high degree of polymerization and low levels of unreacted glycidol and by-product polyglycerol using an industrially efficient method. They then discovered that an emulsion composition using a modified organopolysiloxane obtained from this compound as a surfactant has high emulsifying and moisturizing properties, and exhibits appropriate viscosity and excellent thermal stability, allowing the appropriate amount to be applied evenly to the appropriate areas of the skin.
  • a polyglycerol compound of formula (2) having one alkenyl group per molecule which is a reaction product of a raw material compound of formula (1) having two or more hydroxyl groups per molecule with glycidol
  • a polyglycerol compound characterized in that the rate of feeding glycidol to 1 mole of the raw material compound in the reaction product is 0.3 to 3.5 moles/hr.
  • RO-(CH 2 CH (OH) CH 2 O) m -H (1) (In formula (1), R is an alkenyl group having 3 to 5 carbon atoms and one double bond at the terminal, m represents 1.) RO-(CH 2 CH (OH) CH 2 O) n -H (2) (In formula (2), R is an alkenyl group having 3 to 5 carbon atoms and one double bond at the terminal, n is the average number of moles added, which is 6 to 13.
  • a silicone modifier consisting of the polyglycerin compounds [1] to [3].
  • a polyglycerin-modified silicone characterized by being a reaction product of the silicone modifier of [4] and a hydrogenorganopolysiloxane represented by the following formula (3):
  • p is 1 to 1000, q is 0 to 100, and r is 0 to 1000; q/(p+r) is between 0 and 1;
  • R3 is independently an alkyl group having 1 to 8 carbon atoms,
  • An emulsion composition comprising (A) 0.1 to 40 mass% of the polyglycerin-modified silicone of [5], (B) 1 to 60 mass% of an oil agent that is liquid at 25°C, and (C) 10 to 98 mass% of water.
  • a method for producing a polyglycerol compound comprising subjecting a raw material compound of formula (1) having two or more hydroxyl groups per molecule to an addition reaction of glycidol with the raw material compound at a feeding rate of 0.3 to 3.5 mol/hr relative to 1 mol of the raw material compound, to obtain a polyglycerol compound of formula (2) having one alkenyl group per molecule.
  • RO-(CH 2 CH (OH) CH 2 O) m -H (1) (In formula (1), R is an alkenyl group having 3 to 5 carbon atoms and one double bond at the terminal, m represents 1.) RO-(CH 2 CH (OH) CH 2 O) n -H (2) (In formula (2), R is an alkenyl group having 3 to 5 carbon atoms and one double bond at the terminal, n is the average number of moles added, which is 6 to 13.
  • polyglycerol compounds having one alkenyl group per molecule can be obtained in high yield and in a short period of time.
  • emulsion compositions using modified organopolysiloxanes using the polyglycerin compounds of the present invention as surfactants have high emulsifying and moisturizing properties, and exhibit appropriate viscosity and excellent thermal stability, allowing the appropriate amount to be applied evenly to the appropriate areas of the skin.
  • the polyglycerol compound of formula (2) having one alkenyl group per molecule (hereinafter, also referred to as "the compound of the present invention") is a polyglycerol represented by the following formula (2): RO-(CH 2 CH (OH) CH 2 O) n -H (2)
  • R is an alkenyl group having 3 to 5 carbon atoms and one double bond at the terminal.
  • R include 2-propenyl (allyl), 2-methyl-2-propenyl (methallyl), 3-butenyl, and 3-methyl-3-butenyl groups, with allyl being particularly preferred.
  • the polyglycerol compound of formula (2) having one alkenyl group per molecule according to the present invention is a reaction product obtained by subjecting a raw material compound of formula (1) having two or more hydroxyl groups per molecule to an addition reaction with glycidol.
  • R is an alkenyl group having 3 to 5 carbon atoms and one double bond at the terminal.
  • R include a 2-propenyl group (allyl group), a 2-methyl-2-propenyl group (methallyl group), a 3-butenyl group, and a 3-methyl-3-butenyl group, with an allyl group being preferred.
  • m is 1.
