WO2021200136A1

WO2021200136A1 - Viscous composition

Info

Publication number: WO2021200136A1
Application number: PCT/JP2021/010729
Authority: WO
Inventors: 山口　博史; 亮輔村上
Original assignee: 住友精化株式会社
Priority date: 2020-03-31
Filing date: 2021-03-17
Publication date: 2021-10-07

Abstract

Provided is a viscous composition comprising ascorbic acid or a derivative thereof, and having appropriate viscosity. More specifically, provided is the following composition. A composition comprising: (A) at least 0.3 mass% of a polymer obtained by polymerizing (i), (ii), and (iii), where (i) is 100 parts by mass of (meth)acrylic acid, (ii) is 0.01-1 parts by mass of a compound containing at least two ethylenically unsaturated groups, and (iii) is 0.5-10 parts by mass of a (meth)acrylic acid alkyl ester in which the alkyl group has a C number of 10-30; and (B) ascorbic acid or a derivative thereof.

Description

Viscous composition

The present disclosure relates to a viscous composition or the like.

Ascorbic acid is an ingredient used in compositions for various uses (for example, cosmetics and foods).

International Publication No. 2007/055354

The present inventors have found that when ascorbic acid or a derivative thereof is added to a viscous composition, the viscosity is significantly reduced. Therefore, in order to find a method for providing a viscous composition in which the viscosity is unlikely to decrease even if ascorbic acid or a derivative thereof is blended, and a viscous composition containing ascorbic acid or a derivative thereof and having an appropriate viscosity. Study was carried out.

The present inventors have a viscous composition prepared by using a specific amount of a specific copolymer among the alkyl-modified carboxyl group-containing water-soluble copolymers disclosed in Patent Document 1 (International Publication No. 2007/055354). We have found that even if ascorbic acid or a derivative thereof is blended in the product, it is unlikely that the viscosity will decrease, and further studies have been conducted.

The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
(A) The following (i), (ii), and (iii):
(I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms A composition containing 0.3% by mass or more of a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester, and (B) ascorbic acid or a derivative thereof.
Item 2.
The above (ii) is
A compound having two or more ethylenically unsaturated groups, 0.01 to 0.2 parts by mass.
Item 2. The composition according to Item 1.
Item 3.
Item 2. The composition according to Item 1 or 2, wherein the compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
Item 4.
Item 2. The composition according to any one of Items 1 to 3, which has a viscosity of 5000 mPa · s or more.
Item 5.
Item 2. The composition according to any one of Items 1 to 4, which contains 2.5% by mass or more of the above (B).
Item 6.
At least one ascorbic acid derivative selected from the group consisting of ascorbic acid salt, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl, ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, and glyceryl octyl ascorbic acid. Seed,
Item 8. The composition according to any one of Items 1 to 5.
Item 7.
The above (ii) is
The compound having two or more ethylenically unsaturated groups is 0.01 to 0.2 parts by mass.
The compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
The viscosity is 5000 mPa · s or more,
Containing 2.5% by mass or more of the above (B),
(B) is at least one selected from the group consisting of ascorbic acid, ascorbic acid salt, ascorbic acid glycoside, and ascorbic acid phosphate.
Item 2. The composition according to Item 1.
Item 8.
(A) The following (i), (ii), and (iii):
(I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms Contains a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester.
A thickener for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof.

A composition containing ascorbic acid or a derivative thereof and having an appropriate viscosity is provided.

The viscosity measurement result of the viscous composition containing various polymers and ascorbic acid derivatives is shown. The UV transmittance measurement result of the viscous composition containing various polymers and ascorbic acid derivatives is shown.

Hereinafter, each embodiment included in the present disclosure will be described in more detail. The present disclosure preferably includes, but is not limited to, a composition containing a specific polymer and ascorbic acid or a derivative thereof, its use, a method for producing the same, and the like, and the present disclosure is described herein. Includes everything disclosed and recognizable to those skilled in the art.

The compositions included in the present disclosure include (A) a polymer obtained by polymerizing the following (i), (ii), and (iii) (sometimes referred to as "polymer (A)"), and (B. ) Contains ascorbic acid or a derivative thereof (sometimes referred to as "component (B)").

