JP2017081868A - Oil-in-water emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique which can secure the restorability and high-temperature stability of an oil-in-water emulsified composition comprising hydrophobic modified polyether urethane without being affected by the type or amount of oil solution.SOLUTION: The present invention provides an oil-in-water emulsified composition comprising following components (A)-(E): (A) hydrophobic modified polyether urethane, (B) water-soluble polymer, (C) at least one selected from acyl glutamic acid, diacyl glutamic acid lysine or their alkali metal salt, (D) oil solution and (E) water.SELECTED DRAWING: None

Description

  The present invention relates to an oil-in-water emulsified composition excellent in resilience and high temperature stability.

  Hydrophobic modified polyether urethane is a thickening agent that gives an excellent feeling of use such as elasticity and resilience, but when used alone in an oil-in-water emulsion composition, it cannot have a sufficient yield value, It was necessary to maintain stability by using other water-soluble polymer or higher alcohol together (Patent Documents 1 to 4).

  However, when the amount of the water-soluble polymer or higher alcohol is increased in such an oil-in-water emulsion type composition, the yield value increases and it becomes difficult to express the restorability. In addition, if the amount of the oil agent is small, by using a water-soluble polymer or a higher alcohol together, it is possible to express the resilience while maintaining the high temperature stability, but if the amount of the oil agent increases, the high temperature stability is ensured. When blended with an amount of water-soluble polymer or higher alcohol, it is impossible to develop restorability, and these technologies are applied especially to sunscreens containing many oils and creams with high moisturizing power. I couldn't.

JP 2006-62996 A JP 2007-291026 A JP 2000-239120 A Special table 2011-523630 gazette

  An object of the present invention is to provide a technique capable of ensuring resilience and high-temperature stability in an oil-in-water emulsion-type composition containing a hydrophobically modified polyether urethane, regardless of the type and amount of the oil.

  As a result of diligent research to solve the above problems, the present inventors have formulated a specific surfactant in an oil-in-water emulsion composition containing a hydrophobically modified polyether urethane, a water-soluble polymer, and an oil agent. Thus, the present inventors have found that the above problems can be solved, and completed the present invention.

That is, the present invention includes the following components (A) to (E):
(A) Hydrophobically modified polyether urethane (B) Water-soluble polymer (C) One or more kinds selected from acyl glutamic acid, diacyl glutamic acid lysine or alkali metal salts thereof (D) Oil agent (E) Water An oil-in-water emulsion composition.

  The oil-in-water emulsified composition of the present invention is not affected by the type and amount of the oil agent, has no stickiness, and is excellent in resilience and high-temperature stability.

  The oil-in-water emulsified composition of the present invention is suitable for sunscreens and creams with high moisturizing power because the above effect can be ensured even when the amount of the oil agent is particularly large.

  Furthermore, the oil-in-water emulsified composition of the present invention, for example, is taken out of a container with a finger or a sledge, and after the surface is broken, the surface is immediately restored smoothly. It is excellent.

The oil-in-water emulsion type composition of the present invention contains the following components (A) to (E).
(A) Hydrophobic modified polyether urethane (B) Water-soluble polymer (C) One or more selected from acyl glutamic acid, diacyl glutamic acid lysine or alkali metal salts thereof (D) Oil agent (E) Water

  The component (A) hydrophobically modified polyether urethane is an amphiphilic copolymer having a hydrophilic group as a skeleton and having a hydrophobic portion at the terminal, and exhibits a thickening action when the hydrophobic portions of the copolymer are associated with each other in an aqueous medium. Although it will not specifically limit if it is a thing, For example, what is represented by following General formula (1) etc. is mentioned.

In the above formula ^{(1), R 1, R} 2 and R ⁴ represents a hydrocarbon group which may be the same or different, R ³ represents a hydrocarbon group which may have a urethane bond, R ⁵ Represents a linear, branched or secondary hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, and k and n are independently numbers in the range of 0 to 1000. R ¹ , R ² and R ⁴ preferably have 2 to ⁴ carbon atoms, R ³ has 1 to 10 carbon atoms, and R ⁵ has 8 to 36 carbon atoms. M is preferably 2, h is preferably 1, and k is preferably 1 to 500, more preferably 100 to 300. N is preferably 1 to 200, and more preferably 10 to 100.

