JP2001311099A - Detergent composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition having excellent stability with time and sense of use, capable of finely dispersing an oily component such as a silicone compound, etc., into the composition. SOLUTION: This composition comprises a surfactant selected from an anionic surfactant, an amphoteric surfactant and a nonionic surfactant, (A) a cationic surfactant, (B) a higher alcohol having >=45 deg.C melting point, (C) a polyglycerol fatty acid ester having ⊖7 HLB and preferably (D) an oily component. A liquid crystal phase is formed from the component (A) and the component (B) and the component (C) and, if necessary, the component (D) are kneaded with the liquid crystal phase and then mixed with an emulsion forming water phase containing the surfactant to produce the objective detergent composition of O/W type emulsion type.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition mainly used for hair and the like, and a method for producing the cleaning composition. More specifically, the present invention relates to a cleaning composition having excellent stability over time and feeling during use. And even if the detergent composition comprises a system containing an oily component such as a silicone compound blended as a feel imparting agent, by applying a base having a liquid crystal forming ability, the oily component can be added to the system. Can be finely dispersed
The present invention relates to a method for producing a detergent composition capable of obtaining an O / W emulsion type detergent composition having excellent usability and stability over time.

[0002]

2. Description of the Related Art
For example, various proposals have been made for hair cleaning compositions such as shampoos in order to improve the usability during hair washing. For example, silicone compounds and other insoluble fine particles, or oil components such as ester oil (oil-based components) ) Has been proposed to satisfy the required quality by blending it as a feel imparting agent.

However, since the oily component is difficult to stably disperse in the composition, it is possible to satisfy the above-mentioned required quality by adding a component having excellent dispersion stability in the composition instead of the oily component, or Means for stably dispersing the components in the composition have been desired, but at present the components that have excellent dispersion stability and sufficiently satisfy the required quality have not been developed.

[0004] On the other hand, various means for stably dispersing the oily component in the composition have been proposed.
No. 19310 discloses a mixture of a hydrophobic powder and an oil agent,
Liquid cosmetics dispersed in an aqueous phase containing a cross-linked polyacrylic polymer substance, JP-A-3-135909 discloses:
Hair cosmetics containing high molecular weight silicone and fatty acid alkanolamide, JP-A-5-310538,
Japanese Patent No. 310540 discloses a liquid detergent composition containing water-insoluble silicone, water-insoluble fine particles, a surfactant selected from anionic, amphoteric and nonionic surfactants, and a specific nonionic polymer or cationic polymer. JP-A-7-53340 proposes a shampoo composition containing a surfactant selected from anionic, amphoteric and nonionic surfactants, a copolymer of a dialkyldiallylammonium salt, and a polymeric silicone oil. ing.

[0005] As in these proposals, the state of the oily component in the composition when the oily component is added to the detergent composition may be a solubilized system in which the oily component is dissolved in the system, or a polymer substance. It has been a conventional general method to form a dispersion system in which an oily component, which is an insoluble substance, is uniformly dispersed in the system by adding it. Therefore, as described above, in order to solubilize the oily component, it is necessary to limit the type and amount of the oily component, or a case where a polymer substance is an essential component as a dispersion stabilizer of the oily component. There were many.

However, when a polymer substance, which is an essential component as a dispersion stabilizer of an oily component, is incorporated in, for example, a shampoo composition, there is an effect of reducing creaking during rinsing, etc. In some cases, inconveniences such as the occurrence of stiffness occur.

On the other hand, when the characteristics and physical properties of the oily component to be used are limited, for example, if a silicone compound is used as a feel-imparting agent in a hair cleaning composition, it is generally preferable to use a high molecular weight silicone oil. It is said that it has an excellent texture, but it can be mixed with low molecular weight silicone in terms of dispersion stability and formulation, or by using modified silicone or silicone emulsion that has been subjected to various types of modification. It needed to be stably dispersed in the system. When the oily component is blended for various purposes, when setting the blending amount, taking into account the solubility and dispersion stability of the oily component in the composition, the blending amount at which the maximum effect is obtained is considered. At present, it has to be blended in a small amount.

[0008] As described above, even if the above-mentioned oily component is incorporated into a detergent composition for various purposes, there has been no detergent composition capable of exhibiting the maximum effect in terms of performance and the like.

[0009] The present invention has been made in view of the above circumstances, and has excellent usability and stability over time. Further, even when an oily component is blended, the dispersion stabilization of the oily component has been conventionally required. The detergent composition and the oil component can be stably compounded without depending on the molecular substance, and it is possible to select the type of the oil component to be compounded and the amount of addition without being limited to some extent. In addition, an object of the present invention is to provide a method for producing a detergent composition which can provide an O / W emulsion type detergent composition having excellent stability over time.

[0010]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a cationic surfactant having a liquid crystal forming ability and a specific higher alcohol can be used. By using in combination with a specific polyglycerin fatty acid ester, as shown in Examples and Comparative Examples described later, for example, a detergent composition excellent in use feeling as a hair cleansing composition, and also excellent in stability over time. In addition to the fact that the oily component such as a silicone compound used as a feel-imparting agent in a hair cleansing composition is added to the cleaning composition, the dispersion stabilization of the oily component is conventionally performed. They found that they could be selected without depending on the high molecular substance which was an essential component, and the kind of the oily component and the amount of addition could be selected without any limitation.
The inventors have invented the cleaning composition of the present invention.

As a result of further intensive studies, when producing such a detergent composition, a liquid crystal phase is formed by utilizing the liquid crystal forming ability of the cationic surfactant and the higher alcohol, and the liquid crystal phase is formed. Add an oily component such as a silicone compound and the above-mentioned polyglycerin fatty acid ester into the phase,
After mixing (an oily component is finely dispersed in a liquid crystal phase and an oil phase containing a polyglycerin fatty acid), an (an aqueous phase mainly containing a cleaning base) is gradually added to the oil phase. do it,
By inverting the phase of the oily component, a detergent composition which is stable to coalescence of emulsion particles and has excellent stability over time without the need for a dispersion stabilizer such as a polymer substance can be obtained. I found that.

