WO2023190362A1 - Composition visqueuse contenant de l'alcool - Google Patents
Composition visqueuse contenant de l'alcool Download PDFInfo
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- WO2023190362A1 WO2023190362A1 PCT/JP2023/012241 JP2023012241W WO2023190362A1 WO 2023190362 A1 WO2023190362 A1 WO 2023190362A1 JP 2023012241 W JP2023012241 W JP 2023012241W WO 2023190362 A1 WO2023190362 A1 WO 2023190362A1
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- mass
- copolymer
- viscous composition
- aqueous solution
- meth
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Definitions
- the present disclosure relates to alcohol-containing viscous compositions and the like.
- Alcohol-containing viscous compositions are widely used for disinfection purposes.
- Patent Document 1 describes a disinfectant composition containing alcohol and a thickener (for example, a synthetic polymer such as carboxyvinyl polymer). If the disinfectant composition is acidic, it may further improve the disinfecting action, but synthetic polymers such as carboxyvinyl polymers used as thickeners are usually used with alkali to achieve a thickening effect. There is a need. For this reason, it has been difficult to obtain an acidic alcohol viscous composition that contains a polymer obtained by synthesis such as carboxyvinyl polymer as a thickener and exhibits good viscosity.
- a thickener for example, a synthetic polymer such as carboxyvinyl polymer.
- the present inventors conducted repeated studies in order to obtain an acidic alcohol viscous composition that contains a synthetically obtained polymer as a thickener and exhibits good viscosity.
- the present inventors discovered the possibility that an acidic viscous composition containing specific amounts of a specific copolymer and a specific alcohol aqueous solution could become an alcoholic viscous composition exhibiting good viscosity, and conducted further investigation. Layered.
- Item 1 A viscous composition, (a) 0.5 to 20% by mass of a copolymer obtained by polymerizing at least (meth)acrylic acid and a compound having two or more ethylenically unsaturated groups; and (b) alkyl in the viscous composition.
- the copolymer is (A) At least one copolymer selected from the group consisting of the following (A-1) and (A-2): (A-1) Copolymer obtained by polymerizing the following (i) and (ii) (A-2) Copolymer obtained by polymerizing the following (i), (ii), and (iii) Combined (i) 100 parts by mass of (meth)acrylic acid (ii) 1 part by mass or less of a compound having two or more ethylenically unsaturated groups (iii) Alkyl (meth)acrylate whose alkyl group has 10 to 30 carbon atoms The ester is 5 parts by mass or less, Item 1.
- the viscous composition according to item 1.
- the viscous composition according to Item 1 or 2 wherein the copolymer is a copolymer whose ethanol aqueous solution satisfies the following conditions.
- Section 6 A thickener for thickening an aqueous alkyl alcohol solution having an alkyl alcohol content of 50 to 81% by mass to prepare a viscous composition having a pH of 2 to 5.5 at 25°C, A thickener comprising at least a copolymer obtained by polymerizing (meth)acrylic acid and a compound having two or more ethylenically unsaturated groups.
- the viscous composition preferably also exhibits good transparency (transmittance).
- present disclosure preferably includes, but is not limited to, alcohol-containing viscous compositions and the like, and the present disclosure includes all disclosed herein and recognizable to those skilled in the art.
- the alcohol-containing viscous composition included in the present disclosure includes (a) a copolymer obtained by polymerizing at least (meth)acrylic acid and a compound having two or more ethylenically unsaturated groups. % by mass, and (b) an alkyl alcohol aqueous solution component in which the content of alkyl alcohol in the alkyl alcohol aqueous solution component in the viscous composition is 50 to 81 mass %, and the pH at 25 ° C. is 2 to 5.5. It is a viscous composition.
- the viscous composition included in the present disclosure may be referred to as the composition of the present disclosure.
- (meth)acrylic means acrylic and/or methacryl.
- (meth)acrylic acid either acrylic acid or methacrylic acid may be used alone, or both may be used in combination.
- the copolymer (a) is a copolymer obtained by polymerizing at least (meth)acrylic acid and a compound having two or more ethylenically unsaturated groups, and more preferably the following (A-1 ) and (A-2).