(I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms Acid alkyl ester 0.5-10 parts by mass

In the present specification, "(meth) acrylic" means acrylic and / or methacryl. As the (meth) acrylic acid, either one of acrylic acid and methacrylic acid may be used alone, or both of them may be used in combination.

Alkyl groups have 10 to 30 carbon atoms (10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, Alternatively, the (meth) acrylic acid alkyl ester of 30) is an ester of (meth) acrylic acid and a higher alcohol having an alkyl group having 10 to 30 carbon atoms. The alkyl group preferably has, for example, 12 to 30, 14 to 28, 16 to 26, or 18 to 24 carbon atoms. Such (meth) acrylic acid alkyl ester is not particularly limited, and is, for example, an ester of (meth) acrylic acid and stearyl alcohol, an ester of (meth) acrylic acid and eicosanol, and (meth) acrylic acid and behenyl alcohol. And an ester of (meth) acrylic acid and tetracosanol. Among these (meth) acrylic acid alkyl esters, preferably stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, and tetracosanyl methacrylate can be mentioned. These (meth) acrylic acid alkyl esters may be used alone or in combination of two or more. Further, as such a (meth) acrylic acid alkyl ester, for example, commercially available products such as NOF Corporation's trade name Blemmer VMA70 and Brenmer SMA may be used.

The amount of the (meth) acrylic acid alkyl ester used is 0.5 to 10 parts by mass, preferably 0.5 to 7.5 parts by mass, 0.5 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. It is ~ 5 parts by mass, or 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass.

The compound having two or more ethylenically unsaturated groups is not particularly limited, but for example, ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, penta. Acrylic acid esters with two or more substitutions of polyols such as erythritol, saccharose, and sorbitol; allyl ethers with two or more substitutions of the polyols; diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate. , Divinyl adipate, vinyl crotonic acid, 1,5-hexadiene, divinylbenzene, polyallyl saccharose and the like. Among these compounds having two or more ethylenically unsaturated groups, sucrose allyl ether, pentaerythritol allyl ether (particularly pentaerythritol triallyl ether and pentaerythritol tetraallyl ether are preferable), tetraallyl oxyethane, and the like. Examples thereof include triallyl phosphate and polyallyl saccharose, among which sucrose allyl ether and pentaerythritol allyl ether are more preferable, and pentaerythritol allyl ether is particularly preferable. These compounds having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.

The amount of the compound having two or more ethylenically unsaturated groups used is 0.01 to 1 part by mass with respect to 100 parts by mass of (meth) acrylic acid. The upper or lower limit of the range is, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0. It may be 8, 0.85, 0.9, or 0.95 parts by mass. For example, the range may be about 0.02 to 0.8 parts by mass.

Although not particularly limited, when the amount of the compound having two or more ethylenically unsaturated groups in the polymer (A) used is relatively small, the effect of improving the transparency of the composition of the present disclosure is exhibited. Therefore, it is preferable. In particular, when the composition of the present disclosure is used in the field of cosmetics, etc., transparency is a problem of appearance and is not a feature that directly affects the effect of cosmetics, but the composition is transparent for a certain number of consumers. This is because they are considered to like it. From this viewpoint, the amount of the compound having two or more ethylenically unsaturated groups is preferably about 0.01 to 0.2 parts by mass with respect to 100 parts by mass of (meth) acrylic acid.

In the production of the copolymers of the present disclosure, the method of polymerizing (i), (ii) and (iii) is not particularly limited, and for example, these are polymerized in a polymerization solvent in the presence of a radical polymerization initiator. There is a method of making it.

The radical polymerization initiator is not particularly limited, and is, for example, α, α'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobismethyl. Examples thereof include isobutyrate, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide and the like. These radical polymerization initiators may be used alone or in combination of two or more.

The amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.01 to 0.45 parts by mass and 0.01 to 0.35 parts by mass with respect to 100 parts by mass of (meth) acrylic acid, for example. The portion is more preferable.