That is, as described in the examples below, the present inventors, when producing a detergent composition containing the above oily component, finely disperse the above oily component in the above liquid crystal phase as described above. At the same time, after adding and mixing the polyglycerin fatty acid ester, an aqueous phase (a surfactant solution) containing the cleaning base was gradually added thereto, and the mixture was kneaded into the liquid crystal phase. The oily component inverts in the aqueous phase,
As a result, the particles are dispersed and dispersed in the system.
For this reason, an O / W emulsion type cleaning composition which is stabilized against coalescence in the composition and has excellent stability over time can be obtained without requiring a polymer substance as a dispersion stabilizer. This led to the invention of a method for producing the cleaning composition of the present invention.

Accordingly, the present invention relates to a detergent composition containing one or more surfactants selected from anionic surfactants, amphoteric surfactants and nonionic surfactants. , (A) a cationic surfactant, and (B)
A cleaning composition comprising a higher alcohol having a melting point of 45 ° C. or higher and (C) a polyglycerol fatty acid ester having an HLB of 7 or less, and more preferably (D) a detergent composition containing an oily component. Offer things. Further, the present invention provides (A) a cationic surfactant and (B) a melting point of 45.
C. or higher and a liquid phase for forming a liquid crystal by mixing with a higher alcohol to form a liquid crystal phase. In the liquid crystal phase, (C) a polyglycerol fatty acid ester having an HLB of 7 or less and (D)
After adding and mixing an oil component to prepare an oil phase, one or more surfactants selected from anionic surfactants, amphoteric surfactants and nonionic surfactants are added to the oil phase. A water phase for emulsion formation containing is added and mixed,
Provided is a method for producing a detergent composition, which comprises preparing an O / W emulsion.

Hereinafter, the present invention will be described in more detail. The cleaning composition of the present invention comprises a cleaning base selected from anionic surfactants, amphoteric surfactants, and nonionic surfactants. It contains more than one type of surfactant.
Here, the type of these surfactants is not particularly limited as long as they can be used as a cleaning base. Examples of the anionic surfactant include alkyl sulfonate and alkyl sulfonate. Sulfate, acylated amino acid salt, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, N-acyl-N-methyltaurine salt, α-olefin sulfonate, higher fatty acid ester sulfonate, alkyl ether acetate, Polyoxyethylene alkyl ether acetate, fatty acid soap,
Alkyl phosphate esters and the like.

In the case of the present invention, among these, in particular, polyoxyethylene lauryl ether sulfate, N-lauroyl-N-methyl-β-alanine salt, polyoxyethylene lauryl ether acetate, polyoxyethylene lauryl amide acetate, Monoalkyl phosphates and the like are particularly preferred. In addition, as a salt used here, sodium,
Metal salts such as potassium and magnesium; ammonium salts;
Organic ammonium salts such as monoethanolammonium, diethanolammonium and triethanolammonium salts are preferred.

Examples of the amphoteric surfactant include an alkyl betaine surfactant, an amido betaine surfactant,
Sulfobetaine surfactant, hydroxysulfobetaine surfactant, amide sulfobetaine surfactant,
Examples include phosphobetaine surfactants, imidazolinium betaine surfactants, aminopropionic acid surfactants, amino acid surfactants, and the like. In the case of the present invention, among these, alkyl betaine, amidopropyl betaine, lauryl hydroxysulfo betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl iminodipropionic acid and the like are particularly preferred. Further, amine oxide surfactants and the like are also suitable, and among them, lauryl dimethylamine oxide and the like are particularly preferable.

The nonionic surfactants include, for example, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, polyglycerin fatty acid esters exceeding HLB 7, polyoxyethylene alkyl ether, polyoxyethylene And polyoxypropylene glycol. Among these, polyethylene glycol monostearate, decaglyceryl monolaurate, polyoxyethylene lauryl ether, polyoxyethylene (160) polyoxypropylene (30) glycol, and the like are particularly preferable. Furthermore, other than these, for example, coconut oil fatty acid alkanolamide, sucrose fatty acid ester, alkyl glycoside, alkyl glyceryl glycoside, methyl glucoside fatty acid ester and the like can be mentioned.

The amount of the anionic, amphoteric, or nonionic surfactant in the detergent composition of the present invention is not particularly limited, and is usually 5 to 6 times the total amount of the detergent composition.
0% (% by mass, the same applies hereinafter), particularly 10 to 50%
% Is preferred. If the compounding amount is too large, when the oily component is compounded, a problem may occur in dispersing the oily component, or a suitable viscosity or usability may not be obtained.If the amount is too small, a sufficient cleaning effect may not be obtained. . In particular, when the amphoteric surfactant is blended, the amphoteric surfactant is added to the composition in an amount of 1%.
Addition of the above is preferable because the temporal stability of the composition is improved. One of these surfactants may be used alone, but it is preferable to use a mixture of two or more surfactants selected from anionic, amphoteric and nonionic surfactants.

The cationic surfactant of the component (A) of the present invention may be any one which can be blended in a detergent composition.
The type is not particularly limited, and for example, those which can be used for a hair cleaning composition such as a shampoo composition and have a liquid crystal forming ability are preferable. For example, an alkyl quaternary ammonium salt represented by the following general formula (1) is preferably used.

