WO2012096124A1 - 水溶性ポリアルキレンオキシド変性物 - Google Patents
水溶性ポリアルキレンオキシド変性物 Download PDFInfo
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- WO2012096124A1 WO2012096124A1 PCT/JP2011/080085 JP2011080085W WO2012096124A1 WO 2012096124 A1 WO2012096124 A1 WO 2012096124A1 JP 2011080085 W JP2011080085 W JP 2011080085W WO 2012096124 A1 WO2012096124 A1 WO 2012096124A1
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- polyalkylene oxide
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- soluble polyalkylene
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
Definitions
- the present invention relates to a modified water-soluble polyalkylene oxide. More specifically, the present invention relates to a modified water-soluble polyalkylene oxide having high viscosity and excellent transparency.
- polyurethane thickeners can be thickened by the association of hydrophobic groups at their ends, but they are nonionic and have excellent salt resistance, as well as the ability to impart new rheological properties. Have.
- Non-patent Document 1 As the technique, it is known that the viscosity increases as the chain length of the terminal hydrophobic group increases (Non-patent Document 1).
- the polyurethane thickener has three hydrophobic groups linked by a hydrophilic polyester group having a molecular weight of at least 1,500, and at least two of these hydrophobic groups are at the end groups (Patent Document 1) and (A) at least one water-soluble polyether polyol, (B) at least one water-insoluble organic polyisocyanate; (C) at least one monofunctional hydrophobic organic compound selected from isocyanate-reactive compounds containing hydrogen atoms and organic monoisocyanates, and (d) at least one polyhydric alcohol or polyvalent What is obtained by reaction of polyhydric ether alcohol is known (patent document 2, patent document 3).
- a polyurethane-based thickener characterized by containing a monohydric alcohol having at least one other polar group or a trihydric alcohol as a polyhydric alcohol is also known (Patent Document 4).
- Non-Patent Document 1 the thickening effect of the polyurethane thickener obtained by the prior art increases as the carbon number of the terminal alcohol increases.
- the affinity with water deteriorates, and the transparency of the aqueous solution at the time of thickening tends to decrease, and a sticky feeling is likely to occur.
- the present inventors have found that a water-soluble polyalkylene obtained by reacting a polyalkylene oxide compound, a specific linear diol compound, a monovalent hydrophobic alcohol and a diisocyanate compound.
- the present invention has been completed by finding that an oxide-modified product gives an aqueous solution having a high viscosity in a small amount and excellent in transparency. That is, the present invention relates to the following water-soluble polyalkylene oxide-modified product, an emulsion composition containing the same, and a cosmetic material.
- R 1 represents an alkyl group having 6 to 14 carbon atoms
- R 4 represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, a 3-methyl-3,5,5-trimethylcyclohexylene group, a dimethylphenylene group or a tolylene group
- the polyalkylene oxide compound is selected from the group consisting of polyethylene oxide having a number average molecular weight of 4,000 to 30,000 and a polyethylene oxide / polypropylene oxide copolymer having a number average molecular weight of 4,000 to 30,000.
- Item 2 The water-soluble polyalkylene oxide-modified product according to Item 1, wherein
- Item 3. The water-soluble polyalkylene oxide-modified product according to Item 1 or 2, wherein the amount of the linear diol compound used is 0.5 to 2.5 mol per mol of the polyalkylene oxide compound.
- Item 4. The water-soluble polyalkylene oxide-modified product according to any one of Items 1 to 3, wherein the amount of the hydrophobic alcohol used is 0.5 to 2.5 mol per mol of the polyalkylene oxide compound.
- Item 5. The water-soluble polyalkylene oxide-modified product according to any one of Items 1 to 4.
- Item 6. An emulsion composition containing 0.01 to 10% by mass of the water-soluble polyalkylene oxide-modified product according to any one of items 1 to 5.
- the water-soluble polyalkylene oxide-modified product according to the present invention preferably has a urethane group concentration in the range of 1.0 to 3.0% in the water-soluble polyalkylene oxide-modified product, and the wavelength of the 3% by mass aqueous solution thereof.
- the transmittance of a quartz cell having a length of 425 nm and a length of 1 cm is 30% or more.
- the water-soluble polyalkylene oxide-modified product of the present invention obtained by reacting the compounds represented by the general formulas (I) to (IV) is represented by the following general formula (V):
- R 1 to R 4 and n are the same as defined above in general formulas (I) to (IV), and / represents any order of two types of repeating structural units in the brackets shown before and after that. Shows ester bond with] It is represented by
- the water-soluble polyalkylene oxide modified product represented by the general formula (V) is, for example, the following formula:
- the aqueous solution of the modified water-soluble polyalkylene oxide according to the present invention is excellent in transparency, it can maintain transparency when used in cosmetics and can be thickened with a small amount of addition. Can be reduced.
- the water-soluble polyalkylene oxide modified product of the present invention has a high thickening effect even for paints that have been made water-based in recent years from the viewpoint of environmental problems and safety, and prevents sagging and smoothness when added in small amounts. Can be granted.
- the present invention provides a water-soluble polyalkylene oxide modified product obtained by reacting a monovalent hydrophobic alcohol, a linear diol compound, a polyalkylene oxide compound and a diisocyanate compound.
