JP2023173200A - Water-in-oil emulsion composition - Google Patents

Abstract

To provide a water-in-oil emulsion composition that contains niacinamide and demonstrates a reduced tendency for viscosity decrease over time.SOLUTION: A water-in-oil emulsion composition contains (A) niacinamide, (B) highly polymerized polyether-modified silicone, and (C) silicone-branched polyether-modified silicone. The mass content ratio of the component (C) to the component (B), (C)/(B), is 0.3-1.8.SELECTED DRAWING: None

Description

The present disclosure relates to water-in-oil emulsion compositions and the like.

Niacinamide is a water-soluble vitamin and one of the B vitamins. Niacinamide is known to have whitening effects, wrinkle-improving effects, rough skin-improving effects, etc., and is commonly incorporated into cosmetics and the like.

JP2021-066726A

The present inventors have discovered that when niacinamide is blended into a water-in-oil emulsion composition, the viscosity decreases over time. An object of the present disclosure is to provide a water-in-oil emulsion composition containing niacinamide whose viscosity decreases over time.

The present inventors have discovered that by blending highly polymerized polyether-modified silicone and silicone-branched polyether-modified silicone in a specific ratio, the decrease in viscosity over time can be suppressed, and further improvements are being made. Layered.

The present disclosure encompasses, for example, the subject matter described in the following sections.
Item 1.
(A) Niacinamide,
(B) contains highly polymerized polyether-modified silicone, and (C) silicone branched polyether-modified silicone,
A water-in-oil emulsion composition, wherein the content mass ratio (C)/(B) of the component (C) to the component (B) is 0.3 to 1.8.
Item 2.
Item 2. The water-in-oil emulsion composition according to Item 1, wherein the content of component (A) is 1 to 15% by mass.
Item 3.
Item 3. The water-in-oil emulsion composition according to Item 1 or 2, wherein the components (B) and (C) have an HLB of 5 or less.
Item 4.
Item 4. The water-in-oil emulsion composition according to any one of Items 1 to 3, wherein the component (B) is PEG/PPG-19/19 dimethicone and/or PEG/PPG-18/18 dimethicone.
Item 5.
Item 5. The water-in-oil emulsion composition according to any one of Items 1 to 4, wherein the component (C) is PEG-9 polydimethylsiloxyethyl dimethicone.
Item 6.
Item 5. The water-in-oil emulsion composition according to any one of Items 1 to 5, further comprising an electrolyte.
Section 7.
Item 7. The water-in-oil emulsion composition according to any one of Items 1 to 6, further comprising an oil phase thickener.
Section 8.
Item 8. The water-in-oil emulsion composition according to Item 7, wherein the oil phase thickener is an organically modified clay mineral and/or a silicone elastomer.

In a water-in-oil emulsion composition containing niacinamide, a decrease in viscosity over time can be suppressed.

Each embodiment included in the present disclosure will be described in further detail below.
The water-in-oil emulsion composition encompassed by the present disclosure contains (A) niacinamide, (B) highly polymerized polyether-modified silicone, and (C) silicone branched polyether-modified silicone. In this specification, the water-in-oil emulsion composition may be referred to as "the water-in-oil emulsion composition of the present disclosure." Further, each of the components (A) to (C) may be expressed as "component (A),""component(B),""component(C)," etc.

Niacinamide is an amide of niacin (vitamin B ₃ ) and is also called nicotinamide. Niacinamide is a water-soluble vitamin and one of the B vitamins. Niacinamide may be a natural product or a synthetic product, and is not particularly limited, and may be purified from a natural product or commercially available.

In the water-in-oil emulsion composition of the present disclosure, niacinamide may be contained, for example, in the aqueous phase or in the oil phase. Among these, it is preferably contained in the aqueous phase.

In the water-in-oil emulsion composition of the present disclosure, the content of niacinamide can be, for example, about 1 to 15% by mass. The upper or lower limit of the range may be, for example, about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14% by mass. More specifically, it may be, for example, about 1 to 10% by mass.