The hydrophobically modified polyether urethane represented by the general formula (1) is, for example, one or more polyether polyols represented by R ¹ -[(O—R ² ) _k —OH] _m , and One or more polyisocyanates represented by R ^3- (NCO) _{h + 1} and one or more polyether monoalcohols represented by HO— (R ⁴ —O) _n —R ⁵ ; Can be obtained by reacting.

In this case, R ^{1 to} R ⁵ in the general formula (1) are R ¹ -[(O—R ² ) _k —OH] _m , R ^3- (NCO) _{h + 1} , HO— (R ⁴ ) used in the above reaction. _-O) is determined by n -R ^5. The charging ratio of these three components is not particularly limited, but the ratio of the hydroxyl group derived from polyether polyol and polyether monoalcohol to the isocyanate group derived from polyisocyanate is NCO / OH = 0.8: 1 to 1. It is preferably 4: 1.

  Among the hydrophobic modified polyether urethanes represented by the above general formula (1), those having both ends of polyethylene glycol modified with decyltetradecyl alcohol and having an average weight molecular weight of about 50,000 (GPC method) Are preferably used. Examples of such a hydrophobically modified polyether urethane include polyethylene glycol (PEG) -240 / decyltetradeceth-20 / hexamethylene diisocyanate (HDI) copolymer. This PEG-240 / decyltetradeceth-20 / HDI copolymer is sold by ADEKA Corporation as Adecanol GT-700. In addition, you may use a hydrophobic modified polyether urethane combining various things.

  The content of the component (A) in the oil-in-water emulsion composition of the present invention is not particularly limited, and is, for example, 0.1 to 5% by mass (hereinafter simply referred to as “%”), preferably 0.5 to 3 %.

  The component (B) water-soluble polymer is not particularly limited as long as it is generally used in cosmetics. For example, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, xanthan gum, gelatin, pectin, agar, gellan gum, sodium alginate, And polyacrylic acid amide, (sodium acrylate / acryloyldimethyltaurine sodium) copolymer, and the like. These water-soluble polymers can be used alone or in combination of two or more. Among these water-soluble polymers, carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers, and xanthan gum, in which aqueous solutions have yield values, are preferred. Component (B) does not include component (A).

  Although content of the component (B) in the oil-in-water emulsion type composition of this invention is not specifically limited, For example, it is 0.0005 to 1%, Preferably it is 0.0025 to 0.6%.

  The component (C) acyl glutamic acid or its alkali metal salt is not particularly limited as long as it is a compound in which one acyl group is introduced into glutamic acid or its alkali metal salt. For example, coconut oil fatty acid sodium acyl glutamate, coconut oil fatty acid Palm oil fatty acid glutamic acid such as potassium acyl glutamate or its alkali metal salt, myristoyl glutamic acid such as potassium myristoyl glutamate or its alkali metal salt, lauroyl glutamic acid such as sodium lauroyl glutamate or its alkali metal salt, stearoyl such as stearoyl glutamic acid, sodium stearoyl glutamate Examples thereof include glutamic acid or an alkali metal salt thereof. The diacyl glutamic acid lysine or its alkali metal salt is not particularly limited as long as it is a condensate of 2 mol of acyl glutamic acid and 1 mol of lysine or an alkali metal salt thereof. For example, dilauroyl glutamic acid lysine sodium, dimyristyl glutamic acid lysine sodium, etc. And a compound in which two acyl groups are introduced into the compound. These acyl glutamic acid, diacyl glutamic acid lysine or alkali metal salts thereof can be used alone or in combination of two or more. Of these, those having 8 to 18 carbon atoms in the acyl group in the compound are preferred, and dilauroylglutamic acid lysine or an alkali metal salt thereof in which two acyl groups are introduced in the compound is more preferred. Lauroyl glutamate ricin sodium is preferred.

  Although content of the component (C) in the oil-in-water emulsion type composition of this invention is not specifically limited, For example, it is 0.001 to 5%, Preferably it is 0.01 to 1%.