- the present invention further provides an emulsion composition for cosmetics and paints using the modified water-soluble polyalkylene oxide according to the present invention as a thickener.
- the water-soluble polyalkylene oxide modified product according to the present invention is excellent in transparency and has a high thickening effect when added in small amounts.
- a paint having excellent film smoothness can be provided.
- FIG. 1 shows the relationship between the shear rate and aqueous solution viscosity of the resulting water-soluble polyalkylene oxide-modified product (3% by mass aqueous solution).
- FIG. 2 is a schematic diagram for obtaining the average friction coefficient (MIU) from the monitoring result of the friction coefficient ⁇ .
- FIG. 3 is a schematic diagram for obtaining the variation (MMD) of the average friction coefficient from the monitoring result of the friction coefficient ⁇ .
- the modified water-soluble polyalkylene oxide according to the present invention is obtained by reacting a monovalent hydrophobic alcohol, a linear diol compound, a polyalkylene oxide compound and a diisocyanate compound.
- the monovalent hydrophobic alcohol has the general formula (I):
- R 1 is a hydrocarbon group of the hydrophobic alcohol, and specifically includes an alkyl group such as a linear alkyl group having 6 to 14 carbon atoms or a branched alkyl group.
- Linear alkyl groups include n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n- Examples include tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group and the like.
- Examples of the branched alkyl group include 2-ethylhexyl group, isodecyl group, isotridecyl group, and isostearyl group.
- the monovalent hydrophobic alcohol is preferably a monovalent hydrophobic alcohol having a solubility in water of 0.4% by mass or less.
- hexyl alcohol, heptyl alcohol, octyl alcohol, Nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol and tetradecyl alcohol are preferable, and hexyl alcohol, octyl alcohol and decyl alcohol are more preferable.
- These monovalent hydrophobic alcohols may be used alone or in combination of two or more.
- the amount of the monovalent hydrophobic alcohol used is preferably 0.5 to 2.5 mol, more preferably 0.8 to 2.2, with respect to 1 mol of the polyalkylene oxide compound.
- monohydric hydrophobic alcohol is less than 0.5 mol, there exists a possibility that the aqueous solution viscosity of the water-soluble polyalkylene oxide modified material obtained may become low.
- monohydric hydrophobic alcohol exceeds 2.5 mol, there exists a possibility that the transparency of the aqueous solution of the water-soluble polyalkylene oxide modified material obtained may become low.
- the linear diol compound has the general formula (II):
- R 2 is a hydrocarbon group of a linear diol compound, and specifically includes a linear alkylene group having 5 to 10 carbon atoms of R 2 .
- linear alkylene group examples include n-pentamethylene, n-hexamethylene, n-heptamethylene, n-octamethylene, n-nonamethylene, n-decamethylene and the like.
- the linear diol compound is preferably 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol, more preferably Are 1,6-hexanediol and 1,9-nonanediol.
- a linear diol compound having less than 5 carbon atoms is used, the resulting water-soluble polyalkylene oxide-modified product has extremely low solubility in water and cannot be gelled and used as a thickener.
- the resulting water-soluble polyalkylene oxide modified product has extremely low solubility in water, It cannot be used as a thickener because it gels.
- These linear diol compounds may be used alone or in combination of two or more.
- the amount of the linear diol compound used is preferably 0.5 to 2.5 mol, more preferably 0.8 to 2.2, with respect to 1 mol of the polyalkylene oxide compound.
- the usage-amount of a linear diol compound is less than 0.5 mol, there exists a possibility that transparency of the water-soluble polyalkylene oxide modified material obtained may become low.
- the usage-amount of a linear diol compound exceeds 2.5 mol, there exists a possibility that the solubility to the water of the obtained water-soluble polyalkylene oxide modified material may become extremely low, and it may gelatinize.
- the polyalkylene oxide compound has the general formula (III):
- R 3 is hydrogen or a methyl group, and n is an integer of 90 to 900.
- polyalkylene oxide compound examples include polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide (preferably a copolymer of ethylene oxide and propylene oxide), and the like.
- polyalkylene oxide compounds containing 70% by mass or more of ethylene oxide groups are preferable, and polyalkylene oxide compounds having 95% by mass or more of ethylene oxide groups are more preferable.
- the content of the ethylene oxide group is less than 70% by mass, the aqueous solution viscosity of the obtained water-soluble polyalkylene oxide-modified product may be lowered.
- the number average molecular weight of the polyalkylene oxide compound is preferably 4,000 to 30,000, more preferably 6,000 to 20,000.
- the number average molecular weight of the polyalkylene oxide compound is less than 4,000, the aqueous solution viscosity of the resulting water-soluble polyalkylene oxide-modified product may be lowered.
- the number average molecular weight of the polyalkylene oxide compound exceeds 30,000, the solubility of the resulting water-soluble polyalkylene oxide-modified product in water may be low.
- the diisocyanate compound has the general formula (IV):
- R 4 represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, a 3-methyl-3,5,5-trimethylcyclohexylene group, a dimethylphenylene group or a tolylene group.
- diisocyanate compound examples include 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), and 3-isocyanatomethyl.