As the polymerization method, for example, precipitation polymerization or reverse phase suspension polymerization can be preferably used. Furthermore, reverse phase suspension polymerization may be carried out in a polymerization solvent containing a nonionic surfactant having a polyoxyethylene chain.

Preferred examples of the nonionic surfactant having the polyoxyethylene chain include polyhydric alcohol fatty acid ester ethylene oxide adduct, block copolymer of hydroxy fatty acid and ethylene oxide, and polyoxyethylene castor oil.

As the polyhydric alcohol fatty acid ester ethylene oxide adduct, an ester compound of polyoxyethylene hydrogenated castor oil and polyhydric alcohol fatty acid is preferably mentioned. Further, the polyhydric alcohol fatty acid here is a saturated or unsaturated polyvalent (14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24) having 14 to 24 carbon atoms (14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24). In particular, divalent) alcohol fatty acids are preferable, and more specifically, isopalmitic acid, isostearic acid, isooleic acid and the like are preferably mentioned. The average number of moles of ethylene oxide added to polyoxyethylene in the ester compound of the polyoxyethylene hydrogenated castor oil and the polyhydric alcohol fatty acid is not particularly limited, and examples thereof include about 20 to 100 or about 30 to 70. Particularly preferable as an 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 addition mole number of ethylene oxide of about 2 to 10, and more preferably about 2 to 5.

In other words, the block copolymer of hydroxy fatty acid and ethylene oxide can be said to be a copolymer composed 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, preferably myristic acid, palmitic acid, stearic acid and the like, and examples of the hydroxy fatty acid are hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid and the like. Is preferable, and hydroxystearic acid is particularly preferable. As the hydroxystearic acid, 12-hydroxystearic acid is particularly preferable. As the polyhydroxy fatty acid, polyhydroxystearic acid is particularly preferable. As the block copolymer of hydroxy fatty acid and ethylene oxide, a block copolymer of 12-hydroxystearic acid and ethylene oxide is particularly preferable.

The nonionic surfactant having the polyoxyethylene chain can be used alone or in combination of two or more.

The amount of the nonionic surfactant having the polyoxyethylene chain used is preferably about 0.5 to 10 parts by mass with respect to 100 parts by mass of (i) (meth) acrylic acid. The lower limit of the mass range may be, for example, about 0.75, 1.0, 1.25, or 1.5, and the upper limit of the mass range may be, for example, 9.5, 9, 8. It may be about 5.5, 8, 7.5, 7, 6.5, 6, or 5.5. For example, about 1 to 7.5 parts by mass is more preferable.

The polymerization solvent is not particularly limited, but is a polymer (A) obtained by dissolving (meth) acrylic acid, the (meth) acrylic acid alkyl ester, and a compound having two or more ethylenically unsaturated groups. ) Is preferably a solvent that does not dissolve. Specific examples of such a polymerization solvent include normal pentane, normal hexane, normal heptane, normal octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, ethylene dichloride, ethyl acetate. , Isopropyl acetate, ethyl methyl ketone, isobutyl methyl ketone and the like. Among these polymerization solvents, ethylene dichloride, normal hexane, normal heptane, and ethyl acetate are preferable 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 not particularly limited, but for example, it is preferably 200 to 10000 parts by mass and more preferably 300 to 2000 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. By using the polymerization solvent within the above range, even if the polymerization reaction proceeds, the alkyl-modified carboxyl group-containing water-soluble copolymer is preferably suppressed from agglomeration and uniformly stirred, and the polymerization reaction is made more efficient. It becomes possible to proceed in a targeted manner.

The atmosphere when the polymerization reaction is carried out is not particularly limited as long as the polymerization reaction is possible, and examples thereof include an inert gas atmosphere such as nitrogen gas and argon gas.

The reaction temperature at the time of carrying out the above polymerization reaction is not particularly limited as long as the polymerization reaction is possible, but for example, it is preferably 50 to 90 ° C, more preferably 55 to 75 ° C. By carrying out the polymerization reaction at such a reaction temperature, it is possible to preferably suppress an increase in the viscosity of the reaction solution, facilitate reaction control, and preferably control the bulk density of the obtained polymer (A). can.