[0020]

Embedded image

In the general formula (1), R¹, R^Two, R^Threeas well as
R^FourIs an alkyl group, a hydroxyalkyl group,
Alkenyl group, polyalkylene oxide group or benzyl
R represents a group¹, R^Two, R^ThreeAnd R^FourOne or two of
Linear alkyl having 10 to 24, preferably 16 to 22 carbon atoms
A hydroxy group, a hydroxyalkyl group or an alkenyl group,
The rest is methyl, ethyl, benzyl, or-(C_Two
H_FourO)_q-H,-(C_ThreeH ₆O)_r-H (however, q and r
Is an integer of 1 to 5).
Lenoxide groups, which are identical to each other and
May also be different. Also, Z^-Is a halogen atom
Represents an anion.

Specific examples of the component (A) represented by the general formula (1) include, for example, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetostearyltrimethylammonium chloride, and distearyldimethylammonium chloride. And dibehenyldimethylammonium chloride.

A guanidine derivative represented by the following general formula (2) or a salt thereof can also be suitably used as the cationic surfactant of the component (A).

[0024]

Embedded image[Wherein, R^FiveIs linear or branched having 1 to 22 carbon atoms
Alkyl, alkenyl, or alkyl ether groups of
And m is an integer of 0 or 1. A is CHR ^Ten(C
H_Two)_n[However, R^TenIs a hydrogen atom or COOR¹¹(R¹¹Is
It may be substituted with a hydrogen atom or a hydroxyl group having 1 to 6 carbon atoms.
Branched or linear alkyl or alkenyl
And n is an integer of 0-9. ],
R⁶, R⁷Is substituted with a hydrogen atom or a hydroxyl group having 1 to 12 carbon atoms.
A branched or straight-chain alkyl group which may be
An alkenyl group;⁸, R⁹Is a hydrogen atom, carbon number 1
A branched or straight chain optionally substituted with 6 hydroxyl groups;
X is an inorganic acid or an alkenyl group.
Is an organic acid. ]

Here, the substituent R ⁵ in the above general formula (2)
Is a branched or linear alkyl group, alkenyl group or alkyl ether group having 1 to 22 carbon atoms, preferably 11 to 21 carbon atoms.
_{11 H 23 -, C 12 H} 25 -, C 13 H 27 -, C 14 H 29 -, C 15
_{H 31 -, C 16 H 33} -, C 17 H 35 -, (C 8 H 17) 2 CH
_{-, 4-C 2 H 5} C 15 H 30 - groups, such as are suitable.

R ⁶ and R ⁷ are a hydrogen atom, a branched or straight-chain alkyl or alkenyl group having 1 to 12 carbon atoms.

R ⁸ and R ⁹ are a hydrogen atom, a branched or straight-chain alkyl or alkenyl group having 1 to 6 carbon atoms.

A is represented by CHR ¹⁰ (CH ₂ ) _n , wherein n is an integer of 0 to 9, preferably 1 to 5, and (CH ₂ ) _n is preferably a linear alkylene group; For example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and the like can be mentioned. Also, R ¹⁰
Is represented by hydrogen atom or COOR ^11, R ¹¹ is a hydrogen atom, an alkyl group or alkenyl group having 1 to 6 hydroxyl groups in the optionally substituted branched or straight, for example COOH, COOC ₂ H _{5 and the} like.
Here, m is an integer of 0 or 1.

The above guanidine derivative is usually added in the form of a salt. That is, in the general formula (2), X represents an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid, or glycolic acid, acetic acid, tartaric acid, propionic acid, lactic acid, citric acid, salicylic acid, succinic acid, malic acid, or butyric acid. , P-toluenesulfonic acid, higher fatty acids, L- or DL-pyrrolidone carboxylic acid, acidic amino acids, organic acids such as pyroglutamic acid and the like, but from the viewpoint of solubility in water and the like, inorganic salts are used. In such a case, a hydrochloride or the like, and in the case of an organic acid salt, a glycolate or the like is desirable. In order to form these salts, the guanidine derivative may be neutralized with the acid.

As such guanidine derivatives and salts thereof, more specifically, for example, alkyl guanidines such as hexadecyl guanidine, octadecyl guanidine, 2-octyl dodecyl guanidine, alkylene guanidines such as oleyl guanidine, 2-guanidinoethyl laurones Amide, 4-guanidinobutyl lauroamide, 3-
Alkylamidoguanidines such as guanidinopropyloctanoylamide, 2-guanidinoethylstearoylamide, 6-guanidinohexylmyristoylamide,
Alkylene amide guanidine such as guanidinobutyl olenoylamide guanidine, guanidine derivative such as amide laurate amide butyl guanidine, diguanidine derivative such as 1,8-diguanidinooctane, 1,18-diguanidino olein, N-coconut fatty acid acyl Arginine derivatives such as -L-arginine ethyl, N-coconut fatty acid acyl-L-arginine stearyl, N-lauroyl-L-arginine propyl, N-2-ethylhexanoyl-L-arginine methyl, and salts thereof. Be

Further, as the component (A) of the present invention, an amino acid-based cationic surfactant can also be suitably used,
Examples of the amino acid-based cationic surfactant include mono-
N-long-chain acyl basic amino acid lower alkyl ester salts and the like can be mentioned. Examples of the basic amino acids constituting this compound include natural amino acids such as ornithine, lysine and arginine. It is also possible to use synthetic amino acids such as α, γ-diaminobutyric acid. These may be optically active or racemic.

The acyl group has 8 to 22 carbon atoms.
Is a saturated or unsaturated higher fatty acid residue. These may be natural or synthetic. For example, single higher fatty acid residues such as lauroyl group, myristoyl group, palmitoyl group and stearoyl group, and natural mixed higher fatty acid residues such as coconut oil fatty acid residue and tallow higher fatty acid residue can be employed. .

As the lower alkyl ester component, methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester and the like are preferable.
As the salt, an inorganic acid salt such as hydrochloride or sulfate,
Or an organic acid salt such as acetate, tartrate, citrate, p-toluenesulfonate, higher fatty acid salt, acidic amino acid salt, or pyroglutamate can be employed. L- or DL-pyrrolidone carboxylate and acidic amino acid salt forms are particularly preferred.