- the content of (a) is 0.5 to 20% by mass based on the viscous composition.
- the upper or lower limit of the range is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19% by mass. It's okay.
- the range is preferably 1 to 15% by weight, more preferably 1 to 10% by weight.
- copolymer (A-1) and (A-2) may be referred to as copolymer (A-1) and copolymer (A-2), respectively.
- the copolymer (a), including copolymers (A-1) and (A-2) is a carboxyl group-containing water-soluble copolymer.
- a water-soluble copolymer containing a carboxyl group is a compound in which the carboxyl group contained in the copolymer is not neutralized (unneutralized compound), or a compound in which the carboxyl group contained in the copolymer is not neutralized. Compounds that are partially or completely neutralized (neutralized compounds) are also included.
- copolymer is a compound in which (meth)acrylic acid and a compound (crosslinking agent) having two or more ethylenically unsaturated groups are polymerized (in other words, (meth)
- This concept includes compounds in which acrylic acid is crosslinked with a compound having two or more ethylenically unsaturated groups. Therefore, copolymer (A-1) and copolymer (A-2) are compounds in which, in addition to (meth)acrylic acid, a compound having two or more ethylenically unsaturated groups is also polymerized (in other words, , a compound in which a (meth)acrylic acid polymer is crosslinked with the compound).
- the amount of the above (ii) used is 1 part by mass or less, preferably 0.01 to 1.0 parts by mass, more preferably 0.01 to 0.6 parts by mass, per 100 parts by mass of (meth)acrylic acid. preferable.
- the amount of the above (iii) used is 5 parts by weight or less, preferably 0.5 to 5 parts by weight, and more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of (meth)acrylic acid.
- Examples of the above (ii) include pentaerythritol tetraallyl ether, N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, ethylene glycol diglycidyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, and the like.
- the crosslinking agents can be used alone or in combination of two or more.
- the above (iii) is an ester of (meth)acrylic acid and a higher alcohol whose alkyl group has 10 to 30 carbon atoms.
- the number of carbon atoms in the alkyl group is preferably 12 to 30, 14 to 28, 16 to 26, or 18 to 24, for example.
- Examples of such (meth)acrylic acid alkyl esters include stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, and tetracosanyl methacrylate. These (meth)acrylic acid alkyl esters may be used alone or in combination of two or more.
- a commercially available product such as Bremmer VMA70 (trade name, manufactured by NOF Corporation) may be used.
- the copolymer (a) is obtained by polymerizing at least (meth)acrylic acid and a compound having two or more ethylenically unsaturated groups.
- the polymerization is preferably carried out in a polymerization solvent in the presence of a radical polymerization initiator.
- radical polymerization initiator ⁇ , ⁇ '-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobismethylisobutyrate, 2,2 Examples include '-azobis(2-methylpropionamidine) dihydrochloride, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and tertiary butyl hydroperoxide. These radical polymerization initiators may be used alone or in combination of two or more.
- the amount of the radical polymerization initiator used is preferably 0.01 to 0.45 parts by mass, more preferably 0.01 to 0.4 parts by mass, per 100 parts by mass of (meth)acrylic acid.
- Both copolymers (A-1) and (A-2) can be preferably prepared, for example, by precipitation polymerization or reverse-phase suspension polymerization. Furthermore, the reverse phase suspension polymerization may be carried out in a polymerization solvent containing a nonionic surfactant having a polyoxyethylene chain.
- nonionic surfactant having a polyoxyethylene chain examples include polyhydric alcohol fatty acid ester ethylene oxide adducts, block copolymers of hydroxy fatty acids and ethylene oxide, and polyoxyethylene castor oil.
- ester compounds of polyoxyethylene hydrogenated castor oil and polyhydric alcohol fatty acid are preferably mentioned.
- polyhydric alcohol fatty acid saturated or unsaturated polyhydric (especially dihydric) alcohol fatty acids having 14 to 24 carbon atoms are preferable, and more specifically, isopalmitic acid, isostearic acid, isooleic acid etc. are preferably mentioned.
- the average number of moles of ethylene oxide added to polyoxyethylene is about 20 to 100, or about 30 to 70.