The reaction time for carrying out the above polymerization reaction varies depending on the reaction temperature and cannot be unconditionally determined, but is usually 2 to 10 hours.

After completion of the reaction, for example, the reaction solution can be heated to 80 to 130 ° C. to remove the polymerization solvent, whereby the white fine powder polymer (A) can be isolated.

Derivatives of ascorbic acid include, for example, ascorbate, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl (ester of fatty acid and ascorbic acid), ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, glyceryl octyl ascorbin. Acids and the like can be mentioned. Examples of ascorbic acid salt include sodium ascorbate and calcium ascorbate. Ascorbic acid glycosides are preferably ascorbic acid glucosides, and more specifically, ascorbic acid 2-glucosides, ascorbic acid 6-glucosides and the like can be mentioned. Examples of the ascorbate phosphate include sodium ascorbate phosphate and magnesium ascorbate phosphate. Examples of the fatty acid ascorbyl include ascorbyl palmitate, ascorbyl stearate, and ascorbyl isopalmitate. Examples of the ascorbic acid-phosphoric acid-fatty acid include ascorbic acid-2 phosphoric acid-6 palmitic acid and the like. Ascorbic acid or a derivative thereof can be used alone or in combination of two or more. Although not particularly limited, ascorbic acid or a glycoside thereof is preferable as ascorbic acid or a derivative thereof.

The degree of neutralization of the polymer (A) can be easily adjusted by neutralizing the carboxyl group of acrylic acid and / or methacrylic acid with an alkali. The degree of neutralization here refers to the ratio of the number of moles of neutralized groups to the total number of moles of carboxyl groups of acrylic acid and / or methacrylic acid. Examples of the alkali used for neutralization include sodium hydroxide, potassium hydroxide, triethanolamine, diisopropylamine and the like. The neutralization method is not particularly limited, and examples thereof include a method of neutralizing acrylic acid and / or methacrylic acid in advance, a method of neutralizing a polymer obtained by polymerization, and the like.

Although not particularly limited, the degree of neutralization of the polymer (A) is, for example, preferably 0 to 80%, more preferably 10 to 60%, and even more preferably 20 to 50%.

It is preferable that the composition of the present disclosure further contains water. The water contained is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, or the like can be used.

The composition of the present disclosure may further contain a pH adjuster, if necessary. A pH regulator can preferably be used to adjust the pH of the composition to near neutral. The composition of the present disclosure preferably has a pH of, for example, about 6 to 8. The upper or lower limit of the pH range is 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, It may be 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, or 7.9. For example, the pH range may be about 6.5 to 7.

As the pH adjuster, a known pH adjuster can be used, and a pH adjuster known in the cosmetics field or the food field is preferable. For example, sodium hydroxide, potassium hydroxide and the like can be mentioned.

The viscosity of the composition of the present disclosure is preferably 5000 mPa · s or more, and more preferably about 5000 to 50,000 mPa · s, for example. The upper or lower limit of the range is, for example, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 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, It may be 46000, 47000, 48000, or 49000 mPa · s. For example, the range may be about 5500 to 40,000 mPa · s or about 6000 to 30000 mPa · s. Viscosity is measured using a BH type rotational viscometer. Specifically, it is measured by reading the viscosity value 1 minute after the start of rotation of the rotor at 25 ° C., assuming that the rotation speed of the spindle rotor is 20 rotations per minute. As a guide, if the rotor used for measurement is less than 2000 mPa · s, the rotor No. In the case of 3, 2000 mPa · s or more and less than 5000 mPa · s, the rotor No. If it is 45,000 mPa · s or more and less than 15,000 mPa · s, the rotor No. In the case of 5, 15,000 mPa · s or more and less than 40,000 mPa · s, the rotor No. In the case of 6, 40,000 mPa · s or more, the rotor No. 7. Further, if necessary, before the viscosity measurement, each viscous composition can be used after defoaming by centrifuging (for example, 2000 rpm × 10 to 20 minutes).