  • the compound in which R is an allyl group is glycerin monoallyl ether.
  • Glycerin monoallyl ether can be obtained by distilling a hydrolyzate of the epoxy group of allyl glycidyl ether or an etherified product of glycerin and allyl chloride.
  • Glycerin monoallyl ether is represented by formula (4).
  • CH2 CHCH2O - CH2CH (OH) CH2O -H (4)
  • the method for producing the compound of the present invention involves ring-opening polymerization of a raw material compound of formula (1) having one terminal double bond and two or more hydroxyl groups per molecule with glycidol (2,3-epoxy-1-propanol), to obtain a polyglycerol compound of formula (2) having one alkenyl group per molecule that has one terminal double bond.
  • a known alkali catalyst can be used as the catalyst for the ring-opening polymerization of glycidol.
  • alkali catalysts that can be used include sodium hydroxide, potassium hydroxide, sodium methoxide, a methanol solution of sodium methoxide, and potassium t-butoxide.
  • the amount of alkali used is 0.1 to 3 mol % relative to 1 mole of the raw material compound of formula (1), and preferably 0.2 to 2 mol %.
  • the reaction rate may be slow, requiring a long reaction time, or unreacted glycidol may remain. If the amount of alkali catalyst exceeds 3 mol % relative to 1 mole of the raw material compound of formula (1), the proportion of by-product polyglycerol derivatives not containing alkenyl groups increases. When an alcohol solution is used as the alkali catalyst, the number of moles charged is calculated in terms of the actual amount of alkali catalyst contained.
  • treatment is carried out for 30 minutes to 2 hours at a temperature of 70 to 90°C, under inert gas bubbling, and at a pressure of -0.2 MPa (gauge pressure) or less, whereby water from the raw material compound having two or more hydroxyl groups per molecule, and water or alcohol produced as by-products by alcoholation, can be distilled out of the reaction system under reduced pressure.
  • the reaction temperature during the ring-opening polymerization of glycidol is preferably 100 to 140°C, more preferably 105°C or higher, or more preferably 125°C or lower. If the reaction temperature is below 100°C, stirring efficiency decreases, making the reaction more likely to become non-uniform, and polyglycerol may be produced as a by-product.
  • the feeding rate of glycidol during glycidol ring-opening polymerization is preferably 0.3 to 3.5 mol/hr relative to 1 mol of the polyglycerol compound of formula (1). Since a feeding rate of less than 0.3 mol/hr during glycidol ring-opening polymerization is not industrially efficient, it should be 0.3 mol/hr or higher. From the standpoints of reaction efficiency and safety, it is even more preferable to set the feeding rate of glycidol during glycidol ring-opening polymerization to 0.5 mol/hr or higher.
  • the glycidol feeding rate during glycidol ring-opening polymerization exceeds 3.5 mol/hr, the glycidol concentration in the reactor will increase, causing ring-opening polymerization of glycidol to its hydroxyl groups, which may result in the by-product of polyglycerin, or the reaction rate may be so fast that it becomes difficult to control and safe production may not be possible.
  • the proportion of by-produced polyglycerin increases, the emulsification performance of an emulsion composition using this polyglycerin and a modified silicone as a surfactant will decrease.
  • the glycidol feeding rate during glycidol ring-opening polymerization is set to 3.5 mol/hr or less. From the standpoints of reaction efficiency and safety, it is even more preferable to set the glycidol feeding rate during glycidol ring-opening polymerization to 3.0 mol/hr or less.
  • emulsion compositions containing the compound of the present invention or modified silicones using the compound as a surfactant have a viscosity that allows for easy handling and reduces coloration, it is particularly preferable to set the glycidol feeding rate during glycidol ring-opening polymerization at 1.0 to 3.0 mol/hr, and most preferably 1.5 to 3.0 mol/hr.
  • Glycidol can be added dropwise or from the bottom of the reactor, and it is desirable to keep the addition rate as uniform as possible. It is also desirable to carry out the ring-opening polymerization of glycidol without using a solvent, but organic solvents such as benzene, toluene, xylene, and diglyme may be used to reduce the viscosity in the system and prevent a decrease in stirring efficiency.
