KR20040012357A - Complexed surfactant system - Google Patents

Abstract

PURPOSE: Provided is a mixed surfactant system which increases the cleaning power of anionic surfactant and stability in hard water, and lowers the surface tension and critical micelle concentration (cmc), can control the initial bubble level and bubble maintaining ability according to the mixing ratio of non-ionic surfactant and cationic surfactant, by means of comprising a certain compound having a structure containing at least one non-ionic or cationic group in the anionic surfactant system. CONSTITUTION: The mixed surfactant system comprises: (a) an anionic surfactant; and (b) a compound represented by formula 1, wherein each of R1, R2, R3, and R4 is independently or simultaneously C1-20 of saturated or unsaturated chain, benzyl, hydroxy ethyl, or hydroxy ethyl added with 1-20 of ethylene oxide or propylene oxide; R5 is C1-20 of alkyl, alkyl added with 1-20 of ethylene oxide or propylene oxide, alkyl having one or more hydroxy groups, alkyl containing at least one double bond, or alkyl containing at least one ether group; each of A1 and A2 is independently or together, C1-20 of saturated or unsaturated chain, benzyl, hydroxy ethyl, hydroxy ethyl added with 1-20 of ethylene oxide or propylene oxide, or oxygen anion (O-); n is an integer of 0 to 20; and X is halogen atom, sulfate, methyl sulfate or acetate.

Description

Mixed Surfactant Systems {COMPLEXED SURFACTANT SYSTEM}

The present invention relates to a mixed surfactant system that exhibits excellent performance by controlling interfacial properties such as washing power, foaming force, hard water stability, and surface tension.

All surfactants, such as anionic, cationic, nonionic and amphoteric, exist as single molecules at concentrations below the critical micelle concentration ('cmc'). It is known that the compound exhibits a unique surfactant activity.

By the way, since the surfactant power which one type of surfactant shows cannot be excellent in all the areas | regions, the research for overcoming this is advanced. First, studies have been conducted to mix surfactants having the same ionicity. Since then, studies have been conducted to mix ionic surfactants and nonionic surfactants. However, studies on mixing different ionic surfactants have not been carried out until now, which results in the formation of compounds with neutralized charges as other ionic surfactants are mixed, which do not dissolve in water and precipitate. It is known because it forms.

In general, it is known that when anionic surfactants and cationic surfactants having different ionic properties are simultaneously dissolved in an aqueous solution, they may exist in three states as follows. First, anionic surfactants and cationic surfactants are independently present in a free monolithic state. Second, anionic surfactants and cationic surfactants are complexed and precipitated. Third, anionic surfactants and cationics. The active surfactant forms a mixed micelle and is dissolved in an aqueous solution. In this case, the complex formed by combining anionic and cationic surfactants is called a pseudo-nonionic complex surfactant. The neutral complex has a higher hydrophilicity, such as a nonionic surfactant, solubility in water increases. It is known to be possible. Therefore, the three states of surfactants are greatly influenced by the structure and concentration of the anionic surfactant and the cationic surfactant. As described above, it is known that nonionic surfactants are mixed to prevent precipitation phenomenon, improve phase stability, and improve physical properties, which may occur when the anionic surfactant and the cationic surfactant are mixed to form a surfactant mixture system. In particular, when a nonionic surfactant containing amine oxide or ethylene oxide or propylene oxide is added as a hydrophilic group, not only the phase stability of the mixed surfactant is improved, but also various surfactant activities (for example, solubilizing power, cleaning power, emulsifying power, dispersing power, It has been reported that excellent effects can be obtained at surface tension lowering ability, low cmc concentration, etc. (surfactant science series vol. 46, mixed surfactant systems).

Recently, patents have been published for the purpose of improving the performance of a product by mixing anionic surfactants, cationic surfactants and nonionic surfactants in a proportion.

U. S. Patent No. 5,798, 329 discloses a method for formulating detergents that shows excellent performance in concentrated or general form. Here, excellent performance means excellent foaming power, satisfactory cleaning power, antibacterial power. In the method, at least one anionic surfactant selected from alkylethercarboxylates and alkylethersulfates is used in an amount of about 1 to 40% based on the total weight, and alcohol alkoxylates and alkylphenols are used. Approximately 3-50% of at least one nonionic surfactant selected from alkylphenol ethoxylate, alkylpolyglycosides, amine oxides and alkanolamides is used The cationic surfactant using at least one compound of the ammonium structure is about 1 to 25% of the total weight to improve the cleaning ability. Cationic surfactants used in the above method are generally widely used quaternary ammonium compounds, and nonionic surfactants are also commonly used general-purpose surfactants.

U.S. Patent No. 4,576,729 discloses a method for preparing a liquid detergent having excellent phase stability in which a mixing ratio of nonionic, anionic and cationic surfactants is mixed at a ratio of 2: 4: 1 to 3.5: 5: 1.