In the composition of the present disclosure, the polymer (A) is preferably contained in an amount of 0.3% by mass or more, more preferably 0.4 or 0.5% by mass or more. Further, as described above, the composition of the present disclosure has a characteristic that the viscosity is less likely to decrease as compared with the case where the component (B) is not contained, although the composition contains the component (B). ) When the viscosity is not relatively high when the component (B) is not contained, the amount of decrease in viscosity is small even if the component (B) is blended, so that it can be considered that the effect of the composition of the present disclosure is not sufficiently exhibited. .. From this point of view, it is not preferable that the polymer (A) content in the composition is 0.2% by mass or less. When the content is 0.2% by mass or less, the viscosity when the component (B) is not contained is not relatively high in the first place, so that it can be said that the effect of the composition of the present disclosure is not sufficiently exhibited. ..

The upper limit of the polymer (A) content is not particularly limited as long as the effect of the composition of the present disclosure is not impaired. For example, 5% by mass or less is exemplified. The upper or lower limit of the polymer (A) content range (0.3 to 5% by mass) is, for example, 0.4, 0.5, 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, 2, 2.1, 2.2, 2.3 2, 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, 4.5, 4.6, 4.7, 4.8, or 4. It may be 9% by mass. For example, the range may be about 0.4 to 4.5 or 0.5 to 4% by mass.

In the composition of the present disclosure, the component (B) is preferably contained in an amount of 2.5% by mass or more, and more preferably 3% by mass or more. Further, the upper limit of the content of the component (B) is not particularly limited as long as the effect of the present invention is not impaired. For example, 15% by mass is exemplified. The upper or lower limit of the component (B) content range (2.5 to 15% by mass) is, for example, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7. , 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, or 14.5% by mass There may be. For example, the range may be about 3 to 10% by mass.

The compositions of the present disclosure can be prepared by a known method or a method that can be very easily conceived from a known method. For example, it can be prepared by appropriately mixing the polymer (A), the component (B), and water, and if necessary, a pH adjuster and other components.

The composition of the present disclosure is useful, for example, as a cosmetic composition.

The composition of the present disclosure may contain a component other than the above components as long as the effect is not impaired, and may contain, for example, a component known in the cosmetics field. For example, a thickener may be contained as long as the effect is not impaired. Examples of the thickener include polysaccharide-based water-soluble polymers such as hydroxyethyl cellulose and xanthan gum, carboxyvinyl polymers, and alkyl-modified carboxyvinyl polymers. Furthermore, for example, powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants. Activators, moisturizers, water-soluble polymers, film agents, UV absorbers, metal ion blockers, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins , Antioxidants, antioxidant aids, fragrances and the like may be contained.

When the composition of the present disclosure is used in the field of cosmetics, its form is not particularly limited, but for example, medicated cream, lotion, milky lotion, beauty essence, cream, cream pack, massage cream, cleansing cream, cleansing gel, gel cream, etc. Examples include facial cleansing foams, moisturizing gels, hair setting gels, sunscreens, styling gels, eyeliners, mascara, lipsticks and foundations.

The present disclosure also preferably includes a thickener for preparing a viscous composition containing ascorbic acid or a derivative thereof. The thickener comprises the polymer (A). The thickener is preferably for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof. In addition, all the above-mentioned contents regarding the compositions of the present disclosure may also apply to the thickener.

In this specification, "including" also includes "consisting of" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of."). The present disclosure also includes all combinations of the constituent requirements described herein.

Further, the various characteristics (property, structure, function, etc.) described for each embodiment of the present disclosure described above may be combined in any way in specifying the subject matter included in the present disclosure. That is, the present disclosure includes all subjects consisting of any combination of each combinable property described herein.

Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.

Polymer preparation [Production Example 1]
45 g (0.625 mol) of acrylic acid, Blemmer VMA70 (manufactured by Nippon Oil & Fats Co., Ltd .: 10 to 20 mass of stearyl methacrylate) in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 1.35 g, pentaerythritol tetraallyl ether 0.02 g, normal 150 g of hexane and 0.081 g (0.00035 mol) of 2,2'-azobismethylisobutyrate were charged. After stirring and uniformly mixing the solution, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), raw materials and solvent. Then, it was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off normal hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain a white fine powder of alkyl-modified carboxyl group-containing water-soluble material. 43 g of the copolymer was obtained. Hereinafter, the copolymer may be referred to as polymer 1.