As the above mono-N-long-chain acyl basic amino acid lower alkyl ester salt, more specifically, for example, N- [3-alkyl (12,14) oxy-2-hydroxypropyl] -L-arginine hydrochloride Salts and the like can be mentioned.

As the component (A) of the detergent composition of the present invention, an alkyl quaternary ammonium salt represented by the above formula (1), a guanidine derivative represented by the above formula (2) or a salt thereof and / or When compounding an amino acid-based cationic surfactant such as the above mono-N-long-chain acyl basic amino acid lower alkyl ester salt, the amount thereof is not particularly limited, but is usually 0% based on the whole composition. .
The range is preferably from 0.5 to 5%, more preferably from 0.3 to 5%.
It is in the range of 3%. If the amount is less than 0.05%, the finishing effect may be insufficient or sufficient dispersion stability may not be obtained. If the amount exceeds 5%, stickiness may occur.

As the component (A) of the cleaning composition of the present invention, the above-mentioned cationic surfactants may be used alone or in combination of two or more.

Examples of the higher alcohol having a melting point of 45 ° C. or higher, which is the component (B) of the present invention, include, for example, those having 12 to 26 carbon atoms.
Alcohols having a linear or branched alkyl group or alkenyl group of, for example, more specifically, for example, cetostearyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnavir Alcohol, seryl alcohol and the like are preferred, and these can be used alone or in combination of two or more. Here, in the case of the present invention, these components (B) need to have a melting point of 45 ° C. or higher, preferably 4 ° C.
5-75 ° C. If the melting point is too low, good feeling in use and sufficient dispersion stability cannot be obtained. In the case of the present invention,
A higher alcohol having a melting point of less than 45 ° C. can be used in combination, but in this case, it is desirable that the higher alcohol mixture has a melting point of 45 ° C. or more.

The above (B) in the cleaning composition of the present invention.
The amount of the components is not particularly limited, and usually,
It is preferable to blend the component (A) so as to be 1 to 15 times (mass ratio), more preferably 1 to 10 times the component (A). 1
If it is less than 2 times, for example, when used as a hair cleaning composition, it may not be possible to obtain a sufficient finish feeling or use feeling and sufficient dispersion stability on the hair, and if it exceeds 15 times, it may have higher alcohol. In some cases, the composition itself tends to precipitate and it is difficult to stably formulate the preparation.

The polyglycerol fatty acid ester of the component (C) of the present invention must have an HLB of 7 or less, preferably an HLB of 2 to 6, more preferably an HLB.
Is around 4. If the HLB is too high, for example, when the composition is used as a hair cleaning composition, it may not be possible to obtain a sufficient finished feel, use feeling, and sufficient dispersion stability for hair.

The component (C) of the present invention is not particularly limited as long as it is a polyglycerol fatty acid ester having an HLB of 7 or less. Saturated fatty acids or unsaturated fatty acids having a number of 18 to 22 are esterified with a degree of esterification of 1 to 10, and those having a liquid crystal forming ability are preferably used.

More specifically, for example, diglyceryl monostearate, diglycerin monostearate,
Diglycerin distearate, hexaglycerin hexastearate, hexaglycerin octastearate,
Hexaglycerin tristearate, hexaglycerin pentastearate, decaglycerin pentastearate, decaglycerin decasterate, decaglycerin heptabehenate, pentaglycerin trioleate,
Examples thereof include pentaglycerin tristearate, pentaglycerin hexastearate, tetraglycerin tristearate, and tetraglycerin pentastearate. These can be used alone or in an appropriate combination of two or more.

The above (C) in the cleaning composition of the present invention.
The amount of the components is not particularly limited, and usually,
It is preferably in the range of 0.5 to 10% based on the whole composition,
More preferably, it is 1 to 5%. If the amount is less than 0.5%, the feeling of use may be insufficient or sufficient dispersion stability may not be obtained. If the amount exceeds 10%, the stability over time may be adversely affected.

The detergent composition of the present invention is more effective when an oil component is further blended as the component (D). The type of the oil component in the present invention is not particularly limited. It is possible to use those commonly used in detergent compositions. Examples of such oily components include silicone compounds, ester oils, oil-soluble flavors, oil-soluble antibacterial agents, liquid paraffin, petrolatum, and solid paraffin. And the like, liquid lanolin, lanolin derivatives such as lanolin fatty acids, higher fatty acid esters, higher fatty acids, oils and fats such as long-chain amidoamines having an alkyl or alkenyl group, and animal and vegetable oils and fats such as mink oil and olive oil. , An antioxidant such as α-tocopherol, triclosan, pyroctone olamine, parabens and the like. These may be used singly or in combination of two or more as appropriate. In the case of the present invention, among these, a silicone compound is particularly preferably used.

The type of the silicone compound (D) of the present invention that is preferably used as an oily component is not particularly limited, and examples thereof include dimethylpolysiloxane (including highly polymerized dimethylpolysiloxane and silicone rubber) and methyl Examples thereof include silicone derivatives such as phenylpolysiloxane, polyether-modified silicone oil, and polyamino-modified silicone oil. These can be used alone or in an appropriate combination of two or more. Among these, dimethylpolysiloxane is particularly preferred.

[0045] As the silicone compound, a viscosity at 25 ℃ is 5~10,000,000mm ² / s, in particular, those of 10~1,000,000mm ² / s it is more preferably used. As the silicone compound to be blended as the component (D) of the present invention, those obtained by emulsifying the above silicone derivative with a surfactant to form an emulsion can also be used. In addition, as such an emulsion, there is no particular limitation on an emulsifier and an emulsification method, and various emulsions can be used. However, in the present invention, a silicone oil having a high molecular weight (for example, having a weight average molecular weight of 30,000 or more) is more preferable.