As used herein, "highly polymerized polyether-modified silicone" refers to a high molecular weight silicone in which a portion of the side chains (more specifically, methyl groups) of the silicone chain are substituted with polyether groups. The highly polymerized polyether-modified silicone is a compound represented by the following general formula (I).

［式中、Ｒ’は、同一又は異なって、メチル基、又はフェニル基を示す。
Ｒ’’は、同一又は異なって、メチル基、フェニル基、又は－Ｃ_３Ｈ_６Ｏ（Ｃ_２Ｈ_４Ｏ）_ｆ（Ｃ_３Ｈ_６Ｏ）_ｇＲ’’’（Ｒ’’’は、水素原子、アシル基、又は炭素数１～４のアルキル基を示す。ｆは、５～５０の整数を示し、ｇは、５～５０の整数を示す。）で示されるポリオキシアルキレン基を示す。ただし、式中、Ｒ’’のうち、少なくとも１個は前記ポリオキシアルキレン基を示す。
ｄは、５０～１０００の整数を示し、ｅは、１～４０の整数を示す。］

[In the formula, R' is the same or different and represents a methyl group or a phenyl group.
R'' is the same or different and is a methyl group, a phenyl group, or -C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g R'''(R''' is Represents a hydrogen atom, an acyl group, or an alkyl group having 1 to 4 carbon atoms. f represents an integer of 5 to 50, and g represents an integer of 5 to 50.) Represents a polyoxyalkylene group represented by . However, in the formula, at least one of R'' represents the polyoxyalkylene group.
d represents an integer from 50 to 1000, and e represents an integer from 1 to 40. ]

In general formula (I), R' is preferably a methyl group.

In the general formula (I), R'' is a methyl group or a polyoxyalkylene group represented by -C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g R'' It is preferable that there be.

-C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g In the polyoxyalkylene group represented by R''', f is preferably an integer from 10 to 30, and from 15 to More preferably, it is an integer of 25.

-C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g In the polyoxyalkylene group represented by R''', g is preferably an integer from 10 to 30, and from 15 to More preferably, it is an integer of 25.

-C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g As the acyl group of R''' of the polyoxyalkylene group represented by R''', for example, formyl group, acetyl group, etc. group, propionyl group, benzoyl group, etc.
-C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g R''' of the polyoxyalkylene group represented by R''' is an alkyl group having 1 to 4 carbon atoms, Examples include methyl group, ethyl group, isopropyl group, n-propyl group, t-butyl group, n-butyl group, and the like.
R''' of the polyoxyalkylene group represented by -C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g R''' is preferably a hydrogen atom.

-C ₃ H ₆ O(C ₂ H ₄ O) _f (C ₃ H ₆ O) _g In the polyoxyalkylene group represented by R''', an oxyethylene group (C ₂ H ₄ O) and an oxypropylene group ( The bonding order of C ₃ H ₆ O) is not particularly limited.

In general formula (I), d represents an integer of 50 to 1000. For example, d may be an integer from 150 to 1000.

In general formula (I), d

及びｅ個の

and e number of

の結合順序は、特に限定されない。

The order in which they are combined is not particularly limited.

In general formula (I), d:e is not particularly limited, but can be, for example, about 200:1 to 5:1.

In general formula (I), the content of polyoxyalkylene groups is not particularly limited, but can be, for example, about 20% by mass or more.

The mass average molecular weight of the highly polymerized polyether-modified silicone is not particularly limited, but can be, for example, about 10,000 or more.

The HLB of the highly polymerized polyether-modified silicone is preferably about 5 or less, for example. The upper limit or lower limit of the range may be, for example, about 1, 2, 3, or 4. More specifically, it may be about 1 to 4, for example.

