JP2005146014A - Alkylglycol polyhydric alcohol ether-containing surfactant composition improved in low-temperature stability, and detergent composition comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition which is in a stable liquid state at 20°C and exhibits good mixing stability with various surfactants. <P>SOLUTION: The alkylglycol polyhydric alcohol ether-containing surfactant composition comprises compounds represented by general formulae (1), (2) and (3), where the mixing mass ratio of the compound of formula (1) to the compound of formula (2) is 9/1-4/6 and the total amount of the compounds of formula (1) and formula (2) is at least 50 mass%. The detergent composition comprises the same. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention includes an alkylalkylene glycol polyhydric alcohol ether-containing surfactant composition that is liquid at 20 ° C. and has excellent handling properties and is useful as a detergent base, a cosmetic base, and the like. The present invention relates to a liquid detergent composition.

  Alkyl glycol polyhydric alcohol ether-containing surfactant compositions, especially when formulated into sulfate anionic surfactants, may exhibit thickening, foaming, and foam stabilization superior to fatty acid alkanolamides. For example, it is known from Japanese Patent Application Laid-Open No. 2003-96435 (Patent Document 1).

On the other hand, as a method for producing an alkyl glycol polyhydric alcohol ether-containing surfactant composition, a method of ring-opening an epoxy compound includes, for example, US Pat. No. 4,086,279 (Patent Document 2), JAOCS, 66 (1), 146 (1989) (Non-Patent Document 1), JP-A-5-202108 (Patent Document 3), JP-A-11-315043 (Patent Document 4), and the like.

  In these production methods, acidic catalysts such as fluorinated boron ether complexes, alumina catalysts and zirconia catalysts, or basic catalysts such as metallic sodium, sodium hydroxide and potassium hydroxide are used as the reaction catalyst.

［但し式（４）おいて、Ｒ²は６〜１６個の炭素原子を含むアルキル基またはアルケニル基を表し、［Ｘ¹］は、２〜６個の炭素原子を含む、ｎ¹価の脂肪族基を表し、ｎは、Ｘ¹基の炭素原子数を越えない２〜６の整数を表す〕
で示される化合物の生成が優先し、一般式（４）の化合物は高融点を有し２０℃で固体であるため、これを界面活性剤の用途に用いるときにハンドリング性が悪く、更に配合物の低温保存時にも白濁や結晶析出を起こすなどの問題が見られた。 When a basic catalyst is used, the following general formula (4):

[In the formula (4), R ² represents an alkyl group or an alkenyl group containing 6 to 16 carbon atoms, and [X ¹ ] represents an n ¹ -valent fatty acid containing 2 to 6 carbon atoms. And n represents an integer of 2 to 6 which does not exceed the number of carbon atoms in the X ¹ group]
Since the compound represented by general formula (4) has a high melting point and is solid at 20 ° C., the handling property is poor when it is used for a surfactant. Problems such as white turbidity and crystal precipitation were observed even during low temperature storage.

［但し式（５）において、Ｒ²，Ｘ¹，ｎ¹は前記に同じ
で示される化合物が目的化合物に優先して生成し、この式（６）の化合物は２０℃で液状であるため、得られるアルキルグリコール多価アルコールエーテル混合物は、塩基触媒を使用した場合より低融点を示す、しかし一般式（５）示される化合物のみを選択的に製造することは困難で、一般式（４）の化合物が混在する。この式（４）の化合物は、２０℃でも結晶として析出するため、酸触媒を用いて製造された生成物を、実際に洗浄剤などに配合する場合には一度加熱して均一溶解してから使用する必要があり、時間的にもエネルギー的にもコストがかかるという問題が見られた。 On the other hand, in the reaction using an acid catalyst, the following general formula (5):

[However, in the formula (5), R ² , X ¹ and n ¹ are the same as those described above, and the compound of the formula (6) is liquid at 20 ° C. The resulting alkyl glycol polyhydric alcohol ether mixture has a lower melting point than when a base catalyst is used, but it is difficult to selectively produce only the compound represented by the general formula (5). Compound is mixed. Since the compound of the formula (4) is precipitated as a crystal even at 20 ° C., when the product produced using an acid catalyst is actually blended with a cleaning agent, etc., it is heated once and dissolved uniformly. There was a problem that it was necessary to use it and it took time and energy.

In the compounds of the above formulas (4) and (5),
Although it is possible to reduce the melting point of the compound by shortening the chain length of the alkyl group (R ² ) and improve the handleability, in this case, when the obtained product is used as a liquid detergent Further, there is a problem that the performance required for the alkyl glycol polyhydric alcohol ether, such as the above-mentioned viscosity increasing, foam increasing property and foam stabilization, is substantially lost.
In addition, it is possible to introduce an unsaturated or branched hydrocarbon group into the R ² group to lower the melting point of the resulting compound, but it is difficult to obtain an epoxy compound corresponding to the group to be introduced. Industrial use is difficult.
Therefore, development of an alkyl glycol polyhydric alcohol ether that is liquid at 20 ° C., has excellent handling properties, and exhibits excellent thickening, foaming, and foam stabilization when used as a liquid detergent has been desired. .

JP 2003-96435 A U.S. Pat. No. 4,086,279 JP-A-5-202108 Japanese Patent Laid-Open No. 11-315043 JAOCS, 66 (1), 146 (1989).

