JP5000777B2 - Oil-in-water emulsion composition - Google Patents

Abstract

The present invention provides an oil-in-water type emulsion composition characterized by comprising components (a) to (e) below: (a) an acrylic acid-methacrylic acid alkyl copolymer, (b) a block-type alkylene oxide derivative represented by the following formula (I), R1O-[(AO)l(EO)m(AO)n]-R2 (I) (In the formula: AO is a C3-4 oxyalkylene group; EO is an oxyethylene group; and l, m and n are each independently an average addition mol number of the oxyalkylene group and oxyethylene group, and are 1=m=70 and 1=l+n=70. The ratio of the oxyethylene group with respect to the total of the C3-4 oxyalkylene group and the oxyethylene group is 20-80 mass%. R1 and R2 are the same or different C1-4 hydrocarbon group or a hydrogen atom.), (c) a nonionic surfactant, (d) oil, and (e) water. The objective of the present invention is to provide, with respect to an oil-in-water type emulsion composition comprising (a) an acrylic acid-methacrylic acid alkyl copolymer as a polymeric emulsifier, an oil-in-water type emulsion composition and a cosmetic material which have excellent stability and usability.

Description

  The present invention relates to an oil-in-water emulsion composition. More specifically, the present invention relates to an oil-in-water emulsion composition containing an acrylic acid / alkyl methacrylate copolymer as a polymer emulsifier and having improved emulsion stability, and a cosmetic using the same.

Oil-in-water emulsion compositions used for cosmetics and the like often contain an acrylic acid / alkyl methacrylate copolymer as a polymer emulsifier.
However, an oil-in-water emulsion composition emulsified with an acrylic acid / alkyl methacrylate copolymer has a relatively weak emulsifying power, and it has been difficult to obtain high emulsion stability. In addition, in an oil-in-water emulsion composition emulsified with an acrylic acid / alkyl methacrylate copolymer, a carboxyvinyl polymer is often used in combination as a thickener in order to maintain the emulsion stability. .
However, it has often not always been easy to obtain an oil-in-water emulsion composition having both high emulsification stability and excellent usability.

Patent Document 1 discloses an external composition (oil-in-water emulsion composition) containing an alkyl methacrylate methacrylate copolymer. In the composition for external use of Patent Document 1, succinoglucan and a water-swellable clay mineral are usually blended in place of the carboxyvinyl polymer used as a thickener, and the long-term stability and the feeling of use are improved. .
However, the emulsified composition has a good feeling of use as a result, but until the excellent feeling of use exhibited when it contains a carboxyvinyl polymer and an alkyl methacrylate methacrylate copolymer is obtained. Not reached.

  Further, as a prior art document containing an acrylic acid alkyl methacrylate copolymer as a polymer emulsifier, Patent Document 2 includes an acrylic acid alkyl methacrylate copolymer, 2-acrylamido-2-methylpropanesulfonic acid or a salt / polyester thereof. An oil-in-water emulsified whitened skin cosmetic containing a copolymer of oxyethylene alkyl ether methacrylate, an alkylene oxide derivative and the like is disclosed.

  On the other hand, the block type alkylene oxide derivative (b) having a specific structure, which is an essential component of the present invention, is a known cosmetic compounding ingredient. For example, Patent Document 3 contains a block type alkylene oxide derivative having the specific structure. Gel-like compositions are disclosed and used as cleansing oils and hair oils.

JP 2000-159630 A JP 2009-215283 A JP 2008-19239 A

  In view of the above-mentioned viewpoints, the present inventor is an oil-in-water emulsion composition that exhibits excellent stability and usability in an oil-in-water emulsion composition that contains an acrylic acid / alkyl methacrylate copolymer as a polymer emulsifier. As a result of earnest research to obtain products, an oil-in-water type with excellent stability and excellent usability when combined with a block type alkylene oxide derivative having a specific structure and a nonionic surfactant The inventors have found that an emulsified composition can be obtained and have completed the present invention.

  An object of the present invention is to provide an oil-in-water emulsion composition having excellent stability and feeling of use in an oil-in-water emulsion composition containing an acrylic acid / alkyl methacrylate copolymer as a polymer emulsifier, and the oil-in-water composition. It is providing the cosmetics which consist of a type | mold emulsion composition.