U.S. Patent No. 5,230,823 describes a method of mixing anionic and nonionic surfactants in a gel dishwashing method, wherein the method comprises a specific type of quaternary ammonium type cationic surfactant as a bubble increasing agent. have.

However, these methods, although claiming excellent cleaning power, are not mentioned about other properties such as hard water stability, foaming force and surface tension. In addition, the nonionic surfactants used in the above methods are merely compounds obtained by using general purpose compounds, not compounds prepared for specific performance improvement.

In addition, Korean Patent Publication No. 2000-10944 discloses a laundry detergent composition comprising a dimethyl hydroxyethyl quaternary ammonium cationic surfactant containing an alkyl group of C ₁₂ to C ₁₄ combined with a polyamine soil dispersant for increasing fabric cleaning power. It is disclosed and includes. However, the quaternary ammonium cationic surfactants used in the process have an alkyl group of C ₁₂ to C ₁₄ fixed in length, and the role of the cationic surfactants improves the performance of the polyamines, thus simply providing synthetic fabrics (eg, Polyester) describes the improvement of the dirt removal ability during washing and the content of the detergent composition including the same.

In addition, US Pat. No. 6,022,844 discloses that the addition of a cationic surfactant to a conventional detergent formulation improves oil-removing ability, maintains fragrance for a long time, and has an effect of preventing bleeding. In this case, only the content of the cationic surfactant used in the mixture of about 0.1 to 3% is described, but no new compound is applied for the physical property control.

In view of the problems of the prior art, an object of the present invention is to provide a compound having a novel structure capable of improving the properties of anionic surfactants or mixed mixtures of anionic and cationic surfactants.

Another object of the present invention is to provide a mixed surfactant system which exhibits much better performance when only the anionic surfactant is used using the compound.

Another object of the present invention is to add a nonionic surfactant, a cationic surfactant, or a mixture thereof to the mixture containing the anionic surfactant and the compound, compared with using only a mixture of the anionic surfactant and the compound. It is to provide a mixed surfactant system with further improved performance.

It is another object of the present invention to provide a surfactant system having excellent surfactant activity such as cleaning power, initial bubble power, hard water stability, surface tension, cmc, moisturizing power, and bubble holding power.

It is another object of the present invention to provide a solid, liquid, gel, or paste phase detergent composition which exhibits superior performance over conventional products, including the surfactant system.

In order to achieve the above object, the present invention provides a surfactant system,

a) anionic surfactants; And

b) a compound represented by formula (1)

It provides a surfactant system comprising a.

[Formula 1]

In the formula of Formula 1,

R ₁ , R ₂ , R ₃ , and R ₄ are each independently or simultaneously a hydroxide having 1 to 20 carbon atoms, saturated or unsaturated chain group, benzyl group, hydroxyethyl group, ethylene oxide group or propylene oxide group added. Hydroxyethyl group; R ₅ is an alkyl group having 1 to 20 carbon atoms, an ethylene oxide group or propylene oxide group, an alkyl group having at least one hydroxyl group bonded thereto, an alkyl group having at least one hydroxyl group bonded thereto, or at least one alkyl group or ether group containing at least one double bond; It is an alkyl group contained above; A ₁ and A ₂ each independently or simultaneously represent a hydroxy ethyl group or an oxygen anion in which 1 to 20 carbon atoms are saturated or unsaturated chain group, benzyl group, hydroxy ethyl group, ethylene oxide group or propylene oxide group. O ^-), and; n is an integer from 0 to 20; X is a halogen group element, a sulfate group, a methyl sulfate group, or an acetate group.

The present invention also provides a surfactant system comprising: a) an anionic surfactant; b) a compound represented by Formula 1; And c) nonionic surfactants, cationic surfactants, or mixtures thereof.

The present invention also provides a solid, liquid, gel or paste detergent composition comprising the surfactant system described above.

Hereinafter, the present invention will be described in detail.

In order to solve the problems in the prior art and to show excellent interfacial force (e.g., cleaning force, bubble force, hard water stability, surface tension, cmc, moisturizing force, bubble holding force, etc.) in all areas, By combining a plurality of hydrophilic groups in the neutral complex produced at an appropriate concentration, the compound represented by Chemical Formula 1 can be developed to prevent precipitation and thereby control the physical properties of the anionic surfactant by increasing the solubility in water.

Accordingly, the present invention is to provide a surfactant system exhibiting excellent performance by including a compound represented by the formula (1) in a certain ratio to increase the physical properties of the conventional anionic surfactant.

In the present invention, by using the compound of Formula 1, the desired physical properties can be adjusted and excellent performance can be obtained even by mixing a small amount. In addition, the present invention can improve or control the desired physical properties by preparing a cationic compound of the Gemini structure in order to further improve the dirt removal ability as an additive.