Examples of highly polymerized polyether-modified silicones include PEG/PPG-19/19 dimethicone, PEG/PPG-18/18 dimethicone, and PEG/PPG-30/10 dimethicone. These can be used alone or in combination of two or more. Among these, PEG/PPG-19/19 dimethicone or PEG/PPG-18/18 dimethicone is preferred.

As the highly polymerized polyether-modified silicone, for example, BY25-337, BY11-030, BY22-008M, ES-5226, ES-5227, FB-2540 (manufactured by Dow Corning Toray Industries, Inc.), etc. can be used. Among them, BY25-337, BY11-030, BY22-008M, ES-5226, and ES-5227 (manufactured by Dow Corning Toray Industries) are preferred, and BY25-337 and ES-5227 are more preferred.

In the water-in-oil emulsion composition of the present disclosure, the highly polymerized polyether-modified silicone may be contained, for example, in the aqueous phase or in the oil phase. Among these, it is preferably contained in the oil phase.

In the water-in-oil emulsion composition of the present disclosure, the content of highly polymerized polyether-modified silicone can be, for example, about 0.1 to 5% by mass. The upper or lower limit of the range is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, or 4. It may be about % by mass. More specifically, it may be about 0.2 to 4% by mass, for example.

In this specification, as the "silicone branched polyether-modified silicone", for example, those described in JP-A-2013-53072 can be preferably used. More specifically, the silicone branched polyether-modified silicone is represented by the following general formula (II), and has a structure in which the siloxane chain is branched from a linear polyether-modified siloxane as the main chain, Furthermore, the siloxane main chain may have a moiety co-modified with a long-chain alkyl group.

［式中、Ｒ_２は炭素数１～３０のアルキル基を示す。
ｍはそれぞれ独立して１～４のいずれかの整数を示す。
ｘは０～２００の整数を示す。
ｙは１～３０の整数を示す。
ｚは０～５０の整数を示す。
ｐは１～２０の整数を示す。
ａは０～３０の整数を示す。
ｂは０～３０の整数を示す。
ｃは１～５０の整数を示す。
但し、ａとｂが共に０は除く。
また、各シロキサン単位及び各オキシアルキレン単位は、ランダム結合でもブロック結合でもよく、任意の組み合わせで結合している。］

[In the formula, R ₂ represents an alkyl group having 1 to 30 carbon atoms.
m each independently represents an integer of 1 to 4;
x represents an integer from 0 to 200.
y represents an integer from 1 to 30.
z represents an integer from 0 to 50.
p represents an integer from 1 to 20.
a represents an integer from 0 to 30.
b represents an integer from 0 to 30.
c represents an integer from 1 to 50.
However, both a and b are not 0.
Further, each siloxane unit and each oxyalkylene unit may be bonded randomly or in a block manner, and may be bonded in any combination. ]

Further, the weight average molecular weight of the silicone branched polyether-modified silicone exemplified by formula (II) is not particularly limited, but is preferably, for example, 500 to 200,000, more preferably 1,000 to 10,000.

The HLB of the silicone branched polyether-modified silicone is preferably about 5 or less, for example. The upper limit or lower limit of the range may be, for example, about 1, 2, 3, or 4. More specifically, it may be about 1 to 4, for example.

Examples of the silicone branched polyether-modified silicone include PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and cetyl PEG-9 polydimethylsiloxyethyl dimethicone. These can be used alone or in combination of two or more. Among them, PEG-9 polydimethylsiloxyethyl dimethicone is preferred.

As the silicone branched polyether modified silicone, for example, KF-6028, KF-6028M, KF-6038, etc. can be used. Among these, KF-6028 and KF-6028M are preferred, and KF-6028 is more preferred.

In the water-in-oil emulsion composition of the present disclosure, the silicone branched polyether-modified silicone may be contained, for example, in the aqueous phase or in the oil phase. Among these, it is preferably contained in the oil phase.

In the water-in-oil emulsion composition of the present disclosure, the content of the silicone branched polyether-modified silicone can be, for example, about 0.1 to 5% by mass. The upper or lower limit of the range is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, or 4. It may be about % by mass. More specifically, it may be about 0.2 to 4% by mass, for example.