  The present invention is an alkyl glycol polyhydric alcohol ether that is liquid at 20 ° C., has excellent handling properties, and exhibits excellent thickening, foaming, and foam stabilization when used as a component of a liquid detergent. An object of the present invention is to provide a contained surfactant composition and a liquid detergent composition containing the same.

［但し式（１）において、Ｘは２〜６個の炭素原子を有するｎ価の脂肪族基を表し、ｎは前記Ｘ基の炭素原子数を超えない２〜６の整数を表す。］
下記一般式（２）で示されるアルキルグリコール多価アルコールエーテル化合物と、

［但し、式（２）において、Ｙは２〜６個の炭素原子を有するｍ価の脂肪族基を表し、ｍは前記Ｙ基の炭素原子数を超えない２〜６の整数を表す。］
及び一般式（３）により表される脂肪族多価アルコールエーテル化合物と、

［但し、式（３）において、Ｒ^１は１０〜１２個の炭素原子を含むアルキル基またはアルケニル基を表し、Ｚは、２〜６個の炭素原子を有するｋ価の脂肪族基を表し、ｋはＺ基の炭素原子数を超えない２〜６の整数を表す。］
を含み、前記一般式（１）の化合物と前記一般式（２）の化合物との混合質量比率が９：１から４：６であり、且つ一般式（１）と一般式（２）の合計質量の、一般式（１）、（２）及び（３）の化合物の合計質量に対する比が５０質量％以上であることを特徴とするものである。
本発明のアルキルグリコール多価アルコールエーテル含有界面活性剤組成物の前記一般式（１）、（２）及び（３）において、−Ｏ−〔Ｘ〕−（ＯＨ）_n-1基、−Ｏ−〔Ｙ〕−（ＯＨ）_m-1基及び−Ｏ−〔Ｚ〕−（ＯＨ）_k-1基が、それぞれ互に独立に、１，２−プロパンジオール、１，３−ブタンジオール残基から選ばれることが好ましい。
本発明の洗浄剤組成物は前記本発明の界面活性剤組成物０．１〜１０質量％と、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤、両性界面活性剤、双性界面活性剤、半極性界面活性剤の中から選ばれる少なくとも1種からなり、前記請求項１に記載の界面活性剤組成物とは異なる界面活性剤５〜９５重量％とからなる混合物、ならびに水を含有することを特徴とするものである。 The alkyl glycol polyhydric alcohol ether-containing surfactant composition of the present invention is:
An alkyl glycol polyhydric alcohol ether compound represented by the following general formula (1):

[In the formula (1), X represents an n-valent aliphatic group having 2 to 6 carbon atoms, and n represents an integer of 2 to 6 not exceeding the number of carbon atoms of the X group. ]
An alkyl glycol polyhydric alcohol ether compound represented by the following general formula (2);

[In the formula (2), Y represents an m-valent aliphatic group having 2 to 6 carbon atoms, and m represents an integer of 2 to 6 not exceeding the number of carbon atoms of the Y group. ]
And an aliphatic polyhydric alcohol ether compound represented by the general formula (3);

[In the formula (3), R ¹ represents an alkyl group or alkenyl group having 10 to 12 carbon atoms, Z represents a k-valent aliphatic group having 2 to 6 carbon atoms, k represents the integer of 2-6 which does not exceed the carbon atom number of Z group. ]
The mixture mass ratio of the compound of the general formula (1) and the compound of the general formula (2) is 9: 1 to 4: 6, and the sum of the general formula (1) and the general formula (2) The ratio of the mass to the total mass of the compounds of the general formulas (1), (2) and (3) is 50% by mass or more.
In the general formulas (1), (2) and (3) of the alkyl glycol polyhydric alcohol ether-containing surfactant composition of the present invention, an -O- [X]-(OH) _n-1 group, -O- [Y]-(OH) _m-1 group and -O- [Z]-(OH) _k-1 group are independently of each other from 1,2-propanediol and 1,3-butanediol residues. It is preferable to be selected.
The detergent composition of the present invention comprises 0.1 to 10% by mass of the surfactant composition of the present invention, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, A mixture comprising 5 to 95% by weight of a surfactant different from the surfactant composition according to claim 1, comprising at least one selected from a zwitterionic surfactant and a semipolar surfactant. In addition, it is characterized by containing water.

  According to the present invention, it contains an alkyl glycol polyhydric alcohol ether which is liquid at a temperature of 20 ° C., has excellent handling properties, and exhibits excellent thickening, foaming and foaming stability when used in a liquid detergent. It has become possible to provide a surfactant composition and a liquid detergent containing the same.

The alkyl glycol polyhydric alcohol ether-containing surfactant composition of the present invention is characterized by the alkyl glycol polyhydric alcohol ether type surfactant compound represented by the general formula (1) and the alkyl represented by the general formula (2). An alkylene glycol polyhydric alcohol ether type surfactant compound and the compound represented by the general formula (3), and the surfactant compounds of the general formulas (1) and (2) are mixed in a mass ratio; Exists from 9: 1 to 4: 6.
As described above, even when an epoxyalkane and a polyhydric alcohol are condensed under an acidic catalyst, they are represented by the general formula (5), that is, correspond to the general formulas (1) and (2) in the present invention. In addition to the alkyl glycol polyhydric alcohol ether having the basic skeleton, the alkyl alkylene glycol polyhydric alcohol ether represented by the general formula (4) is generated. Therefore, the alkylalkylene glycol polyhydric alcohol ether-containing surfactant composition of the present invention has the total mass of the compound of general formula (1) and the compound of general formula (2) as the surfactant containing the alkylalkylene glycol polyhydric alcohol ether of the present invention. Although it synthesize | combines so that it may become 50 mass% or more of an agent composition, it contains that the alkylglycol polyhydric-alcohol ether compound shown by General formula (3) is contained as another component.