The present invention improves the solubility of the neutral composite produced by introducing into the molecule a hydroxyl group, ethylene oxide (EO), propylene oxide (PO) which is at least one cationic group or an amine oxide group and a hydrophilic group to exhibit excellent interfacial activity. That is, according to the present invention, an anionic surfactant alone or an anionic surfactant and a nonionic surfactant, a cationic surfactant, or a mixture thereof is increased by the compound represented by Formula 1, and initial bubbles and bubbles are increased. It regulates holding force and also improves hard water stability and lowers surface tension and cmc.

In Formula 1, when A ₁ and A ₂ are oxygen anions, charge cations of nitrogen and anions of oxygen are charge-offset to show the properties of the nonionic compound. In addition, in Formula 1, A ₁ and A ₂ are each independently or simultaneously added 1 to 20 carbon atoms of 1 to 20 saturated or unsaturated chain group, benzyl group, hydroxy ethyl group, ethylene oxide group or propylene oxide group In the case of a hydroxyethyl group, the properties of the cationic compound are shown.

The surfactant system of the present invention will be described in more detail as follows.

In the surfactant system of the present invention, a) the anionic surfactant is used as a compound that can be mixed with the compound of the formula (1) to obtain a mixed system excellent in phase stability. It is generally applicable to all widely used anionic surfactant compounds, especially carboxylate compounds such as soaps, higher alcohols, higher alkyl ethers, and sulfate ester compounds that are sulfated olefins. And sulfate compounds containing alkylbenzensulfonate and phosphate compounds phosphorylated with higher alcohols. Specific examples include sodium lauryl sulfate (hereinafter referred to as 'SLS'), sodium lauryl ether sulfate (SLES), linear alkylbenzenesulfonate (LAS), monoalkyl phosphate (MAP), acyl ise Thionate (acyl isethionate, SCI), and alkyl glyceryl ether sulfonate (AGES), acyl glutamate, acyl taurate, fatty acid metal salt, and the like. It is better to use SLS, SLES, LAS, or SCI, which are widely used.

In addition, in the surfactant system of the present invention, b) the compound of Formula 1 includes a cationic group or an anionic group in the molecular structure and at least one hydrophilic group in the compound. The compound represented by Chemical Formula 1 having such a structure may exhibit excellent performance by increasing the solubility in water of the resulting mixture when combined with an anionic surfactant.

In the compound of Formula 1, when oxygen anion is bonded to A ₁ and A ₂ , that is, in the case of a nonionic compound including an amine oxide group, the preparation method may be used as follows.

The first method comprises the steps of: a) preparing a tertiary amine by reacting a secondary amine with a linker of Formula 2 under alkaline conditions; And b) reacting the tertiary amine obtained in step a) with hydrogen peroxide (H ₂ O ₂ ) to prepare a nonionic compound of Chemical Formula 1.

[Formula 2]

In formula 2, n is an integer of 1 to 20; X 'is a halogen group element; R ₅ is hydrogen or an alkyl or allyl group having 1 to 20 carbon atoms including at least one double bond, a hydroxy group, or an ether group.

The present invention may be a method of preparing a amine oxide by first reacting a secondary amine and a compound of Formula 2 in accordance with the object to first synthesize the tertiary amine in alkaline conditions, and then react with hydrogen peroxide, the synthesis route for For example, it is shown in the following Reaction Scheme 1.

Scheme 1

In Scheme 1, R is a C ₁ to C ₂₀ saturated or unsaturated chain group, benzyl group, hydroxy ethyl group, or hydroxy ethyl group to which 1 to 20 ethylene oxide groups or propylene oxide groups are added; n is an integer from 1 to 20; X 'is a halogen group element; R ₅ is hydrogen or an alkyl or allyl group having 1 to 20 carbon atoms including at least one double bond, a hydroxy group, or an ether group.

The bis (bis) form of the nonionic compound of Formula 1 may be prepared through the route of Scheme 1.

In addition, a method for preparing a compound including three or more amine oxide groups in one molecule of Chemical Formula 1 used in the present invention is as follows.

The present invention can be obtained by reacting primary amine with epichlorohydrin in an equimolar mole in an alcohol solvent to synthesize a secondary amine intermediate, followed by polymerization of the intermediate to prepare a tertiary amine and reacting it with hydrogen peroxide. At this time, by controlling the time and temperature of the polymerization reaction in the synthesis of the tertiary amine, it is possible to control the degree of polymerization of the intermediate. An example of such an oligomeric nonionic compound synthesis route is shown in Scheme 2 below.

Scheme 2

In Scheme 2, R ₁ , n, and X are as defined above.

In the present invention, a nonionic compound can be easily synthesized by selecting and using an appropriate synthesis method according to the desired compound. Compounds thus synthesized can be identified using NMR and MASS analysis.