  The component (D) oil agent is not particularly limited as long as it is an oil agent generally used in cosmetics. For example, polar oil having an ester skeleton, liquid oil such as liquid paraffin, squalene, squalane, microcrystalline wax, dimethylpolysiloxane, Nonpolar oils including silicone oils such as methylphenylpolysiloxane, decamethylcyclopentasiloxane, (dimethicone / vinyldimethicone) crosspolymer, and the like are mentioned, but polar oils are preferably included. Examples of the polar oil include UV absorbers that are hardly soluble in non-polar oils such as hexyl diethylaminohydroxybenzoyl benzoate, t-butylmethoxydibenzoylmethane, bisethylhexyloxyphenol methoxyphenyltriazine, and ethylhexyltriazone. UV absorbers such as 2-ethylhexyl cinnamate, glyceryl tri (capryl / capric acid), glyceryl (caprylic acid / capric acid / coconut oil fatty acid), glyceryl tri-2-ethylhexanoate, glyceryl triisostearate, diisostearic acid di Glyceryl, glyceryl triisopalmitate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, Diglyceryl isostearate, propylene glycol dicaprate, neopentyl glycol dioctanoate, cholesterol fatty acid ester, cetyl isooctanoate, hexyl laurate, isononyl isononanoate, succinate diester, stearic acid hydrogenated castor oil, cetyl 2-ethylhexanoate, batyl Examples thereof include alcohol, phytosterol fatty acid ester, diisostearyl malate, jojoba oil, olive oil, beeswax, and candelilla wax. Among these polar oils, it is particularly preferable to contain an ultraviolet absorber that is hardly soluble in nonpolar oils. These oil agents can be used alone or in combination of two or more.

  Although content of the component (D) in the oil-in-water emulsion type composition of this invention is not specifically limited, For example, it is 0.1-50%, Preferably it is 1-40%, More preferably, it is 9-40%. In component (D), it is preferable that polar oil is contained 50% or more, preferably 60% or more.

  Although content of the said component (E) water is not specifically limited, For example, it is 40 to 95%, Preferably it is 50 to 90%.

  In the oil-in-water emulsion composition of the present invention, the content ratio (B) / (A) of the component (B) and the component (A) is 0.005 to 0.2, preferably 0.008 to 0. .15, more preferably 0.01 to 0.1. If it is this ratio, a restoring property and high temperature stability can be maintained.

  In the oil-in-water emulsion composition of the present invention, the mass ratio (C) / (D) of the component (C) and the component (D) is 0.0005 to 0.2, preferably 0.0008 to 0. .1, more preferably 0.001 to 0.05. When the ratio is in this range, good high temperature stability is obtained.

  Furthermore, in the oil-in-water emulsion composition of the present invention, in addition to the above components (A) to (E), for example, glycerin, propylene glycol, 1 Polyhydric alcohols such as 1,3-butanediol, lower alcohols such as ethanol and propanol, higher alcohols such as stearyl alcohol and behenyl alcohol, anionic surfactants such as sodium lauryl sulfate and alkylsulfosuccinates, quaternary alkylamine salts Cationic surfactants such as amphoteric surfactants such as alkylbetaines, nonionic surfactants such as polyoxyethylene phytosterol and polyethylene glycol monostearate, parabens, preservatives such as chlorhexidine gluconate, talc, silica gel, titanium oxide Powders such as Tocophero Antioxidants such as butylhydroxytoluene, water-soluble UV absorbers such as sodium hydroxymethoxybenzophenone sulfonate, moisturizers such as polyethylene glycol and hyaluronic acid, anti-inflammatory agents such as dipotassium glycyrrhizinate, citrate, and acetate PH adjusting agents such as chelating agents, fragrances, pigments and the like may be included.

  In addition, the oil-in-water emulsion type composition of the present invention can be in the form of an emulsion, a gel, or the like. The oil-in-water emulsion composition of the present invention is particularly preferably a gel.

  The oil-in-water emulsified composition of the present invention described above is added in the same manner as a normal emulsion composition, for example, by adding various optional components to each of the oil phase component and the water phase component as necessary. Can be prepared by a method such as heating to about 70 to 90 ° C., mixing and emulsifying with stirring, and then cooling.

  The oil-in-water emulsified composition of the present invention thus obtained has no stickiness and has resilience and high temperature stability.

