JP6824544B1 - Water-in-oil emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel W / O type emulsion. A W / O type emulsion containing an amide alcohol represented by the formula (I) and at least one component selected from the group consisting of basic amino acids, alkalis and salts. (In the formula, R1 is a C6-C22 hydrocarbon group, R2 is an H or C6-C22 hydrocarbon group, and R3 is a linear or branched chain C2-C21 hydrocarbon group.) Selection diagram] Fig. 1

Description

The present invention relates to compositions using amide alcohols, especially water-in-oil emulsions.

Conventionally, as emulsions for cosmetics, creams, emulsions, beauty essences and the like emulsified from various oily and aqueous raw materials have been widely used. In the production of such emulsions, it is essential to use a surfactant not only to process the raw materials but also to guarantee the stability of the emulsion over time under various strictly set conditions. Was supposed to be. However, in recent years, even higher safety is expected for cosmetics, and from this viewpoint, the presence of a surfactant, particularly a cationic surfactant, may be a problem.

In response to such problems, as a water-in-oil emulsion that does not use a surfactant, for example, one or more oils selected from the group consisting of fatty acids and higher alcohols, and one or more highs that are soluble in the oils. A water-in-oil emulsion comprising a molecule and one or more compounds selected from the group consisting of inorganic salts, organic acid salts, amino acids and salts thereof, and containing no surfactant has been proposed. (Patent Document 1).

Further, an emulsion using a complex of a carboxy group-containing polymer and an amide alcohol has been proposed (Patent Document 2).

Japanese Unexamined Patent Publication No. 2003-252723 Japanese Patent No. 6368064

An object of the present invention is to provide a new W / O type emulsion that can be used in cosmetics and the like.

In order to solve the above problems, the present inventor mixes an oil phase containing an amide alcohol with an aqueous phase containing a component selected from the group consisting of basic amino acids, alkalis and salts in the course of intensive research. As a result, we discovered that a W / O type emulsion can be prepared, and as a result of further research, we have completed the present invention.

That is, the present invention relates to the following [1] to [14].
[1]
(A) Equation (I)
During the ceremony
R ₁ is a C6-C22 hydrocarbon group.
R ₂ is H or C6~C22 hydrocarbon group,
R ₃ is a straight-chain or branched-chain C2~C21 hydrocarbon group,
The amide alcohol represented by, and (B) at least one component selected from the group consisting of basic amino acids, alkalis, and salts.
W / O type emulsion containing.
[2]
(A): The W / O type emulsion according to [1], wherein the molar ratio of (B) is 1: 0.1 to 1:15.

[3]
The W / O type emulsion according to [1] or [2], which comprises a hydrocarbon oil and / or an ester oil.
[4]
(B) The W / O type emulsion according to any one of [1] to [3], which contains 1.0% by weight or more of alkali as a component.
[5]
(B) The W / O type emulsion according to any one of [1] to [3], which contains a salt as a component.
[6]
(B) The W / O type emulsion according to any one of [1] to [3], which contains a basic amino acid as a component.

[7]
The W / O type emulsion according to any one of [1] to [6], which contains more than 60% by weight of an aqueous component.
[8]
The W / O type emulsion according to any one of [1] to [7], which does not contain a carboxy group-containing polymer or contains a carboxy group-containing polymer of less than 0.01% by weight.
[9]
The W / O type emulsion according to any one of [1] to [8], which does not contain a surfactant or contains a surfactant of less than 2.0% by mass.
[10]
The W / O type emulsion according to any one of [1] to [9], which contains an acid.

[11]
-(A) Equation (I)
During the ceremony
R ₁ is a C6-C22 hydrocarbon group.
R ₂ is H or C6~C22 hydrocarbon group,
R ₃ is a straight-chain or branched-chain C2~C21 hydrocarbon group,
Step of preparing an oil phase containing an amide alcohol represented by,
-(B) A step of preparing an aqueous phase containing at least one component selected from the group consisting of basic amino acids, alkalis and salts.
-The process of stirring the oil phase and the aqueous phase,
A method for producing a W / O type emulsion, which comprises.

[12]
The method according to [11], wherein the pH of the aqueous phase is neutral or alkaline in the step of preparing the aqueous phase.
[13]
The method according to [11] or [12], wherein an acid is added to the aqueous phase in the step of preparing the aqueous phase.
[14]
The method according to [11] or [12], which comprises a step of stirring the oil phase and the aqueous phase followed by a step of adding an acid while stirring.

The present invention can provide a new W / O type emulsion.
In addition, the present invention can provide a W / O type emulsion having stability over time.
Furthermore, the present invention can also provide a W / O type emulsion that does not contain a cationic surfactant.
Furthermore, the present invention can also provide a W / O type emulsion having excellent stability.
The present invention also provides a novel method for preparing W / O type emulsions.

It is a figure which shows the microscopic observation result of the reference example which does not contain a component B, and the example which contains a basic amino acid. It is a figure which shows the microscopic observation result of the comparative example containing an acidic amino acid. It is a figure which shows the microscopic observation result of the reference example which does not contain a component B, the example which contains an alkali, and the comparative example which contains an acid. It is a figure which shows the observation result of FF-TEM of Example 1. It is a figure which shows the DSC measurement result of Example 1 and component A. It is a figure which shows the DSC measurement result of Example 4. FIG. It is a figure which shows the DSC measurement result of Example 5. It is a figure which shows the small angle X-ray diffraction pattern of Example 1. FIG. It is a figure which shows the small angle X-ray diffraction pattern of Example 4.