Examples of the nonionic compound of the compound of Formula 1 prepared by the above method include N, N , N -dimethyl lauryl amine oxide; N, N, N -ethyl methyl lauryl amine oxide; N, N , N -dimethyl dodecyl amine oxide; N, N , N -butyl methyl lauryl amine oxide; N, N , N -dimethyl hexadecyl amine oxide; N, N , N -dibutyl lauryl amine oxide; N, N , N- (2-hydroxyethyl lauryl methyl) amine oxide; N, N , N- (di-2-hydroxyethyl lauryl) amine oxide; N, N , N- (2-hydroxyethyl lauryl butyl) amine oxide; N, N , N- (2-hydroxy (EO) ₅ ethyl lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (PO) ₅ lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (EO) ₅ (PO) ₅ lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (EO) ₁₀ lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (EO) ₁₅ lauryl methyl) amine oxide; 1,6- ( N, N -butylmethyl amineoxyl) hexane; 1,6- ( N, N -butylmethyl amineoxyl) dipropyl ether; 1,6- ( N, N -butylmethyl amineoxyl) -3-hydroxyhexane; 1,6- ( N, N -butylmethyl amineoxyl) butane; 1,6- ( N, N -butylmethyl amineoxyl) octane; 1,6- ( N, N -butylmethyl amineoxyl) -2-hydroxypropane; 1,6- [2- ( N -methyl amineoxyl) ethanol] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (EO) ₅ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (PO) ₅ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (EO) ₅ (PO) ₅ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (EO) ₁₀ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol] dipropyl ether; 1,6- [2- ( N -methyl amineoxyl) ethanol] -2-hydroxypropane; 1,6- [2- ( N -methyl amineoxyl) ethanol] butane; And 1,6- [2- ( N -methyl amineoxyl) ethanol] octane.

In addition, in the surfactant system of the present invention, A ₁ and A ₂ of the compound represented by Formula 1 are each independently or simultaneously saturated or unsaturated chain groups having 1 to 20 carbon atoms, benzyl group, hydroxy ethyl group, and ethylene oxide. When it is the hydroxy ethyl group which 1-20 addition of a group or a propylene oxide group becomes, it becomes a compound containing a cationic group.

The following two methods may be used to prepare a compound including a cationic group among the compounds represented by Formula 1.

The first method comprises a) a secondary amine and alkali-containing saturated or unsaturated chain groups, benzyl groups, hydroxy ethyl groups, ethylene oxide groups or hydroxy ethyl groups with 1-20 propylene oxide groups added under alkaline conditions. Reacting the compound to produce a tertiary amine; And b) quaternizing by adding the compound represented by Formula 2 to the tertiary amine obtained in step a), to prepare a cationic compound of Formula 1.

In addition, optionally a) preparing a tertiary amine by reacting the secondary amine and the compound represented by the formula (2) in alkaline conditions; And b) a hydroxy ethyl group having 1 to 20 carbon atoms, saturated or unsaturated chain group, benzyl group, hydroxy ethyl group, ethylene oxide group or propylene oxide group added to the tertiary amine obtained in step a). The cationic compound of Formula 1 may be prepared by the step of quaternizing by combining the compound.

First, the present invention includes secondary amines that meet the purpose, including hydroxy ethyl groups having 1 to 20 carbon atoms, saturated or unsaturated chain groups, benzyl groups, hydroxy ethyl groups, ethylene oxide groups or propylene oxide groups. After the compound to be warmed under basic conditions to prepare a tertiary amine, it can be quaternized by reacting with a linker of the formula (2), an example of the synthetic route for this is as shown in Scheme 3.

Scheme 3

In Scheme 3, R is a C ₁ to C ₂₀ saturated or unsaturated chain group, benzyl group, hydroxy ethyl group, or hydroxy ethyl group to which 1 to 20 ethylene oxide groups or propylene oxide groups are added; n is an integer from 1 to 20; X is a halogen group element, a sulfate group, or an acetate group; X 'is a halogen group element; R ₅ is hydrogen or an alkyl or allyl group having 1 to 20 carbon atoms including at least one double bond, a hydroxy group, or an ether group.

In addition, the present invention by first reacting the secondary amine and the compound of the formula (2) according to the purpose to synthesize the tertiary amine first under alkaline conditions, the carbon atoms of 1 to 20 saturated or unsaturated chain group, benzyl group, hydroxy A method of quaternizing by reacting with a compound including a hydroxy ethyl group to which an ethyl group, an ethylene oxide group, or a propylene oxide group is added by 1 to 20 is used, and an example of a synthetic route thereof is shown in Scheme 4 below.