  Here, the term “restorability” means, for example, that the oil-in-water emulsion composition is taken out of the container with a finger or the like and the surface is quickly restored after the surface is destroyed. Specifically, the oil-in-water emulsion composition is measured with a B-type viscometer, the viscosity at 30 ° C. is 10,000 mPa · s or more, preferably 10,000 to 200,000 mPa · s, and the diameter is 8 cm. A circular resin container is filled to a height of 4 cm, and from a flat surface in a horizontal state, a circular plate having a diameter of 1 cm is pushed to a depth of 2 cm from the surface to make a hole, and then left to stand. The time required for restoration until the original flat state is restored is less than 60 seconds.

  Moreover, high temperature stability means that separation does not occur during high temperature storage, and specifically means that separation does not occur even after one month when stored at 50 ° C.

  Therefore, the oil-in-water emulsified composition of the present invention can be used for cosmetics, skin external preparations and the like, and can be used particularly for cosmetics such as sunscreens and creams with high moisturizing power.

  And since the oil-in-water emulsified composition of the present invention has resilience, it is suitable for cosmetics and the like that are filled in containers such as jar containers and taken out with fingers or sledges during use.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.

Examples 1-12 and Comparative Examples 1-4
Oil-in-water emulsified composition:
An oil-in-water emulsion type composition (gel form) was prepared by the composition shown in Table 1 and the following production method. Table 1 also shows the results of evaluating these oil-in-water emulsion compositions by the following evaluation methods and evaluation criteria.

<Manufacturing method>
A: Components (1) to (9) were uniformly mixed at 80 ° C.
B: Components (10) to (15) were uniformly mixed at 80 ° C.
C: B was added to A, emulsified by stirring at 3,500 rpm for 10 minutes with a homomixer, and then stirred and cooled to room temperature to obtain an oil-in-water emulsion type composition (gel form).

<Sticky evaluation method>
The stickiness when each sample was applied to the skin was evaluated by 20 panelists based on the following evaluation criteria.
(Stickiness evaluation criteria)
Evaluation Content ◎: Feels almost non-sticky ○: Feels almost non-sticky △: Feels slightly sticky ×: Feels very sticky

<Measurement method of time required for restoration>
After filling the sample into a circular resin container with a diameter of 8 cm to a height of 4 cm and opening a hole by pushing a circular plate with a diameter of 1 cm from the surface to a depth of 2 cm from a flat surface in a horizontal state. The time required for resting and returning to the original flat state was measured. The sample temperature was 30 ° C.

<Restorability evaluation method>
The time required for restoration was measured and evaluated based on the following evaluation criteria.
(Restorability evaluation criteria)
Evaluation content ◎: Within 30 seconds ○: Less than 60 seconds △: More than 60 seconds ×: Not horizontal

<High temperature stability evaluation method>
Each sample was placed in a jar and stored at 50 ° C. for 1 month, and then evaluated based on the following evaluation criteria.
(High temperature stability evaluation criteria)
◎: No separation △: No separation, but oil floating is observed on the surface ×: Separation

<Measurement method of viscosity>
The viscosity at 30 ° C. was measured using a B-type viscometer as a measuring instrument.

<Method for evaluating uniformity of coating film>
The oil-in-water emulsion composition of Example 12 was applied to the skin by 20 panels, and the state of the coating film was evaluated based on the following evaluation criteria by visual observation. The reason why the coating film uniformity was evaluated only for the sample of Example 12 was because it contained powder, and the oil-in-water emulsion type compositions of Examples 1 to 11 that did not contain powder. In the first place, since no unevenness was observed in the coating film, it was not evaluated.
(Coating film uniformity evaluation criteria)
Evaluation content ◎: No unevenness ×: Unevenness

  The oil-in-water emulsified compositions of Examples 1 to 12 all have a viscosity of 30,000 mPa · s or more, and are less sticky, have a higher recovery property, and have a higher temperature than the oil-in-water emulsified compositions of Comparative Examples 1 to 4. The stability and uniformity of the coating film were all excellent.