In the water-in-oil emulsion composition of the present disclosure, the mass ratio of component (C) to component (B) ((C)/(B)) is preferably about 0.3 to 1.8. The upper limit or lower limit of the range is, for example, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1. It may be about 4, 1.5, 1.6, or 1.7. More specifically, it may be, for example, about 0.3 to 1.7, or about 0.4 to 1.4.

In the water-in-oil emulsion composition of the present disclosure, the content mass ratio of component (A) to the total amount of components (B) and (C) ((A)/(B)+(C)) is, for example, about 1. It can be more than that. The upper limit or lower limit of the range is, for example, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, It may be about 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10. More specifically, it may be about 1 to 10, or about 1.2 to 6, for example.

The water-in-oil emulsion composition of the present disclosure may include an electrolyte. As used herein, "electrolyte" refers to a substance that ionizes into cations and anions when dissolved in a solvent.
Examples of electrolytes include acids, bases, salts, and the like. These can be used alone or in combination of two or more. Among these, salt is preferred.
Examples of the salt include alkali metal salts, alkaline earth metal salts, inorganic acid salts, organic acid salts, amino acid salts, and the like. Among these, alkali metal salts or alkaline earth metal salts are preferred, and alkali metal salts are more preferred.
Examples of alkali metal salts include sodium salts such as sodium chloride, sodium glutamate, trisodium citrate, and sodium bicarbonate; potassium salts such as potassium chloride; and the like.
Examples of alkaline earth metal salts include calcium salts such as calcium chloride; magnesium salts such as magnesium chloride; and the like.

In the water-in-oil emulsion composition of the present disclosure, the electrolyte may be contained, for example, in the aqueous phase or in the oil phase. Among these, it is preferably contained in the aqueous phase.

Although not wishing to be bound by theory, it is expected that the water-in-oil emulsion composition of the present disclosure can further suppress a decrease in viscosity over time by containing an electrolyte.

In the water-in-oil emulsion composition of the present disclosure, the electrolyte content can be, for example, about 0.1 to 5% by mass. The upper or lower limit of the range is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, or 4. It may be about % by mass. More specifically, it may be about 0.2 to 4% by mass, for example.

The water-in-oil emulsion composition of the present disclosure may include an oil phase thickener. As used herein, "oil phase thickener" refers to a substance that is capable of increasing the viscosity of an oil phase. Examples of the oil phase thickener include organically modified clay minerals, silicone elastomers, sucrose fatty acid esters, and glyceryl fatty acid esters. These can be used alone or in combination of two or more. Among these, organically modified clay minerals or silicone elastomers are preferred.
Examples of organically modified clay minerals include hectorite, montmorillonite, saponite, hectorite, bentonite, smectite, dimethyldistearylammonium hectorite (disteardimonium hectorite), dimethyldistearylammonium bentonite, benzyldimethylstearylammonium hectorite. , dioctadecyldimethylammonium salt-modified montmorillonite, octadecyldimethylbenzylammonium salt-modified montmorillonite, dihexadecyldimethylammonium salt-modified montmorillonite, dimethyldistearylammonium smectite, and the like.
Examples of the silicone elastomer include (dimethicone/vinyl dimethicone) crosspolymer, (dimethicone/phenylvinyl dimethicone) crosspolymer, (vinyl dimethicone/lauryl dimethicone) crosspolymer, and (vinyl dimethicone/methicone silsesquioxane) crosspolymer. Can be mentioned.

In the water-in-oil emulsion composition of the present disclosure, the oil phase thickener may be contained, for example, in the aqueous phase or in the oil phase. Among these, it is preferably contained in the oil phase.

In the water-in-oil emulsion composition of the present disclosure, the content of the oil phase thickener can be, for example, about 1 to 30% by mass. The upper or lower limit of the range may be, for example, about 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25% by mass. More specifically, it may be about 2 to 9% by mass, for example.