The amount of the oily component in the cleaning composition of the present invention can be appropriately selected depending on the kind, the purpose of the mixing, and the like, and is not particularly limited. If it is blended as a texture imparting agent for the product, it is usually 0.1% based on the whole composition.
-5% is preferable, and 0.5-3% is more preferable. If the amount is too small, good feeling after drying may not be exhibited, and if it is too large, stable emulsification and dispersion may not be achieved.

It is also effective to add a small amount of a water-soluble polymer substance to the cleaning composition of the present invention for the purpose of further improving the usability. The types are anionic, nonionic,
The amphoteric, cationic and the like are not particularly limited, and those usually used in detergent compositions can be used.

Specifically, the anionic or nonionic water-soluble polymer substance may be any of natural and synthetic ones, such as pectin, carrageenan, guar gum, locust bean gum, gelatin, xanthan gum and carboxyvinyl polymer. Carboxymethylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, alginate, starch, polyvinyl alcohol, polyacrylate, polymethacrylate, polymethylacrylate, polyethylene glycol, polyethylene oxide, tragarant rubber, and the like. .

Examples of the amphoteric or cationic water-soluble polymer having a cationic residue include dimethyldiallylammonium chloride homopolymer having a functional group of dimethyldiallylammonium halide, dimethyldiallylammonium chloride / acrylamide copolymer, chloride Examples include dimethyldiallylammonium / acrylic acid copolymer, dimethyldiallylammonium chloride / acrylamide / acrylic acid terpolymer, and more specifically, for example, sold under the trade name `` Mercoat '' series from US Calgon, Inc. Can be used. Further, as a polymer substance having another cationic residue, for example, methacryloylethyl betaine-methacrylic acid ester copolymer and the like can be mentioned, and more specifically, for example, a product name `` Yuka Former '' series from Mitsubishi Chemical Corporation. For example, those that are sold can be used.

Further, in addition to cationized cellulose, cationized guar gum, cationized dextran, cationized pullulan, etc., cationic groups are introduced into protein hydrolysates such as cationized hydrolyzed keratin, cationized hydrolyzed silk, and cationized collagen. Can be used.

The above-mentioned polymer substances may be used alone or in combination of two or more. When the above polymer substance is blended, the blending amount in the composition is preferably 0.01 to 5% based on the whole composition, and particularly preferably 0.1 to 5%.
When it is blended at 2%, a detergent composition which is particularly excellent in foaming, has fine foam quality and improved rinsing properties can be obtained.

The cleaning composition of the present invention may contain various commonly used additives in addition to the above components, if necessary, depending on the purpose of use and the like, as long as the effects of the present invention are not impaired. It is. Examples of such additional components include polyols, inorganic salts, organic salts, solubilizers, antioxidants such as dibutylhydroxytoluene (BHT), bactericides such as trichlorocarban, viscosity modifiers,
UV absorbers, plant and animal extracts, antidandruff agents such as zinc pyrithione, anti-inflammatory agents such as dipotassium glycyrrhizinate, benzoic acid and its salts, preservatives such as Caisson CG,
PH adjusters such as citric acid and triethanolamine, pearling agents such as ethylene glycol difatty acid ester,
Emulsifiers, pigments, fragrances, etc. can be optionally added,
The amount of these additives can be a normal dose as long as the effects of the present invention are not hindered.

The cleaning composition of the present invention can be used for various uses, and is particularly suitable as a liquid cleaning composition for the body, for example, a liquid cleaning composition for hair such as shampoo and rinse-in shampoo, It is suitably used as a liquid cleansing composition for skin such as body shampoo and face wash, and is particularly preferably used as a liquid cleansing composition for hair and the like.

The method for producing the detergent composition of the present invention is not particularly limited. For example, (A) a cationic surfactant, (B) a higher alcohol having a melting point of 45 ° C. or more, (C) An oil phase containing a polyglycerin fatty acid ester having an HLB of 7 or less and, if necessary, an oil component (D), and a surfactant (detergent) selected from anionic, amphoteric and nonionic surfactants; The O / W emulsion can be prepared by mixing and stirring water and an aqueous phase containing the above-mentioned water-soluble component as required using a usual emulsification stirrer, and particularly, (D) When an oily component is contained, the above-mentioned oily component is produced by the production method of the present invention in which an O / W emulsion is prepared by a liquid crystal phase inversion method using the liquid crystal forming ability of the above components (A) and (B). Easy to composition during fine It can be dispersed and stably dispersed in the composition for a long period of time, and not only a detergent composition having excellent stability over time can be obtained, but also a large amount of the oily component can be stably dispersed in the composition. Therefore, it is more preferable. Even when the detergent composition of the present invention does not contain (D) an oily component, it is more preferable to prepare it by a liquid crystal phase inversion method.

That is, according to the production method of the present invention, a liquid crystal phase is formed by mixing a system containing the (A) cationic surfactant, the (B) higher alcohol and an aqueous phase for forming a liquid crystal. The above (C) polyglycerin fatty acid ester and (D) oil component are added to and mixed with the liquid crystal phase while stirring to prepare an oil phase. Then, the aqueous phase for forming an emulsion containing the above-mentioned washing base is added to this oil phase. By adding and mixing, the above-mentioned oil component is phase-inverted, refined and dispersed. Hereinafter, the production method of the present invention will be described by dividing into a liquid crystal forming step, an oil phase preparing step, an aqueous phase preparing step, and a phase inversion step.