- MDI 4,4′-diphenylmethane diisocyanate
- HDI 1,6-hexamethylene diisocyanate
- HMDI dicyclohexylmethane-4,4′-diisocyanate
- 3-isocyanatomethyl 3-isocyanatomethyl.
- IPDI isocyanate
- 1,8-dimethylbenzole-2,4-diisocyanate 1,4-tolylene diisocyanate (TDI) and the like.
- dicyclohexylmethane-4,4′-diisocyanate HMDI
- 1,6-hexamethylene diisocyanate HMDI
- HDI dicyclohexylmethane-4,4′-diisocyanate
- the use ratio of the polyalkylene oxide compound, the diol compound, the monovalent hydrophobic alcohol compound and the diisocyanate compound is such that the urethane group concentration of the water-soluble polyalkylene oxide modified product calculated by the following formula is preferably 1.0. It is determined to be ⁇ 3.0%, more preferably 1.5 to 2.8%.
- the urethane group concentration is less than 1.0%, the transparency of the aqueous solution of the resulting water-soluble polyalkylene oxide-modified product may be deteriorated.
- the urethane group concentration exceeds 3.0% the solubility of the resulting water-soluble polyalkylene oxide-modified product in water may be reduced, and gelation may occur.
- a method of reacting a monovalent hydrophobic alcohol, a linear diol compound, a polyalkylene oxide compound and a diisocyanate compound for example, a method of reacting by dissolving or dispersing in a reaction solvent such as toluene, xylene or dimethylformamide;
- a reaction solvent such as toluene, xylene or dimethylformamide
- examples include a method in which a solid is pulverized into a powder form (powder form) or melted in a liquid state, and both are uniformly mixed, and then heated to a predetermined temperature for reaction. From the viewpoint of industrial implementation, a method in which each raw material is continuously supplied in a heated and melted state and mixed and reacted in a multi-screw extruder is preferable.
- the temperature of the reaction is in the range of 70 to 210 ° C., preferably in the range of 90 to 180 ° C., more preferably 100 to 160 ° C.
- the temperature of reaction is less than 70 degreeC, there exists a possibility that reaction may become non-uniform
- the temperature of reaction exceeds 210 degreeC, there exists a possibility that the water-soluble polyalkylene oxide modified material obtained may decompose
- the reaction time can be appropriately set so that the reaction is completed according to the reaction temperature, the type of polyalkylene oxide compound, linear diol compound, monovalent hydrophobic alcohol, and diisocyanate compound used.
- the reaction time is defined as an average residence time determined by the following method in a multi-screw extruder.
- a small amount of colorant for example, ground red chalk, blue No. 5
- the average residence time is in the range of 0.5 to 5.0 minutes, preferably 1.0 to 3.5 minutes, more preferably 1.5 to 3.0 minutes, depending on the supply amount, rotation speed, and screw shape. Adjusted.
- a reaction accelerator such as triethylamine, triethanolamine, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, or triethylenediamine is used in the reaction system.
- the amount of the reaction accelerator used is preferably 200 to 2,000 ppm by mass, more preferably 500 to 1,000 ppm by mass, based on the polyalkylene oxide compound.
- a monovalent hydrophobic alcohol, a linear diol compound, a polyalkylene oxide compound, and a diisocyanate compound are mixed and reacted in an appropriate reactor such as an extruder to react with a water-soluble polyalkylene oxide modified product.
- the water-soluble polyalkylene oxide modified product thus obtained has the following general formula (V):
- R 1 to R 4 and n are the same as defined above in general formulas (I) to (IV), and / represents any order of two types of repeating structural units in the brackets shown before and after that. Shows ester bond with] It is represented by
- the water-soluble polyalkylene oxide modified product represented by the general formula (V) is, for example, the following formula:
- the obtained water-soluble polyalkylene oxide-modified product can be added to cosmetics and emulsion compositions and dissolved in the production process thereof.
- water an aqueous solution containing a salt such as sodium chloride and a surfactant; an aqueous solution of diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol, propylene glycol; It can be used after being diluted. From the viewpoint of maintaining the transparency of the resulting aqueous solution for a long period of time, it is preferably used after being diluted with water or polyethylene glycol 200.
- Transparency can be evaluated by the light transmittance when a 3% by mass aqueous solution of a water-soluble polyalkylene oxide modified product is filled in a 1 cm long quartz glass at 425 nm with an ultraviolet-visible spectrophotometer.
- the transmittance is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more. If the transmittance is less than 30%, the transparency when used as a cosmetic material may deteriorate.
- the viscosity of the 3% by weight aqueous solution of the water-soluble polyalkylene oxide-modified product according to the present invention was determined using a cone plate type rheometer (AR2000 manufactured by TA Instruments Inc.) as a cone (60 mm, cone angle of 1 degree). Is used to measure the viscosity of the shear rate at a temperature of 25 ° C. in the range of 0.0001 to 1,000 [1 / s]. By using a cone plate type rheometer, it is possible to grasp the viscosity behavior in more detail as compared with the measurement using a conventional B type viscometer.
- TI value A (shear rate: 0.01 [1 / S] viscosity / shear rate: 0.1 [1 / S] viscosity in a 3% by weight aqueous solution of the water-soluble polyalkylene oxide modified product according to the present invention.