[Manufacturing Example 2]
As a (meth) acrylic acid alkyl ester having 45 g of acrylic acid and an alkyl group having 18 to 24 carbon atoms in a 500 mL (milliliter) four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a cooling tube. Blemmer VMA70 (manufactured by Nichiyu Co., Ltd., stearyl methacrylate by 10 to 20 parts by mass, eikosanyl methacrylate by 10 to 20 parts by mass, behenyl methacrylate by 59 to 80 parts by mass, and tetracosanyl methacrylate by 1% by mass or less. 1.35 g of the mixture, 0.02 g of pentaerythritol tetraallyl ether as a compound having at least two ethylenically unsaturated groups, 0.116 g of 2,2'-azobis (methyl isobutyrate) as a radical polymerization initiator, and reaction. 230.9 g of normal hexane was charged as a solvent. Subsequently, after the solution was uniformly stirred and mixed, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. The solution was then heated to 60-65 ° C. under a nitrogen atmosphere. Two hours after the temperature of the solution reached 60 ° C., 0.9 g of a block copolymer of 12-hydroxystearic acid and polyoxyethylene (Hypermer B246 manufactured by Croda) was charged into the reaction vessel as a nonionic surfactant. .. Then, after the temperature of the solution reached 60 ° C., it was kept at 60 to 65 ° C. for 3 hours. Then, the generated slurry is heated to 100 ° C., normal hexane is distilled off, the set temperature of the heating device is set to 115 ° C., the set pressure of the decompression device is set to 10 mmHg, and the mixture is dried for 8 hours. , 41 g of white fine particles of an alkyl-modified carboxyl group-containing copolymer was obtained. Hereinafter, the copolymer may be referred to as polymer 2.

[Manufacturing Example 3]
45 g (0.625 mol) of acrylic acid, Blemmer VMA70 (manufactured by Nippon Oil & Fats Co., Ltd .: 10 to 20 mass of stearyl methacrylate) in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 2.25 g, pentaerythritol tetraallyl ether 0.02 g, normal 150 g of hexane and 0.081 g (0.00035 mol) of 2,2'-azobismethylisobutyrate were charged. After stirring and uniformly mixing the solution, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), raw materials and solvent. Then, it was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off normal hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain a white fine powder of alkyl-modified carboxyl group-containing water-soluble material. 43 g of the copolymer was obtained. Hereinafter, the copolymer may be referred to as polymer 3.

[Manufacturing Example 4]
40 g of acrylic acid, Blemmer VMA-70 (manufactured by Nichiyu Co., Ltd., 10 to 20 parts by mass of stearyl methacrylate) in a 500 mL (milliliter) four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. , 10 to 20 parts by mass of eicosanyl methacrylate, 59 to 80 parts by mass of behenyl methacrylate, and a mixture containing tetracosanyl methacrylate in a content of 1% by mass or less) 0.88 g, pentaerythritol tetraallyl ether 0.22 g, 2, 0.116 g of 2'-azobis (methyl isobutyrate) and 230.9 g of normal hexane were charged. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. Then, it was heated to 60-65 ° C. under a nitrogen atmosphere. Then, it was kept at 60-65 ° C. for 3 hours. When it was held at 60 to 65 ° C. for about 1 hour, 2.0 g of normal hexane and 0.26 g of polyoxyethylene castor oil (manufactured by Nikko Chemical Co., Ltd., trade name: CO-3, 3 mol adduct of ethylene oxide) were added. 0.98 g of polyoxyethylene hydrogenated castor oil triisostearate (manufactured by Nippon Emulsion Co., Ltd., trade name: RWIS-350, 50 mol of ethylene oxide adduct) was dissolved and put into a reaction vessel. Then, the produced slurry was heated to 100 ° C. to distill off normal hexane, and further dried under reduced pressure for 8 hours at 115 ° C. and 10 mmHg to obtain an alkyl-modified carboxyl group-containing water-soluble copolymer of fine white powder. A coalescence of 38 g was obtained. Hereinafter, the copolymer may be referred to as polymer 4.