In the liquid crystal forming step of the present invention, a liquid crystal phase is formed by mixing a system composed of the above-mentioned component (A), the above-mentioned component (B), and an aqueous phase for forming a liquid crystal, as described above. The order of addition, conditions for mixing and the like are not particularly limited. However, in order to uniformly mix and dissolve the above components and facilitate liquid crystal formation, the higher alcohol of the above component (B) must be at least its melting point. It is more efficient to dissolve at the above temperature and add and mix other components sequentially while maintaining the system temperature to form a liquid crystal structure. Here, the temperature difference between the system temperature and the melting point of the component (B) can be appropriately selected,
Usually, it is desirable that the temperature of the system is higher than the melting point of the higher alcohol of the component (B) and lower than the phase transition temperature of the liquid crystal composed of the components (B) and (A).

The formation of the liquid crystal phase depends on the component (A) and the component (B).
The amount of the aqueous phase for forming a liquid crystal is not particularly limited because it depends on the balance of the components and the aqueous phase for forming a liquid crystal. However, the amount is about 10% based on the whole composition. If the amount is too small, a liquid crystal phase may not be easily formed. If the amount is too large, it may be difficult to finely disperse and disperse the oily component.

More specifically, for example, the above (B) higher alcohol is heated and dissolved at 40 to 80 ° C. depending on the melting point,
While stirring, the bulk powder or solution of the above (A) cationic surfactant is added and mixed so that the higher alcohol: cationic surfactant (mass ratio) = 1: 1 to 15: 1. . Then, a method of preparing the liquid crystal phase by gradually adding the above-mentioned liquid crystal forming aqueous phase to warm water while stirring the mixture, mixing and kneading the mixture, and the like are mentioned.

Here, the apparatus for preparing the liquid crystal phase is not particularly limited, and a conventionally used stirring apparatus can be used. However, the viscosity of the system may increase with the formation of the liquid crystal phase. For example, in the case of industrial production, it is preferable to carry out the reaction in a stirring tank equipped with a scraping blade such as an ajihomo mixer, an emulsification kettle, etc., and those having a temperature control function are desirable. The stirring conditions at this time are desirably set within the normal use range of these devices, and it is desirable to continue stirring until the whole is uniformly mixed and dissolved.
The formation of the liquid crystal can be confirmed by X-ray diffraction, observation with an optical microscope, observation with an electron microscope, or the like.

In the oil phase preparing step of the present invention, when the above (D) oil component and (C) polyglycerol fatty acid ester are added to the above liquid crystal phase, the method of addition is not particularly limited, but the addition of the above liquid crystal phase is not particularly limited. It is desirable to add and mix the oily component (D) gradually while stirring the phase, disperse the oil component in the liquid crystal phase, and then add and mix the polyglycerin fatty acid ester (C).

In this step, it is desirable that the oily component is sufficiently finely divided so as to be kneaded into the liquid crystal phase. Therefore, the temperature of the entire system is set to be substantially the same as the temperature in the liquid crystal forming step. The stirrer, for example, when manufactured industrially, it is preferable to have a certain shearing force, and it is preferable to use the same device as in the above step so that the whole mixing can be performed. It is desirable to carry out in the normal use range of the apparatus and to continue stirring until the whole becomes uniform.

On the other hand, the aqueous phase preparation step of the present invention is to prepare an aqueous phase for forming an emulsion containing the above-mentioned various kinds of surfactants to be blended as a cleaning base. When an aqueous component is blended as above, it is desirable to form an aqueous solution together with the various surfactants in this step. The amount of water used in the aqueous phase for forming an emulsion is not particularly limited, but is usually preferably 40 to 90%, particularly preferably about 50 to 70%, based on the whole composition.

Here, the mixing order of the aqueous phase component is not particularly limited, and the raw powder or solution of the above-mentioned various surfactants, the water-soluble component and the like may be added sequentially while stirring water. Water may be gradually added to a mixture of various surfactants and the like. In this step, it is desirable that the temperature of the entire system is from room temperature to about 80 ° C., and the same apparatus as in the above step can be suitably used as the stirring device.

In the phase inversion step of the present invention, the mixing procedure of the oil phase and the aqueous phase is not particularly limited, but it is preferable to add the aqueous phase to the oil phase, whereby the oil component is added. It becomes easy to cause phase inversion and finely disperse in the composition. Here, the method for adding the water phase is not particularly limited, but it is desirable to gradually add the water phase while stirring the oil phase. Contrary to this, when the oil phase is added to the aqueous phase, operability problems such as restriction of the number of blended parts and handling occur, and it is difficult to obtain one that is sufficiently satisfactory in terms of stability over time and feel. May be.

Here, it is preferable that the temperature of the aqueous phase added in this step is the same as that of the oil phase.
If the temperature is too high or too low, the system may become non-uniform.

The stirrer is not particularly limited, and a conventionally used stirrer can be used. However, the viscosity of the system may increase as the emulsion is formed. Considering that it is desirable to have a mixing power of a degree or more, a device similar to the liquid crystal forming step is suitably used, and stirring conditions are as follows:
It is desirable that the mixing and stirring be performed within the normal use range of these devices, and until the whole becomes a uniform blue-white to white milky state.

The O / W type emulsion obtained by the above-mentioned manufacturing method is a state in which particles of the oily component finely divided into, for example, an average particle size of about 1 to 100 μm are surrounded by a liquid crystal phase mainly having a layered structure. Because it is dispersed in the aqueous phase,
The emulsion particles are stable against coalescence of the emulsion particles and have excellent dispersion stability. The particle size of the dispersed particles is not particularly limited, but the average particle size is 10 μm.
The degree is particularly preferable. The O / W emulsion may be used as it is as a detergent composition (product), or, if necessary, may be dissolved in water or water as necessary.
It can be further diluted with a dispersed aqueous liquid and used as a detergent composition.

[0068]

According to the cleaning composition of the present invention, there can be obtained a cleaning composition which is excellent in stability over time and feeling in use and can stably incorporate oily components such as silicone compounds into the composition. Further, according to the method for producing a detergent composition of the present invention, it is possible to finely disperse an oily component in the composition, and to obtain a detergent composition having excellent usability and excellent dispersion stability. Can be

[0069]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, all the percentages shown below are based on mass.