It is a figure which shows the microscopic observation result of the reference example which does not contain a component B, and the example which contains a salt. It is a figure which shows the DSC measurement result of Example 6. It is a figure which shows the small angle X-ray diffraction pattern of Example 6. It is a figure which shows the (polarized light) microscope observation result of Example 1-D. It is a figure which shows the DSC measurement result of Example 1-D. It is a figure which shows the microscopic observation result of the emulsion prepared by the manufacturing method 1. It is a figure which shows the microscopic observation result of the emulsion prepared by the manufacturing method 2.

It is a figure which shows the microscopic observation result immediately after the manufacture of Example 17. It is a figure which shows the microscopic observation result after storage of Example 17. It is a figure which shows the microscopic observation result immediately after the manufacture of Example 18. It is a figure which shows the microscopic observation result after storage of Example 18. It is a figure which shows the microscopic observation result immediately after the manufacture of Example 19. It is a figure which shows the microscopic observation result after storage of Example 19. It is a figure which shows the microscopic observation result immediately after the manufacture of Example 20. It is a figure which shows the microscopic observation result after storage of Example 20.

It is a figure which shows the microscopic observation result immediately after the manufacture of Example 21. It is a figure which shows the microscopic observation result after storage of Example 21. It is a figure which shows the microscopic observation result immediately after the manufacture of Example 22. It is a figure which shows the microscopic observation result after storage of Example 22. It is a figure which shows the microscopic observation result immediately after the manufacture of Example 23. It is a figure which shows the microscopic observation result after storage of Example 23. It is a figure which shows the microscopic observation result immediately after the manufacture of Example 24. It is a figure which shows the microscopic observation result immediately after the manufacture of Example 25.

Component (A): Amido Alcohol The amide alcohol used in the present invention is represented by the following formula (I):
In the formula, R ₁ is a C6 to C22 hydrocarbon group.
R ₂ is H or C6~C22 hydrocarbon group,
R ₃ is a straight-chain or branched-chain C2~C21 hydrocarbon group.

In one embodiment of the present invention, the amide alcohol of the formula (I) in which R ₁ is a C10 to C22 hydrocarbon group, R ₂ is H, and R ₃ is a C3 to C12 hydrocarbon group is preferable. The amide alcohol of the formula (I) in which R ₁ is a C12-18 hydrocarbon group, R ₂ is H, and R ₃ is a C3 to C5 hydrocarbon group is particularly preferable.

In another embodiment of the invention, in the formula, R ₁ is a linear or branched unsaturated C10-C22 hydrocarbon group; or a cyclic C6-C22 hydrocarbon group; or a benzyl or phenylethyl group ( The amide alcohol of I) is preferable.
In a preferred embodiment of the present invention, the amide alcohol of the formula (I) has the structures of the following formulas (I-1) to (I-4):

As used herein, "hydrocarbon groups" can be saturated or unsaturated, linear, branched or cyclic, or a combination of linear or branched and cyclic, eg, unless otherwise specified. It contains a hydrocarbon group consisting of a linear or branched hydrocarbon moiety such as a benzyl group or a phenylethyl group and a cyclic hydrocarbon moiety.
That is, the C6 to C22 hydrocarbon groups in R ₁ and R ₂ consist of straight, branched or cyclic C6 to C22 hydrocarbon groups, or straight or branched hydrocarbon moieties and cyclic hydrocarbon moieties. Contains C6-C22 hydrocarbon groups such as cyclohexyl, decahydronaphthyl, tetrahydrodicyclopentadiene, sterol, phenyl, naphthyl, anthracenyl and other cyclic groups, ethylhexyl, isostearyl, octyldodecyl and other branched alkyl groups and dimethyl. , Multi-branched alkyl groups such as trimethyl and tetramethyl, linear alkyl groups such as hexyl, octyl, lauryl, myristyl, cetyl, stearyl, araquil and behenyl, and alkenyl groups such as oleyl and ellaidyl.

In one aspect of the present invention, R ₁ is cyclohexyl, ethylhexyl, octyl, lauryl, myristyl, stearyl, oleyl, preferably benzyl or phenylethyl, lauryl and oleyl are particularly preferred.
In one aspect of the invention, R ₂ is preferably H.

Hydrocarbon group for R ₃ having no cyclic structure, a linear or branched chain C2~C21 hydrocarbon group, examples, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl such as an alkyl group, butylene , Pentylene, hexylene, heptylene and other alkenyl groups.
In one aspect of the present invention, R ₃ is propylene, butylene, be a pentylene or hexylene preferred.

Amido alcohols can be produced using known synthetic methods.
For example
Aminolysis reaction of acid chloride and amine (Schotten-Baumann reaction),
Aminolysis reaction of anhydrous fatty acids and amines,
Aminolysis reaction of methyl ester and amine,
Aminolysis reaction of fatty acids and amines,
Aminolysis reaction of lactone and amine,
And so on.
Specifically, for example, it can be synthesized by the method described in WO2017 / 213177 A1.
The amide alcohol represented by the above formula (I-4) is commercially available from Higher Alcohol Industry Co., Ltd. under the trade name of Aminactol OLH.

Component (B): Basic amino acid, alkali, salt In the present specification, "basic amino acid" means an amino acid having a residue showing basicity in addition to an amino group in the molecule, and is not particularly limited, but an example. Examples thereof include lysine, arginine, histidine, and tryptophan, and these can be used alone or in combination of two or more.

As used herein, "alkali" means a hydroxide of an alkali metal or alkaline earth metal. The alkali is not particularly limited as long as it is an alkali generally used in cosmetics and the like, but typically includes potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide and the like, and these may be used alone or in combination of two. The above can be used in combination.