- the ratio is preferably in the range of 1.0 to 1.8, more preferably 1.0 to 1.5.
- the viscosity at a shear rate of 0.1 to 1.0 [1 / s] is related to the leveling property when the water-soluble polyalkylenoxide modified product according to the present invention is added to paints and cosmetics, and the TI value A is 1. If it is less than 0.0, the storage stability deteriorates, which is not preferable. If it exceeds 1.8, sagging tends to occur during coating, which is not preferable.
- TI value B (shear rate: viscosity of 10 [1 / S] / shear rate: viscosity ratio of 100 [1 / S]) in a 3% by mass aqueous solution of the water-soluble polyalkylene oxide modified product according to the present invention is: Preferably it is in the range of 3.0 to 9.0, more preferably 4.0 to 8.0.
- the viscosity at a shear rate of 10 to 100 [1 / s] is related to the mixing and stirring properties when the water-soluble polyalkylenoxide modified product according to the present invention is added to paints and cosmetics, and the TI value B is 3.
- the TI values A and B can be controlled by the total number of carbon atoms of the linear diol compound of the water-soluble polyalkylene oxide modified product and the carbon number of the monovalent hydrophobic alcohol.
- the sum of the number and carbon number of the monovalent hydrophobic alcohol is preferably in the range of 12 to 19.
- the TI values A and B are less than 1.1, which is not preferable.
- the TI value A is in the range of 1.0 to 1.8, but the TI value B is 9.0. This is not preferable.
- an emulsion composition for cosmetics and paints containing the water-soluble polyalkylene oxide modified product according to the present invention is provided.
- This cosmetic and emulsion composition can be prepared by conventional methods.
- the water-soluble polyalkylene oxide-modified product can be appropriately blended into these cosmetics and emulsion compositions depending on the physical properties such as viscosity and transparency and the concentration and physical properties of other blending components, preferably 0.01 It is blended at ⁇ 10 mass%, more preferably at 0.1-5.0 mass%.
- the pellet-shaped water-soluble polyalkylene oxide-modified product obtained in each example was immersed in liquid nitrogen, and then pulverized so that the median particle diameter was 100 ⁇ m and subjected to the following evaluation.
- Evaluation method (1) Viscosity of aqueous solution 9.0 g of water-soluble polyalkylene oxide-modified product is put into 297 g of ion-exchanged water or 3% by mass sodium chloride aqueous solution, and stirred for 3 hours at 30 ° C. and 300 rpm for water-soluble polyalkylene. A 3% by mass aqueous solution of a modified alkylene oxide was obtained.
- the obtained aqueous solution was subjected to a shear rate of 0.0001 to 1 at a temperature of 25 ° C. using a cone (60 mm, cone angle of 1 degree) using a cone plate type rheometer (AR2000 manufactured by TA Instruments).
- the aqueous solution viscosity in the range of 1,000 [1 / s] was measured.
- the relationship between the shear rate and the aqueous solution viscosity is shown in FIG.
- TI value TI value A and TI value B were calculated from the measurement results of (1) aqueous solution viscosity according to the following formula.
- TI value A (shear rate: 0.01 [1 / s] viscosity / (shear rate: 0.1 [1 / S] viscosity)
- TI value B (shear rate: viscosity of 10 [1 / s] / (shear rate: viscosity of 100 [1 / S])
- Viscosity of cold cream and shampoo The cold creams obtained in Examples 6 to 10 and Comparative Examples 7 to 9 described later, and the shampoos obtained in Examples 11 to 15 and Comparative Examples 10 to 12 were used as corn.
- the viscosity at a shear rate of 1 [1 / s] was measured at a temperature of 25 ° C. using a cone (60 mm, cone angle of 1 degree) with a plate-type rheometer (AR2000 manufactured by TA Instruments).
- FIG. 2 shows a schematic diagram for obtaining the average friction coefficient (MIU) from the monitoring result of the friction coefficient ⁇ .
- the artificial leather coated with cold cream is scanned over and the coefficient of friction ⁇ is monitored.
- the coefficient of friction ⁇ is integrated in the monitor width of 20 mm (shaded area in FIG. 2).
- the average friction coefficient (MIU) is obtained by dividing the integral value by the monitor width (20 mm). When the MIU value is 0.4 or less, it can be said that the slipperiness is good and there is little stickiness.
- FIG. 3 shows a schematic diagram for obtaining the fluctuation range (MMD) of the average friction coefficient from the monitoring result of the friction coefficient.
- the absolute value of the difference between the average friction coefficient (MIU) and the friction coefficient ⁇ is integrated in the monitor width of 20 mm (shaded area in FIG. 3).
- the variation of the average friction coefficient (MMD) is obtained.
- the MMD value is 0.005 to 0.010, it can be said that the smoothness of the surface is good.
- Example 1 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 20,000, 1.18 parts by mass of 1,6-hexanediol, 1.58 parts by mass of decyl alcohol Part and dioctyltin dilaurate at a ratio of 0.1 part by mass, and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the mixture in storage tank A was 110-140 at a rate of 200 [g / min] and the dicyclohexylmethane-4,4′-diisocyanate in storage tank B at a rate of 10.21 [g / min].