That is, this invention provides the oil-in-water type emulsion composition excellent in the freeze stability characterized by containing the following component (a)-(e).
(A) 0.01 to 0.1% by mass of acrylic acid / alkyl methacrylate copolymer based on the total amount of the oil-in-water emulsion composition
(B) Oil-in-water emulsification of one or more selected from the group consisting of POE (22) POP (40) dimethyl ether, POE (35) POP (40) dimethyl ether, POE (50) POP (40) dimethyl ether 0.1 to 0.5% by mass relative to the total amount of the composition
(C) 0.01 to 0.5% by mass of a nonionic surfactant comprising polyoxyethylene glycerin monoisostearate (60E.O.) based on the total amount of the oil-in-water emulsion composition.
(D) 3 to 15% by mass of oil composed of petrolatum, liquid paraffin, isododecane, amino-modified polymer silicone / dimethylpolysiloxane with respect to the total amount of the oil- in-water emulsion composition
(E) 60 to 85% by mass of water with respect to the total amount of the oil-in-water emulsion composition

  Furthermore, this invention provides the cosmetics excellent in the freeze stability characterized by consisting of said oil-in-water emulsion composition.

  According to the present invention, it is possible to provide an oil-in-water emulsion composition having excellent stability and excellent usability, and a cosmetic comprising the oil-in-water emulsion composition.

  Hereinafter, the present invention will be described in detail.

"(A) Acrylic acid / alkyl methacrylate copolymer"
The acrylic acid / alkyl methacrylate copolymer used in the present invention is a compounding component that functions as a polymer emulsifier, such as Carbopol 1342, Pemulen TR-1, Pemulen TR-2. Commercial products known under the trade name of can be used.

  Although the compounding quantity of the acrylic acid alkyl methacrylate copolymer is not specifically limited, 0.3 mass% or less is preferable with respect to the oil-in-water type emulsion composition whole quantity. Especially preferably, it is 0.01-0.1 mass% with respect to the oil-in-water type emulsion composition whole quantity.

  In the present invention, an alkyl-modified carboxyvinyl polymer that is usually used as a thickener, such as Carbopol 941, Sintalen K, Sintalen L, etc. is an essential component of acrylic acid / methacrylic acid. When blended in combination with an alkyl copolymer, a stable oil-in-water emulsion composition having excellent uniformity of emulsified particles can be prepared.

“(B) Block-type alkylene oxide derivative”
The block-type alkylene oxide derivative used in the present invention is represented by the following formula (I).
[Chemical formula 2]
^{R 1 O - [(AO)} l (EO) m (AO) n] -R 2 (I)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, l, m and n are the average added moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ m ≦ 70, 1 ≦ l + n ≦ 70 The ratio of the oxyethylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by mass, and R ¹ and R ² may be the same or different. It is a good C1-C4 hydrocarbon group or hydrogen atom.)

In the above formula (I), AO is an oxyalkylene group having 3 to 4 carbon atoms, and specific examples include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxytrimethylene group, and an oxytetramethylene group. It is done. Preferably, an oxypropylene group and an oxybutylene group are mentioned. Note that EO is an oxyethylene group.
m is the average number of moles of oxyethylene group added, and 1 ≦ m ≦ 70, preferably 5 ≦ m ≦ 55. l and n are the average number of moles of the oxyalkylene group having 3 to 4 carbon atoms, and 1 ≦ l + n ≦ 70, preferably 2 ≦ l + n ≦ 50. When the oxyalkylene group or oxyethylene group having 3 to 4 carbon atoms is 0, the smoothness is lowered, and when it exceeds 70, a sticky feeling after washing tends to appear.

R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. And tert-butyl group. A methyl group and an ethyl group are preferred. Hydrocarbon groups having 5 or more carbon atoms tend to have poor hydrophilicity and a feeling of moisture.
In addition, R ¹ and R ² are the same type, or even if a hydrocarbon group having 1 to 4 carbon atoms and a hydrogen atom are mixed, different hydrocarbon groups having 1 to 4 carbon atoms are mixed. May be. More preferably, R ¹ and R ² are the same or different hydrocarbon groups having 1 to 4 carbon atoms. When R ¹ and R ² are both hydrogen atoms or a mixture of hydrocarbon and hydrogen atoms, the sticky feeling is slightly inferior.