In the present specification, the "salt" means a compound consisting of a positive component of a metal or a base and a negative component of an acid, and is not particularly limited, but is an inorganic substance such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride and the like. Examples thereof include salts and organic acid salts such as EDTA-2Na, EDTA-3Na and EDTA-4Na.

Component B selected from basic amino acids, alkalis and salts can be used alone or in combination of two or more, for example, in combination with basic amino acids and alkalis, or in combination with basic amino acids and salts. it can.

In the present invention, the "W / O type emulsion" means a water-in-oil emulsion, that is, a composition in which an aqueous component is dispersed in a continuous phase containing an oily component.
The W / O type emulsion can be prepared by dispersing an aqueous phase containing an alkali in an oil phase containing an amide alcohol.

In one aspect of the present invention, the W / O type emulsion can be used for all purposes, but typically can be used for external preparations such as pharmaceuticals, quasi-drugs, and cosmetics.
The W / O type emulsion of the present invention is a pharmaceutical product such as an external preparation for skin containing a drug; a non-medicinal product such as medicated cosmetics; a gel lotion, a milky lotion, a cream, a beauty essence, a sunscreen, and a moisturizer for daytime use. Skin care cosmetics such as; can be used in various forms of products such as foundations, makeup bases, make-up cosmetics such as eye shadows and mascara, and hair care cosmetics such as hair treatments.

<Oil component>
The oily component used in the W / O type emulsion of the present invention is not particularly limited as long as it is a component generally used in cosmetics and the like, and examples thereof include animal and vegetable fats and oils, hydrocarbon oils, higher fatty acids, and higher alcohols. , Ester oil, silicone oil and other oils, and these can be used alone or in combination of two or more.

Animal and vegetable fats and oils or hydrogenated animal and vegetable fats and oils include, for example, avocado oil, eno oil, olive oil, cacao butter, lanolin oil, lanolin oil, hardened oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugar cane, southern ka oil. , Saflower oil, shea butter, lanolin oil, cinnamon oil, soybean oil, brown seed oil, camellia oil, evening primrose oil, corn oil, rapeseed oil, germ oil, palm oil, palm kernel oil, sunflower oil, hardened sunflower oil, Sunflower oil, grape oil, jojoba oil, macadamia nut oil, honey wax, cotton seed oil, cotton wax, mokuro, montan wax, coconut oil, hardened coconut oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, Examples include lanolin fatty acid isopropyl and hexyl laurate.

Hydrocarbon oils include, for example, ozokerite, squalane, squalene, ceresin, paraffin, isoparaffin, paraffin wax, liquid paraffin (mineral oil), pristan, polyisobutylene, polyisobutene, hydrogenated polyisobutene, microcrystalline wax, polyethylene wax, petrolatum, etc. Can be mentioned.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, undecylenic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid ( DHA) and the like.
Examples of higher alcohols include myristyl alcohol, cetanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, hydrogenated rapeseed oil alcohol and the like.

Examples of the ester oil include isononyl isononanoate, which is an isononanoic acid ester in monoester, isotridecyl isononanoate, and cetyl ethylhexanoate, which is 2-ethylhexanoic acid, and hexyldecyl ethylhexanoate, which is a myristic acid ester. Isostearates such as isopropyl, isosetyl myristate, octyldodecyl myristate, ethyl isostearates, isopropyl isostearate, hexyldecyl isostearate, isostearyl isostearate, cholesteryl isostearate, phytosteryl isostearate, etc. Isodecyl oleate, which is an oleate ester such as stearyl and octyldodecyl lactate, phytosteryl oleate, octyldodecyl oleate, etc. Examples thereof include hexyl laurate which is a laurate ester such as ethylhexyl palmitate and isoamyl laurate, and octyldodecyl neodecanoate, octyldodecyl ricinoleate, oleyl erucate, octyldodecyl erucate, and lauroyl sarcosin isopropyl.

The diester oils include diisobutyl adipate, diisopropyl adipate, diethylhexyl succinate, neopentyl glycol diisononanoate, neopentyl glycol diethylhexanoate, neopentyl glycol dicaprate, diisostearyl malate, diisopropyl dilinoleate, and ethylene dioctanoate. Glycol, octyldodecyl stearoyloxystearate, diisopropyl sebacate, di lauroyl glutamate (cholesteryl / octyldodecyl), di lauroyl glutamate (phytosteryl / octyldodecyl) and the like can be mentioned.
Examples of the triester oil include trimethylolpropane triethylhexanoin, trimethylolpropane triethylhexanoate, glyceryl tri (caprylic acid / capric acid), triisostea, and trimethylolpropane triisostearate.
Examples of the tetraester oil include pentaerythricyl tetraethylhexanoate and pentaerythrityl tetraisostearate.

Examples of the polyester oil include polyglyceryl-2 isostearate, which is a polyglycerin fatty acid ester, polyglyceryl-2 diisostearate, polyglyceryl-2 triisostearate, and polyglyceryl-2 tetraisostearate.
Highly viscous ester oils include isostearic acid hydrogenated castor oil, dimer dilinoleic acid hydrogenated castor oil, (polyglyceryl isostearate-2 / dimer dilinoleic acid) copolymer, dimer dilinoleic acid (phytosteryl / isostearyl / cetyl /). Stearyl / behenyl), dimer dilinoleyl bis (phytosteryl / behenyl / isostearyl), dimer dilinoleic acid di (isostearyl / phytosteryl), dimer dilinoleyl hydrogenated rosin condensate, diisostearate dimer dilinole Examples thereof include rail, dimer dilinoleyl dimer dilinoleic acid, di lauroyl glutamate (cholesteryl / behenyl / octyldodecyl), di lauroyl glutamate (octyldodecyl / phytosteryl / behenyl), and myritoylmethylalanine (phytosteryl / decyltetradecyl).

Examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, alkyl-modified organopolysiloxane, terminal-modified organopolysiloxane, fluorine-modified organopolysiloxane, amodimethicone, amino-modified organopolysiloxane, volatile silicone, alkyldimethicone, and cyclo. Examples include pentasiloxane.

In one aspect of the present invention, the amount of the oily component containing the amide alcohol in the W / O type emulsion is not particularly limited, but from the viewpoint of usability and stability, particularly suppression of crystal precipitation derived from the amide alcohol, 0. It is 5 to 70% by weight, preferably 0.5 to 30.0% by weight, and more preferably 10.0 to 20.0% by weight.
In a specific aspect of the present invention, the blending amount of the oily component containing amide alcohol in the W / O type emulsion is 0.5% by weight or more and less than 30% by weight.
In one aspect of the present invention, from the viewpoint of providing a stable emulsion for a longer period of time, it is possible to use an oil component such as an oil having high compatibility with component A, for example, a hydrocarbon oil, an ester oil, or the like in a high proportion. It is preferable to use mineral oil in particular.

<Aqueous component>
The aqueous component used in the W / O type emulsion of the present invention is not particularly limited as long as it is a component generally used in cosmetics and the like, but examples thereof include water such as purified water and ion-exchanged water; BG (1). , 3-Butylene glycol), PG (propylene glycol), lower alcohols such as glycerin and ethanol, pH adjusters such as hydrochloric acid, and the like, and these can be used alone or in combination of two or more.
In one aspect of the present invention, the amount of the aqueous component containing the component (B) in the W / O emulsion is not particularly limited, but from the viewpoint of usability, 10.0 to 70.0% by weight, preferably 15. It can be 0 to 65.0% by weight, more preferably 20.0 to 60.0% by weight.
In one aspect of the present invention, the blending amount of water in the W / O type emulsion is not particularly limited, but from the viewpoint of usability, 10.0 to 70.0% by weight, preferably 15.0 to 65.0% by weight. %, More preferably 20.0 to 60.0% by weight.

<Surfactant>
As used herein, the term "surfactant" means a surfactant having both a hydrophilic group and a hydrophobic group in one molecule, and the "cationic surfactant" is positively charged (). It means a surfactant having a hydrophilic group (cationic), and these can be appropriately added to the W / O type emulsion as needed.
In one aspect of the invention, preferably the W / O emulsion is substantially free of surfactants, especially cationic surfactants. Thereby, an emulsifier with less irritation can be provided.
Here, "substantially free" means that the surfactant is not contained in an amount sufficient for emulsification of the entire W / O type emulsion. Further, in the present invention, "substantially free of surfactant" and "substantially free of cationic surfactant" mean that they do not contain any surfactant or cationic surfactant or are not emulsified. Means to include. The amount not emulsified can be appropriately determined by those skilled in the art according to the composition, for example, in one embodiment, less than 2.0% by weight, in another aspect, less than 0.2% by weight, 0. It can be less than 02% by weight.
In a particular aspect of the invention, the conditioning composition is a W / O emulsion that is substantially free of surfactants such as cationic surfactants.

<Carboxylic group-containing polymer>
In the present invention, a W / O type emulsion can be provided without using a carboxy group-containing polymer.
In one aspect of the invention, the W / O emulsion does not contain a carboxy group-containing polymer or contains less than 0.01% by weight.
In a specific aspect of the present invention, when an alkali is contained as the B component, the W / O type emulsion preferably contains no carboxy group or contains less than 0.01% by weight.
In a specific aspect of the present invention, when an alkaline component is contained as the B component, the W / O type emulsion preferably contains no carboxy group or contains less than 0.01% by weight.

In the present specification, the "carboxy group-containing polymer" means a polymer having a carboxy group in the molecule, and specifically, a polymer having a molecular weight of 500,000 to 3 million and a carboxy group content in the molecular weight. A polymer having a molecular weight of about 50 to 70% can be mentioned.
The carboxy group-containing polymer is generally used as a thickener.
Therefore, also in the present invention, a carboxy group-containing polymer can be added for the purpose of thickening the internal aqueous phase.
For example, the W / O type emulsion can be thickened by dispersing an aqueous phase containing an alkali in an oil phase containing an amide alcohol and then adding a carboxy group-containing polymer.
In one aspect of the present invention, in the step of preparing an aqueous phase in the method for producing a W / O type emulsion, the aqueous phase does not contain a carboxy group-containing polymer or contains less than 0.01% by weight.

Examples of carboxy group-containing polymers include carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers such as acrylate / alkyl methacrylate copolymers, alkyl acrylate / alkyl methacrylate polyoxyethylene ester copolymers, and alkyl acrylates. -Acrylic polymers such as alkylpolyoxyethylene ester copolymer of itaconic acid, steareth-10 allyl ether and alkyl acrylate copolymer, and non-acrylic polymers such as methylvinyl ether, maleic anhydride and decadien copolymer can be mentioned. ..

The carboxyvinyl polymer is also called Carbomer (INCI name: Carbomer) and is a polymer having a structure represented by the following formula (II):
During the ceremony
n is an integer, typically 40 to 100.