  The alkyl glycol polyhydric alcohol ether type surfactant represented by the general formula (1) and the alkyl glycol polyhydric alcohol ether type surfactant represented by the general formula (2) were separately synthesized under an acid catalyst, In the present invention, 1,2-epoxydodecane may be used as a raw material for the compound of the general formula (1), and 1,2-epoxytetradecane may be used as a raw material for the compound of the general formula (2). After mixing in advance at a mixing ratio corresponding to the mixing ratio of the composition, a condensation reaction with a polyhydric alcohol is performed to obtain the alkyl glycol polyhydric alcohol ether-containing surfactant composition of the present invention.

  Examples of the 1,2-epoxyalkane used as a raw material for the alkyl glycol polyhydric alcohol ether compound of the general formula (3) used in the present invention include 1,2-epoxydecane, 1,2-epoxydodecane, 1,2 -1 type, or 2 or more types of mixtures chosen from an epoxy tetradecane, 1, 2- epoxy hexadecane, 1, 2- epoxy octadecane, etc. are mentioned.

  The mixing ratio of the compound of general formula (1) and the compound of general formula (2) used in the composition of the present invention is preferably 9: 1 to 4: 6, and 8.5: 1.5. It is particularly preferred that it is ˜5: 5. When the mixing ratio is higher than 9: 1, the melting point of the resulting composition is not sufficiently lowered, and the handling property is insufficiently improved such as crystal precipitation at 20 ° C. Further, when it is lower than 4: 6, the handling property of the resulting composition is improved, but the effect of thickening, foam increasing and foam stabilization at the time of blending with other surfactants is insufficient. Become.

In the alkyl glycol polyhydric alcohol ether compounds represented by the general formulas (1), (2) and (3) of the present invention, -O- [X]-(OH) _n-1 group, -O- [Y]-( OH) The starting polyhydric alcohol for forming the _m-1 group and -O- [Z]-(OH) _k-1 group is independently ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, Aliphatic diols such as 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, glycerin, diglycerin, trimethylolpropane, pentaerythritol Can be selected aliphatic polyols such as Le, arabinose, ribose, xylose, glucose, galactose, fructose, mannose, from monosaccharides like. Furthermore, among these, the alkyl glycol polyhydric alcohol ether obtained is selected from 1,2-propanediol and 1,3-butanediol from the viewpoints of handling properties, thickening properties, foam increasing properties, and foam stabilization effects. It is particularly preferred to use more than one species.

  The amount of the alkyl glycol polyhydric alcohol ether-containing surfactant composition of the present invention is not particularly limited when it is blended with a detergent or cosmetic, but is usually 0.1 to 10% by weight, particularly 0. It is preferably 5 to 8% by weight.

  The alkyl glycol polyhydric alcohol ether-containing surfactant composition of the present invention comprises an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, and a semipolar interface. It can be used as a detergent composition in combination with at least one selected from active agents and different from the surfactant composition of the present invention.

  As the anionic surfactant for the detergent composition of the present invention, all anionic surfactants used in usual shampoos, body soaps, kitchen detergents and the like can be applied. Examples of such anionic surfactants include fatty acid soap such as soap base, sodium laurate, sodium palmitate, coconut soap, ether carboxylic acid such as POE lauryl ether carboxylate, POP · POE ether myristine. Acid salts; higher alkyl sulfates such as sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate; alkyl ether sulfates such as POE lauryl sulfate triethanolamine, sodium POE lauryl sulfate; N-acyl amino acid salts such as Lauroyl sarcosine sodium, sodium lauroyl-N-methyl-β-alanine, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N -Myristoyl-L-glutamate monosodium, N-palmitoyl aspartate diethanolamine; higher fatty acid amide sulfonates such as N-myristoyl-N-methyltaurine sodium, palm fatty acid methyltaurine sodium, lauroylmethyltaurine sodium, POE laurylamide ether sulfone Sodium phosphate; Phosphate ester salts such as POE oleyl ether sodium phosphate, POE stearyl ether phosphate, POE laurylamide ether sodium phosphate; sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide Sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate; alkylbenzene Sulfation of sulfonates such as sodium lineardodecylbenzene sulfonate, triethanolamine linear dodecyl benzene sulfonate, linear dodecyl benzene sulfonic acid; higher fatty acid ester sulfates such as hydrogenated coconut oil fatty acid sodium glycerol sulfate, funnel oil, etc. Oil, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamide succinate, and sodium caseinate. Sulfate ester type such as sulfate ester, polyoxyethylene alkyl sulfate, fatty acid amide ether sulfate, acyl isethionate, sulfosuccinate, etc. or sulfonic acid Examples thereof include salt type surfactants, ether carboxylates, fatty acid amide ether carboxylates, N-acyliminodiacetic acids, carboxylic acid type surfactants such as N-acylamino acid salts, and the like, and one or more of these may be used. it can. Among these, alkyl sulfate ester salts and polyoxyethylene alkyl sulfate ester salts are preferable in that they are inexpensive and advantageous in terms of cost and can enhance foaming properties. Is particularly preferred.

(式中R³及びR⁴はそれぞれ互に独立に7〜21個の炭素原子を有するアルキル基またはアルケニル基を表し、A^-はアニオンを表す。) As the cationic surfactant for the detergent composition of the present invention, all of the cationic surfactants used in usual shampoos, rinses, body soaps, kitchen detergents and the like can be applied. Examples of these cationic interfacial agents are quaternary ammonium such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyltrimethylammonium chloride, cetylpyridinium chloride, alkyldimethylbenzylammonium chloride, benzethonium chloride, and benzalkonium chloride. Salts; amidoamine salt-type cationic surfactants such as stearic acid diethylaminoethylamide glutamate and lanolin fatty acid diethylaminoethylamide glutamate; lauric acid amidoguanidine hydrochloride; quaternary nitrogen-containing cationic polymer compound; 6) L-arginine derivatives represented by (7) and the like can be mentioned, and one or more of these can be used.

(Wherein R ³ and R ⁴ each independently represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, and A ⁻ represents an anion.)

  In addition, the quaternary nitrogen-containing cationic polymer compound includes an ammonium group bonded to a polymer chain, and examples thereof include a cationized cellulose derivative, a cationic starch, and a cationized guar gum derivative. One or more of them can be used. Among these, a cationized cellulose derivative is particularly preferable from the viewpoint of usability.

  As the nonionic surfactant for the cleaning composition of the present invention, all of the nonionic surfactants used in usual shampoos, body soaps, kitchen detergents, etc. can be applied, and these are exemplified. For example, glyceryl fatty acid esters such as glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl monoisostearate; polyoxyethylene glyceryl fatty acid esters such as POE glyceryl monostearate, POE glyceryl monooleate; polyglyceryl fatty acid Esters such as diglyceryl monostearate, tetraglyceryl tristearate, decaglyceryl pentastearate; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan sesquistearate, monoolein Sorbitan. Polyoxyethylene sorbitan fatty acid esters such as monococonut fatty acid POE sorbitan, tristearic acid POE sorbitan, trioleic acid POE sorbitan; polyoxyethylene sorbite fatty acid esters such as monolauric acid POE sorbite, tetraoleic acid POE sorbit; Such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate; and propylene glycol monofatty acid esters such as propylene glycol monolaurate and propylene glycol monomyristate; Monododecyl ether, glycerin monocetyl ether Alkyl polyhydric alcohol ethers such as glycerin monostearyl ether and pentaerythritol monododecyl ether; polyoxyethylene alkyl ethers such as POE lauryl ether, POE cetyl ether, POE stearyl ether; polyoxyethylene polyoxypropylene alkyl ethers such as POE / POP cetyl ether, POE / POP decyl tetradecyl ether, polyoxyethylene alkylphenyl ethers, POE nonylphenyl ether, POE octylphenyl ether, POE branched octylphenyl ether; polyoxyethylene alkylamines such as POE stearylamine , POE oleylamine; fatty acid alkanolamides such as coconut fatty acid diethanolamide, lauric acid diethanolamide, palm kernel oil Fatty acid diethanolamide; Acylmethyl glucamides such as methyl glucamide laurate, methyl fatty acid palm glucamide; Other acetylene glycol, POE acetylene glycol, POE lanolin, POE lanolin alcohol, POE castor oil, POE hydrogenated castor oil, POE phytosterol , POE cholestanol, POE nonylphenyl formaldehyde condensate, and the like, and one or more of these can be used.

As the amphoteric surfactant that can be used in the cleaning composition of the present invention, all the amphoteric surfactants used in ordinary shampoos, body soaps, kitchen detergents and the like can be applied, and these are exemplified. N-alkyl acetate betaine, N-alkylhydroxysulfobetaine, fatty acid amidopropyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminohydroxysulfobetaine, and the like; sulfobetaine-type amphoteric surfactants and amidoamine-type amphoteric interfaces An activator is mentioned and 1 or more types of these can be used. Of these, fatty acid amidopropyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminohydroxysulfobetaine, and amidoamine type amphoteric surfactants are preferably used.
The amphoteric reaction during the production of these amphoteric surfactants proceeds in the presence of alkali, and the production of salts as by-products is inevitable. The type of salt corresponds to the type of alkali used during the reaction. For example, when caustic soda is used as the alkali, sodium chloride is generated. When used in the composition of the present invention, the salt can be used as it is, but when the polymer compound is added, the salt can be removed as necessary. As a method for removing the salt, a known method such as a reverse osmosis membrane treatment method or an electrodialysis method can be mentioned. From the viewpoint of cost, the reverse osmosis membrane treatment method is preferable.

(式（８）中R⁵は9〜19個の炭素原子を有するアルキル基またはアルケニル基を表す。)と下記一般式(９)により表されるクロロ酢酸塩：
(式中Mは水素原子、アルカリ金属原子、アンモニウム基あるいはアルカノールアミンまたは低級脂肪族の陽イオン残基を表す。)
との反応で生成する化合物であって、その主生成物は、下記一般式（１０）

(式中R⁵、Mは前記定義に同じ)
で示される。
上記の反応はアルカリの存在下に進行するもので、副生物としての塩類の生成が不可避である。この塩の種類は反応時に使用されるアルカリの種類に対応し、例えばアルカリとして苛性ソーダを用いた場合には食塩が生成する。この生成物を本発明の洗浄剤組成物に用いるときには必要に応じてこの塩を除去したものを使用することができる。塩を除去する方法としては公知の方法、例えば逆浸透膜処理法や、電気透析法などが挙げられるがコストの点から考えると逆浸透膜処理法が好ましい。
本発明ではこれら両性界面活性剤のうちの任意の1種、または2種以上を選んで使用することができる。 The amidoamine type amphoteric surfactant used in the cleaning composition of the present invention is an imidazoline compound represented by the following general formula (8):

(In formula (8), R ⁵ represents an alkyl or alkenyl group having 9 to 19 carbon atoms) and a chloroacetate salt represented by the following general formula (9):
(In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, an alkanolamine, or a lower aliphatic cation residue.)
The main product of the compound produced by the reaction with the following general formula (10)

(Wherein R ⁵ and M are as defined above)
Indicated by
The above reaction proceeds in the presence of alkali, and formation of salts as a by-product is inevitable. The type of salt corresponds to the type of alkali used during the reaction. For example, when caustic soda is used as the alkali, sodium chloride is generated. When this product is used in the cleaning composition of the present invention, it is possible to use a product from which this salt has been removed, if necessary. As a method for removing the salt, a known method such as a reverse osmosis membrane treatment method or an electrodialysis method can be mentioned. From the viewpoint of cost, the reverse osmosis membrane treatment method is preferable.
In the present invention, any one or two or more of these amphoteric surfactants can be selected and used.

  As the semipolar surfactant that can be used in the cleaning composition of the present invention, all of the semipolar surfactants used in ordinary shampoos, body soaps, kitchen detergents, and the like can be applied. For example, lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, isostearyl dimethylamine oxide, coconut fatty acid alkyl dimethylamine oxide, caprylic amidopropyl dimethylamine oxide, capric amidopropyl dimethylamine oxide, Lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, Sostearic acid amidopropyl dimethylamine oxide, oleic acid amidopropyl dimethylamine oxide, ricinoleic acid amidopropyl dimethylamine oxide, 12-hydroxystearic acid amidopropyl dimethylamine oxide, palm fatty acid amidopropyl dimethylamine oxide, palm kernel oil fatty acid amidopropyl Dimethylamine oxide, castor oil fatty acid amidopropyl dimethylamine oxide, lauric acid amidoethyl dimethylamine oxide, myristic amidoethyl dimethylamine oxide, palm fatty acid amidoethyl dimethylamine oxide, lauric acid amidoethyl diethylamine oxide, myristic amidoethyl diethylamine oxide , Palm fatty acid amidoethyl diethylamine oxide, lauric acid De ethyl dihydroxy ethyl amine oxides, myristic acid amide ethyl dihydroxy ethyl amine oxides, coconut fatty acid amide ethyl dihydroxy ethyl amine oxides, and the like, can be used one or more of these. Among these, lauryl dimethylamine oxide, myristyl dimethylamine oxide, coconut fatty acid alkyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, coconut fatty acid amidopropyl dimethylamine oxide, palm kernel oil fatty acid amidopropyl Particularly preferred are dimethylamine oxide and castor oil fatty acid amidopropyldimethylamine oxide.

  When the surfactant composition of the present invention is blended in cosmetics, other surfactants and oil components generally used as cosmetic ingredients as necessary within a range not impairing the effects of the present invention. , Moisturizer, UV absorber, alcohol, chelating agent, pH adjuster, thickener, pearlizing agent, antioxidant, preservative, anti-dandruff agent, dye, fragrance, anionic polymer, silicone derivative, etc. And can be a cream, lotion, lotion, lipstick, foundation, shampoo, hair rinse, hair treatment, hair conditioner, conditioning blowing agent, and the like.

Examples Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Production Example 1
A synthetic thermometer of lauryl glycol hydroxypropyl ether (1a) , a reflux condenser, a stirrer, a distillation apparatus, and a dropping apparatus were charged with 276.5 g (1.50 mol) of 1,2-epoxide decane in a 1000 ml capacity reaction vessel, Under water cooling, 0.6 g (0.0045 mol) of 75% sulfuric acid was added with stirring. After stirring for 15 minutes, 342.4 g (4.50 mol) of 1,2-propanediol was added, and the temperature was raised to 80 ° C. Thereafter, the reaction was performed at 80 to 85 ° C. for 16 hours. The disappearance of the raw material 1,2-epoxydodecane was confirmed by gas chromatography, 0.3 g (0.004 mol) of powdered magnesium hydroxide was added to the reaction solution, and the reaction solution was neutralized by stirring for 1 hour. After the excess 1,2-propanediol was distilled off under reduced pressure, the precipitated crystals were separated by filtration to obtain 395.4 g (yield 99.5%) of lauryl glycol hydroxypropyl ether (1a).

Production Example 2
A synthetic thermometer of myristyl glycol hydroxypropyl ether (2a) , a reflux condenser, a stirrer, a distillation apparatus, and a dropping apparatus were charged with 318.6 g (1.50 mol) of 1,2-epoxytetradodecane in a 1000 ml capacity reaction vessel. Under water cooling, 0.6 g (0.0045 mol) of 75% sulfuric acid was added with stirring. After stirring for 15 minutes, 342.4 g (4.50 mol) of 1,2-propanediol was added, and the temperature was raised to 80 ° C. Thereafter, the reaction was performed at 80 to 85 ° C. for 16 hours. The disappearance of the raw material 1,2-epoxydodecane was confirmed by gas chromatography, 0.3 g (0.004 mol) of powdered magnesium hydroxide was added to the reaction solution, and the reaction solution was neutralized by stirring for 1 hour. Excess 1,2-propanediol was distilled off under reduced pressure, and the precipitated crystals were separated by filtration to obtain 429.2 g (yield 99.2%) of myristyl glycol hydroxypropyl ether (2a).
[Examples 1-4 and Comparative Examples 1-3]

  In each of Examples 1 to 4 and Comparative Examples 1 to 3, the compounds produced in Production Examples 1 and 2 were mixed at the mixing ratio shown in Table 1. Table 1 shows the properties of this mixture at 20 ° C.

〔実施例５〜１２及び比較例４〜９〕

[Examples 5 to 12 and Comparative Examples 4 to 9]

  In each of Examples 5 to 12 and Comparative Examples 4 to 9, the mixture of Examples 1 to 4 and Comparative Examples 1 to 3 shown in Table 1 was mixed with polyoxyethylene (3) sodium lauryl ether sulfate (SLES). ) At the mass ratios shown in Table 2, and the performance of the following items of the obtained composition was evaluated.

(1) Thickening effect (viscosity measurement)
B type rotational viscometer model B8M manufactured by TOKIMEC
Measurement temperature 25 degrees
(2) Each sample made in the low temperature stability thickening test was allowed to stand at −5 ° C. for 3 days, and then the sample was taken out and observed. The results were evaluated in the following two stages.
× Those with cloudiness or crystal precipitation ○ Those with a transparent solution form

(3) Foaming power Diluted with distilled water so that the solute solid content in each blended sample was 0.25% by weight, and the Ross Miles foaming power in a constant temperature state of 40 degrees was measured.
(4) Usability test (foam quality, comprehensive evaluation)
For each detergent sample, 10 panelists conducted a use test by hand washing,
Foaming during use (foam volume), foam quality (foam shape, firmness, foamy creaminess), feel when rinsing (easy to rinse, with a null), and overall feel (after hand washing) A sensory test was conducted by 10 inspectors for a comprehensive evaluation including a sense of tension. The evaluation is based on the performance of the composition of Comparative Example 4 in Table 2 as a standard 3 points, relative evaluation is performed in 5 stages of 1 to 5 points, the average score of the evaluation results is calculated, and the calculated average value is 4.5 or more Very good (◎)
Good in case of 4.5-3.5 (○)
The case of 3.5-3.0 is normal (△),
If it is 3.0 or less, it is bad (×)
It was.
The evaluation results are shown in Table 2.

As is clear from Tables 1 and 2, the alkyl glycol polyhydric alcohol ether compound compositions shown in Examples 1 to 4 are compared with the single chain length lauryl glycol polyhydric alcohol ether composition shown in Comparative Example 1. It has a low melting point, excellent handling properties, and excellent use that shows the effect of improving the foam quality and improving the foam quality without lowering the thickening and foaming effects when blended with other surfactants. I showed a feeling.
[Example 13] (Cleaning agent composition (1))

A sterilized hand soap having the following mass composition was prepared.
Lauric acid 5.5%
Lauric acid amidopropyldimethylamine oxide 30% solution 3.0%
POE (3) lauryl ether acetic acid 30% aqueous solution 3.0%
Benzalkonium chloride 50% solution 1.0%
Benzethonium chloride 50% solution 0.5%
Composition of Example 1 2.0%
N-coconut fatty acid acyl-N′-carboxymethyl-N′-ethylenediamine sodium salt 9.5%
Amount to make triethanolamine pH = 7.8 Glycerin 3.0%
Amount of purified water to 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained hand soap composition exhibited rich foaming and refreshing washing, and had a moist texture even after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
[Example 14] (Cleaning agent composition (2))

A pearly luster body shampoo having the following mass composition was prepared.
Palm fatty acid potassium salt 4.0%
Lauric acid amidopropyl betaine 30% solution 15.0%
Polyoxyethylene sodium lauryl sulfate 25% solution 20.0%
Lauroyl-N-methyl -.- alanine sodium 30% solution 10.0%
Composition of Example 2 3.0%
Ethylene glycol distearate 2.0%
Glycerol 3.0%
Amount to make citric acid pH = 7.5 EDTA disodium 0.2%
Methylparaben 0.2%
Amount of purified water to 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained body shampoo composition exhibited rich foaming and a refreshing wash, and had a moist texture even after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
[Example 15] (Cleaning agent composition (3))

A pearly luster body shampoo having the following mass composition was prepared.
Lauric acid 6.0%
Myristic acid 8.0%
Palmitic acid 2.0%
Potassium hydroxide 48% aqueous solution 8.1%
Lauric acid amidopropyl hydroxysulfobetaine 30% solution 10.0%
Lauroyl-N-methyl-β-alanine potassium 30% solution 5.0%
Composition of Example 3 3.0%
Palm oil fatty acid acylglycine potassium salt 30% solution 1.6%
Glycerin 5.0%
Ethylene glycol distearate 2.0%
Hydroxypropyl methylcellulose 0.2%
EDTA.4 sodium 0.2%
Methylparaben 0.2%
Amount of purified water to 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained body shampoo composition was rich in foaming, refreshed to wash, and moist after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
[Example 16] (Cleaning agent composition (4))

A weakly acidic body shampoo having the following mass composition was prepared.
Coconut oil fatty acid acylglutamate triethanolamine 30% solution 33.0%
Lauroyl-N-methyl -.- alanine potassium 30% solution 6.7%
Lauroyl hydrolyzed silk peptide sodium salt 20% solution 5.0%
Lauric acid amidopropyl hydroxysulfobetaine 30% solution 10.0%
Palm oil fatty acid acylglycine potassium salt 1.0%
Composition of Example 2 3.0%
EDTA disodium 0.2%
Methylparaben 0.2%
Propylparaben 0.1%
Amount that makes citric acid pH = 5.2 Amount that makes the total amount of purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained body shampoo composition exhibited rich foaming and a refreshing wash, and had a moist texture even after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
[Example 17] (Cleaning composition (5))

A shampoo having the following mass composition was prepared.
Lauric acid amidopropyldimethylamine oxide 30% solution 26.7%
Lauroyl-N-methyl -.- alanine sodium 30% solution 18.7%
Laminate amidopropyldimethylaminoacetate betaine 30% solution 8.0%
Composition of Example 3 2.0%
Cationized cellulose 0.5%
Piroctone olamine 0.8%
Methylparaben 0.2%
Propylparaben 0.1%
EDTA disodium 0.2%
Amount that makes citric acid pH = 6.2 Amount that makes purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained shampoo composition showed rich foaming, no squeaks at the time of rinsing, a refreshing finish, and a moist texture after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
[Example 18] (Cleaning composition (6))

A shampoo having the following mass composition was prepared.
POE (3) lauryl ether sulfate sodium salt 25% solution 30.0%
Lauroyl-N-methyl -.- alanine sodium 30% solution 10.0%
Coconut oil fatty acid acyl glutamic acid triethanolamine 30% solution 3.3%
Lauroyl hydrolyzed silk peptide sodium salt 20% solution 2.5%
Lauric acid amidopropyl hydroxysulfobetaine 30% solution (desalted product)
10.0%
Composition of Example 2 2.0%
Lauroyl sarcosine isopropyl ester 0.2%
Guar hydroxypropyltrimonium chloride 0.2%
Dimethicone copolyol 0.2%
Cationized cellulose 0.2%
EDTA · 2Na 0.2%
Methylparaben 0.2%
Pilopylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 5.4 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained shampoo composition showed rich foaming, no squeaks at the time of rinsing, a refreshing finish, and a moist texture after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 19

A shampoo having the following mass composition was prepared.
Lauric acid amidopropyldimethylamine oxide 30% solution 10.0%
Behenyl alcohol 0.8%
POE (3) lauryl ether sulfate sodium salt 25% solution 52.0%
N- [3-alkyl (12,14) oxy-2-hydroxypropyl]
-L-arginine hydrochloride 60% solution 0.3%
Composition of Example 4 2.0%
Cationized cellulose 0.3%
1-hydroxyethane-1,1-diphosphonic acid 60% solution 0.5%
Methylparaben 0.2%
Propylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 6.0 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained shampoo composition showed rich foaming, no squeaks at the time of rinsing, a refreshing finish, and a moist texture after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 20

A shampoo having the following mass composition was prepared.
Lauric acid amidopropyldimethylamine oxide 30% solution 11.7%
Stearyl alcohol 0.4%
POE (3) lauryl ether sulfate sodium salt 25% solution 28.0%
30% solution of amidopropyldimethylaminoacetic acid betaine laurate (desalted product)
11.7%
Composition of Example 3 1.0%
Cationized cellulose 0.3%
1-hydroxyethane-1,1-diphosphonic acid 60% solution 0.2%
Citric acid 0.3%
Methylparaben 0.2%
Propylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 6.2 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained shampoo composition showed rich foaming, no squeaks at the time of rinsing, a refreshing finish, and a moist texture after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 21

A shampoo having the following mass composition was prepared.
Lauric acid amidopropyldimethylamine oxide 30% solution 11.7%
Stearyl alcohol 0.4%
POE (3) lauryl ether sulfate sodium salt 25% solution 28.0%
N-coconut fatty acid acyl-N′-carboxymethyl-N′-ethylenediamine sodium salt 30% solution (desalted product) 11.7%
Composition of Example 1 1.5%
Cationized cellulose 0.3%
1-hydroxyethane-1,1-diphosphonic acid 60% solution 0.2%
Citric acid 0.6%
Methylparaben 0.2%
Propylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 6.2 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained shampoo composition showed rich foaming, no squeaks at the time of rinsing, a refreshing finish, and a moist texture after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
[Example 22]

A shampoo having the following mass composition was prepared.
Lauric acid amidopropyldimethylamine oxide 30% solution 13.3%
Stearyl alcohol 0.4%
POE (3) lauryl ether sulfate sodium salt 25% solution 40.0%
POE (4.2) lauryl ether 1.5%
Composition of Example 2 1.0%
Polyether-modified silicone 0.3%
1-hydroxyethane-1,1-diphosphonic acid 60% solution 0.2%
Salt 0.3%
Methylparaben 0.2%
Propylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 6.0 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained shampoo composition showed rich foaming, no squeaks at the time of rinsing, a refreshing finish, and a moist texture after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 23

A shampoo having the following mass composition was prepared.
Lauric acid amidopropyldimethylamine oxide 30% solution 26.7%
Stearyl alcohol 0.3%
Lauroyl-N-methyl-β-alanine sodium 30% solution 18.7%
Laminate amidopropyldimethylaminoacetate betaine 30% solution 8.0%
Composition of Example 4 2.0%
1,3-butanediol 2.0%
1-hydroxyethane-1,1-diphosphonic acid 60% solution 0.3%
Citric acid 0.6%
Methylparaben 0.2%
Propylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 6.2 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The obtained shampoo composition showed rich foaming, no squeaks at the time of rinsing, a refreshing finish, and a moist texture after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 24

A shampoo having the following mass composition was prepared.
Lauric acid amidopropyldimethylamine oxide 30% solution 16.7%
Cetanol 0.3%
Lauroyl-N-methyl--alanine sodium 30% solution 33.3%
30% solution of amidopropyldimethylaminoacetic acid betaine laurate (desalted product)
6.7%
Stearyltrimethylammonium chloride 50% solution 0.3%
Composition of Example 4 2.0%
1-hydroxyethane-1,1-diphosphonic acid 60% solution 0.2%
Methylparaben 0.2%
Propylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 6.2 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. The resulting shampoo composition showed very fine and rich foaming, no squeak when rinsing, and a moist and smooth feel after drying. When stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 25

A weakly acidic high-viscosity gel face cleanser having the following mass composition was prepared.
Composition of weakly acidic high viscosity gel facial cleanser Lauroyl-N-methyl--alanine sodium 30% solution 9.6%
Myristoyl-N-methyl --- alanine sodium 30% solution 46.1%
Lauric acid amidopropyl betaine 30% solution 30.0%
Lauric acid amidopropylamine oxide 30% solution 6.7%
Composition of Example 3 3.0%
Dipotassium glycyrrhizinate 0.2%
Amount to make citric acid pH = 6.0 Purified water Amount to make the total amount 100% The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. When this facial cleansing composition was stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 26

A pasty facial cleanser having the following mass composition was prepared.
Lauric acid 7.6%
Myristic acid 13.7%
Palmitic acid 3.1%
Stearic acid 2.2%
Potassium hydroxide 48% aqueous solution 11.7%
Lauric acid amidopropylamine oxide 30% solution 10.0%
Composition of Example 2 2.0%
Glycerin 20.0%
Ethylene glycol distearate 2.0%
EDTA.4 sodium 0.2%
Methylparaben 0.2%
Propylparaben 0.1%
Fragrance 0.1%
Amount to make citric acid pH = 6.0 Amount to make purified water 100%

The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. When this facial cleansing composition was stored at −5 ° C. for 3 days, no change in appearance was observed.
Example 27

A weakly acidic concentrated kitchen detergent having the following mass composition was prepared.
Polyoxyethylene sodium lauryl sulfate 70% solution 14.3%
Lauric acid amidopropylamine oxide 30% solution 33.3%
Palm fatty acid diethanolamide 15.0%
POE (10) lauryl ether 8.0%
Composition of Example 1 2.0%
Hydroxyethanediphosphonic acid 60% solution 0.8%
Sodium p-toluenesulfonate 1.0%
Ethanol 5.0%
Dipropylene glycol 5.0%
Amount to make citric acid pH = 6.5 Amount to make purified water 100%

  The above components were mixed, heated to 80 ° C. to dissolve uniformly, and then cooled. When this concentrated kitchen detergent composition was stored at −5 ° C. for 3 days, no change was observed in its appearance.

  The alkyl glycol polyhydric alcohol ether-containing surfactant composition of the present invention is liquid at room temperature (20 ° C.), has good handling properties, and has excellent thickening and foaming properties for various surfactants. Cosmetics and detergent compositions, which exhibit foam stability, and thus comprise the surfactant composition of the present invention, form stable liquid compositions, in particular detergent compositions containing this It has excellent practicality.

Claims (3)

An alkyl glycol polyhydric alcohol ether compound represented by the following general formula (1):

[In the formula (1), X represents an n-valent aliphatic group having 2 to 6 carbon atoms, and n represents an integer of 2 to 6 not exceeding the number of carbon atoms of the X group. ]
An alkyl glycol polyhydric alcohol ether compound represented by the following general formula (2);

[In the formula (2), Y represents an m-valent aliphatic group having 2 to 6 carbon atoms, and m represents an integer of 2 to 6 not exceeding the number of carbon atoms of the Y group. ]
And an aliphatic polyhydric alcohol ether compound represented by the general formula (3);

[In the formula (3), R ¹ represents an alkyl group or an alkenyl group containing 10 or 12 carbon atoms, Z represents a k-valent aliphatic group having 2 to 6 carbon atoms, k represents the integer of 2-6 which does not exceed the carbon atom number of Z group. ]
The mixture mass ratio of the compound of the general formula (1) and the compound of the general formula (2) is 9: 1 to 4: 6, and the sum of the general formula (1) and the general formula (2) An alkyl glycol polyhydric alcohol ether-containing surfactant composition, wherein the ratio of the mass to the total mass of the compounds of the general formulas (1), (2) and (3) is 50% by mass or more. In the general formulas (1), (2) and (3), a —O— [X] — (OH) _n−1 group, a —O— [Y] — (OH) _m−1 group and a —O— [ The alkyl glycol polyhydric alcohol ether-containing product according to claim 1, wherein the Z]-(OH) _k-1 groups are each independently selected from 1,2-propanediol and 1,3-butanediol residues. Surfactant composition.   0.1 to 10% by mass of the surfactant composition according to claim 1, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, It comprises at least one selected from polar surfactants, a mixture comprising 5 to 95% by weight of a surfactant different from the surfactant composition according to claim 1, and water. A cleaning composition.