Specific examples of the alkylene oxide derivative used in the present invention include POE (9) POP (2) dimethyl ether, POE (14) POP (7) dimethyl ether, POE (10) POP (10) dimethyl ether, and POE (6) POP. (14) Dimethyl ether, POE (15) POP (5) Dimethyl ether, POE (25) POP (25) Dimethyl ether, POE (7) POP (12) Dimethyl ether, POE (22) POP (40) Dimethyl ether, POE (35) POP (40) dimethyl ether, POE (50) POP (40) dimethyl ether, POE (55) POP (30) dimethyl ether, POE (30) POP (34) dimethyl ether, POE (25) POP (30) dimethyl ether, POE (27) POP 14) dimethyl ether, POE (55) POP (28) dimethyl ether, POE (36) POP (41) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (17) POP (4) dimethyl ether, POE (9) POB ( 2) Dimethyl ether, POE (14) POB (7) Dimethyl ether, POE (10) POP (10) Diethyl ether, POE (10) POP (10) Dipropyl ether, POE (10) POP (10) Dibutyl ether, POE ( 52) POB (32) dimethyl ether, POE (34) POB (14) dimethyl ether, POE (35) POB (32) dimethyl ether, POE (23) POB (32) dimethyl ether, POE (45) POB (28) dimethyl ether, PO (35) POP (30) glycol, POE (35) POB (32) glycol and the like.
Particularly preferred is one or more selected from the group consisting of POE (22) POP (40) dimethyl ether, POE (35) POP (40) dimethyl ether, POE (50) POP (40) dimethyl ether.
The POE, POP, and POB are abbreviations for polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively, and may be abbreviated as follows.

  Said (b) block-type alkylene oxide derivative can be manufactured by a well-known method. For example, it can be obtained by subjecting a compound having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms, and then subjecting an alkyl halide to an ether reaction in the presence of an alkali catalyst.

The blending amount of the block-type alkylene oxide derivative is preferably from 0.01 to 1% by mass, more preferably from 0.1 to 0.5% by mass, based on the total amount of the oil-in-water emulsion composition. If the blending amount is less than 0.01% by mass, the effect of blending may not be sufficiently exhibited. If the blending amount exceeds 1% by mass, slimming may be felt during application.

“(C) Nonionic surfactant”
As the nonionic surfactant used in the present invention, a hydrophilic nonionic surfactant can be used. Specific examples are given below.

  Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan tetraoleate, etc.); POE sorbit fatty acid esters ( For example, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc .; POE-glycerin fatty acid esters (eg, POE-glycerin monostearate, POE- POE-monooleate such as glycerin monoisostearate and POE-glycerin triisostearate); POE-fatty acid esters (eg POE-distearate, POE-monodiolate, ethylene glycol distearate); POE-alkyl ethers ( For example, POE-lauryl ether, POE-oleyl Ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic type (for example, Pluronic etc.); POE / POP-alkyl ethers (for example, POE POP-cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); tetra-POE / tetra-POP-ethylenediamine condensates (For example, Tetronic etc.); POE-castor oil hydrogenated castor oil derivative (eg, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc.); POE-beeswax lanolin derivative For example, POE-sorbite beeswax, etc.); Alkanolamides (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; Sugar fatty acid ester; alkylethoxydimethylamine oxide; trioleyl phosphate and the like.

  A particularly preferred nonionic surfactant for the present invention is polyoxyethylene glycerin monoisostearate (60E.O.).

  Although the compounding quantity of a nonionic surfactant is not specifically limited, 0.01-1 mass% is preferable with respect to the oil-in-water type emulsion composition whole quantity, More preferably, it is 0.01-0.5 mass%.

“(D) Oil”
The oil component used in the present invention is not particularly limited, and examples thereof include hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils and the like that are commonly used in cosmetics, and dissolve the (b) alkylene oxide derivative. One or more kinds of oils can be used.
Particularly preferred oils are petrolatum, liquid paraffin, isododecane, amino-modified polymer silicone / dimethylpolysiloxane and the like.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.

  Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid ( DHA) and the like.

  Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol) ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol and the like.

  Synthetic ester oils include, for example, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, Myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate , Diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, triisostearate Methylolpropane, tetra-2-ethylhexanoic acid pentaerythritol, tri-2-ethylhexanoic acid glycerin, trioctanoic acid glycerin, triisopalmitic acid glycerin, triisostearic acid trimethylolpropane, cetyl 2-ethylhexanoate, 2-ethylhexyl Palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid 2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyl adipate Shirudeshiru, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa Siloxane etc.) Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicones forming a three-dimensional network structure Etc.

Although the compounding quantity of an oil component is not specifically limited, 1-25 mass% or less is preferable with respect to the oil-in-water-type emulsion composition whole quantity, More preferably, it is 3-15 mass% or less.
When the oil content is less than 1% by mass, the usability is impaired, and when it exceeds 25% by mass, there may be a problem in stability.

“(E) Water”
The water used in the present invention is not particularly limited, and specific examples thereof include purified water and ion exchange water.
The amount of water is preferably 50 to 95% by mass, more preferably 60 to 85% by mass with respect to the oil-in-water emulsion composition, although it depends on the amount of the alkylene oxide derivative and the oil.
When the blending amount of water is out of the above range, the stability of the oil-in-water emulsion composition may be impaired.

"Oil-in-water emulsion composition"
The oil-in-water emulsion composition of the present invention is a moisturizer, powder, alcohol, natural polymer, synthetic polymer, ultraviolet absorber, saccharide, antioxidant, as long as the effects of the present invention are not impaired in addition to the above essential components Ingredients usually blended in cosmetics such as agents, various extracts, pigments, and fragrances can be blended, and they are produced by conventional methods.
The oil-in-water emulsion composition of the present invention is an emulsion composition having extremely excellent stability.

"Cosmetics"
The cosmetic of the present invention comprises the oil-in-water emulsion composition described above, and can be produced by a conventional method by blending any cosmetic ingredients within a range that does not impair the effects of the present invention, depending on the purpose of the cosmetic. .
The cosmetic of the present invention has an excellent feeling of use in terms of freshness, moistness, speed of familiarity, and non-stickiness, and is suitably used as, for example, an O / W type emulsion or an O / W type cream. Is done.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In addition, unless there is particular notice, a compounding quantity represents the mass% with respect to the whole quantity.

  With the formulations shown in “Table 1” and “Table 2”, an emulsion which is an oil-in-water emulsion composition was produced by a conventional method, and the following evaluation was performed.

"Freezing stability"
The sample was left to stand in a freezer at −20 ° C. for 2 days or more and frozen, and then left in a constant temperature bath at 30 ° C. for 1 day to completely thaw. Using samples after thawing, the freeze stability of Examples and Comparative Examples was evaluated according to the following evaluation criteria.

Evaluation criteria of freezing stability are as follows.
"Evaluation criteria"
○: Oil floating and rainbow floating are not visually observed.
Δ: A rainbow floats (the oil appears to shine and shine)
×: Oil floats (you can see oil droplets)

"Usage"
Ten researchers have applied the emulsions of Examples and Comparative Examples to the arms and conducted an actual use test. Each of the freshness, moistness, speed of familiarity, and non-stickiness was evaluated according to the following evaluation criteria.

<Mizumizushi>
○: 6 or more responded that they are refreshing.
(Triangle | delta): Three to five persons answered that it was excellent in freshness.
× Less than 2 respondents said that they are refreshing.
<Moistness>
○: 6 or more responded that they were moist.
Δ: 3 to 5 people answered that they were moist.
X: Less than 2 people answered that they were moist.
<Familiar speed>
○: 6 or more responded that they were very familiar.
Δ: 3 to 5 people answered that they were excellent in familiarity.
×: Less than 2 responded that they were very familiar.
<No stickiness>
○: Six or more people answered that they were not sticky.
Δ: 3 to 5 people answered that they were not sticky.
X: Less than 2 responded that they were not sticky.