Alkylated carboxyvinyl polymers are copolymers of acrylic acid and / or methacrylic acid and their alkyl acrylates and / or alkyl methacrylate.
Specific examples of the alkyl-modified carboxyvinyl polymer include acrylicates / C10-30 Alkyl Acrylates Cross polymer (also referred to as acrylic acid / alkyl methacrylate copolymer), ACrylates / C10-30 Alkyl Acrylates Cross polymer. Examples thereof include polymers having a structure represented by the following formula (III):
During the ceremony
R is a C10-30 alkyl group
x and y are integers, each of which can be arbitrarily selected from one or more integers, typically x + y = 40-100.
When y is 2 or more, R may be the same or different.

<Other ingredients>
The emulsion of the present invention may contain any component used in cosmetics or the like in an external preparation such as cosmetics.
Examples of these additional ingredients are UV absorbers such as ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoyl benzoate; thickeners / gelling agents such as dextrin palmitate, xanthan gum; quality of antioxidants, preservatives, etc. Retaining ingredients; skin softeners (emollients); medicinal ingredients / active ingredients such as whitening agents, anti-wrinkle agents, and antioxidants; colorants such as fragrances, pigments, and pigments.

In one aspect of the present invention, the external oil phase can be oil-gelled with an oil gelling agent in order to improve the stability of the W / O type emulsion.
As a component used for oil gelation, an organically modified clay mineral and / or a polymer ester of sugar and fatty acid can be used.
The organically modified clay mineral used in the preparation of the W / O type emulsion of the present invention and the polymer ester containing sugar and fatty acid are not particularly limited as long as they are components generally used in cosmetics and the like.

As the organically modified clay mineral, a convertible cation intervening between crystal layers of a water-swellable clay mineral (for example, montmorillonite, saponite, hectorite, bentonite, etc.) is used as an organic polar compound or an organic cation (for example, a quaternary ammonium salt type). Examples thereof include those substituted with a cationic surfactant).
In the present invention, commercially available organically modified clay minerals can be used. For example, from Elementis Specialties, BENTONE 27V (stealalconium hectorite), BENTONE 27VCG (stearalconium hectorite), BENTONE 38V (diste). Aldimonium Hectorite), BENTONE 38VCG (Distear Dimonium Hectorite), etc. are commercially available.

Organically modified clay minerals are also commercially available as premixes dissolved in silicone oils, ester oils and / or other oils, and premixes may also be used in the present invention, for example, Elementis Specialties. It is commercially available under the following trade names.
BENTONE GEL 1002V (cyclopentasiloxane, disteardimonium hectorite, propylene carbonate), BENTONE GEL ABO V (cranbear bicinica seed oil, stearalconium hectorite, propylene carbonate), BENTONE GEL CAO V (sunflower oil, steer) Larconium hectorite, propylene carbonate), BENTONE GEL EUG V (octyldodecanol, disteardimonium hectorite, propylene carbonate), BENTONE GTCC V (tri (caprylic acid / capric acid) glyceryl, stearalconium hectorite, carbonic acid Propylene), BENTONE HSO V (tri (caprylic acid / capric acid) glyceryl, stearalconium hectorite, propylene carbonate), BENTONE IHD V (isohexadecane, disteardimonium hectorite, propylene carbonate), BENTONE IPM V (myristine) Isopropyl acid, stearalconium hectorite, propylene carbonate), BENTONE ISD V (isododecan, disteardimonium hectorite, propylene carbonate), BENTONE LOI V (liquid lanolin, isopropyl palmitate, stearalconium hectorite, propylene carbonate) , BENTONE MSO (V) (Meadowfoam oil, disteardimonium hectorite, propylene carbonate), BENTONENGD V (neopentyl glycol diheptate, disteardimonium hectorite, propylene carbonate), BENTONE OLV V (olive fruit oil, Stearalconium hectorite, propylene carbonate), BENTONE OMS V ((C11,12) isoparaffin, disteardimonium hectorite, modified alcohol), BENTONE PTIS V (pentaerythrityl tetraisostearate, disteardimonium hectorite, Propylene carbonate), BENTONE SS71V (petroleum volatiles, disteardimonium hectorite, propylene carbonate) BENTONE TMF V (methyltrimethicone, disteardimonium hectorite, triethyl citrate), BENTONE TNV (alkyl benzoate (C12-) 15), stearalconium hectorite, propylene carbonate), BENTONE VS-5V (V) (cyclopentasiloxane, disteal) Dimonium hectorite, denatured alcohol), BENTONE VS-5PC V (HV) (cyclopentasiloxane, disteardimonium hectorite, propylene carbonate).
Examples of the polymer ester composed of sugar and fatty acid include those marketed by Chiba Flour Milling Co., Ltd. under the trade name of Leopard.

In one aspect of the invention, the molar ratio of component (A): component (B) is 1: 0.1 to 1:15, preferably 1: 0.1 to 1:10, more preferably 1: 0.5. ~ 1: 1.5, particularly preferably about 1: 1.

The blending amount of the component (A) and the amide alcohol in the W / O type emulsion can be appropriately selected depending on the type and amount of the oil agent to be used, the required viscosity and the like, but is typically 0.1. It is ~ 14.0% by weight, preferably 0.5 to 10.0% by weight, and more preferably 1.0 to 8.0% by weight.

When the component (B) in the W / O type emulsion is a basic amino acid, the blending amount thereof can be appropriately selected depending on the type and amount of the oil agent to be used, the required viscosity and the like, but is typical. Is 0.5 to 3.0% by weight, preferably 0.5 to 2.0% by weight, and more preferably 0.5 to 1.5% by weight.

When the component (B) in the W / O type emulsion is a salt, the blending amount thereof can be appropriately selected depending on the type and amount of the oil agent to be used, the required viscosity and the like, but is typically , 0.5 to 5.0% by weight, preferably 0.5 to 4.0% by weight, and more preferably 1.0 to 3.0% by weight.