Example 13
Massage cream (oil-in-water emulsified gel):
(Ingredient) (%)
1. Sodium lauroyl glutamate 0.2
2. Water remaining 3. (PEG-240 / decyltetradeceth-20 / HDI) copolymer 1
4. Alkyl-modified carboxyvinyl polymer 0.05
5. Hydroxypropyl methylcellulose 0.01
6. Potassium hydroxide 0.042
7. Glyceryl tri-2-ethylhexanoate 10
8. Behenyl alcohol 1
9. Glyceryl stearate 0.5
10. Beeswax 1
11. Dimethylpolysiloxane 0.5
12. Fragrance 0.5

(Production method)
A: Components (1) to (6) were uniformly heated and dissolved at 80 ° C.
B: Components (7) to (12) were uniformly dissolved by heating at 70 ° C.
C: B was added to A and emulsified.
D: After cooling, C was filled into a jar container.

  The cream of Example 13 had no stickiness, had a restoring property of 22 seconds, and was excellent in high-temperature stability.

Example 14
Gel cream (oil-in-water emulsified gel):
(Ingredient) (%)
1. Sodium stearoyl glutamate 0.2
2. Water remaining 3. (PEG-240 / decyltetradeceth-20 / HDI) copolymer 1
4. Carboxyvinyl polymer 0.05
5. Gellan gum 0.01
6. Potassium hydroxide 0.042
7. Glyceryl tri-2-ethylhexanoate 20
8. Lauroyl glutamate di (phytosteris / octyldodecyl) (Note 3)
0.05
9. Wheat germ oil 0.05
10. Rice germ oil 0.05
11. Almond oil 0.05
12. Lavender oil 0.05
13. Astaxanthin (Note 4) 0.01
14. Tocopherol 0.02
15. Dibutylhydroxytoluene 0.02
(Note 3) El Dew PS-203 (Ajinomoto Co., Inc.)
(Note 4) Astaxanthin-5C (manufactured by Oriza Oil Refiner)

(Production method)
A: Components (1) to (6) were uniformly heated and dissolved at 80 ° C.
B: Components (7) to (15) were uniformly heated and dissolved at 70 ° C.
C: B was added to A and emulsified.
D: After cooling, C was filled into a jar container.

  The gel cream of Example 14 had no stickiness, had a restoring property of 18 seconds, and had excellent high temperature stability.

Example 15
Emulsion (oil-in-water emulsion type emulsion):
(Ingredient) (%)
1. Palm oil fatty acid sodium acyl glutamate 0.2
2. Water remaining 3. (PEG-240 / decyltetradeceth-20 / HDI) copolymer 0.15
4. Carrageenan 0.03
5. BG 2
6. DPG 4
7. Glycerin 2
8. Ethanol 5
9. EDTA-2Na 0.01
10. Liquid paraffin 5
11. Glyceryl tri-2-ethylhexanoate 4
12. Trimethylolpropane triisostearate 4
13. Hydrogenated palm oil 2
14. Hydrogenated palm oil 0.1
15. Hydrogenated lecithin 0.1
16. Phenoxyethanol 0.1
17. Methylparaben 0.1
18. Fragrance 0.1

(Production method)
A: Components (1) to (9) were uniformly dissolved by heating at 80 ° C.
B: Components (10) to (18) were uniformly heated and dissolved at 70 ° C.
C: B was added to A and emulsified.
D: After cooling, C was filled into a bottle container.

  The emulsion of Example 15 had no stickiness, had a viscosity value of 16,100 mPa · s, and was excellent in high-temperature stability.

Example 16
Moisturizing cream (oil-in-water emulsified gel):
(Ingredient) (%)
1. Palm oil fatty acid acyl potassium potassium glutamate 0.2
2. Water remaining 3. (PEG-240 / decyltetradeceth-20 / HDI) copolymer 1
4. Carboxyvinyl polymer 0.05
5. Locust bean gum 0.01
6. Potassium hydroxide 0.042
7. BG 10
8. Glycerin 1
9. Diglycerin 4
10.Sorbit liquid 3
11. Polyoxyethylene methyl glucoside 1
12. Cetostearyl alcohol 0.5
13. Behenyl alcohol 0.5
14. Glyceryl tri-2-ethylhexanoate 0.5
15. Phenoxyethanol 0.1
16. Methylparaben 0.1
17. Fragrance 0.1

(Production method)
A: Components (1) to (11) were uniformly heated and dissolved at 80 ° C.
B: Components (12) to (17) were uniformly dissolved by heating at 70 ° C.
C: B was added to A and emulsified.
D: After cooling, C was filled into a jar container.