Scheme 4

In Scheme 4, R is a C ₁ to C ₂₀ saturated or unsaturated chain group, benzyl group, hydroxy ethyl group, or hydroxy ethyl group to which 1 to 20 ethylene oxide groups or propylene oxide groups are added; n is an integer from 1 to 20; X is a halogen group element, a sulfate group, or an acetate group; X 'is a halogen group element; R ₅ is hydrogen or an alkyl or allyl group having 1 to 20 carbon atoms including at least one double bond, a hydroxy group, or an ether group.

The bis form of the cationic compound of Formula 1 may be prepared through the reaction route of Scheme 3 or 4.

In addition, the cationic compound containing three or more cationic groups in one molecule used in the present invention, after reacting the secondary amine and epichlorohydrin in equimolar moles in an alcohol solvent to synthesize an intermediate, the intermediate is subjected to a polymerization reaction. Can get through. At this time, the degree of polymerization of the cationic compound can be adjusted by adjusting the time and temperature of the polymerization reaction. The cationic compound synthesis route in this oligomeric or polymer form is shown in Scheme 5 below.

Scheme 5

In Scheme 5, R ₁ and R ₂ are as defined above, n is an integer of 1 to 20.

In the present invention, cationic compounds can be easily synthesized by selecting and using an appropriate method according to the desired compound. Compounds thus synthesized can be identified using NMR and MASS analysis.

Specific examples of the compound containing a cationic group among the compounds represented by Formula 1 include dimethyl octyl ethanol ammonium, dimethyl decyl ethanol ammonium, dimethyl lauryl ethanol ammonium, dimethyl octyl ethanol (EO) ₅ ammonium, dimethyl decyl ethanol (EO) ₅ Ammonium, Dimethyl Lauryl Ethanol (EO) ₅ Ammonium, Dimethyl Octyl Ethanol (EO) ₁₀ Ammonium, Dimethyl Decyl Ethanol (EO) ₁₀ Ammonium, Dimethyl Lauryl Ethanol (EO) ₁₀ Ammonium, Dimethyl Octyl Ethanol (EO) ₁₅ , Dimethyl Decyl ethanol (EO) ₁₅ , dimethyl lauryl ethanol ammonium (EO) ₁₅ , trimethyl octyl ammonium, tridecyl lauryl ammonium, trimethyl lauryl ammonium, 1,6- [2- ( N -dimethyl amino) ethanol] hexane, 1 , 6- [2- ( N, N -ethylmenylamino) ethanol] hexane, 1,6- [2- ( N, N -butylmethyl amino) ethanol] hexane, 1,6- [2- ( N, N methyl octyl amino) ethanol] hexane, 1,6- [2- (N, N-dodecyl-methylamino) ethanol; Acid, 1,8- [2- (N - dimethylamino) ethanol] octane, 1,8- [2- (N, N - ethyl-methyl-amino) ethanol] octane, 1,8- [2- (N, N -Butylmethyl amino) ethanol] octane, 1,8- [2- ( N, N -methyloctylamino) ethanol] octane, 1,8- [2- ( N, N -dodecylmethyl amino) ethanol] octane, 1,6- [2- ( N -dimethylamino) ethanol (EO) ₂ ] hexane, 1,6- [2- ( N, N -ethylmethyl amino) ethanol (EO) ₂ ] hexane, 1,6- [ 2- ( N, N- Butylmethyl amino) ethanol (EO) ₂ ] hexane, 1,6- [2- ( N, N -methyloctyl amino) ethanol (EO) ₂ ] hexane, 1,6- [2- ( N, N -dodecylmethyl amino) ethanol (EO) ₂ ] hexane, 1,6- [2- ( N -dimethylamino) ethanol (EO) ₄ ] hexane, 1,6- [2- ( N, N -Ethylmethyl amino) ethanol (EO) ₄ ] hexane, 1,6- [2- ( N, N -butylmethyl amino) ethanol (EO) ₄ ] hexane, 1,6- [2- ( N, N -methyl Octylamino) ethanol (EO) ₄ ] hexane, 1,6- [2- ( N, N -dodecylmethyl amino) ethanol (EO) ₄ ] hexane, 1,8- [2- ( N -dimethylamino) ethanol (EO) ₂ ] octane, 1,8- [2- ( N, N -ethylmethyl amino No) ethanol (EO) ₂ ] octane, 1,8- [2- ( N, N -butylmethyl amino) ethanol (EO) ₂ ] octane, 1,8- [2- ( N, N -methyloctyl amino) Ethanol (EO) ₂ ] Octane, 1,8- [2- ( N, N -dodecylmethyl amino) ethanol (EO) ₂ ] Octane, 1,8- [2- ( N -dimethyl amino) ethanol (EO) ₄ ] Octane, 1,8- [2- ( N, N -ethylmethyl amino) ethanol (EO) ₄ ] Octane, 1,8- [2- ( N, N -butylmethyl amino) ethanol (EO) ₄ ] Octane, 1,8- [2- ( N, N -methyloctylamino) ethanol (EO) ₄ ] Octane, 1,8- [2- ( N, N -dodecylmethyl amino) ethanol (EO) ₄ ] Octane , 1,6- [2- ( N -dimethylamino) ethanol (PO) ₂ ] hexane, 1,6- [2- ( N, N -ethylmethylamino) ethanol (PO) ₂ ] hexane, 1,6- [2- ( N, N -Butylmethyl amino) ethanol (PO) ₂ ] Hexane, 1,6- [2- ( N, N -methyloctyl amino) ethanol (PO) ₂ ] Hexane, 1,6- [2 -( N, N -dodecylmethyl amino) ethanol (PO) ₂ ] hexane, 1,6- [2- ( N -dimethylamino) ethanol (PO) ₄ ] hexane, 1,6- [2- ( N, N - ethyl-methyl-amino) ethanol (PO) _4] hexane, 1,6- [2- (N, N - butyl O-methyl No) ethanol (PO) _4] hexane, 1,6- [2- (N, N - methyl octyl amino) ethanol (PO) _4] hexane, 1,6- [2- (N, N - dodecyl amino methyl ) Ethanol (PO) ₄ ] hexane, 1,8- [2- ( N -dimethylamino) ethanol (PO) ₂ ] octane, 1,8- [2- ( N, N -ethylmethyl amino) ethanol (PO) ₂ ] octane, 1,8- [2- ( N, N -butylmethyl amino) ethanol (PO) ₂ ] Octane, 1,8- [2- ( N, N -methyloctyl amino) ethanol (PO) ₂ ] Octane, 1,8- [2- ( N, N -dodecylmethyl amino) ethanol (PO) ₂ ] Octane, 1,8- [2- ( N -dimethyl amino) ethanol (PO) ₄ ] Octane, 1, 8- [2- ( N, N -ethylmethyl amino) ethanol (PO) ₄ ] octane, 1,8- [2- ( N, N -butylmethyl amino) ethanol (PO) ₄ ] octane, 1,8- [2- ( N, N -methyloctylamino) ethanol (PO) ₄ ] 1 from octane, and 1,8- [2- ( N, N -dodecylmethyl amino) ethanol (PO) ₄ ] octane. It is preferable that it is a compound selected from species or more.