The water-in-oil emulsion composition of the present disclosure preferably contains an oily base in the oil phase, for example. Examples of oily bases include silicone oils such as dimethicone, cyclopentasiloxane, and diphenylsiloxyphenyl trimethicone; hydrocarbon oils such as hydrogenated polyisobutene, mineral oil, and petrolatum; ethylhexyl palmitate, isononyl isononanoate, isotridecyl isononanoate, etc. ester oil; etc.

In the water-in-oil emulsion composition of the present disclosure, the content of the oily base can be, for example, about 10 to 90% by mass. The upper or lower limit of the range may be, for example, about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by mass. More specifically, it may be, for example, about 35 to 65% by mass.

The water-in-oil emulsion composition of the present disclosure preferably contains water in the oil phase, for example.
The water-in-oil emulsion composition of the present disclosure can have a water content of, for example, about 10 to 90% by mass. The upper or lower limit of the range may be, for example, about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by mass. More specifically, it may be, for example, about 35 to 65% by mass.

The water-in-oil emulsion composition of the present disclosure includes the components described above, and may further include other components. The other ingredients include pharmacologically (food hygiene) acceptable bases, carriers, solvents, dispersants, emulsifiers, buffers, stabilizers, excipients, binders, disintegrants, and lubricants. , thickeners, surfactants (for example, component (B) such as PEG-10 dimethicone, or silicone surfactants other than component (C), etc.), antioxidants, preservatives, coating agents, colorants, Examples include active ingredients such as preservatives, fragrances, pH adjusters, and plant extracts, and/or other components and materials that can be used as food or feed. These components can be used alone or in combination of two or more.
In addition, the water-in-oil emulsion composition of the present disclosure includes ultraviolet scattering agents such as zinc oxide and titanium oxide; ultraviolet absorbers such as ethylhexyl methoxycinnamate, t-butylmethoxydibenzoylmethane, and octocrylene; pigments; and volatile oil agents. ; Solid oil; does not contain component (B), component (C), or a polyether-modified silicone emulsifier other than PEG-10 dimethicone, a polyglycerin-modified silicone emulsifier, and/or a volatile silicone such as cyclopentasiloxane. Good too.

The method for producing the water-in-oil emulsion composition of the present disclosure is not particularly limited, and can be produced by employing methods and arbitrary conditions known in the technical field. For example, it can be produced by preparing an oil phase containing the component (B) and the component (C) and an aqueous phase containing the component (A), respectively, and mixing and emulsifying the aqueous phase and the oil phase. .

The shape of the water-in-oil emulsion composition of the present disclosure is not particularly limited. For example, it may be in liquid, gel, cream, or solid form.

The water-in-oil emulsion composition of the present disclosure may be, for example, a composition for external use. Furthermore, the water-in-oil emulsion composition of the present disclosure may be, for example, a pharmaceutical, a quasi-drug, a cosmetic, or the like.

Note that in this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Additionally, the present disclosure encompasses any and all combinations of the features described herein.

Further, the various characteristics (properties, structures, functions, etc.) described for each embodiment of the present disclosure described above may be combined in any manner in order to specify the subject matter covered by the present disclosure. That is, the present disclosure encompasses all subject matter consisting of any and all combinations of the combinable features described herein.

The content of the present disclosure will be specifically explained using the following examples. However, the present disclosure is not limited thereto. In the following, unless otherwise specified, experiments are conducted under atmospheric pressure and room temperature conditions. In addition, the blending amount of each component listed in each table is expressed in "% by mass" unless otherwise specified.