[Manufacturing Example 5]
40 g of acrylic acid, Blemmer VMA-70 (manufactured by Nichiyu Co., Ltd., 10 to 20 parts by mass of stearyl methacrylate) in a 500 mL (milliliter) four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. , 10 to 20 parts by mass of eicosanyl methacrylate, 59 to 80 parts by mass of behenyl methacrylate, and a mixture containing tetracosanyl methacrylate in a content of 1% by mass or less) 0.4 g, pentaerythritol tetraallyl ether 0.19 g, 2, 0.116 g of 2'-azobis (methyl isobutyrate) and 230.9 g of normal hexane were charged. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. Then, it was heated to 60-65 ° C. under a nitrogen atmosphere. Then, it was kept at 60-65 ° C. for 3 hours. After holding at 60 to 65 ° C. for about 1 hour, 1.6 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. , Put into a reaction vessel. Then, the produced slurry was heated to 100 ° C. to distill off normal hexane, and further dried under reduced pressure for 8 hours at 115 ° C. and 10 mmHg to obtain an alkyl-modified carboxyl group-containing water-soluble copolymer of fine white powder. A coalescence of 39 g was obtained. Hereinafter, the copolymer may be referred to as polymer 5.

[Manufacturing Example 6]
45 g (0.625 mol) of acrylic acid, 0.27 g of pentaerythritol tetraallyl ether, 150 g of n-hexane and 2, in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 0.081 g (0.00035 mol) of 2'-azobismethylisobutyrate was added to prepare a reaction solution. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel, the raw material and the solvent. Then, the reaction solution was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off n-hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain 42 g of a carboxyvinyl polymer. Hereinafter, the carboxyvinyl polymer may be referred to as polymer 6.

[Manufacturing Example 7]
40 g of acrylic acid, 0.22 g of pentaerythritol tetraallyl ether, 2,2'-azobis (methyl isobutyrate) in a 500 mL (milliliter) four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 0.116 g and 230.9 g of normal hexane were charged. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. Then, it was heated to 60-65 ° C. under a nitrogen atmosphere. Then, 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. , Put into a reaction vessel. Then, the produced slurry was heated to 100 ° C., normal hexane was distilled off, and the slurry was further dried under reduced pressure at 115 ° C. and 10 mmHg for 8 hours to obtain 38 g of a fine white carboxyvinyl polymer. Hereinafter, the carboxyvinyl polymer may be referred to as polymer 7.

Preparation and evaluation of viscous compositions Using polymers 1 to 7 and ascorbic acid glycosides (ascorbic acid 2-glucoside), the concentration of each polymer was 1% by mass and the concentration of ascorbic acid glycosides was 0 to 5% by mass. It was dissolved / dispersed in ion-exchanged water so as to obtain a viscous composition. The pH was adjusted to 6.5-6.8 with NaOH as needed (using a pH meter). More specifically, the ascorbic acid glycoside is dissolved in ion-exchanged water, 50 g of a separately prepared 2% polymer aqueous dispersion is added thereto, and the pH of a 6% NaOH aqueous solution becomes 6.5 to 6.8. Finally, ion-exchanged water was added so that the total weight of the system was 100 g, and each viscous composition was prepared.

Table 1 summarizes the composition of the obtained viscous composition and the composition of each polymer. PETA represents pentaerythritol tetraallyl ether.

The viscosity of each of the obtained viscous compositions was measured. The viscosity was measured using a BH type rotational viscometer. Assuming that the rotation speed of the spindle rotor was 20 rotations per minute, the viscosity value 1 minute after the start of rotation of the rotor was read at 25 ° C. Rotor No. 3, No. 4, No. 5, No. 6 or No. 7 was used. Before the viscosity measurement, each viscous composition was defoamed by centrifugation (2000 rpm × 10 to 20 minutes) before use.

In addition, the transparency of each of the obtained viscous compositions was evaluated. Specifically, the UV (425 nm) transmittance (% T) was measured.