When the component (B) in the W / O type emulsion is alkaline, the blending amount thereof can be appropriately selected depending on the type and amount of the oil agent to be used, the required viscosity and the like, but is typically , 0.1 to 2.0% by weight, preferably 0.1 to 1.5% by weight, and more preferably 0.2 to 1.0% by weight.

The pH of the W / O type emulsion of the present invention can be appropriately selected to be a value suitable for the target product.
For example, when the aqueous phase is alkaline due to the presence of the component (B), a W / O type emulsion having an alkaline internal aqueous phase can be prepared, but an acidic component is added to the aqueous phase or the emulsion is acidic after emulsification. By adding ingredients, acidic or neutral W / O type emulsions can also be prepared.
Similarly, when an acidic salt is contained as the component (B) and the aqueous phase is acidic, a W / O type emulsion having an acidic internal aqueous phase can be prepared, but is it possible to add an alkaline component to the aqueous phase? It is also possible to prepare an alkaline or neutral W / O type emulsion by adding an alkaline component after emulsification.
Further, if the pH of the aqueous phase containing the component (B) is neutral, a neutral W / O type emulsion can be prepared, but an alkaline or acidic component is added to the aqueous phase or emulsified. An alkaline or acidic W / O type emulsion can also be prepared by adding an alkaline or acidic component later.

The viscosity of the W / O type emulsion of the present invention can be appropriately selected depending on the characteristics of the target product.
In one aspect of the present invention, from the viewpoint of obtaining a creamy emulsion, it is preferable to have a viscosity higher than 10,000 mP · s, and from the viewpoint of obtaining a stable milky emulsion, from 3,000 to It preferably has a viscosity of about 100,000 mP · s.
In one aspect of the present invention, from the viewpoint of using the W / O type emulsion as a cosmetic, the viscosity of the emulsion can be appropriately selected within the range of 3,000 to 1,000,000 mP · s.

In one aspect, the present invention
-(A) Equation (I)
During the ceremony
R ₁ is a C6-C22 hydrocarbon group.
R ₂ is H or C6~C22 hydrocarbon group,
R ₃ is a straight-chain or branched-chain C2~C21 hydrocarbon group,
Step of preparing an oil phase containing an amide alcohol represented by,
-(B) A step of preparing an aqueous phase containing at least one component selected from the group consisting of basic amino acids, alkalis and salts.
-The process of stirring the oil phase and the aqueous phase,
Provided is a method for producing a W / O type emulsion, which comprises.

In one aspect of the present invention, the aqueous phase is neutral or alkaline in the step of preparing the aqueous phase.
Further, in one aspect of the present invention, the production method of the present invention can further include a step of adding an acid when the pH of the aqueous phase is neutral or alkaline.
In certain aspects of the invention, acids can be added in the step of preparing the aqueous phase.
In another embodiment, a step of stirring the oil phase and the aqueous phase is followed by a step of adding an acid with stirring.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples, and various changes can be made without departing from the technical idea of the present invention. It is possible. In addition, in this specification,% means weight% unless otherwise specified.

[Test Example 1]
The basic formulations shown in Tables 1 and 2 below were prepared.
In each basic formulation, the molar ratio of component A: component B was prepared at 1: 1.

(Manufacturing method)
(1) Raw materials 1 and 2 were weighed in a suitable container and dissolved by heating to obtain an oil phase (80 ° C.).
(2) Raw materials 3 to 4 were weighed in a suitable container and heated to obtain an aqueous phase (80 ° C.).
(3) The aqueous phase was added while stirring the oil phase with an agitator (1500 rpm).
(4) After emulsification, the mixture was stirred with an agitator (2000 rpm, 3 min).
(5) The mixture was slowly cooled to room temperature with manual stirring.
The pH of the aqueous phase was measured with a HORIBA pH meter LAQUA act pH / ORP METER D-72.
It was confirmed that the obtained emulsion had no conductivity and was a W / O type.
In order to evaluate the storage stability, the obtained emulsion was stored at 50 ° C. for 1 month.

As component A, under the product name of Aminactol OLH, commercially available from Higher Alcohol Co., Ltd., in formula (I), R ₁ is unsaturated C18 alkyl (oleyl), R ₂ is H, and R ₃ is C 5. That is, an amide alcohol having the following structure (I-4) was used.

(Evaluation)
1. 1. Measurement of Emulsified Particle Size by Microscopic Observation The emulsified particle size of the emulsion of Examples was evaluated by observing at 400 times using "BX-53" manufactured by Olympus Corporation. The results are shown in FIGS. 1, 2 and 3.
2. 2. Observation with a Transmission Electron Microscope The emulsion of Example 1 was observed with a transmission electron microscope, JEM-1400 Flash (manufactured by JEOL Ltd.), as a sample prepared by the freeze-cutting replica method according to a conventional method. The results are shown in FIG.

3. 3. DSC measurement Using a high-sensitivity differential scanning calorimeter DSC7000X (manufactured by Hitachi High-Tech Science Corporation), DSC measurement was performed on Aminactol OLH alone and the emulsions of Examples 1, 4 and 5. The results are shown in FIGS. 5, 6 and 7.
-Measurement conditions Measurement range: 30 to 90 ° C
Temperature rise: 1 ° C / 1 min
The results are shown in FIG.
4. XRD diffraction XRD measurement of the emulsions of Examples 1 and 4 was performed using an XRD measuring device, Smart lab (manufactured by Rigaku Co., Ltd.).
-Measurement conditions X-ray source: Cu K-α
X-ray wavelength: 1.5405 Å
The results are shown in FIGS. 8 and 9.