- L / D 40
- a screw outer diameter of 26 mm set at °C mixed and reacted in the extruder, and a strand was taken out from the outlet of the extruder and pelletized by a pelletizer.
- a water-soluble polyalkylene oxide modified product was obtained.
- the raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- Example 2 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 20,000, 1.18 parts by mass of 1,6-hexanediol, 1.29 parts by mass of octyl alcohol. Part and dioctyltin dilaurate at a ratio of 0.1 part by mass, and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the mixture in storage tank A was 110-140 at a rate of 250 [g / min] and the dicyclohexylmethane-4,4′-diisocyanate in storage tank B at a rate of 12.78 [g / min].
- L / D 40
- a screw outer diameter of 26 mm set at °C mixed and reacted in the extruder, and a strand was taken out from the outlet of the extruder and pelletized by a pelletizer.
- a water-soluble polyalkylene oxide modified product was obtained.
- Table 1 and Table 2 The raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- Example 3 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 10,000, 2.08 parts by mass of 1,9-nonanediol, 1.55 parts by mass of octyl alcohol Part and dioctyltin dilaurate at a ratio of 0.1 part by mass, and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, hexane diisocyanate was added to storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the outer diameter of the screw set at 110 to 140 ° C. at a rate of 167 [g / min] for the mixture in storage tank A and hexane diisocyanate at storage tank B at a rate of 9.62 [g / min]
- Water-soluble polyalkylene oxide modified by continuously feeding to a 26 mm twin screw extruder (L / D 40), mixing and reacting in the extruder, taking out the strand from the outlet of the extruder, and pelletizing with a pelletizer I got a thing.
- the raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- hexane diisocyanate was added to storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the outer diameter of the screw set at 110-140 ° C. at a rate of 167 [g / min] for the mixture in storage tank A and hexane diisocyanate in storage tank B at a rate of 5.60 [g / min]
- Water-soluble polyalkylene oxide modified by continuously feeding to a 26 mm twin screw extruder (L / D 40), mixing and reacting in the extruder, taking out the strand from the outlet of the extruder, and pelletizing with a pelletizer I got a thing.
- the raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- Example 5 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 6,000, 0.98 parts by mass of 1,6-hexanediol, 2.53 parts by mass of hexyl alcohol Part and dioctyltin dilaurate at a ratio of 0.1 part by mass, and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, isophorone diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- Comparative Example 1 Ratio of 100 parts by mass of fully dehydrated polyethylene oxide with a number average molecular weight of 20,000, 1.57 parts by mass of decyl alcohol and 0.1 part by mass of dioctyltin dilaurate in storage tank A with a stirrer kept at 80 ° C. And stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the mixture in storage tank A was 110-140 at a rate of 200 [g / min] and dicyclohexylmethane-4,4′-diisocyanate in storage tank B at a rate of 4.54 [g / min].
- L / D 40
- a screw outer diameter of 26 mm set at °C mixed and reacted in the extruder, and a strand was taken out from the outlet of the extruder and pelletized by a pelletizer.
- a water-soluble polyalkylene oxide modified product was obtained.
- Table 1 and Table 2 The raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- Comparative Example 2 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 20,000, 1.18 parts by mass of hexanediol, 0.04 parts by mass of amyl alcohol, and dioctyltin The dilaurate was added at a ratio of 0.1 part by mass and stirred in a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the mixture in storage tank A was 110-140 at a rate of 250 [g / min] and dicyclohexylmethane-4,4′-diisocyanate in storage tank B at a rate of 7.40 [g / min].
- L / D 40
- a screw outer diameter of 26 mm set at °C mixed and reacted in the extruder, and a strand was taken out from the outlet of the extruder and pelletized by a pelletizer.
- a water-soluble polyalkylene oxide modified product was obtained.
- Table 1 and Table 2 The raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- Comparative Example 3 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 10,000, 2.08 parts by mass of 1,3-propanediol, 2.58 parts by mass of octyl alcohol Part and dioctyltin dilaurate at a ratio of 0.1 part by mass, and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, hexane diisocyanate was added to storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- the raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- Comparative Example 5 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 20,000, 0.9 parts by mass of trimethylolpropane, 4.71 parts by mass of decyl alcohol and dioctyl Tin dilaurate was added at a ratio of 0.1 part by mass and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the mixture in storage tank A was 110-140 at a rate of 167 [g / min] and the dicyclohexylmethane-4,4′-diisocyanate in storage tank B was at a rate of 12.43 [g / min].
- L / D 40
- a screw outer diameter of 26 mm set at °C mixed and reacted in the extruder, and a strand was taken out from the outlet of the extruder and pelletized by a pelletizer.
- a water-soluble polyalkylene oxide modified product was obtained.
- the raw materials used and the results are shown in Table 1 and Table 2, respectively.
- Comparative Example 6 In a storage tank A with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 20,000, 0.45 parts by mass of trimethylolpropane, 3.14 parts by mass of decyl alcohol and dioctyl Tin dilaurate was added at a ratio of 0.1 part by mass and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.
- the mixture in storage tank A is 110-140 at a rate of 167 [g / min] and the dicyclohexylmethane-4,4′-diisocyanate in storage tank B is 8.45 [g / min].