  • organic solvents such as benzene, toluene, xylene, and diglyme may be used to reduce the viscosity in the system and prevent a decrease in stirring efficiency.
  • the compound of the present invention becomes a polymer with a complex branched chemical structure.
  • the actual reaction product is a mixture of numerous polymers with these branched structures.
  • the polymerization reaction product is purified and filtered to obtain a compound from which salts derived from the alkali catalyst have been removed.
  • the product can be diluted with a solvent that is a poor solvent for salts and a good solvent for polyglycerol having one alkenyl group per molecule to reduce the viscosity and allow filtration.
  • This purification can be carried out as follows.
  • An acid is used as a purification treatment agent to neutralize the alkaline catalyst.
  • acids it is preferable to use a strong acid.
  • strong acids include sulfuric acid, hydrochloric acid, and phosphoric acid, with hydrochloric acid being more preferred.
  • water can be added during the purification process to reduce viscosity, increase stirring efficiency, and promote neutralization with acid.
  • the amount of water added is 2 to 10% by weight based on the total amount of the raw material compound of formula (1) and glycidol charged.
  • Treatment conditions are preferably a temperature of 50 to 70°C, a treatment time of 20 minutes to 2 hours, and stirring.
  • the purification process is preferably carried out at a temperature of 100 to 120°C, under inert gas bubbling, and at a pressure of -0.05 MPa (gauge pressure) or less for approximately 1 to 3 hours.
  • the inert gas is used to prevent double bonds and ether bonds from being oxidized by contact with oxygen; specifically, nitrogen, helium, neon, argon, etc. are preferred.
  • precipitated salts can be removed by filtration, but if necessary, further purification can be carried out using activated clay, synthetic zeolite adsorbents, or ion exchange resins.
  • the added solvent must be a poor solvent for the alkali metal salt and a good solvent for the polyethers.
  • solvents include alcohols, pentane, hexane, octane, benzene, acetone, ethyl acetate, and diethyl ether. Of these, alcohols are preferred.
  • These alcohols are not particularly limited and may be saturated aliphatic alcohols such as methanol or ethanol, unsaturated aliphatic alcohols, or aromatic alcohols such as phenol. They may also be linear or branched, or may have a cyclic structure. They may also be polyhydric alcohols such as dihydric alcohols. Although not particularly limited, alcohols with 1 to 8 carbon atoms are preferred, and alcohols with 1 to 4 carbon atoms are particularly preferred.
  • the above alcohols and nonpolar solvents may be used alone or in combination of two or more. It is preferable to reduce the amount of the above solvent added to a polyether containing an alkali metal salt to a level that allows for easy filtration.
  • antioxidants such as 2,6-di-t-butyl-p-cresol (BHT) or 4,4'-butylidene-bis-(6-t-butyl-3-methylphenol), or antioxidants such as tocopherol.
  • BHT 2,6-di-t-butyl-p-cresol
  • antioxidants such as tocopherol.
  • storage after production to prevent oxidation, it is preferable to store the product in an airtight container or by replacing the air with an inert gas.
  • the kinematic viscosity of the compound of the present invention at 100° C. is 300 to 600 mm 2 /s, preferably 300 to 500 mm 2 /s, and more preferably 400 to 450 mm 2 /s.
  • the silicone modifier of the present invention comprises a polyglycerin compound of formula (2) having one alkenyl group per molecule, which is a compound of the present invention that functions as a silicone modifier.
  • the polyglycerin-modified silicone of the present invention is a reaction product between the compound of the present invention, which functions as a silicone modifier, and a hydrogenorganopolysiloxane represented by the following formula (3):
  • this reaction product is a hydrosilylation product of the compound of the present invention with the hydrogenorganopolysiloxane represented by the following formula (3):
  • p is 1 to 1000, q is 0 to 100, r is 0 to 1000, and q/(p+r) is 0 to 1.
  • p is preferably 900 or less, more preferably 800 or less, and may be 100 or less.
  • q is preferably 80 or less, more preferably 50 or less, and particularly preferably 10 or less.