<Transmittance measurement method>
The transmittance of the evaluation sample was measured using a spectrophotometer (model number: UV-1850) manufactured by Shimadzu Corporation. First, the sample was placed in a cell for UV measurement (optical path length 1 cm), and defoamed by a centrifuge at 2,000 rpm for 5 minutes. When the defoaming was not completed, the same operation was performed with a centrifuge, and it was confirmed that the bubbles were completely removed from the upper part of the sample. Then, the sample was set in a spectrophotometer, and the transmittance was measured with the measurement wavelength set to 425 nm. Distilled water was calibrated so as to have a transmittance of 100%.

The viscosity measurement result is shown in FIG. 1, and the UV (425 nm) transmittance measurement result is shown in FIG. 2, respectively.

Regarding the viscosity, when 3% by mass of ascorbic acid glycoside was blended, the composition having 5000 mPa · s or more was evaluated as ◯, and the other compositions were evaluated as ×. Regarding the transparency, when 3% by mass of the ascorbic acid glycoside was blended, the composition having a UV (425 nm) transmittance of 80 (% T) or more was evaluated as ◯, and the other compositions were evaluated as x. The evaluation is shown in Table 1.

For the polymer 3, a viscous composition having a polymer concentration of 0.6% by mass or 0.8% by mass and an ascorbic acid glycoside concentration of 3% by mass was prepared in the same manner as described above, and the viscosity and UV ( When the transmittance (425 nm) was measured, the viscosity was 7650 mPa · s and the UV transmittance was 97.2 (% T) at a polymer concentration of 0.6% by mass, and the viscosity was 16000 mPa · s at a polymer concentration of 0.8% by mass. The UV transmittance was 97.3 (% T).

Further, with respect to the polymers 1 and 2, a viscous composition having a polymer concentration of 1% by mass and an ascorbic acid glycoside concentration of 7% by mass was prepared in the same manner as described above, and the viscosity was measured. The product had a viscosity of 5,800 mPa · s, and the polymer 2-containing viscous composition had a viscosity of 13,600 mPa · s.

A viscous composition (Example a) was prepared in the same manner as in Example 1 except that magnesium L-ascorbic acid phosphate (L-ascorbic magnesium phosphate) was used instead of the ascorbic acid glycoside. When the viscosity and UV (425 nm) transmittance were measured, the viscosity was 12,600 mPa · s and the UV transmittance was 94.7 (% T).

Further, the viscous composition (the former is the same as in Example 2) except that magnesium L-ascorbic acid phosphate (L-ascorbic magnesium phosphate) or sodium L-ascorbic acid was used instead of the ascorbic acid glycoside. The composition used: Example b1, the composition using the latter: Example b2) was prepared, and the viscosity and UV (425 nm) permeability were measured. As a result, the composition using magnesium L-ascorbic acid phosphate was used. The viscosity was 16,600 mPa · s and the UV transmission rate was 96.4 (% T), and the composition using sodium L-ascorbic acid had a viscosity of 5,160 mPa · s and a UV transmission rate of 90.6 (% T). rice field.

Claims

(A) The following (i), (ii), and (iii):
(I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms A composition containing 0.3% by mass or more of a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester, and (B) ascorbic acid or a derivative thereof.
The above (ii) is
A compound having two or more ethylenically unsaturated groups, 0.01 to 0.2 parts by mass.
The composition according to claim 1.
The composition according to claim 1 or 2, wherein the compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
The composition according to any one of claims 1 to 3, which has a viscosity of 5000 mPa · s or more.
The composition according to any one of claims 1 to 4, which contains 2.5% by mass or more of the above (B).
At least one ascorbic acid derivative selected from the group consisting of ascorbic acid salt, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl, ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, and glyceryl octyl ascorbic acid. Seed,
The composition according to any one of claims 1 to 5.
The above (ii) is
The compound having two or more ethylenically unsaturated groups is 0.01 to 0.2 parts by mass.
The compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
The viscosity is 5000 mPa · s or more,
Containing 2.5% by mass or more of the above (B),
(B) is at least one selected from the group consisting of ascorbic acid, ascorbic acid salt, ascorbic acid glycoside, and ascorbic acid phosphate.
The composition according to claim 1.
(A) The following (i), (ii), and (iii):
(I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms Contains a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester.
A thickener for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof.