WO2023026766A1 - Viscous composition - Google Patents

Viscous composition Download PDF

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Publication number
WO2023026766A1
WO2023026766A1 PCT/JP2022/029245 JP2022029245W WO2023026766A1 WO 2023026766 A1 WO2023026766 A1 WO 2023026766A1 JP 2022029245 W JP2022029245 W JP 2022029245W WO 2023026766 A1 WO2023026766 A1 WO 2023026766A1
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Prior art keywords
polyacrylic acid
soluble polymer
water
based water
polysaccharide
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PCT/JP2022/029245
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French (fr)
Japanese (ja)
Inventor
美来 田口
真智子 中川
真喜子 宮本
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住友精化株式会社
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Publication of WO2023026766A1 publication Critical patent/WO2023026766A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides

Definitions

  • the present disclosure relates to viscous compositions and the like, and more particularly to viscous compositions containing polyacrylic acid-based water-soluble polymers and polysaccharides. It should be noted that the contents of all documents mentioned herein are hereby incorporated by reference.
  • Polyacrylic acid-based water-soluble polymers are widely used as thickeners, and are used, for example, in the cosmetics field to give appropriate viscosity to cosmetic compositions.
  • the composition does not feel slimy when applied to the skin, yet gives a moist feel and suppresses stickiness after application.
  • the present inventors discovered the possibility of solving the above problems by using a specific polyacrylic acid-based water-soluble polymer in combination with a polysaccharide, and made further improvements.
  • Section 1 A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide, The powder of the polyacrylic acid-based water-soluble polymer has an angle difference of 9° or more before and after impact when measured with a spatula angle. Composition.
  • Section 2. A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide, The polyacrylic acid-based water-soluble polymer has a particle size of 30 ⁇ m or more when swollen with water. Composition. Item 3.
  • a viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide The polyacrylic acid-based water-soluble polymer has a difference in angle before and after impact when measured with a spatula angle of 9° or more, and a particle size when swollen with water of 30 ⁇ m or more.
  • Poly(meth)acrylic acid-based water-soluble polymer may be crosslinked by a crosslinking agent, poly(meth)acrylic acid or its salt, starch/(meth)acrylic acid graft polymer or its salt, and acrylates crosspolymer Item 5.
  • Item 7. Item 7.
  • a viscous composition that does not feel slimy when applied to the skin, yet gives a moist feel and suppresses stickiness after application.
  • the composition is useful, for example, as a cosmetic composition or an external composition.
  • the present disclosure preferably includes, but is not limited to, a viscous composition containing a specific polyacrylic acid-based water-soluble polymer and a polysaccharide, and uses thereof. It includes all disclosed and recognizable to one skilled in the art.
  • the viscous composition included in the present disclosure contains a specific polyacrylic acid-based water-soluble polymer and polysaccharide.
  • the viscous composition may be referred to as the viscous composition of the present disclosure.
  • the polyacrylic acid-based water-soluble polymer used in the viscous composition of the present disclosure is a polyacrylic acid-based water-soluble polymer that satisfies either or both of the following (i) and (ii).
  • the angle difference before and after impact when measuring the spatula angle of the powder is 9° or more
  • the particle diameter when swollen with water is 30 ⁇ m or more
  • the spatula angle is a value used as an index of fluidity of powder, and is one of Carr's fluidity indexes (for example, J. Jpn. Soc. Colour Mater., 78 [11] (2005), and (See Hosokawa Micron Corporation's web page for powder testers).
  • the spatula angle can be measured using a powder tester (model number: PT-X) manufactured by Hosokawa Micron Corporation.
  • the measurement of the spatula angle by the powder tester can be explained as follows. First, 0.7 wt % of silicon dioxide (powder) is added to 100 wt % of each polyacrylic acid-based water-soluble polymer (powder) to be measured and mixed well. As silicon dioxide (powder), silicon dioxide having a particle size of 1 to 20 ⁇ m is used. Next, surround the spatula (12.7 cm long x 2.2 cm wide metal spatula) with a spatula frame (9.5 cm long x 4.5 cm wide x 3.0 cm high), 8.0 cm wide by 4.0 cm wide by 2.0 cm high). Gently lift the spatula out of the powder bed.
  • the angle of the powder pile deposited on the spatula with respect to the horizontal is measured to obtain the spatula angle.
  • the spatula is then tapped (ie, impacted) and the angle (spatula angle) is determined in the same manner. If the difference between these two angles (spatula angle) is large, it can be judged that the fluidity of the powder is high.
  • the difference in the angle of the polyacrylic acid-based water-soluble polymer powder before and after impact when measuring the spatula angle is 9° or more.
  • the upper limit is not particularly limited, it is preferably 30° or less, for example.
  • the upper or lower limit of the range (9 to 30°) is, for example, It may be 28 or 29 degrees.
  • the range may be 10-25°.
  • the particle size when swollen with water is the particle size (median size) when the polyacrylic acid-based water-soluble polymer is swollen with water, and can be obtained by a laser diffraction/scattering method.
  • the particle size can be measured using, for example, a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation).
  • the particle size is preferably 30 ⁇ m or more as described above.
  • the upper limit is not particularly limited, but may be 300 ⁇ m, for example.
  • the upper or lower limit of the range (30 to 300 ⁇ m) is, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125 , 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250 , 255, 260, 265, 270, 275, 280, 285, 290, or 295 ⁇ m.
  • the particle size range is preferably 45-250 ⁇ m, more preferably 50-220 ⁇ m.
  • polyacrylic acid-based water-soluble polymers include poly(meth)acrylic acid or salts thereof, starch/(meth)acrylic acid graft polymers or salts thereof, acrylates crosspolymers or salts thereof, and the like. mentioned. Moreover, as a salt here, an alkali metal salt is preferable, and a sodium salt or a potassium salt is more preferable.
  • polyacrylic acid-based water-soluble polymer among others, polyacrylic acid or its sodium salt, starch/acrylic acid graft polymer or its sodium salt, acrylates crosspolymer or its sodium salt are preferable.
  • the polyacrylic acid-based water-soluble polymer can be used singly or in combination of two or more.
  • the polyacrylic acid-based water-soluble polymer may be crosslinked with a crosslinking agent.
  • cross-linking agents include water-soluble sucrose allyl ether (especially tri- or tetra-allyl ether), pentaerythritol tetraallyl ether, N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, ethylene glycol diglycidyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, and the like.
  • a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • Polysaccharides used as thickeners are preferred as polysaccharides.
  • thickeners thickeners
  • naturally-derived polysaccharides are preferred, and natural gums are more preferred. More specific examples include xanthan gum, gellan gum, tamarind gum, guar gum and the like.
  • Polysaccharides can be used individually by 1 type or in combination of 2 or more types.
  • the content mass ratio of the polyacrylic acid-based water-soluble polymer and the polysaccharide is 1:9 to 9:1. It is preferably 1:5 to 5:1 or more preferably 1:4 to 4:1, even more preferably 1:2 to 2:1.
  • the content ratio by mass of the polyacrylic acid-based water-soluble polymer and xanthan gum is preferably 1:0.1 to 5. : more preferably 0.5 to 2.
  • the total content of the polyacrylic acid-based water-soluble polymer and polysaccharide is preferably 0.5 to 2% by mass.
  • the upper or lower limit of the range is 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1 .7, 1.8, 1.9% by mass.
  • the range may be, for example, 0.6-1.8% by weight.
  • the viscosity of the viscous composition of the present disclosure is preferably about 1000-60000 mPa ⁇ s.
  • the upper or lower limit of the range is, for example, 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000 ⁇ 23000 ⁇ 24000 ⁇ 25000 ⁇ 26000 ⁇ 27000 ⁇ 28000 ⁇ 29000 ⁇ 30000 ⁇ 31000 ⁇ 32000 ⁇ 33000 ⁇ 34000 ⁇ 35000 ⁇ 36000 ⁇ 37000 ⁇ 38000 ⁇ 39000 ⁇ 40000 ⁇ 41000 ⁇ 42000 ⁇ 43000 ⁇ 44000 ⁇ 45000 ⁇ 46000 ⁇ 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, or 59000 mPa ⁇ s.
  • the range may be 1500-59000 mPa ⁇ s.
  • the viscosity is measured by immersing the evaluation sample in a constant temperature water bath adjusted to 25 ° C. for 60 minutes or more, using a viscometer manufactured by BrookField (model number: DV1MRVTJ0, spindle: RV), and rotating the speed every time. It is a value obtained by measuring the viscosity one minute after starting the rotation of the rotor at 20 rotations per minute.
  • the rotor used for the measurement is rotor No. when the pressure is less than 2,000 mPa ⁇ s. 3. Rotor No. in the case of 2,000 mPa ⁇ s or more and less than 5,000 mPa ⁇ s.
  • each viscous composition is centrifuged (for example, 2,000 rpm ⁇ 10 minutes) to remove air bubbles before use for the measurement.
  • the viscous composition of the present disclosure contains a solvent in addition to the polyacrylic acid-based water-soluble polymer and polysaccharide. Water is preferred as the solvent.
  • other components may be included as long as the effects of the viscous composition of the present disclosure are not impaired. Examples of such components include known components contained in external preparation compositions and cosmetic compositions. organic acids such as lactic acid and citric acid; alkaline compounds such as potassium hydroxide and sodium hydroxide; lipids such as phosphatidylglycerol and phosphatidylethanolamine; carbohydrates such as trehalose, lactulose and maltitol; Examples include, but are not limited to, polyhydric alcohols such as glycol.
  • the method for preparing the viscous composition of the present disclosure is also not particularly limited.
  • it can be prepared by appropriately mixing a polyacrylic acid-based water-soluble polymer, a polysaccharide, water, and, if necessary, other components. Since polyacrylic acid-based water-soluble polymers and polysaccharides have a thickening effect, it is preferable to prepare an aqueous solution having an appropriate concentration (for example, 1 to 2% by mass), and then add water to the aqueous solution. and optionally other ingredients to prepare the viscous composition of the present disclosure.
  • n-heptane 330 g was placed in a 2000 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and a surfactant sorbitan monostearate (NOF stock) was added.
  • a surfactant sorbitan monostearate 2.7 g of "Nonion SP-60R" manufactured by the company was added, and this was dispersed and dissolved in n-heptane.
  • the acrylic acid-containing raw material liquid prepared previously was added.
  • nitrogen gas is blown into the solution to replace the inside of the system with nitrogen, while the bath temperature is maintained at 60 ° C.
  • the polymer may be referred to as Production Example 1 polymer.
  • n-heptane 330 g was placed in a 2000 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and a surfactant sorbitan monostearate (NOF stock) was added.
  • a surfactant sorbitan monostearate 2.7 g of "Nonion SP-60R" manufactured by the company was added, and this was dispersed and dissolved in n-heptane.
  • the acrylic acid-containing raw material liquid prepared previously was added.
  • nitrogen gas is blown into the solution to replace the inside of the system with nitrogen, while the bath temperature is maintained at 60 ° C.
  • the polymer may be referred to as Production Example 2 polymer.
  • n-heptane 356 g was placed in a 2000 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and maleic anhydride-modified ethylene/propylene was added as a polymeric dispersant.
  • 0.736 g of a copolymer (Hi-Wax 1105A, manufactured by Mitsui Chemicals, Inc.) was added and dispersed and dissolved in n-heptane.
  • the acrylic acid-containing raw material liquid prepared previously was added thereto.
  • sucrose stearate (surfactant, manufactured by Mitsubishi Kagaku Foods Co., Ltd., Ryoto Sugar Ester S-370, HLB value: 3) is dissolved in 6.62 g of n-heptane by heating.
  • the surfactant solution was added to the separable flask.
  • nitrogen gas is blown into the solution to remove oxygen present in the atmosphere, raw materials, and solvent in the reaction vessel, and the bath temperature is maintained at 70 ° C. while replacing the system with nitrogen. Polymerization was carried out over time.
  • Each polyacrylic acid-based water-soluble polymer is mixed with water, and the particle size (gel particle size) of each polyacrylic acid-based water-soluble polymer swollen with water is measured using a laser diffraction particle size distribution method manufactured by Shimadzu Corporation. Measurement was performed using a measurement device (model number: SALD-2300 using flow cell). More specifically, 50 g of pure water is placed in a 100 ml plastic beaker, and each polyacrylic acid-based water-soluble polymer is added to a concentration at which the gel particles are sufficiently dispersed and can be measured (for example, a concentration at which the viscosity starts to increase).
  • the spatula angle of each polyacrylic acid-based water-soluble polymer (powder) was measured by selecting "spatula angle" from the measurement menu. . Specifically, it was measured as follows. A horizontal metal plate (spatula) attached to the device was surrounded by a frame for the spatula attached to the device, and using a scoop attached to the device, the powder was lightly placed so that the height was 3 to 5 cm, and the frame was removed. . After that, the angle (1) formed by the slope and the horizontal plane was measured when the metal plate was raised to a specified position. Furthermore, a fixed impact was applied once by the device to drop the deposited powder, and the angle (2) formed by the slope and the horizontal plane was measured again.
  • Polysaccharide Various commercially available natural polysaccharides (all powders) were purchased and used. Specifically, xanthan gum (product name: echo gum, manufactured by DSP Gokyo Food & Chemical Co., Ltd.), gellan gum (product name: Kelcogel, manufactured by DSP Gokyo Food & Chemical Co., Ltd.), guar gum (product number: RG500, Mitsubishi Chemical Foods) Co., Ltd.) and tamarind gum (product name: Griloid 6C, manufactured by DSP Gokyo Food & Chemical Co., Ltd.) were purchased and used.
  • xanthan gum product name: echo gum, manufactured by DSP Gokyo Food & Chemical Co., Ltd.
  • gellan gum product name: Kelcogel, manufactured by DSP Gokyo Food & Chemical Co., Ltd.
  • guar gum product number: RG500, Mitsubishi Chemical Foods) Co., Ltd.
  • tamarind gum product name: Griloid 6C, manufactured by DSP Gokyo Food & Chemical Co.
  • ⁇ Guar Gum, Tamarind Gum> 245 g of ion-exchanged water was weighed into a 1000 ml plastic beaker equipped with a three-one motor (general-purpose stirrer BL1200, Sintokagaku Co., Ltd.), and 5 g of guar gum or tamarind gum was gradually added while stirring at 400 rpm. By continuing stirring for 1 hour without changing the stirring speed, a 2% by mass aqueous solution of guar gum or tamarind gum was obtained. The above steps were carried out in a hot bath (40°C).
  • each polymer aqueous solution that is, each polyacrylic acid-based water-soluble polymer 2% by mass aqueous solution and each polysaccharide 2% by mass aqueous solution
  • ion-exchanged water were stirred in a 200 ml plastic beaker at 500 rpm with a three-one motor (Sintokagaku Co., Ltd. general-purpose stirrer BL1200) for 10 minutes. A mixture of each component was thus prepared.
  • Example 1 the blending ratio of the polyacrylic acid-based water-soluble polymer and the polysaccharide is 1:1, and the total concentration of these polymers is 1% by mass, so 2% by mass of the polymer in Production Example 1 It was prepared by mixing 25 g each of an aqueous solution and a 2% by mass xanthan gum aqueous solution, and 50 g of ion-exchanged water. As a result, the composition of Production Example 1 has a polymer concentration of 0.5% by mass and a xanthan gum concentration of 0.5% by mass, resulting in a blending mass ratio of 1:1 and a total polymer concentration of 1% by mass. satisfies the composition of
  • the numerical value of each component described in Table 2 is the percentage when the obtained composition is 100% by mass, and the actual preparation was performed on a total of 100 g scale. Moreover, the viscosity was measured after defoaming with a centrifuge (for example, 2000 rpm ⁇ 10 minutes). Moreover, sensory evaluation was performed about each viscous composition. These results are also shown in Table 2.
  • the viscosity measurement and sensory test were performed as follows. The same applies to the following.
  • ⁇ Sensory test> The feeling of use of the evaluation samples (each viscous composition) was evaluated by 10 panelists. Specifically, 0.20 g of an evaluation sample was placed on the skin (on the back of the hand) of a panelist, and the tactile sensation when applied by hand was evaluated. Specifically, the evaluation of tactile sensation is as follows: (1) lack of slimy feeling at the time of application (higher points if absent), (2) moist feeling after application (higher point if there is moist feeling), and (3) ) Absence of stickiness after application (no stickiness is scored higher). The results are shown as the average score of 10 panelists.
  • compositions of Examples and Comparative Examples were prepared.
  • Example A ion-exchanged water and a polyacrylic acid-based water-soluble polymer (manufacturing example 1 polymer) were placed in a 200 ml plastic beaker at a three-one motor (Sintokagaku Co., Ltd. general-purpose stirrer BL1200) at 500 rpm. Stirred for 10 minutes. Furthermore, after adding butylene glycol and a natural polysaccharide (tamarind gum), the mixture was stirred at 500 rpm for 10 minutes using the three-one motor. Further, di(phytosteryl/octyldodecyl) lauroylglutamate and phenoxyethanol were added and stirred at 500 rpm for 10 minutes with the same three-one motor.
  • Comparative Example A ion-exchanged water and polyacrylic acid-based water-soluble polymer (manufacturing example 3 polymer) were stirred in a 200 ml plastic beaker at 500 rpm for 10 minutes with a three-one motor (Sintokagaku Co., Ltd. general-purpose stirrer BL1200). bottom. Furthermore, after adding potassium hydroxide, the mixture was stirred for 10 minutes at 500 rpm with the same three-one motor. In addition, after adding butylene glycol and natural polysaccharide (tamarind gum), the mixture was stirred at 500 rpm for 10 minutes using the same three-one motor. Further, di(phytosteryl/octyldodecyl) lauroylglutamate and phenoxyethanol were added and stirred at 500 rpm for 10 minutes with the same three-one motor.
  • each component shown in Table 3 is the percentage when the obtained composition is 100% by mass, and the actual preparation was performed on a scale of 100 g in total. Moreover, the viscosity was measured after defoaming with a centrifuge (for example, 2000 rpm ⁇ 10 minutes). Moreover, sensory evaluation was performed about each viscous composition. These results are also shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Provided is a viscous composition that is not slimy when being used on the skin, and imparts a moisturized feeling and has limited stickiness after use. Specifically, provided is a viscous composition containing a water-soluble polyacrylic acid polymer and a polysaccharide, wherein the water-soluble polyacrylic acid polymer powder has a difference of 9° or more between angles before and after an impact during an angle of spatula measurement.

Description

粘性組成物Viscous composition
　本開示は、粘性組成物等に関し、より詳細には、ポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物に関する。なお、本明細書に記載される全ての文献の内容は参照により本明細書に組み込まれる。 The present disclosure relates to viscous compositions and the like, and more particularly to viscous compositions containing polyacrylic acid-based water-soluble polymers and polysaccharides. It should be noted that the contents of all documents mentioned herein are hereby incorporated by reference.
　ポリアクリル酸系水溶性高分子は増粘剤として広く用いられており、例えば化粧品分野では適当な粘性を化粧品組成物に与えるために利用されている。 Polyacrylic acid-based water-soluble polymers are widely used as thickeners, and are used, for example, in the cosmetics field to give appropriate viscosity to cosmetic compositions.
国際公開第２０１７／０２２７０２号WO2017/022702 国際公開第２０１６／１４３６６３号WO2016/143663 特開第２０００－１４３４３６号公報Japanese Patent Application Laid-Open No. 2000-143436 特開第２００２－１２１１０９号公報Japanese Unexamined Patent Publication No. 2002-121109
　化粧品分野においては、化粧品組成物を皮膚に適用した場合の使用感が重要視される。特に、皮膚に適用する際にはぬるつきがない一方で、適用後にはしっとりとした感触を与えるとともにべたつきが抑制されていることが好ましい。 In the field of cosmetics, importance is attached to the feeling of use when a cosmetic composition is applied to the skin. In particular, it is preferable that the composition does not feel slimy when applied to the skin, yet gives a moist feel and suppresses stickiness after application.
　そこで、本発明者らは、上述の優れた粘性組成物を提供することを主な目的として検討を行った。 Therefore, the present inventors conducted studies with the main objective of providing the above-described excellent viscous composition.
　本発明者らは、特定のポリアクリル酸系水溶性高分子に、さらに多糖類を組み合わせて用いることによって、上記課題を解決できる可能性を見いだし、さらに改良を重ねた。 The present inventors discovered the possibility of solving the above problems by using a specific polyacrylic acid-based water-soluble polymer in combination with a polysaccharide, and made further improvements.
　本開示は例えば以下の項に記載の主題を包含する。
項１．
ポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物であって、
前記ポリアクリル酸系水溶性高分子の粉体が、スパチュラ角測定時の衝撃前後の角度の差が９°以上である、
組成物。
項２．
ポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物であって、
前記ポリアクリル酸系水溶性高分子が、水膨潤時の粒子径が３０μｍ以上である、
組成物。
項３．
ポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物であって、
前記ポリアクリル酸系水溶性高分子が、スパチュラ角測定時の衝撃前後の角度の差が９°以上であり、且つ、水膨潤時の粒子径が３０μｍ以上である、
組成物。
項４．
ポリアクリル酸系水溶性高分子と多糖類との含有質量比が、１：９～９：１である、項１～３のいずれかに記載の組成物。
項５．
ポリアクリル酸系水溶性高分子が、架橋剤により架橋されていてもよい、ポリ（メタ）アクリル酸又はその塩、デンプン・（メタ）アクリル酸グラフト重合体又はその塩、並びに、アクリレーツクロスポリマー又はその塩からなる群より選択される少なくとも１種の高分子である、項１～４のいずれかに記載の組成物。
項６．
多糖類が、キサンタンガム、ジェランガム、タマリンドガム、及びグアーガムからなる群より選択される少なくとも１種である、項１～５のいずれかに記載の組成物。
項７．
ポリアクリル酸系水溶性高分子と多糖類と合計含有量が組成物に対して０．５～２質量％である、項１～６のいずれかに記載の組成物。 The disclosure includes, for example, subject matter described in the following sections.
Section 1.
A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide,
The powder of the polyacrylic acid-based water-soluble polymer has an angle difference of 9° or more before and after impact when measured with a spatula angle.
Composition.
Section 2.
A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide,
The polyacrylic acid-based water-soluble polymer has a particle size of 30 μm or more when swollen with water.
Composition.
Item 3.
A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide,
The polyacrylic acid-based water-soluble polymer has a difference in angle before and after impact when measured with a spatula angle of 9° or more, and a particle size when swollen with water of 30 μm or more.
Composition.
Section 4.
Item 4. The composition according to any one of items 1 to 3, wherein the content ratio by mass of the polyacrylic acid-based water-soluble polymer and the polysaccharide is 1:9 to 9:1.
Item 5.
Poly(meth)acrylic acid-based water-soluble polymer may be crosslinked by a crosslinking agent, poly(meth)acrylic acid or its salt, starch/(meth)acrylic acid graft polymer or its salt, and acrylates crosspolymer Item 5. The composition according to any one of Items 1 to 4, wherein the composition is at least one polymer selected from the group consisting of or salts thereof.
Item 6.
Item 6. The composition according to any one of Items 1 to 5, wherein the polysaccharide is at least one selected from the group consisting of xanthan gum, gellan gum, tamarind gum, and guar gum.
Item 7.
Item 7. The composition according to any one of Items 1 to 6, wherein the total content of the polyacrylic acid-based water-soluble polymer and the polysaccharide is 0.5 to 2% by mass relative to the composition.
　皮膚に適用する際にはぬるつきがない一方で、適用後にはしっとりとした感触を与えるとともにべたつきが抑制されている粘性組成物が提供される。当該組成物は、例えば化粧品組成物や外用組成物として有用である。 Provided is a viscous composition that does not feel slimy when applied to the skin, yet gives a moist feel and suppresses stickiness after application. The composition is useful, for example, as a cosmetic composition or an external composition.
　以下、本開示に包含される各実施形態について、さらに詳細に説明する。本開示は、特定のポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物、並びにその用途等を好ましく包含するが、これらに限定されるわけではなく、本開示は本明細書に開示され当業者が認識できる全てを包含する。 Each embodiment included in the present disclosure will be described in further detail below. The present disclosure preferably includes, but is not limited to, a viscous composition containing a specific polyacrylic acid-based water-soluble polymer and a polysaccharide, and uses thereof. It includes all disclosed and recognizable to one skilled in the art.
　本開示に包含される粘性組成物は、特定のポリアクリル酸系水溶性高分子及び多糖類を含有する。当該粘性組成物を、本開示の粘性組成物ということがある。 The viscous composition included in the present disclosure contains a specific polyacrylic acid-based water-soluble polymer and polysaccharide. The viscous composition may be referred to as the viscous composition of the present disclosure.
　本開示の粘性組成物に用いられるポリアクリル酸系水溶性高分子は、以下の（ｉ）及び（ｉｉ）いずれか若しくは両方を満たすポリアクリル酸系水溶性高分子である。
（ｉ）粉体のスパチュラ角測定時の衝撃前後の角度の差が９°以上
（ｉｉ）水膨潤時の粒子径が３０μｍ以上 The polyacrylic acid-based water-soluble polymer used in the viscous composition of the present disclosure is a polyacrylic acid-based water-soluble polymer that satisfies either or both of the following (i) and (ii).
(i) The angle difference before and after impact when measuring the spatula angle of the powder is 9° or more (ii) The particle diameter when swollen with water is 30 μm or more
　スパチュラ角とは、粉体の流動性の指数として用いられる値であり、Ｃａｒｒの流動性指数の一つである（例えばJ. Jpn. Soc. Colour Mater., 78 〔11〕 (2005)、及びホソカワミクロン株式会社のパウダテスタに関するウェブページ等を参照）。 The spatula angle is a value used as an index of fluidity of powder, and is one of Carr's fluidity indexes (for example, J. Jpn. Soc. Colour Mater., 78 [11] (2005), and (See Hosokawa Micron Corporation's web page for powder testers).
　スパチュラ角は、ホソカワミクロン株式会社製のパウダテスタ（型番：ＰＴ－Ｘ）を用いて測定することができる。 The spatula angle can be measured using a powder tester (model number: PT-X) manufactured by Hosokawa Micron Corporation.
　当該パウダテスタ（型番：ＰＴ－Ｘ）によるスパチュラ角の測定は、より具体的には、次の様に説明できる。まず、測定対象である各ポリアクリル酸系水溶性高分子（粉体）１００ｗｔ％に対して０．７ｗｔ％の二酸化ケイ素（粉体）を添加しよく混合する。なお、二酸化ケイ素（粉体）としては、粒子径が１～２０μｍの二酸化ケイ素を用いる。次にスパチュラ（長さ１２．７ｃｍ×　幅２．２ｃｍの金属のへら）の周りをスパチュラ用枠（長さ９．５ｃｍ×幅４．５ｃｍ×高さ３．０ｃｍ）で囲み、スコップ（長さ８．０ｃｍ×幅４．０ｃｍ×高さ２．０ｃｍ）にて粉体を堆積させる。スパチュラを静かに持ち上げ粉体層から取り出す。このとき、スパチュラの上に堆積した粉体の山の、水平に対する角度を測定して、スパチュラ角を求める。次にスパチュラを軽くたたき（すなわち、衝撃を与え）、同じ要領で角度（スパチュラ角）を求める。この二つの角度（スパチュラ角）の差が大きいと、粉体の流動性が高いと判断できる。 More specifically, the measurement of the spatula angle by the powder tester (model number: PT-X) can be explained as follows. First, 0.7 wt % of silicon dioxide (powder) is added to 100 wt % of each polyacrylic acid-based water-soluble polymer (powder) to be measured and mixed well. As silicon dioxide (powder), silicon dioxide having a particle size of 1 to 20 μm is used. Next, surround the spatula (12.7 cm long x 2.2 cm wide metal spatula) with a spatula frame (9.5 cm long x 4.5 cm wide x 3.0 cm high), 8.0 cm wide by 4.0 cm wide by 2.0 cm high). Gently lift the spatula out of the powder bed. At this time, the angle of the powder pile deposited on the spatula with respect to the horizontal is measured to obtain the spatula angle. The spatula is then tapped (ie, impacted) and the angle (spatula angle) is determined in the same manner. If the difference between these two angles (spatula angle) is large, it can be judged that the fluidity of the powder is high.
　ポリアクリル酸系水溶性高分子の粉体の、スパチュラ角測定時の衝撃前後の角度の差が９°以上であることが好ましい。また、上限は特に限定はされないが、例えば３０°以下が好ましい。当該範囲（９～３０°）の上限又は下限は例えば１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４、２５、２６、２７、２８、又は２９°であってもよい。例えば当該範囲は１０～２５°であってもよい。 It is preferable that the difference in the angle of the polyacrylic acid-based water-soluble polymer powder before and after impact when measuring the spatula angle is 9° or more. Although the upper limit is not particularly limited, it is preferably 30° or less, for example. The upper or lower limit of the range (9 to 30°) is, for example, It may be 28 or 29 degrees. For example, the range may be 10-25°.
　また、水膨潤時の粒子径とは、ポリアクリル酸系水溶性高分子を水により膨潤させたときの粒子径（メジアン径）であり、レーザ回折・散乱法により求められる。当該粒子径の測定は、例えばレーザ回折式粒子径分布測定装置（ＳＡＬＤ　－２３００：株式会社島津製作所製）を用いて行うことができる。 In addition, the particle size when swollen with water is the particle size (median size) when the polyacrylic acid-based water-soluble polymer is swollen with water, and can be obtained by a laser diffraction/scattering method. The particle size can be measured using, for example, a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation).
　当該粒子径は上記の通り３０μｍ以上であることが好ましい。また、上限は特に限定はされないが、例えば３００μｍが挙げられる。当該範囲（３０～３００μｍ）の上限又は下限は例えば３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０、９５、１００、１０５、１１０、１１５、１２０、１２５、１３０、１３５、１４０、１４５、１５０、１５５、１６０、１６５、１７０、１７５、１８０、１８５、１９０、１９５、２００、２０５、２１０、２１５、２２０、２２５、２３０、２３５、２４０、２４５、２５０、２５５、２６０、２６５、２７０、２７５、２８０、２８５、２９０、又は２９５μｍであってもよい。例えば当該粒子径範囲は４５～２５０μｍが好ましく、５０～２２０μｍがより好ましい。 The particle size is preferably 30 μm or more as described above. Also, the upper limit is not particularly limited, but may be 300 μm, for example. The upper or lower limit of the range (30 to 300 μm) is, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125 , 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250 , 255, 260, 265, 270, 275, 280, 285, 290, or 295 μm. For example, the particle size range is preferably 45-250 μm, more preferably 50-220 μm.
　ポリアクリル酸系水溶性高分子としては、具体的には例えばポリ（メタ）アクリル酸又はその塩、デンプン・（メタ）アクリル酸グラフト重合体又はその塩、アクリレーツクロスポリマー又はその塩、等が挙げられる。また、ここでの塩としては、アルカリ金属塩が好ましく、ナトリウム塩又はカリウム塩がより好ましい。ポリアクリル酸系水溶性高分子としては、中でも、ポリアクリル酸又はそのナトリウム塩、デンプン・アクリル酸グラフト重合体又はそのナトリウム塩、アクリレーツクロスポリマー又はそのナトリウム塩、が好ましい。ポリアクリル酸系水溶性高分子は、１種単独で又は２種以上を組み合わせて用いることができる。 Specific examples of polyacrylic acid-based water-soluble polymers include poly(meth)acrylic acid or salts thereof, starch/(meth)acrylic acid graft polymers or salts thereof, acrylates crosspolymers or salts thereof, and the like. mentioned. Moreover, as a salt here, an alkali metal salt is preferable, and a sodium salt or a potassium salt is more preferable. As the polyacrylic acid-based water-soluble polymer, among others, polyacrylic acid or its sodium salt, starch/acrylic acid graft polymer or its sodium salt, acrylates crosspolymer or its sodium salt are preferable. The polyacrylic acid-based water-soluble polymer can be used singly or in combination of two or more.
　なお、ポリアクリル酸系水溶性高分子は、架橋剤により架橋されていてもよい。このような架橋剤としては、例えば水溶性ショ糖アリルエーテル（特にトリ若しくはテトラアリルエーテル）、ペンタエリスリトールテトラアリルエーテル、Ｎ，Ｎ’－メチレンビスアクリルアミド、エチレングリコールジメタクリレート、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジメタクリレート、ポリエチレングリコールジグリシジルエーテル等が挙げられる。架橋剤は、１種単独で又は２種以上を組み合わせて用いることができる。 The polyacrylic acid-based water-soluble polymer may be crosslinked with a crosslinking agent. Examples of such cross-linking agents include water-soluble sucrose allyl ether (especially tri- or tetra-allyl ether), pentaerythritol tetraallyl ether, N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, ethylene glycol diglycidyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, and the like. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
　多糖類としては、増粘剤として用いられる多糖類（増粘多糖類）が好ましい。また、天然由来の多糖類が好ましく、天然ガムがより好ましい。より具体的には、例えば、キサンタンガム、ジェランガム、タマリンドガム、グアーガム等が挙げられる。多糖類は１種単独で又は２種以上を組み合わせて用いることができる。 Polysaccharides used as thickeners (thickening polysaccharides) are preferred as polysaccharides. In addition, naturally-derived polysaccharides are preferred, and natural gums are more preferred. More specific examples include xanthan gum, gellan gum, tamarind gum, guar gum and the like. Polysaccharides can be used individually by 1 type or in combination of 2 or more types.
　本開示の粘性組成物における、ポリアクリル酸系水溶性高分子と多糖類との含有質量比（ポリアクリル酸系水溶性高分子：多糖類）は、１：９～９：１であることが好ましく、１：５～５：１又は１：４～４：１であることがより好ましく、１：２～２：１であることがさらに好ましい。 In the viscous composition of the present disclosure, the content mass ratio of the polyacrylic acid-based water-soluble polymer and the polysaccharide (polyacrylic acid-based water-soluble polymer:polysaccharide) is 1:9 to 9:1. It is preferably 1:5 to 5:1 or more preferably 1:4 to 4:1, even more preferably 1:2 to 2:1.
　また、特に限定される訳ではないが、多糖類としてキサンタンガムを用いる場合、ポリアクリル酸系水溶性高分子とキサンタンガムとの含有質量比は、１：０．１～５であることが好ましく、１：０．５～２であることがより好ましい。 Although not particularly limited, when xanthan gum is used as the polysaccharide, the content ratio by mass of the polyacrylic acid-based water-soluble polymer and xanthan gum is preferably 1:0.1 to 5. : more preferably 0.5 to 2.
　また、本開示の粘性組成物においては、ポリアクリル酸系水溶性高分子及び多糖類の合計含有量が、０．５～２質量％となることが好ましい。当該範囲の上限又は下限は０．６、０．７、０．８、０．９、１、１．１、１．２、１．３、１．４、１．５、１．６、１．７、１．８、１．９質量％であってもよい。当該範囲は例えば０．６～１．８質量％であってもよい。 Further, in the viscous composition of the present disclosure, the total content of the polyacrylic acid-based water-soluble polymer and polysaccharide is preferably 0.5 to 2% by mass. The upper or lower limit of the range is 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1 .7, 1.8, 1.9% by mass. The range may be, for example, 0.6-1.8% by weight.
　本開示の粘性組成物の粘度は、１０００～６００００ｍＰａ・ｓ程度であることが好ましい。当該範囲の上限又は下限は例えば１５００、２０００、３０００、４０００、５０００、６０００、７０００、８０００、９０００、１００００、１１０００、１２０００、１３０００、１４０００、１５０００、１６０００、１７０００、１８０００、１９０００、２００００、２１０００、２２０００、２３０００、２４０００、２５０００、２６０００、２７０００、２８０００、２９０００、３００００、３１０００、３２０００、３３０００、３４０００、３５０００、３６０００、３７０００、３８０００、３９０００、４００００、４１０００、４２０００、４３０００、４４０００、４５０００、４６０００、４７０００、４８０００、４９０００、５００００、５１０００、５２０００、５３０００、５４０００、５５０００、５６０００、５７０００、５８０００、又は５９０００ｍＰａ・ｓであってもよい。例えば当該範囲は１５００～５９０００ｍＰａ・ｓであってもよい。 The viscosity of the viscous composition of the present disclosure is preferably about 1000-60000 mPa·s. The upper or lower limit of the range is, for example, 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, ２２０００、２３０００、２４０００、２５０００、２６０００、２７０００、２８０００、２９０００、３００００、３１０００、３２０００、３３０００、３４０００、３５０００、３６０００、３７０００、３８０００、３９０００、４００００、４１０００、４２０００、４３０００、４４０００、４５０００、４６０００、 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, or 59000 mPa·s. For example, the range may be 1500-59000 mPa·s.
　なお、本明細書において、粘度は、評価サンプルを２５℃に調整した恒温水槽に６０分以上浸した後に、ＢｒｏｏｋＦｉｅｌｄ社製の粘度計（型番：ＤＶ１ＭＲＶＴＪ０、スピンドル：ＲＶ）を用い、回転速度を毎分２０回転としてローターの回転を開始してから１分後の粘度を測定した値である。なお、測定に使用するローターは、２，０００ｍＰａ・ｓ未満の場合はローターＮｏ．３、２，０００ｍＰａ・ｓ以上５，０００ｍＰａ・ｓ未満の場合はローターＮｏ．４、５，０００ｍＰａ・ｓ以上１５，０００ｍＰａ・ｓ未満の場合はローターＮｏ．５、１５，０００ｍＰａ・ｓ以上４０，０００ｍＰａ・ｓ未満の場合はローターＮｏ．６、４０，０００ｍＰａ・ｓ以上の場合はローターＮｏ．７である。また、当該粘度測定の前に、各粘性組成物を遠心することで（例えば、２，０００ｒｐｍ×１０分）、脱泡してから測定に用いる。 In this specification, the viscosity is measured by immersing the evaluation sample in a constant temperature water bath adjusted to 25 ° C. for 60 minutes or more, using a viscometer manufactured by BrookField (model number: DV1MRVTJ0, spindle: RV), and rotating the speed every time. It is a value obtained by measuring the viscosity one minute after starting the rotation of the rotor at 20 rotations per minute. The rotor used for the measurement is rotor No. when the pressure is less than 2,000 mPa·s. 3. Rotor No. in the case of 2,000 mPa·s or more and less than 5,000 mPa·s. 4, 5,000 mPa·s or more and less than 15,000 mPa·s, rotor No. 5, 15,000 mPa·s or more and less than 40,000 mPa·s, rotor No. Rotor No. 6, 40,000 mPa·s or more. 7. In addition, before the viscosity measurement, each viscous composition is centrifuged (for example, 2,000 rpm×10 minutes) to remove air bubbles before use for the measurement.
　本開示の粘性組成物には、ポリアクリル酸系水溶性高分子及び多糖類の他に溶媒が含まれる。溶媒としては、水が好ましい。また、本開示の粘性組成物の効果を妨げない範囲で、その他の成分が含まれてもよい。このような成分としては、例えば外用剤組成物や化粧品組成物に含有される公知の成分が挙げられる。例えば、殺菌剤；乳酸、クエン酸などの有機酸；水酸化カリウム、水酸化ナトリウム等のアルカリ性化合物；ホスファチジルグリセロール、ホスファチジルエタノールアミン等の脂質；トレハロース、ラクチュロース、マルチトール等の糖質；グリセリン、ブチレングリコールなどの多価アルコール等が挙げられるが、これらに限定されるものではない。 The viscous composition of the present disclosure contains a solvent in addition to the polyacrylic acid-based water-soluble polymer and polysaccharide. Water is preferred as the solvent. In addition, other components may be included as long as the effects of the viscous composition of the present disclosure are not impaired. Examples of such components include known components contained in external preparation compositions and cosmetic compositions. organic acids such as lactic acid and citric acid; alkaline compounds such as potassium hydroxide and sodium hydroxide; lipids such as phosphatidylglycerol and phosphatidylethanolamine; carbohydrates such as trehalose, lactulose and maltitol; Examples include, but are not limited to, polyhydric alcohols such as glycol.
　本開示の粘性組成物の調製方法もとくには限定されない。例えば、ポリアクリル酸系水溶性高分子、多糖類、及び水、並びに必要に応じてその他の成分を適宜混合することで調製することができる。ポリアクリル酸系水溶性高分子及び多糖類については、増粘効果があることから、好ましくは、それぞれ適当な濃度（例えば１～２質量％）の水溶液を調製したうえで、当該水溶液をさらに水や必要に応じてその他の成分と混合することで本開示の粘性組成物を調製することができる。 The method for preparing the viscous composition of the present disclosure is also not particularly limited. For example, it can be prepared by appropriately mixing a polyacrylic acid-based water-soluble polymer, a polysaccharide, water, and, if necessary, other components. Since polyacrylic acid-based water-soluble polymers and polysaccharides have a thickening effect, it is preferable to prepare an aqueous solution having an appropriate concentration (for example, 1 to 2% by mass), and then add water to the aqueous solution. and optionally other ingredients to prepare the viscous composition of the present disclosure.