- a particularly preferred ester compound of polyoxyethylene hydrogenated castor oil and polyhydric alcohol fatty acid is polyoxyethylene hydrogenated castor oil isostearate.
- the polyoxyethylene castor oil preferably has an added mole number of ethylene oxide of about 2 to 10, more preferably about 2 to 5.
- the block copolymer of hydroxy fatty acid and ethylene oxide can be said to be a copolymer consisting of polyhydroxy fatty acid and polyoxyethylene.
- the fatty acid of the polyhydroxy fatty acid is preferably a fatty acid having about 14 to 22 carbon atoms, and preferred examples include myristic acid, palmitic acid, stearic acid, etc., and examples of the hydroxy fatty acid include hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, etc. are preferred, with hydroxystearic acid being particularly preferred.
- As the hydroxystearic acid 12-hydroxystearic acid is particularly preferred.
- polyhydroxy fatty acid polyhydroxystearic acid is particularly preferred.
- As the block copolymer of hydroxy fatty acid and ethylene oxide a block copolymer of 12-hydroxystearic acid and ethylene oxide is particularly preferred.
- the nonionic surfactants having polyoxyethylene chains can be used alone or in combination of two or more.
- the amount of the nonionic surfactant having a polyoxyethylene chain used is preferably 0.5 to 10 parts by weight, more preferably 1 to 7.5 parts by weight, based on 100 parts by weight of (meth)acrylic acid.
- the polymerization solvent is preferably a solvent that dissolves (i), (ii), and (iii) but does not dissolve the resulting copolymer.
- Specific examples of such polymerization solvents include normal pentane, normal hexane, normal heptane, normal octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, ethylene dichloride, and ethyl acetate.
- ethylene dichloride, n-hexane, n-heptane, and ethyl acetate are preferred from the viewpoint of stable quality and easy availability.
- These polymerization solvents may be used alone or in combination of two or more.
- the amount of the polymerization solvent used is preferably 200 to 10,000 parts by mass, more preferably 300 to 2,000 parts by mass, per 100 parts by mass of (meth)acrylic acid.
- an inert gas atmosphere such as nitrogen gas or argon gas can be mentioned.
- the reaction temperature when carrying out the above polymerization reaction is preferably 50 to 90°C, more preferably 55 to 75°C.
- the reaction time when carrying out the above polymerization reaction is usually 2 to 10 hours.
- the copolymer as a fine white powder can be isolated by heating the reaction solution to 80 to 130°C and removing the polymerization solvent.
- the viscous composition of the present disclosure contains an alkyl alcohol aqueous solution having an alkyl alcohol content of 50 to 81% by mass.
- an alkyl alcohol aqueous solution component in which the content of alkyl alcohol in the alkyl alcohol aqueous solution component in the viscous composition is 50 to 81% by mass the description does not refer to each component constituting the viscous composition.
- the alkyl alcohol aqueous solution is considered as one component, the alkyl alcohol content in the alkyl alcohol aqueous solution is 50 to 81% by mass.
- the upper or lower limit of the alkyl alcohol content range (50 to 81% by mass) in the alkyl alcohol aqueous solution is, for example, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, It may be 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80% by mass.
- the range may be 55-75% by weight.
- the content of alkyl alcohol in the viscous composition of the present disclosure is preferably 50 to 80% by mass.
- the upper or lower limit of the range (50 to 80% by mass) is, for example, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, It may be 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, or 79% by mass.
- the range may be 55-75% by weight.
- the viscous composition of the present disclosure is prepared, for example, by first preparing an aqueous alkyl alcohol solution, adding the copolymer (a) to the aqueous solution, and adding a pH adjuster and other components as necessary. be able to.
- alkyl alcohol linear or branched alkyl alcohols having 1 to 6 carbon atoms are preferably mentioned. Among them, ethanol, isopropanol (IPA), 1,3-butanediol, and propylene glycol are preferred, and ethanol is particularly preferred. Alkyl alcohols can be used alone or in combination of two or more.
- the pH of the viscous composition of the present disclosure is between 2 and 5.5.
- the upper or lower limit of the range is, for example, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, It may be 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, or 5.4.