- L / D 40
- a screw outer diameter of 26 mm set at °C mixed and reacted in the extruder, and a strand was taken out from the outlet of the extruder and pelletized by a pelletizer.
- a water-soluble polyalkylene oxide modified product was obtained.
- the raw materials used and the evaluation results are shown in Table 1 and Table 2, respectively.
- the water-soluble polyalkylene oxide-modified product obtained by the present invention has a high viscosity aqueous solution viscosity, good handling properties and coating properties, and is excellent in transmittance.
- Comparative Examples 7-9 Using the modified water-soluble polyalkylene oxides of Comparative Examples 1 to 3, the same compositions as those of the cold creams (water-soluble polyalkylenes) were prepared as Comparative Examples 7 to 9, respectively, as described in Examples 6 to 10. A cold cream having an oxide modified product was obtained. The results are shown in Table 3.
- Comparative Examples 10-12 Using the modified water-soluble polyalkylene oxides of Comparative Examples 1 to 3, the same compositions as those shampoos (water-soluble polyalkylene oxides) were prepared by the preparation methods described in Examples 11 to 15 as Comparative Examples 10 to 12, respectively. A shampoo having a modified product was obtained. The results are shown in Table 3.
- a water-soluble polyalkylene oxide-modified product having high viscosity and excellent transparency can be provided.
- a cosmetic material containing the water-soluble polyalkylene oxide-modified product with less stickiness, a paint with excellent sagging prevention, and smoothness of the coating film.
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Abstract
Description
(a)少なくとも1種の水溶性ポリエーテルポリオール、
(b)少なくとも1種の水不溶性の有機ポリイソシアネート、
(c)イソシアネートと反応性の水素原子を含む化合物と、有機モノイソシアネートとから選ばれた、少なくとも1種の一官能性の疎水性有機化合物、および
(d)少なくとも1種の多価アルコールまたは多価エーテルアルコールの反応により得られるものが知られている(特許文献2、特許文献3)。
すなわち、本発明は、以下に示す水溶性ポリアルキレンオキシド変性物、これを含むエマルション組成物、および化粧品料に関する。
で表される一価の疎水性アルコールと、一般式(II):
で表される直鎖状ジオール化合物と、一般式(III):
で表されるポリアルキレンオキシド化合物と、一般式(IV):
項2.ポリアルキレンオキシド化合物が、数平均分子量4,000~30,000のポリエチレンオキシドおよび数平均分子量4,000~30,000のポリエチレンオキシド/ポリプロピレンオキシド共重合体からなる群より選ばれたポリアルキレンオキシド化合物である項1に記載の水溶性ポリアルキレンオキシド変性物。
項4.疎水性アルコールの使用量が、ポリアルキレンオキシド化合物1モルに対して0.5~2.5モルである項1~3のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物。
項5.ジイソシアネート化合物が、ジシクロヘキシルメタン-4,4’-ジイソシアネート、1,6-ヘキサメチレンジイソシアネートおよび3-イソシアナトメチル-3,5,5-トリメチルシクロヘキシル=イソシアネートからなる群より選ばれた少なくとも1種である項1~4のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物。
項6.項1~5のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物を0.01~10質量%含有するエマルション組成物。
項7.項1~5のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物を0.01~10質量%含有する化粧品料。
で表される。
で表されるものである。
分岐アルキル基としては、2-エチルヘキシル基、イソデシル基、イソトリデシル基およびイソステアリル基等が挙げられる。
これらの一価の疎水性アルコールはそれぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
なお、炭素数が5未満の直鎖状ジオール化合物を用いた場合、得られる水溶性ポリアルキレンオキシド変性物は水への溶解性が極端に低くなり、ゲル化し増粘剤として使用できない。
これらの直鎖状ジオール化合物は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ウレタン基濃度が1.0%未満の場合、得られる水溶性ポリアルキレンオキシド変性物の水溶液の透明性が悪化するおそれがある。ウレタン基濃度が3.0%を超える場合、得られる水溶性ポリアルキレンオキシド変性物の水への溶解性が低下して、ゲル化するおそれがある。
で表される。
で表されるものである。
評価方法
(1)水溶液粘度
水溶性ポリアルキレンオキシド変性物9.0gを、297gのイオン交換水または3質量%塩化ナトリウム水溶液に投入し、30℃、300rpmの条件で3時間攪拌して水溶性ポリアルキレンオキシド変性物の3質量%水溶液を得た。
得られた水溶液を、コーンプレート型レオメーター(ティー・エイ・インスツルメント社製AR2000)により、コーン(60mm、コーン角度1度)を用いて、温度25℃において、剪断速度0.0001~1,000[1/s]の範囲の水溶液粘度を測定した。