　なお、本明細書において「含む」とは、「本質的にからなる」と、「からなる」をも包含する（The term "comprising" includes "consisting essentially of” and "consisting of."）。また、本開示は、本明細書に説明した構成要件の任意の組み合わせを全て包含する。 In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Also, the present disclosure encompasses any and all combinations of the constituent elements described herein.
　また、上述した本開示の各実施形態について説明した各種特性（性質、構造、機能等）は、本開示に包含される主題を特定するにあたり、どのように組み合わせられてもよい。すなわち、本開示には、本明細書に記載される組み合わせ可能な各特性のあらゆる組み合わせからなる主題が全て包含される。 In addition, the various characteristics (property, structure, function, etc.) described for each embodiment of the present disclosure described above may be combined in any way to specify the subject matter included in the present disclosure. That is, the present disclosure encompasses all subject matter consisting of any and all possible combinations of the features described herein.
　以下、例を示して本開示の実施形態をより具体的に説明するが、本開示の実施形態は下記の例に限定されるものではない。 Hereinafter, the embodiments of the present disclosure will be described more specifically with examples, but the embodiments of the present disclosure are not limited to the following examples.
ポリアクリル酸系水溶性高分子の調製
［製造例１］
＜水溶性ショ糖アリルエーテルの合成＞
　１０００ｍＬ容のセパラブルフラスコに撹拌機、還流冷却管及び滴下ロートを取り付けた。この中で、水１４４ｇに水酸化ナトリウム４８ｇ（１．２モル）を溶解した。次いで、ショ糖１３６．８ｇ（０．４モル）を加え、７０～８５℃で１２０分間撹拌して、アルカリショ糖水溶液を得た。得られたアルカリショ糖水溶液に、臭化アリル１４５．２ｇ（１．２モル）を７０～８５℃で１．５時間かけて滴下し、その後、８０℃で３時間反応して、ショ糖をアリルエーテル化した。冷却後、水４４０ｇを添加し、分液ロートで余分な油分を分離して、粗ショ糖アリルエーテル水溶液を得た。得られた粗ショ糖アリルエーテルに塩酸を加えてｐＨを６～８に調整した後、ロータリーエバポレーターを用いて、水溶液の質量が４８０ｇになるまで水分を除去した。次いで、エタノール２００ｇを添加して副生成物の臭化ナトリウム等の塩類を析出させ、析出物を濾別により水溶液から除去した。さらに、エバポレーターを用いて水溶液から余分な水分を除去し、エーテル化度２．４の水溶性ショ糖アリルエーテル１６６ｇを得た。 Preparation of polyacrylic acid-based water-soluble polymer [Production Example 1]
<Synthesis of water-soluble sucrose allyl ether>
A 1000 mL separable flask was equipped with a stirrer, a reflux condenser and a dropping funnel. In this, 48 g (1.2 mol) of sodium hydroxide was dissolved in 144 g of water. Then, 136.8 g (0.4 mol) of sucrose was added and stirred at 70 to 85° C. for 120 minutes to obtain an alkaline sucrose aqueous solution. To the resulting alkaline sucrose aqueous solution, 145.2 g (1.2 mol) of allyl bromide was added dropwise at 70 to 85 ° C. over 1.5 hours, and then reacted at 80 ° C. for 3 hours to remove sucrose. Allyl etherified. After cooling, 440 g of water was added, excess oil was separated with a separating funnel, and a crude sucrose allyl ether aqueous solution was obtained. Hydrochloric acid was added to the resulting crude sucrose allyl ether to adjust the pH to 6 to 8, and water was removed using a rotary evaporator until the mass of the aqueous solution reached 480 g. Next, 200 g of ethanol was added to precipitate salts such as sodium bromide as a by-product, and the precipitate was removed from the aqueous solution by filtration. Further, excess water was removed from the aqueous solution using an evaporator to obtain 166 g of water-soluble sucrose allyl ether having a degree of etherification of 2.4.
＜ポリアクリル酸系水溶性高分子の合成＞
　５００ｍＬ容のセパラブルフラスコに撹拌機、還流冷却管及び滴下ロートを取り付けた。このセパラブルフラスコの中にアクリル酸７２ｇ及び水を入れ、８０質量％のアクリル酸水溶液９０ｇを調製した。アクリル酸水溶液を冷却しながら、３０質量％の水酸化ナトリウム水溶液５４ｇを滴下して、中和度４０％のアクリル酸中和水溶液を調製した。次いで、上で得た水溶性ショ糖アリルエーテル０．３２ｇ（アクリル酸水溶液に対して０．３５質量％）と、開始剤としての２，２’－アゾビス（２－メチルプロピオンアミジン）２塩酸塩（和光純薬工業株式会社製「Ｖ－５０」）０．０４ｇとを加えて、アクリル酸含有原料液を調製した。 <Synthesis of polyacrylic acid-based water-soluble polymer>
A 500 mL separable flask was equipped with a stirrer, a reflux condenser and a dropping funnel. 72 g of acrylic acid and water were put into this separable flask to prepare 90 g of an 80% by mass acrylic acid aqueous solution. While cooling the acrylic acid aqueous solution, 54 g of a 30% by mass sodium hydroxide aqueous solution was added dropwise to prepare an acrylic acid neutralized aqueous solution having a degree of neutralization of 40%. Then, 0.32 g of the water-soluble sucrose allyl ether obtained above (0.35% by mass with respect to the acrylic acid aqueous solution) and 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator ("V-50" manufactured by Wako Pure Chemical Industries, Ltd.) was added to prepare an acrylic acid-containing raw material solution.
　これとは別に、撹拌機、還流冷却管、滴下ロート及び窒素ガス導入管を取り付けた２０００ｍＬ容のセパラブルフラスコにｎ－ヘプタン３３０ｇを入れ、さらに界面活性剤であるソルビタンモノステアレート（日油株式会社製「ノニオンＳＰ－６０Ｒ」）２．７ｇを加え、これをｎ－ヘプタンに分散及び溶解させた。次いで、先に調製したアクリル酸含有原料液を加えた。反応容器内の雰囲気、原料および溶媒中に存在している酸素を除去するために溶液中に窒素ガスを吹き込んで系内を窒素置換しながら、浴温を６０℃に保持して、撹拌回転数を１０００ｒｐｍで撹拌して、１時間反応を行った。反応終了後、水およびｎ－ヘプタンを留去して、アクリル酸及びそのナトリウム塩の重合体を得た。以下、当該重合体を製造例１ポリマーと表記することがある。 Separately, 330 g of n-heptane was placed in a 2000 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and a surfactant sorbitan monostearate (NOF stock) was added. 2.7 g of "Nonion SP-60R" manufactured by the company was added, and this was dispersed and dissolved in n-heptane. Then, the acrylic acid-containing raw material liquid prepared previously was added. In order to remove oxygen present in the atmosphere, raw materials and solvent in the reaction vessel, nitrogen gas is blown into the solution to replace the inside of the system with nitrogen, while the bath temperature is maintained at 60 ° C. and the stirring speed is was stirred at 1000 rpm and reacted for 1 hour. After completion of the reaction, water and n-heptane were distilled off to obtain a polymer of acrylic acid and its sodium salt. Hereinafter, the polymer may be referred to as Production Example 1 polymer.
［製造例２］
＜水溶性ショ糖アリルエーテルの合成＞
　製造例１に記載の方法に従って水溶性ショ糖アリルエーテルを調製した。 [Production Example 2]
<Synthesis of water-soluble sucrose allyl ether>
A water-soluble sucrose allyl ether was prepared according to the method described in Production Example 1.
＜ポリアクリル酸系水溶性高分子の合成＞
　５００ｍＬ容のセパラブルフラスコに撹拌機、還流冷却管及び滴下ロートを取り付けた。このセパラブルフラスコの中にアクリル酸７２ｇ及び水を入れ、８０質量％のアクリル酸水溶液９０ｇを調製した。アクリル酸水溶液を冷却しながら、３０質量％の水酸化ナトリウム水溶液２７ｇを滴下して、中和度２０％のアクリル酸中和水溶液を調製した。次いで、上で得た水溶性ショ糖アリルエーテル０．３２ｇ（アクリル酸水溶液に対して０．３５質量％）と、開始剤としての２，２’－アゾビス（２－メチルプロピオンアミジン）２塩酸塩（和光純薬工業株式会社製「Ｖ－５０」）０．０３６ｇとを加えて、アクリル酸含有原料液を調製した。 <Synthesis of polyacrylic acid-based water-soluble polymer>
A 500 mL separable flask was equipped with a stirrer, a reflux condenser and a dropping funnel. 72 g of acrylic acid and water were put into this separable flask to prepare 90 g of an 80% by mass acrylic acid aqueous solution. While cooling the acrylic acid aqueous solution, 27 g of a 30% by mass sodium hydroxide aqueous solution was added dropwise to prepare an acrylic acid neutralized aqueous solution having a degree of neutralization of 20%. Then, 0.32 g of the water-soluble sucrose allyl ether obtained above (0.35% by mass with respect to the acrylic acid aqueous solution) and 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator ("V-50" manufactured by Wako Pure Chemical Industries, Ltd.) was added to prepare an acrylic acid-containing raw material solution.
　これとは別に、撹拌機、還流冷却管、滴下ロート及び窒素ガス導入管を取り付けた２０００ｍＬ容のセパラブルフラスコにｎ－ヘプタン３３０ｇを入れ、さらに界面活性剤であるソルビタンモノステアレート（日油株式会社製「ノニオンＳＰ－６０Ｒ」）２．７ｇを加え、これをｎ－ヘプタンに分散及び溶解させた。次いで、先に調製したアクリル酸含有原料液を加えた。反応容器内の雰囲気、原料および溶媒中に存在している酸素を除去するために溶液中に窒素ガスを吹き込んで系内を窒素置換しながら、浴温を６０℃に保持して、撹拌回転数を１０００ｒｐｍで撹拌して、１時間反応を行った。反応終了後、水およびｎ－ヘプタンを留去して、アクリル酸及びそのナトリウム塩の重合体を得た。以下、当該重合体を製造例２ポリマーと表記することがある。 Separately, 330 g of n-heptane was placed in a 2000 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and a surfactant sorbitan monostearate (NOF stock) was added. 2.7 g of "Nonion SP-60R" manufactured by the company was added, and this was dispersed and dissolved in n-heptane. Then, the acrylic acid-containing raw material liquid prepared previously was added. In order to remove oxygen present in the atmosphere, raw materials and solvent in the reaction vessel, nitrogen gas is blown into the solution to replace the inside of the system with nitrogen, while the bath temperature is maintained at 60 ° C. and the stirring speed is was stirred at 1000 rpm and reacted for 1 hour. After completion of the reaction, water and n-heptane were distilled off to obtain a polymer of acrylic acid and its sodium salt. Hereinafter, the polymer may be referred to as Production Example 2 polymer.