In addition, in the surfactant system of the present invention, c) the nonionic surfactant is preferably used in combination with the anionic surfactant and the compound of the formula (1) showing excellent phase stability. In the surfactant system of the present invention, the nonionic surfactant is alcohol alkoxylate, alkylphenol ethoxylate, alkylpolyglycosides, amine oxide, and alkanol It is preferred that at least one member be selected from the group consisting of medi (alkanolamide).

In addition, in the surfactant system of the present invention, it is preferable to use d) the cationic surfactant which is mixed with the anionic surfactant and the compound represented by the above formula (1) and exhibits excellent phase stability. As the cationic surfactant used in the present invention, a cationic surfactant widely used in the art may be used. For example, compounds in the form of amine salts, compounds containing quaternary ammonium, monoalkyl dimethyl amine derivatives, dialkyl monomethyl amine derivatives, imidazoline derivatives, quaternary quaternary ammonium compounds, and oligomeric quaternary ammonium forms It can be used by selecting one or more from the group consisting of cationic surfactants.

Such a surfactant system of the present invention comprises an anionic surfactant and the compound of formula (1).

In addition, the surfactant system of the present invention is a mixed surfactant system showing a better performance by mixing a nonionic surfactant, a cationic surfactant, or a mixture thereof in a mixed system of the anionic surfactant and the compound of formula (1) Can be formed.

In the surfactant system of the present invention, in the case of a mixed system comprising the a) anionic surfactant and b) the compound of the formula (1), the mixing ratio is preferably 1: 0.0001 to 1: 1.0 in molar ratio. In this case, when the molar ratio of a) the anionic surfactant and b) the compound of Chemical Formula 1 is less than 1: 0.0001, it is difficult to see the physical property change of the surfactant mixing system by mixing the nonionic compound, and the molar ratio is greater than 1: 1.0. Mixing the compounds of 1 is not economically advantageous.

Further, in the surfactant system of the present invention, the a) anionic surfactant; In the case of a mixed system of b) a compound of the formula (1) and c) a nonionic surfactant, the mixing ratio is preferably in a molar ratio of 1: 0.0001: 0.0001 to 1: 1.0: 0.5.

In addition, in the surfactant system of the present invention, in the case of a mixed system of a) an anionic surfactant, b) a compound of Formula 1, and a cationic surfactant, the mixing ratio is 1: 0.0001: 0.0001 to 1: 1.0: It is preferable that it is 0.5.