  • r is preferably 900 or less, more preferably 800 or less, and may be 100 or less.
  • q/(p+r) is preferably 0.4 or less, and more preferably 0.2 or less.
  • Each R3 is independently an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, or an octyl group, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group.
  • Examples of the alkyl group having 1 to 8 carbon atoms constituting R4 and R5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group, and preferred are a methyl group and an ethyl group.
  • the hydrogen organopolysiloxane represented by formula (3) can be produced by known methods, but commercially available products can also be used. Examples of such products include Gelest's "Methyl H Siloxane-Dimethylsiloxane Copolymer" product codes HMS-013 (in formula (4), R 3 , R 4 , and R 5 are all methyl groups, p is 701, q is 7.1, and r is 0) and HMS-082 (in formula (4), R 3 , R 4 , and R 5 are all methyl groups, p is 74, q is 6.4, and r is 0).
  • HMS-013 in formula (4), R 3 , R 4 , and R 5 are all methyl groups, p is 701, q is 7.1, and r is 0
  • HMS-082 in formula (4), R 3 , R 4 , and R 5 are all methyl groups, p is 74, q is 6.4, and r is 0).
  • the reaction between the compound of the present invention and the hydrogenorganopolysiloxane is usually carried out by mixing the two in the presence of a catalyst.
  • catalysts that can be used include chloroplatinic acid hexahydrate, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinylsiloxane complex.
  • the amount of catalyst used is preferably 500 ppm or less, and particularly preferably 200 ppm or less, calculated as platinum, based on the total mass of the compound of the present invention and the hydrogenorganopolysiloxane.
  • the reaction temperature is preferably 50 to 130° C., more preferably 60 to 110° C. Completion of the reaction can be confirmed by FT-IR measurement, and the reaction is carried out until the absorption at 2100 to 2300 cm ⁇ 1 derived from the SiH group disappears.
  • the emulsion composition of the present invention contains (A) 0.1 to 40% by mass of the polyglycerin-modified silicone of the present invention, (B) 1 to 60% by mass of an oil agent that is liquid at 25°C, and (C) 10 to 98% by mass of water.
  • the total amount of component (A), component (B), and component (C) is defined as 100% by mass.
  • the emulsion composition of the present invention is a water-in-oil emulsion composition
  • it preferably contains (A) 0.1 to 40 mass% of the polyglycerin-modified silicone of the present invention, (B) 10 to 60 mass% of an oil agent that is liquid at 25°C, and (C) 10 to 80 mass% of water.
  • the content of component (A) is more preferably 10 to 40 mass%, and even more preferably 20 to 40 mass%.
  • the content of component (B) is more preferably 25 to 50 mass%, and the content of component (C) is more preferably 10 to 50 mass%.
  • the emulsion composition of the present invention when it is an oil-in-water emulsion composition, it preferably contains (A) 0.1 to 40 mass% of the polyglycerin-modified silicone of the present invention, (B) 1 to 50 mass% of an oil agent that is liquid at 25°C, and (C) 10 to 98 mass% of water.
  • the content of component (A) is more preferably 0.5 to 30 mass%, and even more preferably 1 to 20 mass%.
  • the content of component (B) is more preferably 2 to 40 mass%, and more preferably 5 to 30 mass%, and the content of component (C) is more preferably 20 to 90 mass%.
  • Component (A) used in the emulsion composition of the present invention is the polyglycerin-modified silicone described above, which functions as a surfactant.
  • the content of component (A) in the emulsion composition of the present invention is 0.1 to 40% by mass. If the content of component (A) is too low, the surface activity of component (A) will be too low, and a stable emulsion composition may not be obtained; therefore, the content is set to 0.1% by mass or more. From this perspective, the content of component (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, and may even be 20% by mass or more.
  • component (A) is set to 40% by mass or less.
  • Component (B) oil that is liquid at 25°C
  • the oil of component (B) is preferably one or more oils 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.
  • Preferred examples include liquid paraffin and hydrogenated polyisobutene.