  The moisturizing cream of Example 16 had no stickiness, had a restorability of 18 seconds, and was excellent in high temperature stability.

Example 17
Liquid foundation (oil-in-water emulsified gel):
(Ingredient) (%)
1. Dilauroyl ricin sodium glutamate 0.2
2. Water remaining 3. (PEG-240 / decyltetradeceth-20 / HDI) copolymer 1
4. Carboxyvinyl polymer 0.05
5. Potassium hydroxide 0.042
6. BG 2
7. Glycerin 2
8. Sodium chloride 0.05
9. Ethanol 5
10.BG 12
11. Hydrogenated soybean phospholipid 1.5
12. Titanium oxide 7
13. Zinc oxide 7
14. Iron oxide 2
15. Talc 0.5
16. Mica 0.5
17. Cyclomethicone 15
18. Dimethylpolysiloxane 5
19. Ethylhexyl methoxycinnamate 5
20. Isotridecyl isononanoate 5
21. Dicapric acid PG 2
22. Isododecane 2
23. Methylenebisbenzotriazolyltetramethylbutylphenol 0.5
24. Diethylaminohydroxybenzoyl hexyl benzoate 0.5
25. Phenoxyethanol 0.1
26. Methylparaben 0.1
27. Fragrance 0.1

(Production method)
A: Components (1) to (9) were uniformly dissolved by heating at 80 ° C.
B: Components (10) to (16) were dispersed.
C: B was added to A and mixed uniformly at 70 ° C.
D: Components (17) to (27) were uniformly dissolved by heating at 70 ° C.
E: D was added to C and emulsified.
F: After cooling, E was filled in a jar container.

  The liquid foundation of Example 17 had no stickiness, had a restorability of 10 seconds, and was excellent in high-temperature stability and coating film uniformity.

The oil-in-water emulsified composition of the present invention has no stickiness and is excellent in resilience and high-temperature stability and can be used in various cosmetics.

that's all

Claims (10)

Next ingredient (A)-(E)
(A) Hydrophobically modified polyether urethane (B) Water-soluble polymer (C) One or more kinds selected from acyl glutamic acid, diacyl glutamic acid lysine or alkali metal salts thereof (D) Oil agent (E) Water An oil-in-water emulsion composition.   The oil-in-water emulsion composition according to claim 1, wherein component (A) is a (polyethylene glycol-240 / decyltetradeceth-20 / hexamethylene diisocyanate) copolymer.   The oil-in-water emulsion composition according to claim 1 or 2, wherein the component (B) is one or more selected from the group consisting of a carboxyvinyl polymer, an alkyl-modified carboxyvinyl polymer, and xanthan gum.   The oil-in-water emulsion composition according to any one of claims 1 to 3, wherein the component (C) is diacylglutamic acid lysine or an alkali metal salt thereof.   The oil-in-water emulsion composition according to any one of claims 1 to 4, which contains 0.1 to 50% by mass of component (D).   The oil-in-water emulsified composition according to claim 5, wherein component (D) contains a polar oil.   The content mass ratio (B) / (A) of the component (B) and the component (A) is 0.005 to 0.2, The oil-in-water emulsion composition according to any one of claims 1 to 6 .   The oil-in-water emulsion composition according to any one of claims 1 to 7, wherein the mass ratio (C) / (D) of the component (C) and the component (D) is from 0.0005 to 0.2. .   A state in which the viscosity at 30 ° C. is 10,000 mPa · s or more as measured with a B-type viscometer, and a circular resin container having a diameter of 8 cm is filled to a height of 4 cm, and the surface is flat in a horizontal state. 2. The time required for restoration from returning to the original flat state after pushing a circular plate having a diameter of 1 cm to a depth of 2 cm from the surface to make a hole and leaving the plate flat is less than 60 seconds. The oil-in-water emulsion-type composition of any one of -8.   Cosmetics which filled the jar container with the oil-in-water emulsion type composition of any one of Claims 1-9.