- the range is preferably 3.5 to 5.5, more preferably 4.5 to 5.5.
- the said pH is the value measured with the pH meter at 25 degreeC.
- This condition can also be expressed as the transmittance of the aqueous solution (II) being higher than the transmittance of the aqueous solution (I).
- aqueous solution (I) and/or (II) cannot be prepared (for example, if the copolymer (a) does not dissolve in its entirety and lumps remain, or if it separates), it is not possible to measure the transmittance. Therefore, copolymers for which aqueous solutions (I) and/or (II) cannot be prepared do not fall under the preferred copolymers (a). Therefore, in order to obtain the preferred copolymer (a), both aqueous solutions (I) and (II) can be prepared, and the transmittance of aqueous solution (II) is higher than that of aqueous solution (I). It can be said that it is necessary to use a copolymer that increases transmittance.
- the upper and lower limits of the range are, for example, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, It may be 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, or 14.5.
- ⁇ is more preferably from 5 to 12, and even more preferably from 6 to 10.5.
- ⁇ is preferably a positive number, for example, and preferably from 5 to 60, although it is not particularly limited.
- the viscous composition of the present disclosure may contain a pH adjuster, as described above.
- Preferred examples of the pH adjuster include organic amines.
- Preferred organic amines include diisopropanolamine, 2-amino-2-methyl-1-propanol (AMP), and triethanolamine.
- Such pH adjusters can be used alone or in combination of two or more.
- organic acids e.g. citric acid, etc.
- salts thereof e.g. alkali metal salts
- inorganic acids e.g. phosphoric acid
- salts thereof e.g. alkali metal salts
- the composition of the present disclosure does not contain organic acids and their salts and/or inorganic acids and their salts.
- the viscous composition of the present disclosure may contain components other than the above-mentioned components as long as the effects are not impaired.
- examples of such other ingredients include various ingredients used in the field of external compositions (particularly cosmetic compositions).
- the viscous composition of the present disclosure preferably has a viscosity of about 8,000 to 125,000 mPa ⁇ s.
- the upper and lower limits of the range are, for example, 8500, 9000, 9500, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, 70000, 75000, 80000, 85000, 9 0000, 95000, It may be 100,000, 105,000, 110,000, 115,000, or 120,000 mPa ⁇ s.
- the range may be 8500 to 120000 mPa ⁇ s.
- the viscosity value was determined by measuring the viscosity of the viscous composition at 25° C. after 1 minute using a BrookField viscometer (model number: DV1MRVTJ0) at a rotational speed of 20 revolutions per minute.
- the viscous composition of the present disclosure preferably has a transmittance of 70% or more, and 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, More preferably, it is 85, 86, 87, 88, 89, 90, 91, 92, 93, or 94% or more.
- the transmittance is a value obtained by placing the viscous composition in a cell with an optical path length of 1 cm and measuring the transmittance at a measurement wavelength of 425 nm using a spectrophotometer (ratio when the transmittance of distilled water is taken as 100%). ).
- the viscous composition of the present disclosure can be preferably used, for example, as a composition for external use.
- an external composition it is preferred because it has high permeability and is smooth. Since the viscous composition contains a relatively high alcohol concentration and exhibits excellent thickening properties, it can be particularly suitably used as an alcohol-containing external composition.
- it can be preferably used as an external composition for disinfection (particularly for hand disinfection).
- the viscous composition of the present disclosure may contain components that are known to be added to external compositions within a range that does not impair the effects.
- the present disclosure provides a method for thickening an aqueous alkyl alcohol solution having an alkyl alcohol content of 50 to 81% by mass to prepare a viscous composition having a pH of 2 to 5.5 at 25°C.
- Thickeners that include at least a copolymer obtained by polymerizing (meth)acrylic acid and a compound having two or more ethylenically unsaturated groups are also preferably included.
- the content explained regarding the viscous composition of the present disclosure also applies to the alcohol aqueous solution and the copolymer in the thickener.