In addition, in the surfactant system of the present invention, in the case of a mixed system of a) the anionic surfactant, b) the compound of Formula 1, c) nonionic surfactant, and d) cationic surfactant, the mixing ratio is 1 in molar ratio. : 0.0001: 0.0001: 0.0001 to 1: 1.0: 0.5: 0.5 is preferable.

Changes in the physical properties of the anionic surfactants (typically SLS) in the mixed system prepared under such conditions were carried out in the items of kraft point change, bubble force (initial bubble and bubble holding force), surface tension change, and hard water stability change. It can know by measuring over.

In the surfactant system of the present invention, a kraft point, which is a temperature at which a surfactant precipitates under cooling conditions, is mixed by mixing a compound including a nonionic group and an anionic surfactant in the compound of Formula 1 below 0 ° C. Improve. This indicates that the phase stability of the surfactant system is very good at low temperatures. In the case of the kraft point, the mixing system according to the present invention shows a result of 0 ° C. or less under most of the sample conditions, and this result means that the phase stability is excellent even though the mixing ratio of the nonionic compound is low. Therefore, by mixing the nonionic compound of Formula 1 with an anionic surfactant, it is possible to secure the disadvantages of the anionic surfactant precipitated at low temperatures, and in particular it can be a great help in maintaining the phase stability of the product including the winter surfactant .

In addition, as a result of experiments in terms of bubble power (initial bubble and bubble stability), regardless of the mixing ratio of the nonionic additive, the initial bubble of the mixed system is the same as the anionic surfactant and the bubble is maintained for a long time, and the initial bubble is generated. Was excellent, but the bubble gradually decreased over time. This means that the foaming power of the product can be controlled by selecting and applying a nonionic compound according to the applied product, and it can be applied to various products such as kitchen utensils, shampoo, body cleanser and laundry detergent.

In the case of the surface tension change, the surface tension decreases as the mixing ratio of the nonionic compound increases, and the surface tension is maintained even at a considerably low concentration. From this, the mixed system has a cmc lower than the anionic surfactant (SLS). It can be expected to have. This low surface tension and cmc mean that a good cleaning power can be obtained even with a small amount.

The hard water stability of the mixed system was about two times higher than that of using only anionic surfactant alone. This will be applicable to products that need to be washed with water containing a lot of amphoteric metal ions such as dish detergent or laundry detergent. In addition, it can be said that the ionicity of the anionic surfactant forms a mixed micelle with the nonionic compound from the increase of hard water stability. As described above, the better the anionic surfactant and the nonionic compound form the mixed micelle, the physical properties of the surfactant mixture can be sufficiently changed.

In addition, nonionic compounds prepared using secondary amines having an average of 2 to 15 moles of ethylene oxide (EO) or propylene oxide (PO) added are also anionic surfactants or mixtures of anionic and cationic surfactants. It is possible to change the physical properties by mixing with.

In addition, the surfactant system of the present invention improves the kraft point, which is the temperature at which the surfactant precipitates under cooling conditions, by mixing the cationic compound of Formula 1 and the anionic surfactant to 0 ° C. or less. This indicates that the phase stability of the surfactant system is very good at low temperatures.

In the case of the kraft point, the mixed system according to the present invention shows a result of 0 ° C. or less at most sample conditions. These results indicate that the alkyl group of the cationic compound is hardly affected by the mixing ratio and the long and short. . Therefore, by mixing the cationic additives with the anionic surfactant, it is possible to secure the disadvantages of the anionic surfactant precipitated at a low temperature, it can be particularly helpful in maintaining the phase stability of the winter product.

In addition, when the cationic compound is included, the experiment was conducted in terms of foaming power (initial foaming and bubble stability), and the longer the alkyl group of the cationic additive, the lower the initial foaming degree of the mixed system when the mixing ratio was 2 / 0.75 or more, This shows a weakening result. This is a property required for a laundry detergent for a dishwasher or a drum washing machine that needs to be easily turned off as bubbles are generated after using abundant bubbles such as anionic surfactants. In particular, in the case of a mixed system using a cationic compound in which a dodecyl group is introduced as an alkyl group, bubbles are hardly generated. From these results, it can be seen that the cationic additive can be used as an antifoaming agent by applying the product in which anionic surfactant is the main compound (for example, a low foaming laundry detergent).

In the case of the surface tension change, when the mixing ratio is 2 / 0.1 or more, the surface tension decreases as the mixing ratio of the cationic compound increases, and the surface tension is maintained even at a low concentration. From this, the mixed system has anionic surfactant activity (SLS). It can be expected that it may have a lower cmc. As such, the low surface tension and cmc may show excellent cleaning power even in a small amount when the product is applied.