  • Triglycerides which are liquid at 25°C, are esters of glycerin and fatty acids, such as caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, isotridecanoic acid, isopalmitic acid, isostearic acid, eicosanoic acid, and oleic acid.
  • esters of glycerin and fatty acids such as caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, isotridecanoic acid, isopalmitic acid, isostearic acid, eicosanoic acid, and oleic acid.
  • the oil agent component (B) used in the present invention is preferably silicone oil, from the standpoint of compatibility with the surfactant component (A).
  • the content of component (B) in the emulsion composition of the present invention is 1 to 60% by mass. If the content of component (B) is too low, the field for component (A) to function will be too small, reducing the stability of the emulsion composition; therefore, the content is set to 1% by mass or more. From this perspective, the content of component (B) is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and can also be 25% by mass or more. Furthermore, if the content of component (B) is too high, the field for component (A) to function will be too large, preventing a stable emulsion composition from being obtained; therefore, the content is set to 60% by mass or less. From this perspective, the content of component (B) is preferably 50% by mass or less.
  • the component (C) used in the emulsion composition of the present invention is water.
  • the water is not particularly limited.
  • purified water such as distilled water or ion-exchanged water, physiological saline, phosphate buffer solution, etc. can be used.
  • the content of component (C) in the emulsion composition of the present invention is 10 to 98% by mass. If the content of component (C) is too low or too high, excessive viscosity may be imparted, causing partial gelation and making it impossible to obtain a stable emulsion composition, so the content is set to 10 to 98% by mass. From this perspective, the content of component (C) is preferably 20% by mass or more. From this perspective, the content of component (C) is preferably 90% by mass or less, more preferably 80% by mass or less, and may be 50% by mass or less.
  • the ratio of the mass of component (B) to the mass of component (A) ((B)/(A)) is preferably 0.5 to 10, more preferably 1 to 3, from the viewpoints of emulsion stability and a refreshing feel upon application.
  • the emulsion composition of the present invention is prepared by blending component (A) and component (B) with component (C), water.
  • additive components can be blended into the emulsion composition of the present invention as needed.
  • moisturizers, preservatives, antioxidants, UV absorbers, cosmetic ingredients, fragrances, water-soluble polymers, coloring matter, pigments, organic powders, etc. can be blended.
  • the total amount of additive components other than components (A) to (C) is preferably 3 to 30% by mass, and more preferably 5 to 15% by mass.
  • the total amount of these additive components may even be 0% by mass.
  • the form of the emulsion composition of the present invention is not particularly limited, but it can be used in a wide range of applications, such as cosmetic materials and paints, which have excellent emulsion stability. In the field of cosmetic materials, it is particularly suitable for use in oil-based cosmetics such as emulsions, cleansing oils, and hair oils.
  • HPLC main unit Agilent 6430 triple quadrupole LC/MS system (Agilent Technologies, Inc.)
  • Flow rate 0.4mL/min
  • Glycidol was added dropwise to the glycerin monoallyl ether at a rate of 0.6 mol/hr for 15.9 hours under conditions of 105 to 115°C and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another 2 hours.
  • the temperature was then lowered to 85-95°C, and unreacted glycidol was removed by nitrogen bubbling at -0.097 MPa (gauge pressure) or less.
  • 47.3 g of water (5 wt% of the total raw material charge) was then added, and the pH (unified) was adjusted to a weak acidity of 4-6 with hydrochloric acid, followed by stirring for 30 minutes.
  • Water was then removed for 2 hours by nitrogen bubbling at 105-115°C and -0.097 MPa (gauge pressure) or less, and the precipitated salt was finally filtered off to obtain 906 g of silicone modifier (A-1).
  • the degree of unsaturation was 1.13 meq/g
  • the kinematic viscosity (100°C) was 458 mm 2 /s
  • the APHA was 500 or more
  • the polyglycerin content was 5.3%.
  • Glycidol was added dropwise to the glycerin monoallyl ether at a rate of 1.8 mol/hr for 5.3 hours at 105-115°C and 0.5 MPa (gauge pressure) or less. The reaction was continued for another 2 hours.