From the results of FIG. 1, in the reference example in which the aqueous phase does not contain component B, the emulsion is separated with time and creaming occurs after one month, whereas the aqueous phase contains basic amino acids as component B. In the example, it can be understood that an emulsion having stability over time was obtained.
From the results of FIG. 2, it can be understood that the emulsifying property of the comparative example containing the acidic amino acid instead of the component B (basic amino acid) was lower than that of the reference example of the component A alone.

From the results of FIG. 3, it can be understood that an emulsion having stability over time was obtained in each of the examples in which the aqueous phase contained an alkali as the component B as compared with the reference example. Further, it can be understood that in Comparative Example 3 in which the acid was contained instead of the component B (alkali), the emulsifying property was lower than that in the reference example of the component A alone.

As shown in FIG. 4, the lamination can be confirmed around the water droplets.
As shown in FIGS. 5, 6 and 7, the emulsion had no melting peak of the amide alcohol raw material alone by differential scanning calorimetry (DSC), and a melting peak other than the raw material alone was confirmed. Both emulsions have a melting point near 48 ° C., and it is considered that they form the same structure.
Further, as shown in FIG. 7, even after storage at 50 ° C. for 1 month, the main peak hardly changed, and it can be understood that stable purification is excellent.
As shown in FIG. 8, the emulsion of Example 1 has repeated peaks (1: 1/2: 1) of 53.20 Å, 26.95 Å, and 13.39 Å in small-angle X-ray scattering (SAXS). / 4) was obtained, and the existence of lamination was confirmed.
As shown in FIG. 9, the emulsion of Example 4 containing an alkali as component B also had repeated peaks (1:) of 53.30 Å, 26.86 Å, and 13.47 Å in small-angle X-ray scattering (SAXS). 1/2: 1/4) was obtained, and the presence of lamination was confirmed.
From these results, it can be determined that the emulsion has a lamellar structure.

[Test Example 2]
The basic formulation shown in Table 3 below containing salt as component B was prepared by the same method as in Test Example 1.

(Evaluation)
The emulsified particle size and the XRD measurement were carried out in the same manner as in Test Example 1. The results are shown in FIGS. 10 and 11.
From the results of FIG. 10, it can be understood that an emulsion having stability over time was obtained even when the salt was used as the component B regardless of whether the salt was acidic, neutral or alkaline. ..
As shown in FIG. 11, the emulsion had no melting peak of the amide alcohol raw material alone by differential scanning calorimetry (DSC), and a melting peak other than the raw material alone was confirmed. The melting peak of the emulsion of Example 6 is similar to that of Examples 1, 4 and 5, and it can be understood that the emulsion has a similar structure.
As shown in FIG. 11, the emulsion of Example 6 containing a salt as component B also had repeated peaks (1:) of 53.30 Å, 26.86 Å, and 13.47 Å in small-angle X-ray scattering (SAXS). 1/2: 1/4) was obtained, and the presence of lamination was confirmed.

[Test Example 3]
Formulations having different ratios of component A and component B shown in Tables 4 and 5 below were prepared in the same manner as in Test Example 1.
The formulations shown in Table 4 are based on the basic formulation of Example 1.
・ Ratio of oil agent in oil phase to component A,
・ Ratio of component B in the aqueous phase to water,
1-B to E were designed so as to increase the proportion of the oil phase in the emulsion while maintaining each of the above.

In the formulations shown in Tables 5 to 8 below, the ratio of component A to component B is adjusted by changing the amount of component B in the aqueous phase while keeping the oil phase constant based on the basic formulations of Examples 6 to 9. Was a different prescription.

(Evaluation)
-Viscosity The viscosity was measured at a rotation speed of 20 rpm using a Brookfield viscometer and SPINDLE of S64.
-Emulsified particle size The emulsified particle size was measured in the same manner as in Test Example 1.
The results are shown in Tables 4 and 5.

-Observation with a polarizing microscope The emulsion of Example 1-D was polarized and observed at 400 times using "BX-53" manufactured by Olympus Corporation. The results are shown in FIG.
As shown in FIG. 13, in the polarization observation (sensitive color) of the emulsion, yellow and blue images are projected, and it can be understood that the structure has regularity.

-DSC measurement In the same manner as in Test Example 1, DSC measurement of the emulsion of Example 1-D was performed. The results are shown in FIG.
From these results, it is assumed that the oil phase of the emulsion forms an oil gel.

In order to examine the effect of pH when the alkaline component B was used, an acid-added emulsion was prepared according to the following production methods 1 and 2, respectively, according to the formulation shown in Table 9.

(Manufacturing method 1)
(1) Raw materials 1 and 2 were weighed in a suitable container and dissolved by heating to obtain an oil phase (80 ° C.).
(2) Raw materials 3 to 5 were weighed in a suitable container and heated to obtain an aqueous phase (80 ° C.).
(3) The aqueous phase was added while stirring the oil phase with an agitator (1500 rpm).
(4) After emulsification, the mixture was stirred with an agitator (2000 rpm, 3 min).
(5) The mixture was slowly cooled to room temperature with manual stirring.

(Manufacturing method 2)
(1) Raw materials 1 and 2 were weighed in a suitable container and dissolved by heating to obtain an oil phase (80 ° C.).
(2) Raw materials 3 and 5 were weighed in a suitable container and heated to obtain an aqueous phase (80 ° C.).
(3) The aqueous phase was added while stirring the oil phase with an agitator (1500 rpm).
(4) After emulsification, the mixture was stirred with an agitator (2000 rpm, 3 min).
(5) Raw material 4 was added (2000 rpm) while stirring (4) with an agitator.
(6) After emulsification, the mixture was stirred with an agitator (2000 rpm, 3 min).
(7) The mixture was slowly cooled to room temperature with manual stirring.