Manufacturing method A water-in-oil emulsion composition was prepared according to the formulation shown in Table 1. In the table, I indicates an oil phase and II indicates a component contained in an aqueous phase. The details are as follows.
First, the components of oil phase I were uniformly mixed at room temperature using a disper. Additionally, the components of aqueous phase II were uniformly mixed at room temperature using a stirrer. Water phase II was gradually added to oil phase I while stirring with a disper, and when the entire amount was added, the rotation speed of the disper was increased to perform emulsification. Finally, defoaming was performed to obtain a water-in-oil emulsion composition. In the table, the HLB of components (B) and (C) is 2 for PEG/PPG-19/19 dimethicone (BY25-337 (manufactured by Toray Dow Corning)) and 2 for PEG/PPG-18/18 dimethicone. (ES-5227 (manufactured by Dow Corning Toray)) is 2, and PEG-9 polydimethylsiloxyethyl dimethicone (KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)) is 4.

Evaluation method
1. Viscosity Stability Evaluation Method The obtained water-in-oil emulsion composition was filled into a 50 ml glass bottle so as not to entrap air, and this was used as a measurement sample. The measurement sample was left still in a 55° C. thermostat, and the torque value of the measured viscosity was recorded one week and four weeks later by the following method.

2. Viscosity measurement method The measurement sample was kept at a constant temperature of 25°C, and was measured using a B-type viscometer and rotor No. The rotation speed was set for each lot under the conditions of 4 and 60 seconds, and the torque value of the viscosity on the day of manufacture was closest to 50%. Samples in which the value obtained by subtracting the torque value after 4 weeks from the torque value after 1 week was 4 or less were accepted. The results are also shown in Table 1.

As shown in Comparative Examples 2 to 5, it was confirmed that the viscosity of water-in-oil emulsion compositions containing niacinamide decreased over time. On the other hand, in Examples 1 to 8 containing components (B) and (C) in a specific ratio, it was confirmed that the value obtained by subtracting the torque value after 4 weeks from the torque value after 1 week was 4 or less. Further, as shown in Comparative Examples 6 to 12, even if components (B) and (C) were contained, when the ratio was outside the specific range, the thinning of the viscosity over time was not suppressed. In addition, a comparative example in which polysilicone 13 (linear polyether-modified silicone; a linear block copolymer in which polyether and silicone are alternately bonded) was blended instead of component (B) or (C). In Samples No. 13 and 14, no effect of suppressing the decrease in viscosity over time was observed.

Table 2 shows formulation examples of the water-in-oil emulsion composition of the present disclosure. In addition, the blending amount values of each component described in the table also indicate "mass %" unless otherwise specified.

Claims (9)

(A) Niacinamide,
(B) contains highly polymerized polyether-modified silicone, and (C) silicone branched polyether-modified silicone,
A water-in-oil emulsion composition, wherein the content mass ratio (C)/(B) of the component (C) to the component (B) is 0.3 to 1.8. The water-in-oil emulsion composition according to claim 1, wherein the content of the component (A) is 1 to 15% by mass. The water-in-oil emulsion composition according to claim 1 or 2, wherein the components (B) and (C) have an HLB of 5 or less. The water-in-oil emulsion composition according to claim 1 or 2, wherein the component (B) is PEG/PPG-19/19 dimethicone and/or PEG/PPG-18/18 dimethicone. The water-in-oil emulsion composition according to claim 1 or 2, wherein the component (C) is PEG-9 polydimethylsiloxyethyl dimethicone. The water-in-oil emulsion composition according to claim 1 or 2, further comprising an electrolyte. The water-in-oil emulsion composition according to claim 1 or 2, further comprising an oil phase thickener. The water-in-oil emulsion composition according to claim 7, wherein the oil phase thickener is an organically modified clay mineral and/or a silicone elastomer. The composition according to claim 1, having at least one of the following characteristics (i) to (vi).
(i) The content of the component (A) is 1 to 15% by mass. (ii) The HLB of the components (B) and (C) is 5 or less. (iii) The component (B) is PEG/PPG. -19/19 dimethicone and/or PEG/PPG-18/18 dimethicone (iv) the component (C) is PEG-9 polydimethylsiloxyethyl dimethicone (v) further containing an electrolyte (vi) Additionally, it contains an oil phase thickener.