Examples 1 to 18, Comparative Examples 1 to 5
The cleaning compositions of Examples and Comparative Examples having the compositions shown in No. 3 were manufactured according to the following manufacturing methods, and the obtained compositions were evaluated for dispersion state immediately after preparation, stability over time, and feeling of use (feel after drying) as follows. The method was evaluated. Here, a shampoo composition was evaluated as a representative example of the cleaning composition.

<Production Method> Oil-soluble components such as component (A), component (B), component (C), and component (D) are heated and dissolved at 45 to 80 ° C. to prepare an oil phase. Wash base and other aqueous components in purified water at room temperature to 80
Prepare an aqueous phase by dissolving at 0 ° C. Add oil phase to water phase, stir with Ajihomo mixer,
/ W type emulsion is formed. The mixture is gradually cooled to room temperature while stirring with a paddle mixer, and the pH is adjusted as necessary to obtain a shampoo composition.

(1) Evaluation of dispersion state immediately after preparation <Evaluation method> Uniform dispersibility of the prepared shampoo composition was evaluated by visual observation of its appearance and an electron microscope observation image.

(Evaluation criteria) Very good ◎ Good ○ Normal △ Poor ×

(2) Evaluation of stability over time <Evaluation method> The prepared shampoo composition was treated at -5 ° C for 5 hours.
It was stored at 0 ° C. for one month and its uniform dispersibility was evaluated.
The evaluation was based on the above evaluation criteria at each temperature.

(3) Evaluation of feeling of use (feel after drying) The hair was divided into two parts, the standard shampoo shown below was applied on one side, and the composition shown in Examples or Comparative Examples was applied on the other side. After lathering, the hair was rinsed with warm water. Further, the following standard conditioner was applied to the side treated with the standard shampoo, and the hair was rinsed with warm water. Then, after drying, about the feeling of use, after rinsing ~
The evaluation of the texture until after the drying was evaluated based on the following criteria by the report of 10 panelists.

<Standard Shampoo> Sodium polyoxyethylene lauryl ether sulfate: 15 (%) (average number of moles of polyoxyethylene added: 3 mol) Coconut fatty acid amide propyl betaine: 3 Coconut fatty acid diethanolamide: 1.5 cationization Cellulose: 0.2 Fragrance: 0.4 Citric acid: Adjusted to pH 6.0 Purified water: Total balance : 100

<Standard Conditioner> Stearyltrimethylammonium chloride: 1 (%) Cetostearyl alcohol: 3 Trimethylsilyl group-terminated dimethylpolysiloxane: 2 (viscosity at 25 ° C .; 10,000 mm ² / s) Sorbitan coconut oil fatty acid: 0.5 Vaseline : 0.5 Fragrance: 0.5 Purified water: Total balance : 100

(Score) +3 points: clearly better than the standard sample. +2 points: better than the standard sample. +1 point: slightly better than the standard sample. 0 point: equivalent to a standard sample. -1 point: Slightly worse than the standard sample. -2 points: bad compared with the standard sample. -3 points: clearly worse than the standard sample.

Next, the total of the scores by the ten panelists was calculated and judged as follows. Judgment criteria ：: 20 to 30 points ：: 10 to 19 points △: -10 to 9 points ×: -30 to -11 points

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

From the results shown in Tables 1 to 3, it was confirmed that the shampoo compositions of the examples, which are the detergent compositions of the present invention, have good dispersibility immediately after preparation, and are excellent in stability over time and feeling upon use. Can be On the other hand, in the compositions of the present invention lacking the components (A) to (C) (Comparative Examples 1 to 5), it is recognized that sufficient dispersion stability and feeling of use cannot be obtained. Further, in the examples shown in Table 3, storage stabilizers and the like, which are components that are desirable to be blended when the composition of the present invention is commercialized, are contained. It is understood that there is no adverse effect on the effect of the present invention. The effect of the present invention is not limited to the shampoo composition, but is exerted over the entire detergent.

Example 19 A stirring vessel was placed in a bath set to 75 ° C., and 3 parts by weight of cetostearyl alcohol was heated and dissolved while stirring the propeller using a three-one motor at 300 rpm. While adding 1 part by weight of stearyltrimethylammonium chloride, gradually adding about 10 parts by weight of water at 75 ° C., and further adding 2.5 parts of a highly polymerized dimethylpolysiloxane (viscosity at 25 ° C .; 100,000 mm ² / s). Parts by weight, then 3 parts by weight of tetraglycerin tristearate,
The oily phase was prepared by stirring until the whole became homogeneous.
In addition, the preparation time of this small oil phase was about 10 minutes.

Separately, at 75 ° C., 28% of sodium polyoxyethylene lauryl ether sulfate (3EO) was added.
The solution was sampled so as to have 15 parts by weight of sodium polyoxyethylene lauryl ether sulfate (3EO) in the composition, and a 30% solution of amidopropyl betaine laurate contained 5% of amide propyl betaine laurate in the composition. It was sampled so as to be parts by weight, these were mixed, and purified water was further added to prepare an aqueous solution of about 80 parts by weight to obtain a small aqueous phase. While stirring the oil phase particles, the aqueous phase particles were added to the oil phase particles little by little and stirred for about 30 minutes until uniform. The stirring vessel was taken out of the bath, cooled slowly to room temperature while stirring, and then purified water was added so that the total amount was 100 parts by weight.