［製造例３］
　３００ｍＬ容のセパラブルフラスコに撹拌機、還流冷却管及び滴下ロートを取り付けた。このセパラブルフラスコの中にアクリル酸及び水を入れ、８０．５質量％のアクリル酸水溶液９２ｇを調製した。アクリル酸水溶液を冷却しながら、２０．９質量％ｔ－ブチルメトキシジベンゾイルメタンの水酸化ナトリウム水溶液１４７．７ｇを滴下して、水溶液を中和した。さらに、開始剤としての過硫酸カリウム０．０７４ｇ（０．２７４ミリモル）とを加えて、アクリル酸含有原料液を調製した。 [Production Example 3]
A 300 mL separable flask was equipped with a stirrer, a reflux condenser and a dropping funnel. Acrylic acid and water were placed in this separable flask to prepare 92 g of an 80.5% by mass acrylic acid aqueous solution. While cooling the aqueous acrylic acid solution, 147.7 g of an aqueous sodium hydroxide solution containing 20.9% by mass of t-butylmethoxydibenzoylmethane was added dropwise to neutralize the aqueous solution. Further, 0.074 g (0.274 mmol) of potassium persulfate was added as an initiator to prepare an acrylic acid-containing stock solution.
　これとは別に、撹拌機、還流冷却管、滴下ロート及び窒素ガス導入管を取り付けた２０００ｍＬ容のセパラブルフラスコにｎ－ヘプタン３５６ｇを入れ、さらに高分子系分散剤として無水マレイン酸変性エチレン・プロピレン共重合体（三井化学株式会社製、ハイワックス１１０５Ａ）０．７３６ｇを加え、これをｎ－ヘプタンに分散及び溶解させた。そこに、先に調製したアクリル酸含有原料液を加えた。その後、ｎ－ヘプタン６．６２ｇにショ糖ステアリン酸エステル（界面活性剤、三菱化学フーズ株式会社製、リョートーシュガーエステルＳ－３７０、ＨＬＢ値：３）０．７３６ｇを加熱溶解することにより得られた界面活性剤溶液をセパラブルフラスコに添加した。そして、反応容器内の雰囲気、原料および溶媒中に存在している酸素を除去するために溶液中に窒素ガスを吹き込んで系内を窒素置換しながら、浴温を７０℃に保持して、１時間かけて重合を行った。 Separately, 356 g of n-heptane was placed in a 2000 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and maleic anhydride-modified ethylene/propylene was added as a polymeric dispersant. 0.736 g of a copolymer (Hi-Wax 1105A, manufactured by Mitsui Chemicals, Inc.) was added and dispersed and dissolved in n-heptane. The acrylic acid-containing raw material liquid prepared previously was added thereto. After that, 0.736 g of sucrose stearate (surfactant, manufactured by Mitsubishi Kagaku Foods Co., Ltd., Ryoto Sugar Ester S-370, HLB value: 3) is dissolved in 6.62 g of n-heptane by heating. The surfactant solution was added to the separable flask. Then, nitrogen gas is blown into the solution to remove oxygen present in the atmosphere, raw materials, and solvent in the reaction vessel, and the bath temperature is maintained at 70 ° C. while replacing the system with nitrogen. Polymerization was carried out over time.
　その後、１２５℃の油浴で反応液を昇温し、ｎ－ヘプタンを還流しながら１２０ｇの水を系外へ抜き出した。そして、フラスコに架橋剤として２質量％のエチレングリコールジグリシジルエーテル水溶液７．２７ｇ（エチレングリコールジグリシジルエーテル：０．８３５ミリモル）を添加した後、８３℃で２時間保持し、９０．３ｇのアクリル酸及びそのナトリウム塩の重合体を得た。以下、当該アクリル酸及びそのナトリウム塩の重合体を製造例３ポリマーと表記することがある。 After that, the temperature of the reaction solution was raised in an oil bath of 125°C, and 120 g of water was extracted from the system while refluxing n-heptane. Then, after adding 7.27 g of a 2 mass% ethylene glycol diglycidyl ether aqueous solution (ethylene glycol diglycidyl ether: 0.835 mmol) as a cross-linking agent to the flask, it was held at 83 ° C. for 2 hours, and 90.3 g of acrylic A polymer of the acid and its sodium salt was obtained. Hereinafter, the polymer of acrylic acid and its sodium salt may be referred to as Production Example 3 polymer.
［製造例４］
　撹拌機、温度計、窒素吹き込み管及び冷却管を備えた５００ｍＬのセパラブルフラスコに、アクリル酸４０ｇ、ペンタエリスリトールテトラアリルエーテル０．２２ｇ、２，２’－アゾビス（イソ酪酸メチル）０．１１６ｇ、及びノルマルヘキサン２３０．９ｇを仕込んだ。溶液を撹拌して均一に混合した後、反応容器（セパラブルフラスコ）の上部空間、原料及び反応溶媒中に存在している酸素を除去するために、溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、６０～６５℃まで加熱した。その後、３時間６０～６５℃に保持した。６０～６５℃で１時間程度、保持した時点で、ノルマルヘキサン２．０ｇに１２－ヒドロキシステアリン酸とポリオキシエチレンのブロック共重合体（クローダ製、Ｈｙｐｅｒｍｅｒ　Ｂ２４６）２．０ｇを溶解させたものを、反応容器に投入した。その後、生成したスラリーを１００℃に加熱して、ノルマルヘキサンを留去し、さらに１１５℃、１０ｍｍＨｇの条件で、８時間減圧乾燥することにより、白色微粉末のカルボキシビニルポリマー３８ｇを得た。以下当該カルボキシビニルポリマーを製造例４ポリマーと表記することがある。 [Production Example 4]
40 g of acrylic acid, 0.22 g of pentaerythritol tetraallyl ether, 0.116 g of 2,2'-azobis(methyl isobutyrate), and 230.9 g of normal hexane were charged. After the solution was stirred and uniformly mixed, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel (separable flask), raw materials and reaction solvent. Then, it was heated to 60-65° C. under a nitrogen atmosphere. After that, it was kept at 60-65° C. for 3 hours. After holding at 60 to 65° C. for about 1 hour, 2.0 g of a block copolymer of 12-hydroxystearic acid and polyoxyethylene (Hypermer B246, manufactured by Croda) was dissolved in 2.0 g of normal hexane. , was charged into the reaction vessel. Thereafter, the resulting slurry was heated to 100° C. to distill off n-hexane, and dried under reduced pressure at 115° C. and 10 mmHg for 8 hours to obtain 38 g of white fine powder of carboxyvinyl polymer. Hereinafter, the carboxyvinyl polymer may be referred to as Production Example 4 polymer.
ポリアクリル酸系水溶性高分子の特性
　各ポリアクリル酸系水溶性高分子（粉体）の特性を以下の様にして検討した。結果を表１に示す。 Properties of Polyacrylic Acid-Based Water-Soluble Polymer The properties of each polyacrylic acid-based water-soluble polymer (powder) were examined as follows. Table 1 shows the results.
＜ゲル粒子径＞
　各ポリアクリル酸系水溶性高分子を水と混合し、水で膨潤した各ポリアクリル酸系水溶性高分子の粒子径（ゲル粒子径）を、株式会社島津製作所製のレーザ回折式粒子径分布測定装置（型番：ＳＡＬＤ　－２３００　フローセル使用）を用いて測定した。より具体的には、１００ｍｌ容のプラスチックビーカーに純水５０ｇを入れ、さらに各ポリアクリル酸系水溶性高分子をゲル粒子が十分に分散し測定が可能な濃度（例えば、増粘しだす濃度）に調製した水溶液５ｇ加えて、薬さじを使用して手攪拌で混ぜ合わせた。その後、アズワン株式会社製の超音波洗浄機（型番：Ｖｓ－１００）を用い、５分間超音波照射してから、前記レーザ回折式粒子径分布測定装置にて、ゲル粒子径（メジアン径）を測定した。 <Gel particle size>
Each polyacrylic acid-based water-soluble polymer is mixed with water, and the particle size (gel particle size) of each polyacrylic acid-based water-soluble polymer swollen with water is measured using a laser diffraction particle size distribution method manufactured by Shimadzu Corporation. Measurement was performed using a measurement device (model number: SALD-2300 using flow cell). More specifically, 50 g of pure water is placed in a 100 ml plastic beaker, and each polyacrylic acid-based water-soluble polymer is added to a concentration at which the gel particles are sufficiently dispersed and can be measured (for example, a concentration at which the viscosity starts to increase). 5 g of the prepared aqueous solution was added and mixed by hand stirring using a spatula. After that, using an ultrasonic cleaner (model number: Vs-100) manufactured by AS ONE Corporation, ultrasonic irradiation is performed for 5 minutes, and the gel particle diameter (median diameter) is measured by the laser diffraction particle size distribution measuring device. It was measured.
＜スパチュラ角＞
サンプル調製
　各ポリアクリル酸系水溶性高分子（粉体）１００ｗｔ％に対して、０．７ｗｔ％の二酸化ケイ素（粉体）を添加した。二酸化ケイ素は粒子径が１～２０μｍのものを用いた。 <Spatula angle>
Sample Preparation 0.7 wt % of silicon dioxide (powder) was added to 100 wt % of each polyacrylic acid-based water-soluble polymer (powder). Silicon dioxide having a particle size of 1 to 20 μm was used.