  • the temperature was then lowered to 85-95°C, and unreacted glycidol was removed by nitrogen bubbling at -0.097 MPa (gauge pressure) or less.
  • 47.3 g of water (5 wt% of the total raw material charge) was then added, and the pH (unified) was adjusted to a weak acidity of 4-6 with hydrochloric acid, followed by stirring for 30 minutes.
  • Water was then removed by nitrogen bubbling at 105-115°C and -0.097 MPa (gauge pressure) or less for 2 hours, and the precipitated salt was finally filtered off to obtain 917 g of silicone modifier (A-2).
  • the degree of unsaturation was 1.14 meq/g
  • the kinematic viscosity (100°C) was 403 mm 2 /s
  • the APHA was 30, and the polyglycerin content was 6.6%.
  • Glycidol was added dropwise to the glycerin monoallyl ether at a rate of 3.0 mol/hr for 3.2 hours at 105-115°C and 0.5 MPa (gauge pressure) or less. The reaction was continued for another 2 hours.
  • Glycidol was added dropwise to the glycerin monoallyl ether at a rate of 0.6 mol/hr for 7.1 hours at 105-115°C and 0.5 MPa (gauge pressure) or less. The reaction was continued for another 2 hours.
  • the temperature was then lowered to 85-95°C, and unreacted glycidol was removed by nitrogen bubbling at -0.097 MPa (gauge pressure) or less. Then, 16.8 g of water (5 wt% of the total raw material charge) was added, and the pH was adjusted to a weak acidity of 4-6 with hydrochloric acid, followed by stirring for 30 minutes. Water was then removed by nitrogen bubbling at 105-115°C and -0.097 MPa (gauge pressure) or less for 2 hours, and finally, the precipitated salt was filtered off to obtain 325 g of silicone modifier (A-4). The degree of unsaturation was 2.16 meq/g, the kinematic viscosity (100°C) was 108 mm 2 /s, the APHA was 500 or more, and the polyglycerin content was 6.9%.
  • Glycidol was added dropwise to the glycerin monoallyl ether at a rate of 0.2 mol/hr for 47.7 hours at 105-115°C and 0.5 MPa (gauge pressure) or less. The reaction was continued for another 2 hours.
  • the temperature was then lowered to 85-95°C, and unreacted glycidol was removed by nitrogen bubbling at -0.097 MPa (gauge pressure) or less.
  • 31.5 g of water (5 wt% based on the total amount of raw materials charged) was then added, and the pH was adjusted to a weak acidity of 4-6 with hydrochloric acid, followed by stirring for 30 minutes.
  • Water was then removed by nitrogen bubbling at 105-115°C and -0.097 MPa (gauge pressure) or less for 2 hours, and the precipitated salt was finally filtered off to obtain 598 g of silicone modifier (A-5).
  • the degree of unsaturation was 1.13 meq/g
  • the kinematic viscosity (100°C) was 483 mm 2 /s
  • the APHA was 500 or more
  • the polyglycerin content was 4.6%.
  • Glycidol was added dropwise to the glycerin monoallyl ether at a rate of 4.1 mol/hr for 2.3 hours at 105-115°C and 0.5 MPa (gauge pressure) or less. The reaction was continued for another 2 hours.
  • the temperature was then lowered to 85-95°C, and unreacted glycidol was removed by nitrogen bubbling at -0.097 MPa (gauge pressure) or less.
  • 31.5 g of water (5 wt% based on the total amount of raw materials charged) was then added, and the pH was adjusted to a weak acidity of 4-6 with hydrochloric acid, followed by stirring for 30 minutes.
  • Water was then removed for 2 hours by nitrogen bubbling at 105-115°C and -0.097 MPa (gauge pressure) or less, and finally the precipitated salt was filtered off to obtain 613 g of silicone modifier (A-6).
  • the degree of unsaturation was 1.11 meq/g
  • the kinematic viscosity (100°C) was 370 mm 2 /s
  • the APHA was 50
  • the polyglycerin content was 9.5%.