Example 20 A stirring vessel was placed in a bath set at 75 ° C., and 5 parts by weight of cetostearyl alcohol was heated and dissolved while stirring the inside of the vessel with a propeller using a three-one motor at 300 rpm. While adding 0.5 parts by weight of amidobutylguanidine acetate laurate, and gradually adding about 10 parts by weight of water at 75 ° C.,
Furthermore, highly polymerized dimethylpolysiloxane (viscosity at 25 ° C; 1
100,000 mm ² / s) and low-polymerized dimethylpolysiloxane (2
3 parts by weight (mixture with 5 ° C. viscosity; 30 mm ² / s) (ratio; high polymerization: low polymerization = 3: 7) are added, and then 2 parts by weight of pentaglycerin hexastearate are added, and the whole is uniformly mixed. The mixture was stirred until the oil phase became small. In addition, the preparation time of this small oil phase was about 10 minutes.

Separately, a 50% solution of decaglyceryl monolaurate was collected at 75 ° C. so that the content of decaglyceryl monolaurate was 10 parts by weight in the composition, and a 30% solution of amidopropyl betaine laurate was added to the composition. And 10 parts by weight of amidopropyl betaine laurate were collected, mixed, and purified water was added to prepare an aqueous solution of about 80 parts by weight to obtain a small aqueous phase. While stirring the oil phase particles, the aqueous phase particles were added to the oil phase particles little by little and stirred for about 30 minutes until uniform. The stirring container was taken out of the bath, cooled slowly to room temperature while stirring, and then purified water was added so that the total amount was 100 parts by weight to prepare a shampoo composition.

Example 21 A stirring vessel was placed in a bath set to 75 ° C., and 2.5 parts by weight of stearyl alcohol was heated and dissolved while stirring the propeller using a three-one motor at 300 rpm. with continued stirring, it was added 1 part by weight of behenyl trimethyl ammonium chloride, adding 75 ° C. water of about 10 parts by weight gradually, further, glycerin 5 parts by weight, highly polymerized dimethyl polysiloxane (25 ° C. viscosity: 100,000 mm ² / S) and 3 parts by weight of a mixture of low-polymerized dimethylpolysiloxane (viscosity at 25 ° C .; 30 mm ² / s) (ratio; high-polymerization: low-polymerization = 3: 7), and then tetraglycerin tristearate 2 A part by weight was added, and the mixture was stirred until the whole became uniform to prepare a small oil phase. The preparation time of this oil phase accessory is about 10
Minutes

Separately, at 75 ° C., 10 parts by weight of sodium polyoxyethylene lauryl ether sulfate (3EO), 5% sodium α-olefin sulfonate in the composition
A 36% solution of sodium α-olefin sulfonate in an amount to be parts by weight, 5 parts by weight of amidopropyl betaine laurate, 0.3 parts by weight of cationized cellulose, and 2.5 parts by weight of ethylene glycol difatty acid ester were mixed. Purified water was added to prepare an aqueous solution of about 80 parts by weight to obtain a small aqueous phase. While stirring the oil phase particles, the aqueous phase particles were added to the oil phase particles little by little and stirred for about 30 minutes until uniform. Take out the stirring container from the bath, slowly cool to room temperature while stirring, and then add an appropriate amount of preservative and pH adjuster,
A shampoo composition was prepared by adding 0.5 parts by weight of a fragrance and further adding purified water so that the total amount was 100 parts by weight.

The shampoo compositions of Examples 19 to 21 were evaluated for dispersion state immediately after preparation, stability over time and feeling of use (feel after drying) in the same manner as in the above Examples. It was also found to be very excellent and also excellent in usability. Furthermore, as a result of X-ray diffraction,
A regular diffraction pattern was observed. When these were observed with a polarizing microscope, the tissue images showed optical anisotropy, and when observed with a cryo-scanning electron microscope, the thin layers were overlapped. It is recognized that a W-type emulsion is one in which fine particles of an oily component are dispersed in a state surrounded by a liquid crystal phase mainly having a layered structure. Therefore, if the O / W emulsion type cleaning composition is manufactured by the manufacturing method of the cleaning composition of the present invention, the above-described conventional solubilization system or the dispersion system stabilized by the polymer substance can be used. Also, it is possible to incorporate a large amount of oily components into the system, for example, when preparing a hair cleaning composition such as a shampoo composition, the amount of adsorption of oily components such as a feeling imparting agent to the hair after washing and It is recognized that the water retention ability, which leads to the moisturizing effect, is increased, and a hair cleaning composition that is extremely excellent in use feeling can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C11D 17/08 C11D 17/08 F term (Reference) 4C083 AA112 AB352 AB442 AC071 AC072 AC122 AC182 AC242 AC302 AC312 AC392 AC421 AC422 AC482 AC562 AC582 AC622 AC642 AC692 AC712 AC782 AC792 AC852 AC862 AD132 AD152 AD162 AD392 AD532 AD662 BB04 BB05 BB06 BB07 BB11 CC38 DD33 EE01 EE06 4H003 AA03 AB05 AB10 AB15 AB27 AB31 AB46 AC03 AC08 AC15 AD02 AD04 AE05 EB05 EB04 EB05 EB05 EB05 EB05 FA16 FA21

Claims (3)

[Claims] 1. A detergent composition containing one or more surfactants selected from an anionic surfactant, an amphoteric surfactant and a nonionic surfactant,
A cleaning composition comprising (A) a cationic surfactant, (B) a higher alcohol having a melting point of 45 ° C. or higher, and (C) a polyglycerol fatty acid ester having an HLB of 7 or lower. . 2. The cleaning composition according to claim 1, further comprising (D) an oily component. 3. A cationic surfactant, and (B) a cationic surfactant.
A higher alcohol having a melting point of 45 ° C. or higher is mixed with an aqueous phase for forming a liquid crystal to form a liquid crystal phase.
Is added and mixed with a polyglycerol fatty acid ester having a molecular weight of 7 or less and, if necessary, an oil component, to prepare an oil phase. A method for producing a detergent composition comprising adding and mixing an aqueous phase for forming an emulsion containing one or more surfactants selected from surfactants to prepare an O / W emulsion. .