- Polymer production example 1 In a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube, and condenser, 45 g of acrylic acid, 0.13 g of pentaerythritol tetraallyl ether, 150 g of n-hexane, and 2,2'-azobismethyl were added. 0.153 g of isobutyrate was added to prepare a reaction solution. After the solution was stirred to mix uniformly, nitrogen gas was blown into the solution to remove oxygen present in the head space of the reaction vessel, the raw materials, and the solvent. Next, the reaction solution was maintained at 60 to 65° C. and reacted for 4 hours under a nitrogen atmosphere.
- the resulting slurry was heated to 90°C to distill off n-hexane, and then dried under reduced pressure at 110°C and 10 mmHg for 8 hours to form a (meth)acrylic acid-based water-soluble polymer. 42 g of a certain acrylic acid polymer was obtained.
- the polymer may be referred to as Production Example 1 polymer.
- the resulting slurry was heated to 90°C to distill off n-hexane, and then dried under reduced pressure at 110°C and 10 mmHg for 8 hours to form a (meth)acrylic acid-based water-soluble polymer. 42 g of a certain acrylic acid polymer was obtained.
- the polymer may be referred to as Production Example 2 polymer.
- a mixed solvent consisting of 250 g of methyl isobutyl ketone, 200 g of methanol, and 50 g of water was added to the obtained neutralized mixture to form a slurry liquid, and hydroxyethyl cellulose was filtered from this slurry liquid. Washing with a mixed solvent having the above composition and filtration were repeated three times in total to obtain 250 g of wet hydroxyethyl cellulose and 1530 g of a filtrate containing neutralized salt and the like. The yield of hydroxyethyl cellulose after drying was 82 g.
- the hydroxyethyl cellulose may be referred to as Production Example 5 polymer.
- each polymer (Production Examples 1 to 5 polymer or HPC) was added. After stirring for 60 minutes, the pH was adjusted to 2.5 to 5.5 with a pH adjuster as necessary, and further stirred at 300 rpm for 15 minutes to prepare a viscous composition.
- AMP as a pH adjuster
- 2-amino-2-methyl-1-propanol manufactured by ANGUS CHEMICAL was diluted with ion-exchanged water to prepare a 25% AMP aqueous solution, and this was added.
- citric acid citric acid manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used.
- samples Each of the obtained viscous compositions (hereinafter referred to as samples) was evaluated for pH, viscosity, transmittance, and smoothness in the following manner. The results are also shown in Table 1.
- pH The pH was measured at 25° C. using a pH meter (manufactured by Horiba, model number: D-51).
- unpreparable refers to a state in which lumps remain and the polymer is not completely dissolved.
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Abstract
L'invention concerne une composition visqueuse contenant de l'alcool acide qui présente une bonne viscosité. Plus particulièrement, l'invention concerne une composition visqueuse contenant : (a) 0,5 à 20 % en masse d'un copolymère obtenu par polymérisation d'au moins un acide (méth)acrylique et d'un composé ayant au moins deux groupes à insaturation éthylénique ; et (b) un composant de solution aqueuse d'alcool alkylique, la teneur en alcool alkylique du composant de solution aqueuse d'alcool alkylique dans la composition visqueuse étant de 50 à 81 % en masse, et la composition visqueuse ayant un pH à 25 °C de 2 à 5,5.
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JP2012144481A (ja) * | 2011-01-12 | 2012-08-02 | Kao Corp | 手指消毒剤組成物 |
JP2019026592A (ja) * | 2017-07-28 | 2019-02-21 | イーダ株式会社 | アルコール系消毒剤 |
JP2021187756A (ja) * | 2020-05-27 | 2021-12-13 | 株式会社大阪製薬 | 手指消毒剤用エアゾール製品 |
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JP2001261550A (ja) * | 2000-03-15 | 2001-09-26 | Asahi Denka Kogyo Kk | ゲル状手指殺菌洗浄剤組成物 |
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JP2012144481A (ja) * | 2011-01-12 | 2012-08-02 | Kao Corp | 手指消毒剤組成物 |
JP2019026592A (ja) * | 2017-07-28 | 2019-02-21 | イーダ株式会社 | アルコール系消毒剤 |
JP2021187756A (ja) * | 2020-05-27 | 2021-12-13 | 株式会社大阪製薬 | 手指消毒剤用エアゾール製品 |
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