  • Example B Preparation of emulsion composition
  • Examples 1 to 6 Comparative Examples 1 and 2
  • Emulsion cosmetics were prepared using the compositions shown in Table 2 by the following production method. Samples of each composition were then evaluated for emulsification performance, moisturizing performance upon application, viscosity, and thermal stability, and the results are shown in Table 2.
  • Step I Components (A) and (B) shown in each table were placed in a beaker and stirred at room temperature (25°C) until homogeneous.
  • Step II Component (C) (water) was gradually added to the composition prepared in Step I while stirring with a homomixer to obtain a sample.
  • the silicone oil of component (B) is KF-995 (decamethylcyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the shear viscosity (Pa ⁇ s) was measured at a shear rate of 0.1 (s ⁇ 1 ) at 25° C.
  • the measuring equipment was as follows. Measuring equipment Paar Physica MCR-300 Measuring jig CP 25-2 The measurement results of shear viscosity (Pa ⁇ s) were evaluated according to the following criteria. ⁇ : 2.0 Pa ⁇ s or more and less than 30 Pa ⁇ s. Good: Viscosity is 30 Pa ⁇ s or more, or 1 Pa ⁇ s or more and less than 2.0 Pa ⁇ s. ⁇ : Viscosity is 0.1 Pa ⁇ s or less.
  • thermo stability A 10 g sample of each emulsion composition was placed in a 20 ml transparent glass container and allowed to stand at 80° C. for 5 hours, after which the appearance was visually inspected and evaluated according to the following criteria. ⁇ : The sample was uniformly cloudy and formed an emulsion. ⁇ : The sample was separated and non-uniform.
  • Comparative Example 1 differs from the present invention in that the average number of moles of silicone modifier added, n, is less than 6, and polyglycerin-modified silicone with this silicone modifier is used. As a result, the moisturizing performance, viscosity, and thermal stability were inferior to those of the Examples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Silicon Polymers (AREA)

Abstract

Le problème décrit par la présente invention est d'obtenir, à un rendement élevé et en un court laps de temps, un composé de polyglycérol ayant un groupe alcényle par molécule par réalisation d'une polymérisation par ouverture de cycle sur du glycidol en présence d'un catalyseur alcalin, avec un composé de matière première ayant deux groupes hydroxyle ou plus par molécule. La solution selon l'invention porte sur un composé de polyglycérol qui comprend un produit de réaction du glycidol et d'un composé de matière première qui est représenté par la formule (1) et qui a deux groupes hydroxyle ou plus par molécule, qui est représenté par la formule (2) et qui a un groupe alcényle par molécule, le débit d'alimentation du glycidol étant de 0,3 à 3,5 mol/h par rapport à 1 mole du composé de matière première dans le produit de réaction.　Formule (1) : RO-(CH2CH(OH)CH2O)m-H (Dans la formule, R est un groupe alcényle en C3-5 ayant une double liaison au niveau d'une terminaison de celui-ci, et m représente 1.)　Formule (2) : RO-(CH2CH(OH)CH2O)n-H (Dans la formule, R est un groupe alcényle en C3-5 ayant une double liaison au niveau d'une terminaison de celui-ci, et n est le nombre moyen de moles ajoutées et varie de 6 à 13.)