スパチュラ角測定
　ホソカワミクロン株式会社製のパウダテスタ（型番：ＰＴ－Ｘ）を用い、測定メニューの「スパチュラ角」を選択して、各ポリアクリル酸系水溶性高分子（粉体）のスパチュラ角を測定した。具体的には、次の様にして測定した。水平にした装置付属の金属板（スパチュラ）を装置付属のスパチュラ用の枠で囲み、装置付属のスコップを使用して、粉体を高さ３～５ｃｍになるように軽く乗せ、枠を外した。そのあと、金属板が規定の位置まで上昇した際の斜面と水平面がなす角度（１）を測定した。更に、装置により一定の衝撃を１回加えて、堆積した粉体を落とし、再度、斜面と水平面がなす角度（２）を測定した。 Spatula angle measurement Using a powder tester (model number: PT-X) manufactured by Hosokawa Micron Co., Ltd., the spatula angle of each polyacrylic acid-based water-soluble polymer (powder) was measured by selecting "spatula angle" from the measurement menu. . Specifically, it was measured as follows. A horizontal metal plate (spatula) attached to the device was surrounded by a frame for the spatula attached to the device, and using a scoop attached to the device, the powder was lightly placed so that the height was 3 to 5 cm, and the frame was removed. . After that, the angle (1) formed by the slope and the horizontal plane was measured when the metal plate was raised to a specified position. Furthermore, a fixed impact was applied once by the device to drop the deposited powder, and the angle (2) formed by the slope and the horizontal plane was measured again.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
多糖類
　各種市販天然系多糖類（いずれも粉体）を購入して用いた。具体的には、キサンタンガム（製品名：エコーガム、ＤＳＰ五協フード＆ケミカル株式会社製）、ジェランガム（製品名：ケルコゲル、ＤＳＰ五協フード＆ケミカル株式会社製）、グアーガム（品番：ＲＧ５００、三菱ケミカルフーズ株式会社製）、及びタマリンドガム（製品名：グリロイド６Ｃ、ＤＳＰ五協フード＆ケミカル株式会社製）を購入して用いた。 Polysaccharide Various commercially available natural polysaccharides (all powders) were purchased and used. Specifically, xanthan gum (product name: echo gum, manufactured by DSP Gokyo Food & Chemical Co., Ltd.), gellan gum (product name: Kelcogel, manufactured by DSP Gokyo Food & Chemical Co., Ltd.), guar gum (product number: RG500, Mitsubishi Chemical Foods) Co., Ltd.) and tamarind gum (product name: Griloid 6C, manufactured by DSP Gokyo Food & Chemical Co., Ltd.) were purchased and used.
ポリアクリル酸系水溶性高分子水溶液（濃度：２質量％）の調製
＜製造例１及び２ポリマー＞
　スリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）を備えた５００ｍｌ容のプラスチックビーカーにイオン交換水２４５ｇを量り取り、３００ｒｐｍで攪拌しながら各ポリマー５ｇを徐々に添加した。添加後は攪拌速度を５００ｒｐｍに変更し、１時間攪拌を継続することにより、各ポリマー２質量％水溶液を得た。 Preparation of polyacrylic acid-based water-soluble polymer aqueous solution (concentration: 2% by mass) <Production Examples 1 and 2 polymer>
245 g of ion-exchanged water was weighed into a 500 ml plastic beaker equipped with a three-one motor (general-purpose stirrer BL1200, manufactured by Sintokagaku Co., Ltd.), and 5 g of each polymer was gradually added while stirring at 300 rpm. After the addition, the stirring speed was changed to 500 rpm, and stirring was continued for 1 hour to obtain a 2% by mass aqueous solution of each polymer.
＜製造例３ポリマー＞
　スリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）を備えた５００ｍｌ容のプラスチックビーカーにイオン交換水２１２．６ｇを量り取り、製造例３ポリマー５ｇを添加し、５分放置した。攪拌速度を４００ｒｐｍで１５分攪拌した後、６％ＮａＯＨ水溶液３２．４ｇを添加した。攪拌速度を２００ｒｐｍに変更し、１５分攪拌を継続することにより、製造例３ポリマー２質量％水溶液を得た。 <Production Example 3 Polymer>
212.6 g of deionized water was weighed into a 500 ml plastic beaker equipped with a three-one motor (general-purpose stirrer BL1200, manufactured by Sintokagaku Co., Ltd.), 5 g of the polymer of Production Example 3 was added, and the mixture was allowed to stand for 5 minutes. After stirring for 15 minutes at a stirring speed of 400 rpm, 32.4 g of 6% NaOH aqueous solution was added. By changing the stirring speed to 200 rpm and continuing stirring for 15 minutes, a 2% by mass polymer aqueous solution of Production Example 3 was obtained.
多糖類水溶液（濃度：２質量％）の調製
＜キサンタンガム＞
　スリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）を備えた１０００ｍｌ容のプラスチックビーカーにイオン交換水２４５ｇを量り取り、４００ｒｐｍで攪拌しながらキサンタンガム５ｇを徐々に添加した。攪拌速度は変更せず、３０分攪拌を継続することにより、キサンタンガム２質量％水溶液を得た。なお、上記の工程は温浴（４０℃）下にて実施した。 Preparation of polysaccharide aqueous solution (concentration: 2% by mass) <xanthan gum>
245 g of ion-exchanged water was weighed into a 1000 ml plastic beaker equipped with a three-one motor (general-purpose stirrer BL1200, Sintokagaku Co., Ltd.), and 5 g of xanthan gum was gradually added while stirring at 400 rpm. By continuing stirring for 30 minutes without changing the stirring speed, a 2% by mass xanthan gum aqueous solution was obtained. The above steps were carried out in a hot bath (40°C).
＜ジェランガム＞
　スリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）を備えた１０００ｍｌ容のプラスチックビーカーにイオン交換水２４５ｇを量り取り、４００ｒｐｍで攪拌しながらポリマー５ｇを徐々に添加した。攪拌速度は変更せず、３０分攪拌した。なお、上記の工程は温浴（８０℃）下にて実施した。さらに、温浴から取り出して同スリーワンモーター２００ｒｐｍにて攪拌しながら、水溶液が常温になるまで２～３時間攪拌を継続することにより、ジェランガム２質量％水溶液を得た。 <Gellan gum>
245 g of ion-exchanged water was weighed into a 1000 ml plastic beaker equipped with a three-one motor (general-purpose stirrer BL1200, manufactured by Sintokagaku Co., Ltd.), and 5 g of polymer was gradually added while stirring at 400 rpm. Stirring was continued for 30 minutes without changing the stirring speed. The above steps were carried out in a hot bath (80°C). Further, the mixture was removed from the hot bath and stirred at 200 rpm for the same three-one motor, and the stirring was continued for 2 to 3 hours until the aqueous solution reached normal temperature, thereby obtaining a 2% by mass gellan gum aqueous solution.
＜グアーガム、タマリンドガム＞
　スリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）を備えた１０００ｍｌ容のプラスチックビーカーにイオン交換水２４５ｇを量り取り、４００ｒｐｍで攪拌しながらグアーガム又はタマリンドガム５ｇを徐々に添加した。攪拌速度は変更せず、１時間攪拌を継続することにより、グアーガム又はタマリンドガムの２質量％水溶液を得た。なお、上記の工程は温浴（４０℃）下にて実施した。 <Guar Gum, Tamarind Gum>
245 g of ion-exchanged water was weighed into a 1000 ml plastic beaker equipped with a three-one motor (general-purpose stirrer BL1200, Sintokagaku Co., Ltd.), and 5 g of guar gum or tamarind gum was gradually added while stirring at 400 rpm. By continuing stirring for 1 hour without changing the stirring speed, a 2% by mass aqueous solution of guar gum or tamarind gum was obtained. The above steps were carried out in a hot bath (40°C).
粘性組成物の調製
　上述した各ポリマー水溶液（つまり、各ポリアクリル酸系水溶性高分子２質量％水溶液及び各多糖類２質量％水溶液）及びイオン交換水を用いて、表２の組成に従い、各実施例及び比較例の組成物を調製した。具体的には、２００ｍｌ容のプラスチックビーカーにイオン交換水と各ポリマー２質量％水溶液をスリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）５００ｒｐｍにて１０分間攪拌した。このようにして各成分の混合物を調製した。例えば、実施例１は、ポリアクリル酸系水溶性高分子と多糖類との配合割合が１：１であり、これらポリマー合計濃度が１質量％であることから、製造例１ポリマーの２質量％水溶液及びキサンタンガム２質量％水溶液を２５ｇずつ、並びにイオン交換水を５０ｇ、混合することで調製した。これにより、組成物における製造例１ポリマー濃度は０．５質量％、キサンタンガム濃度は０．５質量％となり、よって配合質量比１：１、ポリマー合計濃度１質量％となり、表１の実施例１の組成を満たす。 Preparation of viscous composition According to the composition in Table 2, each polymer aqueous solution (that is, each polyacrylic acid-based water-soluble polymer 2% by mass aqueous solution and each polysaccharide 2% by mass aqueous solution) and ion-exchanged water were used to prepare each polymer. Example and Comparative Example compositions were prepared. Specifically, ion-exchanged water and a 2% by mass aqueous solution of each polymer were stirred in a 200 ml plastic beaker at 500 rpm with a three-one motor (Sintokagaku Co., Ltd. general-purpose stirrer BL1200) for 10 minutes. A mixture of each component was thus prepared. For example, in Example 1, the blending ratio of the polyacrylic acid-based water-soluble polymer and the polysaccharide is 1:1, and the total concentration of these polymers is 1% by mass, so 2% by mass of the polymer in Production Example 1 It was prepared by mixing 25 g each of an aqueous solution and a 2% by mass xanthan gum aqueous solution, and 50 g of ion-exchanged water. As a result, the composition of Production Example 1 has a polymer concentration of 0.5% by mass and a xanthan gum concentration of 0.5% by mass, resulting in a blending mass ratio of 1:1 and a total polymer concentration of 1% by mass. satisfies the composition of
　表２に記載の各成分の数値は、得られる組成物を１００質量％とした時の百分率であり、実際の調製は合計１００ｇスケールで行った。また、遠心分離機（例えば、２０００ｒｐｍ×１０分）にて脱泡をした後に粘度の測定を行った。また、各粘性組成物について、官能評価を行った。これらの結果も表２にあわせて示す。 The numerical value of each component described in Table 2 is the percentage when the obtained composition is 100% by mass, and the actual preparation was performed on a total of 100 g scale. Moreover, the viscosity was measured after defoaming with a centrifuge (for example, 2000 rpm×10 minutes). Moreover, sensory evaluation was performed about each viscous composition. These results are also shown in Table 2.
　なお、粘度測定及び官能試験は、次の様にして行った。以下も同様である。 The viscosity measurement and sensory test were performed as follows. The same applies to the following.