The emulsified state was confirmed in the same manner as in Test Example 1. The results are shown in FIGS. 15 and 16.
From the results of FIGS. 15 and 16, it can be understood that an emulsion can be produced and the stability over time is excellent even when an acid is added to the aqueous phase or when an acid is added after emulsification.

[Test Example 5]
In the above-mentioned test example, only mineral oil was used as the oil agent, but the formulations containing various esters shown in Table 10 were prepared. In addition, a moisturizing ingredient was added to the aqueous phase, assuming use as a cosmetic product.

(Manufacturing method)
(1) Raw materials 1 to 4 were weighed in a suitable container and dissolved by heating to obtain an oil phase (80 ° C.).
(2) Raw materials 5 to 8 were weighed in a suitable container and heated to obtain an aqueous phase (80 ° C.).
(3) The aqueous phase was added while stirring the oil phase with an agitator (1500 rpm).
(4) After emulsification, the mixture was stirred with an agitator (2000 rpm, 3 min).
(5) The mixture was slowly cooled to room temperature with manual stirring.

The particle size was measured immediately after production and after storage at 50 ° C. for 1 month by the same method as in Test Example 3. The results are shown in FIGS. 17 to 30.
From these results, it can be understood that a W / O type emulsion containing an ester oil can be prepared and its stability over time is also excellent.

[Test Example 6]
In the above-mentioned test example, only mineral oil was used as the oil agent, but the formulations containing various silicone oils shown in Table 11 were prepared. In addition, a moisturizing ingredient was added to the aqueous phase, assuming use as a cosmetic product.

(Manufacturing method)
(1) Raw materials 1 to 4 were weighed in a suitable container and dissolved by heating to obtain an oil phase (80 ° C.).
(2) Raw materials 5 to 7 were weighed in a suitable container and heated to obtain an aqueous phase (80 ° C.).
(3) The aqueous phase was added while stirring the oil phase with an agitator (1500 rpm).
(4) After emulsification, the mixture was stirred with an agitator (2000 rpm, 3 min).
(5) The mixture was slowly cooled to room temperature with manual stirring.

The particle size was measured after storage immediately after production by the same method as in Test Example 3. The results are shown in FIGS. 31 and 32.
From these results, a W / O type emulsion containing silicone oil can be prepared.

The present invention can provide a W / O type emulsion by combining an amide alcohol with a component selected from the group consisting of basic amino acids, alkalis and salts.
Such an emulsion can be used for applications such as cosmetics.

Claims (13)

(A) Equation (I)
During the ceremony
R ₁ is a C6-C22 hydrocarbon group.
R ₂ is H or C6~C22 hydrocarbon group,
R ₃ is a straight-chain or branched-chain C2~C21 hydrocarbon group,
The amide alcohol represented by, and (B) at least one component selected from the group consisting of basic amino acids, alkalis, and salts.
Only including,
Contain no carboxyl group-containing polymer, including a less than 0.01 wt% carboxy group-containing polymer, W / O type emulsion. The W / O type emulsion according to claim 1, wherein the molar ratio of (A): (B) is 1: 0.1 to 1:15. The W / O type emulsion according to claim 1 or 2, which comprises a hydrocarbon oil and / or an ester oil. (B) The W / O type emulsion according to any one of claims 1 to 3, which contains 1.0% by weight or more of alkali as a component. (B) The W / O type emulsion according to any one of claims 1 to 3, which contains a salt as a component. (B) The W / O type emulsion according to any one of claims 1 to 3, which contains a basic amino acid as a component. The W / O type emulsion according to any one of claims 1 to 6, which contains more than 60% by weight of an aqueous component. The W / O type emulsion according to any one of claims 1 to 7 , which contains no surfactant or contains less than 2.0% by mass of a surfactant. The W / O type emulsion according to any one of claims 1 to 8 , which contains an acid. -(A) Equation (I)
During the ceremony
R ₁ is a C6-C22 hydrocarbon group.
R ₂ is H or C6~C22 hydrocarbon group,
R ₃ is a straight-chain or branched-chain C2~C21 hydrocarbon group,
Step of preparing an oil phase containing an amide alcohol represented by,
-(B) A step of preparing an aqueous phase containing at least one component selected from the group consisting of basic amino acids, alkalis and salts.
-The process of stirring the oil phase and the aqueous phase,
including,
A method for producing a W / O type emulsion that does not contain a carboxy group-containing polymer or contains a carboxy group-containing polymer of less than 0.01% by weight . -(A) Equation (I)
During the ceremony
R ₁ is a C6-C22 hydrocarbon group.
R ₂ is H or C6~C22 hydrocarbon group,
R ₃ is a straight-chain or branched-chain C2~C21 hydrocarbon group,
Step of preparing an oil phase containing an amide alcohol represented by,
-(B) A step of preparing an aqueous phase containing at least one component selected from the group consisting of basic amino acids, alkalis and salts.
-The process of stirring the oil phase and the aqueous phase,
Including
A method for producing a W / O type emulsion in which the pH of the aqueous phase is neutral or alkaline in the step of preparing the aqueous phase. In the step of preparing an aqueous phase, adding an acid to the aqueous phase, the method according to claim 1 0 or 1 1. After the step of stirring the oil phase and aqueous phase, comprising the step of adding an acid with stirring, The method of claim 1 0 or 1 1.