PCT/JP2025/013077 2024-05-14 2025-03-31 Composé de polyglycérol, son procédé de production, modificateur de silicone, silicone modifiée par un polyglycérol, et composition en émulsion Pending WO2025239041A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024078560 2024-05-14
JP2024-078560 2024-05-14

Publications (1)

Publication Number Publication Date
WO2025239041A1 true WO2025239041A1 (fr) 2025-11-20

Family

ID=97719779

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/013077 Pending WO2025239041A1 (fr) 2024-05-14 2025-03-31 Composé de polyglycérol, son procédé de production, modificateur de silicone, silicone modifiée par un polyglycérol, et composition en émulsion

Country Status (1)

Country Link
WO (1) WO2025239041A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5601754A (en) * 1995-04-21 1997-02-11 Betz Laboratories, Inc. Water treatment polymer containing poly[oxy-[(hydroxymethyl)-1,2-ethanediyl]] macromonomers and methods of use thereof
JP2009256616A (ja) * 2008-03-21 2009-11-05 Shin Etsu Chem Co Ltd グリセリン変性シリコーン及びそれを含む化粧料
JP2013151656A (ja) * 2011-12-27 2013-08-08 Dow Corning Toray Co Ltd ジグリセリン誘導体変性シリコーン、それを含有してなる油中水型エマルション用乳化剤、外用剤および化粧料
JP2023001070A (ja) * 2021-06-18 2023-01-04 三洋化成工業株式会社 熱伝導性組成物用の分散剤および熱伝導性組成物
CN116410065A (zh) * 2022-12-01 2023-07-11 杭州蔚远医药科技有限公司 一种烯丙基甘油醚低聚物的合成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5601754A (en) * 1995-04-21 1997-02-11 Betz Laboratories, Inc. Water treatment polymer containing poly[oxy-[(hydroxymethyl)-1,2-ethanediyl]] macromonomers and methods of use thereof
JP2009256616A (ja) * 2008-03-21 2009-11-05 Shin Etsu Chem Co Ltd グリセリン変性シリコーン及びそれを含む化粧料
JP2013151656A (ja) * 2011-12-27 2013-08-08 Dow Corning Toray Co Ltd ジグリセリン誘導体変性シリコーン、それを含有してなる油中水型エマルション用乳化剤、外用剤および化粧料
JP2023001070A (ja) * 2021-06-18 2023-01-04 三洋化成工業株式会社 熱伝導性組成物用の分散剤および熱伝導性組成物
CN116410065A (zh) * 2022-12-01 2023-07-11 杭州蔚远医药科技有限公司 一种烯丙基甘油醚低聚物的合成方法

Similar Documents

Publication Publication Date Title
CA2680674C (fr) Systemes emulsifiants pour emulsions huile-dans-l'eau utilisees a des fins cosmetiques et pharmaceutiques
JP6313540B2 (ja) ジグリセリン誘導体変性シリコーン、それを含有してなる油中水型エマルション用乳化剤、外用剤および化粧料
JP6105920B2 (ja) 共変性オルガノポリシロキサン、それを含有してなる油中水型エマルション用乳化剤、外用剤および化粧料
KR102674461B1 (ko) 신규 실리콘 화합물 및 이것을 포함하는 화장료
EP2301987B1 (fr) Polysiloxanes réticulés, procédé pour leur préparation et leur utilisation dans des systèmes émulsifiants pour des émulsions eau dans l'huile
EP1230292A1 (fr) Elastomeres de polyethersiloxane compatibles avec des solvants polaires
WO2010074297A1 (fr) Émulsion, son procédé de fabrication, et matière première de produit cosmétique formée à partir de celle-ci
JP6392669B2 (ja) 透明乃至半透明の液状のグリセリン誘導体変性シリコーン組成物の製造方法
CN105189430B (zh) 高纯度含单烯基甘油衍生物及其制造方法
JP3493535B2 (ja) シリコーン化合物及びそれを含有する化粧料
JP6538351B2 (ja) 高純度有機ケイ素化合物の製造方法
WO2025239041A1 (fr) Composé de polyglycérol, son procédé de production, modificateur de silicone, silicone modifiée par un polyglycérol, et composition en émulsion
EP2940063A1 (fr) Procédé de production de silicone de haute pureté, modifiée par un dérivé du glycérol
CN116096786A (zh) 羧酸共改性聚有机硅氧烷及其用途
JP7070247B2 (ja) シリコーン架橋剤、界面活性剤および乳化組成物
JP2017148774A (ja) シリコーン変性剤、界面活性剤、および乳化組成物
WO2024219323A1 (fr) Composé polyoxyalkylène contenant un groupe alcényle, modificateur de silicone, silicone modifiée par polyoxyalkylène et composition d'émulsion
JPH07304627A (ja) 化粧料
JP6153070B2 (ja) シリコーン変性剤、界面活性剤および乳化組成物
JP6394948B2 (ja) シリコーン変性剤、界面活性剤および乳化組成物
JP2025178144A (ja) 化粧料用基剤および化粧料