また、実施例1および比較例1により得られた水溶性ポリアルキレンオキシド変性物については、剪断速度と水溶液粘度の関係を図1に示した。
上記(1)水溶液粘度の測定結果より、以下の式により、TI値A、TI値Bを算出した。
TI値A=(剪断速度:0.01[1/s]の粘度/(剪断速度:0.1[1/S]の粘度)
TI値B=(剪断速度:10[1/s]の粘度/(剪断速度:100[1/S]の粘度)
上記(1)と同様の方法で得られた、水溶性ポリアルキレンオキシド変性物を3質量%含有する水溶液および3質量%塩化ナトリウム水溶液の各4.5ml、ならびに、後述の実施例11~15および比較例10~12で得られたシャンプー4.5mlを1cm厚みの石英ガラスに充填した後、各々、遠心分離機(1,800rpm)により気泡を除去し、紫外-可視分光光度計(UV-3150:島津製作所)により、425nmにおける光線透過率を測定し、透明性の評価とした。
後述の実施例6~10および比較例7~9で得られたコールドクリーム、ならびに、実施例11~15および比較例10~12で得られたシャンプーを、コーンプレート型レオメーター(ティー・エイ・インスツルメント社製AR2000)により、コーン(60mm、コーン角度1度)を用いて、温度25℃において、剪断速度1[1/s]における粘度を測定した。
後述の実施例1~4および比較例7~9で得られたコールドクリーム0.2mlを、人工皮革(出光石油化学製サプラーレ)に塗りつけて引き伸ばした後に、東レ摩擦感テスター(カトーテック株式会社製、型式:KES-SE)を用いて、以下の試験条件下、平均摩擦係数μと平均摩擦係数の変動幅(MMD)を測定した。
センサー:シリコーン
荷重 :50[g]
速度 :5[mm/秒]
平均摩擦係数は、表面をこする時に感じる滑りやすさ、および滑りにくさと相関性がある。この値が大きくなるほどすべりにくくなる。
摩擦係数μのモニター結果から平均摩擦係数(MIU)を求める概略図を、図2に示す。
MIUの値が0.4以下のとき、滑り性が良好でベタツキが少ないといえる。
平均摩擦係数の変動幅は、表面をこする時に感じるなめらかさ、およびざらつき感と相関性がある。この値が大きいほど表面がざらざらしている。
摩擦係数のモニター結果から平均摩擦係数の変動幅(MMD)を求める概略図を、図3に示す。
MMDの値が0.005~0.010のとき、表面のなめらかさが良好といえる。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量20,000のポリエチレンオキシド100質量部、1,6-ヘキサンジオール1.18質量部、デシルアルコール1.58質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにジシクロヘキシルメタン-4,4’-ジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量20,000のポリエチレンオキシド100質量部、1,6-ヘキサンジオール1.18質量部、オクチルアルコール1.29質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにジシクロヘキシルメタン-4,4’-ジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量10,000のポリエチレンオキシド100質量部、1,9-ノナンジオール2.08質量部、オクチルアルコール1.55質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにヘキサンジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量15,000のエチレンオキシド/プロピレンオキシド(=75/25)100質量部、1,9-ノナンジオール1.04質量部、オクチルアルコール1.29質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにヘキサンジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量6,000のポリエチレンオキシド100質量部、1,6-ヘキサンジオール0.98質量部、ヘキシルアルコール2.53質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにイソホロンジイソシネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量20,000のポリエチレンオキシド100質量部、デシルアルコール1.57質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにジシクロヘキシルメタン-4,4’-ジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量20,000のポリエチレンオキシド100質量部、ヘキサンジオール1.18質量部、アミルアルコール0.04質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにジシクロヘキシルメタン-4,4’-ジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量10,000のポリエチレンオキシド100質量部、1,3-プロパンジオール2.08質量部、オクチルアルコール2.58質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにヘキサンジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量15,000のエチレンオキシド/プロピレンオキシド(=75/25)100質量部、プロパンジオール2.08質量部、オクチルアルコール2.02質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにヘキサンジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量20,000のポリエチレンオキシド100質量部、トリメチロールプロパン0.9質量部およびデシルアルコール4.71質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにジシクロヘキシルメタン-4,4’-ジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および結果を各々、表1および表2に示す。
80℃に保温された攪拌機のついた貯蔵タンクAに、十分に脱水した数平均分子量20,000のポリエチレンオキシド100質量部、トリメチロールプロパン0.45質量部およびデシルアルコール3.14質量部およびジオクチルスズジラウレート0.1質量部の割合で投入し、窒素ガス雰囲気下で攪拌して均一な混合物とした。これとは別に、30℃に保温された貯蔵タンクBにジシクロヘキシルメタン-4,4’-ジイソシアネートを投入し、窒素ガス雰囲気下で貯蔵した。
使用した原料および評価結果を各々、表1および表2に示す。
実施例6~10
実施例1~5の水溶性ポリアルキレンオキシド変性物を用いて、各々、実施例6~10として下記のフォーミュレーションおよび調製方法によりコールドクリームを得た。
結果を表3に示す。
アクペック501ER(住友精化株式会社製) 0.2質量部
A相 メトキシケイヒ酸オクチル 7.5質量部
オクチルトリアゾン 1質量部
流動パラフィン 8質量部