＊１：ペミュレン(Pemulen)TR-2

* 1: Pemulen TR-2

＊１：ペミュレン(Pemulen)TR-2

* 1: Pemulen TR-2

＊１：ペミュレン(Pemulen)TR-2 (Goodrich社)

* 1: Pemulen TR-2 (Goodrich)

From the results of the above “Table 1” to “Table 3”, in the oil-in-water emulsion composition containing the acrylic acid / alkyl methacrylate copolymer, a comparison between Comparative Examples 1 to 6 and Example 1 shows that (c ) It can be seen that freezing stability is not improved by the nonionic active agent alone.
In addition, comparison between Comparative Example 7 and Example 1 shows that (b) the block-type alkylene oxide derivative alone does not improve the freezing stability. Therefore, in order to improve the freezing stability, (b) the block-type alkylene It can be seen that both an oxide derivative and (c) a nonionic active agent are necessary.
Furthermore, by comparing Example 2 and Comparative Example 8, even when the oil composition changes, the freeze stability can be improved by the combination of (b) and (c). In addition, even when (b) and (c) are used in combination, the excellent feeling of use of the acrylic acid / alkyl methacrylate copolymer can be maintained.
From the above results, it can be seen that the examples of the present invention are excellent in stability and in use feeling.

  Other examples are given below.

Example 8: O / W type emulsion formulation component
(1) Ethanol 5
(2) Glycerin 3
(3) Dipropylene glycol 5
(4) Phenoxyethanol 0.5
(5) Sorbitol 2
(6) Vaseline 1
(7) Liquid paraffin 1.4
(8) Isododecane 7
(9) Amino-modified polymer silicone / dimethylpolysiloxane
20CS (10%) 0.4
(10) Xanthan gum 0.01
(11) Carboxyvinyl polymer 0.2
(12) Acrylic acid / alkyl methacrylate copolymer 0.1
(13) Potassium hydroxide 0.12
(14) Polystearic acid polyoxyethylene glycerol (5E.O.) 0.2
(15) POE (35) POP (40) Dimethyl ether 0.2
(16) Sodium metaphosphate appropriate amount
(17) edetate 2-sodium
(18) POE (14) POP (7) Dimethyl ether 0.1
(19) Purified water residue

Example 9: O / W type emulsion formulation component
(1) Ethanol 5
(2) Glycerin 3
(3) Dipropylene glycol 5
(4) Phenoxyethanol 0.5
(5) Sorbitol 2
(6) Vaseline 1
(7) Liquid paraffin 1.4
(8) Isododecane 7
(9) Amino-modified polymer silicone / dimethylpolysiloxane
20CS (10%) 0.4
(10) Xanthan gum 0.01
(11) Carboxyvinyl polymer 0.2
(12) Acrylic acid / alkyl methacrylate copolymer 0.1
(13) Potassium hydroxide 0.12
(14) Polyoxyethylene hydrogenated castor oil (60E.O.) 0.2
(15) POE (35) POP (40) Dimethyl ether 0.2
(16) Sodium metaphosphate appropriate amount
(17) edetate 2-sodium
(18) POE (14) POP (7) Dimethyl ether 0.1
(19) Purified water residue

  The oil-in-water emulsified composition of the present invention is extremely useful as a cosmetic because it has excellent emulsification stability and usability.

Claims (2)

An oil-in-water emulsion composition excellent in freezing stability, comprising the following components (a) to (e):
(A) 0.01 to 0.1% by mass of acrylic acid / alkyl methacrylate copolymer based on the total amount of the oil-in-water emulsion composition
(B) Oil-in-water emulsification of one or more selected from the group consisting of POE (22) POP (40) dimethyl ether, POE (35) POP (40) dimethyl ether, POE (50) POP (40) dimethyl ether 0.1 to 0.5% by mass relative to the total amount of the composition
(C) 0.01 to 0.5% by mass of a nonionic surfactant comprising polyoxyethylene glycerin monoisostearate (60E.O.) based on the total amount of the oil-in-water emulsion composition.
(D) 3 to 15% by mass of oil composed of petrolatum, liquid paraffin, isododecane, amino-modified polymer silicone / dimethylpolysiloxane with respect to the total amount of the oil- in-water emulsion composition
(E) 60 to 85% by mass of water with respect to the total amount of the oil-in-water emulsion composition A cosmetic having excellent freezing stability, comprising the oil-in-water emulsion composition according to claim 1.