＜粘度測定＞
　評価サンプル（各粘性組成物）を２５℃に調整した恒温水槽に６０分以上浸した後に、ＢｒｏｏｋＦｉｅｌｄ社製の粘度計（型番：ＤＶ１ＭＲＶＴＪ０、スピンドル：ＲＶ）を用い、回転速度を毎分２０回転として、１分後の２５℃における粘度を測定した。測定に使用したローターは、２，０００ｍＰａ・ｓ未満の場合はローターＮｏ．３、２，０００ｍＰａ・ｓ以上５，０００ｍＰａ・ｓ未満の場合はローターＮｏ．４、５，０００ｍＰａ・ｓ以上１５，０００ｍＰａ・ｓ未満の場合はローターＮｏ．５、１５，０００ｍＰａ・ｓ以上４０，０００ｍＰａ・ｓ未満の場合はローターＮｏ．６、４０，０００ｍＰａ・ｓ以上の場合はローターＮｏ．７である。 <Viscosity measurement>
After immersing the evaluation sample (each viscous composition) in a constant temperature water bath adjusted to 25 ° C. for 60 minutes or more, a viscometer manufactured by BrookField (model number: DV1MRVTJ0, spindle: RV) was used, and the rotation speed was 20 rotations per minute. , and the viscosity at 25° C. after 1 minute was measured. The rotor used for the measurement was rotor No. when it was less than 2,000 mPa·s. 3. Rotor No. in the case of 2,000 mPa·s or more and less than 5,000 mPa·s. 4, 5,000 mPa·s or more and less than 15,000 mPa·s, rotor No. 5, 15,000 mPa·s or more and less than 40,000 mPa·s, rotor No. Rotor No. 6, 40,000 mPa·s or more. 7.
＜官能試験＞
　評価サンプル（各粘性組成物）の使用感を１０名のパネラーにより評価した。具体的には、パネラーの皮膚上（手の甲上）に評価サンプル０．２０ｇのせ、手で塗布した際の触感を評価した。触感の評価は、具体的には、（１）塗布時のぬるつきのなさ（ない方が点が高い）、（２）塗布後のしっとり感（しっとり感があるほうが点が高い）、及び（３）塗布後のべたつきのなさ（べたつきがない方が点が高い）、の３項目につき、それぞれ１～５点を選択する５段階評価で行った。結果は１０名のパネラーの平均点で示した。 <Sensory test>
The feeling of use of the evaluation samples (each viscous composition) was evaluated by 10 panelists. Specifically, 0.20 g of an evaluation sample was placed on the skin (on the back of the hand) of a panelist, and the tactile sensation when applied by hand was evaluated. Specifically, the evaluation of tactile sensation is as follows: (1) lack of slimy feeling at the time of application (higher points if absent), (2) moist feeling after application (higher point if there is moist feeling), and (3) ) Absence of stickiness after application (no stickiness is scored higher). The results are shown as the average score of 10 panelists.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
化粧品組成物の調製
　表３の組成に従い、各実施例及び比較例の組成物を調製した。 Preparation of Cosmetic Compositions According to the composition shown in Table 3, compositions of Examples and Comparative Examples were prepared.
　具体的には、実施例Ａでは、２００ｍｌ容のプラスチックビーカーにイオン交換水とポリアクリル酸系水溶性高分子（製造例１ポリマー）をスリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）５００ｒｐｍにて１０分間攪拌した。さらに、ブチレングリコールと天然系多糖類（タマリンドガム）を添加した後に、同スリーワンモーター５００ｒｐｍにて１０分間攪拌した。さらに、ラウロイルグルタミン酸ジ（フィトステリル／オクチルドデシル）とフェノキシエタノールを添加して、同スリーワンモーター５００ｒｐｍにて１０分間攪拌した。 Specifically, in Example A, ion-exchanged water and a polyacrylic acid-based water-soluble polymer (manufacturing example 1 polymer) were placed in a 200 ml plastic beaker at a three-one motor (Sintokagaku Co., Ltd. general-purpose stirrer BL1200) at 500 rpm. Stirred for 10 minutes. Furthermore, after adding butylene glycol and a natural polysaccharide (tamarind gum), the mixture was stirred at 500 rpm for 10 minutes using the three-one motor. Further, di(phytosteryl/octyldodecyl) lauroylglutamate and phenoxyethanol were added and stirred at 500 rpm for 10 minutes with the same three-one motor.
　また、比較例Ａでは、２００ｍｌ容のプラスチックビーカーにイオン交換水とポリアクリル酸系水溶性高分子（製造例３ポリマー）をスリーワンモーター（新東科学株式会社　汎用攪拌機　ＢＬ１２００）５００ｒｐｍにて１０分間攪拌した。さらに、水酸化カリウムを添加した後に、同スリーワンモーター５００ｒｐｍにて１０分間攪拌した。加えて、ブチレングリコールと天然系多糖類（タマリンドガム）を添加した後に、同スリーワンモーター５００ｒｐｍにて１０分間攪拌した。さらに、ラウロイルグルタミン酸ジ（フィトステリル／オクチルドデシル）とフェノキシエタノールを添加して、同スリーワンモーター５００ｒｐｍにて１０分間攪拌した。 In Comparative Example A, ion-exchanged water and polyacrylic acid-based water-soluble polymer (manufacturing example 3 polymer) were stirred in a 200 ml plastic beaker at 500 rpm for 10 minutes with a three-one motor (Sintokagaku Co., Ltd. general-purpose stirrer BL1200). bottom. Furthermore, after adding potassium hydroxide, the mixture was stirred for 10 minutes at 500 rpm with the same three-one motor. In addition, after adding butylene glycol and natural polysaccharide (tamarind gum), the mixture was stirred at 500 rpm for 10 minutes using the same three-one motor. Further, di(phytosteryl/octyldodecyl) lauroylglutamate and phenoxyethanol were added and stirred at 500 rpm for 10 minutes with the same three-one motor.
　なお、表３に記載の各成分の数値は、得られる組成物を１００質量％とした時の百分率であり、実際の調製は合計１００ｇスケールで行った。また、遠心分離機（例えば、２０００ｒｐｍ×１０分）にて脱泡をした後に粘度の測定を行った。また、各粘性組成物について、官能評価を行った。これらの結果も表３にあわせて示す。 The numerical value of each component shown in Table 3 is the percentage when the obtained composition is 100% by mass, and the actual preparation was performed on a scale of 100 g in total. Moreover, the viscosity was measured after defoaming with a centrifuge (for example, 2000 rpm×10 minutes). Moreover, sensory evaluation was performed about each viscous composition. These results are also shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Claims (7)

  1. ポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物であって、
    前記ポリアクリル酸系水溶性高分子の粉体が、スパチュラ角測定時の衝撃前後の角度の差が９°以上である、
    組成物。     A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide,
    The powder of the polyacrylic acid-based water-soluble polymer has an angle difference of 9° or more before and after impact when measured with a spatula angle.
    Composition.
  2. ポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物であって、
    前記ポリアクリル酸系水溶性高分子が、水膨潤時の粒子径が３０μｍ以上である、
    組成物。     A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide,
    The polyacrylic acid-based water-soluble polymer has a particle size of 30 μm or more when swollen with water.
    Composition.
  3. ポリアクリル酸系水溶性高分子及び多糖類を含有する粘性組成物であって、
    前記ポリアクリル酸系水溶性高分子が、スパチュラ角測定時の衝撃前後の角度の差が９°以上であり、且つ、水膨潤時の粒子径が３０μｍ以上である、
    組成物。     A viscous composition containing a polyacrylic acid-based water-soluble polymer and a polysaccharide,
    The polyacrylic acid-based water-soluble polymer has a difference in angle before and after impact when measured with a spatula angle of 9° or more, and a particle size when swollen with water of 30 μm or more.
    Composition.
  4. ポリアクリル酸系水溶性高分子と多糖類との含有質量比が、１：９～９：１である、請求項１又は２に記載の組成物。 3. The composition according to claim 1, wherein the content ratio by weight of the polyacrylic acid-based water-soluble polymer and the polysaccharide is 1:9 to 9:1.
  5. ポリアクリル酸系水溶性高分子が、架橋剤により架橋されていてもよい、ポリ（メタ）アクリル酸又はその塩、デンプン・（メタ）アクリル酸グラフト重合体又はその塩、並びに、アクリレーツクロスポリマー又はその塩からなる群より選択される少なくとも１種の高分子である、請求項１又は２に記載の組成物。 Poly(meth)acrylic acid-based water-soluble polymer may be crosslinked by a crosslinking agent, poly(meth)acrylic acid or its salt, starch/(meth)acrylic acid graft polymer or its salt, and acrylates crosspolymer 3. The composition according to claim 1 or 2, which is at least one polymer selected from the group consisting of or salts thereof.
  6. 多糖類が、キサンタンガム、ジェランガム、タマリンドガム、及びグアーガムからなる群より選択される少なくとも１種である、請求項１又は２に記載の組成物。 3. The composition according to claim 1 or 2, wherein the polysaccharide is at least one selected from the group consisting of xanthan gum, gellan gum, tamarind gum, and guar gum.
  7. ポリアクリル酸系水溶性高分子と多糖類と合計含有量が組成物に対して０．５～２質量％である、請求項１又は２に記載の組成物。 The composition according to claim 1 or 2, wherein the total content of the polyacrylic acid-based water-soluble polymer and the polysaccharide is 0.5 to 2% by mass based on the composition.
PCT/JP2022/029245 2021-08-26 2022-07-29 Viscous composition WO2023026766A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003306515A (en) * 2002-02-18 2003-10-31 Nippon Fine Chem Co Ltd Cationic copolymer
WO2009084469A1 (en) * 2007-12-28 2009-07-09 Sumitomo Seika Chemicals Co., Ltd. (meth)acrylic acid/alkyl (meth)acrylate ester copolymer and cosmetic preparation containing the same
JP2015151336A (en) * 2014-02-10 2015-08-24 住友精化株式会社 Thickener for mildly acidic cosmetic, and mildly acidic cosmetic containing the thickener
WO2017022702A1 (en) * 2015-08-04 2017-02-09 住友精化株式会社 Gel-form composition
JP2017178828A (en) * 2016-03-29 2017-10-05 株式会社マンダム Emulsified composition for skin

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003306515A (en) * 2002-02-18 2003-10-31 Nippon Fine Chem Co Ltd Cationic copolymer
WO2009084469A1 (en) * 2007-12-28 2009-07-09 Sumitomo Seika Chemicals Co., Ltd. (meth)acrylic acid/alkyl (meth)acrylate ester copolymer and cosmetic preparation containing the same
JP2015151336A (en) * 2014-02-10 2015-08-24 住友精化株式会社 Thickener for mildly acidic cosmetic, and mildly acidic cosmetic containing the thickener
WO2017022702A1 (en) * 2015-08-04 2017-02-09 住友精化株式会社 Gel-form composition
JP2017178828A (en) * 2016-03-29 2017-10-05 株式会社マンダム Emulsified composition for skin

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