トリ(カプリル酸/カプリン酸)グリセリル 1質量部
シクロペンタシロキサン 2質量部
ソルビタンモノオレエート 0.1質量部
ビタミンE酢酸エステル 0.1質量部
フェノキシエタノール 1質量部
B相 水溶性ポリアルキレンオキシド変性物 3.2質量部
プロピレングリコール 5質量部
セテアレス-25 0.5質量部
水 70.4質量部
C相 水酸化ナトリウム 0.05質量部
アクペック501ER0.2質量部を予めよく混合したA相に入れて分散させた後にフェノキシエタノールを添加した。その後完全溶解させたB相にゆっくり添加し、ホモジナイザー(50℃、8000rpm×10分間)にかけて、水酸化ナトリウムにて中和してコールドクリームを得た。
実施例11~15
実施例1~5の水溶性ポリアルキレンオキシド変性物を用いて、各々、実施例11~15として下記のフォーミュレーションおよび調製方法によりシャンプーを得た。
その結果を表3に示す。
A相 アクペック501ER(住友精化株式会社製)0.15質量部
水溶性ポリアルキレンオキシド変性物 0.15質量部
水 14.7質量部
B相 硫酸アンモニウム=ドデシル(25%) 40.8質量部
ラウレス-2硫酸アンモニウム(23%) 11.4質量部
5%水酸化カリウム水溶液 3.5質量部
水 12.5質量部
C相 コカミドMEA 1.5質量部
水 12.4質量部
ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン(30%)
2.4質量部
フェノキシエタノール 0.5質量部
アクペック501ERを分散させたA相に水溶性ポリアルキレンオキシド変性物を溶解し、B相を加えた。そこにC相を加えて75℃で15分攪拌した。最後にヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン(30%)2.4質量部とフェノキシエタノール0.5質量部を加えて透明シャンプーを得た。
比較例1~3の水溶性ポリアルキレンオキシド変性物を用いて、各々、比較例7~9として、実施例6~10に記載の調製方法により、それらのコールドクリームと同一組成(水溶性ポリアルキレンオキシド変性物を除く)を有するコールドクリームを得た。
結果を表3に示す。
比較例1~3の水溶性ポリアルキレンオキシド変性物を用いて、各々、比較例10~12として、実施例11~15に記載の調製方法により、それらのシャンプーと同一組成(水溶性ポリアルキレンオキシド変性物を除く)を有するシャンプーを得た。
結果を表3に示す。
Claims (7)
- 一般式(I):
で表される一価の疎水性アルコールと、一般式(II):
で表される直鎖状ジオール化合物と、一般式(III):
で表されるポリアルキレンオキシド化合物と、一般式(IV):
で表されるジイソシアネート化合物とを反応させることにより得られる水溶性ポリアルキレンオキシド変性物。 - ポリアルキレンオキシド化合物が、数平均分子量4,000~30,000のポリエチレンオキシドおよび数平均分子量4,000~30,000のポリエチレンオキシド/ポリプロピレンオキシド共重合体からなる群より選ばれたポリアルキレンオキシド化合物である請求項1に記載の水溶性ポリアルキレンオキシド変性物。
- 直鎖状ジオール化合物の使用量が、ポリアルキレンオキシド化合物1モルに対して0.5~2.5モルである請求項1または2に記載の水溶性ポリアルキレンオキシド変性物。
- 疎水性アルコールの使用量が、ポリアルキレンオキシド化合物1モルに対して0.5~2.5モルである請求項1~3のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物。
- ジイソシアネート化合物が、ジシクロヘキシルメタン-4,4’-ジイソシアネート、1,6-ヘキサメチレンジイソシアネートおよび3-イソシアナトメチル-3,5,5-トリメチルシクロヘキシル=イソシアネートからなる群より選ばれた少なくとも1種である請求項1~4のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物。
- 請求項1~5のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物を0.01~10質量%含有するエマルション組成物。
- 請求項1~5のいずれか1項に記載の水溶性ポリアルキレンオキシド変性物を0.01~10質量%含有する化粧品料。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013137290A1 (ja) * | 2012-03-13 | 2013-09-19 | 住友精化株式会社 | 化粧料組成物 |
KR20160097288A (ko) * | 2013-12-10 | 2016-08-17 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | 고탄성 열가소성 폴리우레탄 |
WO2020062327A1 (zh) * | 2018-09-30 | 2020-04-02 | 上海万华科聚化工科技发展有限公司 | 非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用 |
WO2022172453A1 (ja) * | 2021-02-15 | 2022-08-18 | 株式会社資生堂 | 分散体、水系組成物の製造方法、及び水系組成物 |
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FR3041964B1 (fr) * | 2015-10-05 | 2017-10-20 | Coatex Sas | Agent epaississant pour systemes aqueux, formulations le contenant et utilisations. |
JPWO2020009054A1 (ja) * | 2018-07-04 | 2021-08-05 | 住友精化株式会社 | 研磨用組成物 |
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WO2013137290A1 (ja) * | 2012-03-13 | 2013-09-19 | 住友精化株式会社 | 化粧料組成物 |
EP2826463A4 (en) * | 2012-03-13 | 2015-12-02 | Sumitomo Seika Chemicals | COSMETIC COMPOSITION |
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KR20160097288A (ko) * | 2013-12-10 | 2016-08-17 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | 고탄성 열가소성 폴리우레탄 |
KR102283445B1 (ko) | 2013-12-10 | 2021-07-28 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | 고탄성 열가소성 폴리우레탄 |
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WO2022172453A1 (ja) * | 2021-02-15 | 2022-08-18 | 株式会社資生堂 | 分散体、水系組成物の製造方法、及び水系組成物 |
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