The hard water stability of the mixed system shows a very improved result when the alkyl group is at least 2 / 0.5 with a cationic compound having a butyl group or more and an anionic surfactant. In particular, in the case of the cationic compound containing a butyl group, the water hardness stability of about 4 times increased compared to using only anionic surfactant alone. This will be applicable to products that need to be washed with water containing a lot of amphoteric metal ions such as dish detergent or laundry detergent. In addition, it can be seen that the ionicity of the anionic surfactant is combined with the cationic compound to form a complex from the increase of hard water stability. In this way, the stronger the bond between the anionic surfactant and the cationic compound is, the smaller the amount of the cationic compound can change the properties of the anionic surfactant sufficiently.

In order to compare the ability of the cationic compound of Formula 1 to change the physical properties of the anionic surfactant, a quaternary ammonium compound containing alkyl and hydroxyl ethyl groups of the same length was prepared and evaluated for physical properties under the same conditions. In addition, the cationic compound, which is an object of the present invention, showed a lower kraft point and improved bubble control ability, lower surface tension, and improved hard water stability even at a lower mixing ratio than the comparative compound. From these results, it can be seen that as the cationic group increases in one molecule, the ability to change the physical properties of the anionic surfactant is improved.

In addition, even when a cationic compound is prepared using secondary amines having an average of 2 moles and 4 moles of ethylene oxide (EO) and propylene oxide (PO) added to a hydroxy group, the ability to change the physical properties of the anionic surfactant can be improved. Can be.

As such, the surfactant system in which the compound of Formula 1 and the anionic surfactant are mixed in the present invention has excellent surfactant activity, and thus, solid, liquid, gel, and paste detergents, for example, shampoos and skin cleaners. Including products such as soaps, kitchen detergents, residential detergents, industrial detergents, toothpastes, and powder detergents in prescription formulations can provide products with superior performance over conventional products.

Hereinafter, the present invention will be described with reference to the following examples. However, these examples are only for illustrating the present invention, and the present invention is not limited thereto.

EXAMPLE

(Nonionic Compounds Containing Amine Oxide Groups in Molecules)

1-1. Synthesis of Nonionic Compounds

The desired nonionic compound was prepared using the synthetic route as in Schemes 1 and 2.

Synthesis Example 1

N -Dimethyl lauryl amine oxide synthesis

27.3 g (0.24 mol; 30 wt% solution) of hydrogen peroxide solution were added dropwise at room temperature to 42.7 g (0.2 mol) of N -dimethyl lauryl amine, and the reaction was carried out for 17 hours after raising the temperature to 40 ° C. After the reaction was completed, the resultant was purified by distillation under reduced pressure and vacuum drying.

Molecular Weight: 229 g / mol

Phase: Yellow Oil Phase

¹ H NMR (CDCl ₃ , δ ppm): 0.81 (3H), 1.19 (18H), 1.80 (2H), 3.11 (6H), 3.18 (2H)

Mass (FAB +): m / e 230 [M + H] ⁺ , 212

Synthesis Example 2

N Synthesis of-(2-hydroxyethyl lauryl methyl) amine

150.22 g (2 mol) of 2- (methyl amino) ethanol was dissolved in 175 g of isopropyl alcohol (IPA), followed by 408 g (2 mol) of 1-chlorododecane and 318 g (3 mol) of sodium carbonate (Na ₂ CO ₃ ). ) Was added and reacted for 25 hours. After completion of the reaction, the resultant was purified by filtration, distillation under reduced pressure and vacuum drying.

Molecular Weight: 243 g / mol

Phase: yellow oil

¹ H NMR (CDCl ₃ , δ ppm): 0.86 (3H), 1.26 (20H), 2.18 (3H), 2.39 (2H), 2.52 (2H), 3.42 (2H)

Mass (FAB +): m / e 244 [M + H] ⁺

Synthesis Example 3

N Synthesis of-(2-hydroxyethyl lauryl methyl) amine oxide

To 10.5 g of methanol, 30.64 g (0.126 mol) of N- (2-hydroxyethyl lauryl methyl) amine and 21.5 g (0.189 mol) of hydrogen peroxide solution were added dropwise at room temperature, and the temperature was raised to reflux for 31 hours. The resultant was purified by filtration, distillation under reduced pressure and vacuum drying.

Molecular Weight: 259 g / mol

Phase: yellow solution

¹ H NMR (CDCl ₃ , δ ppm): 0.81 (3H), 1.23 (18H), 1.69 (2H), 3.14 (3H), 3.29 (4H), 4.07 (2H)

Mass (FAB +): m / e 260 [M + H] ⁺

Synthesis Example 4

1,6- ( N, N -Butylmethyl amino) hexane Synthesis

96 g (1.1 mol) of 2- ( N, N -butylmethyl) amine, 77.53 g (0.5 mol) of 1,6-dichlorohexane, and 133 g of Na ₂ CO ₃ were mixed with 92 g of IPA, and then at a temperature of 70 ° C. The reaction was for 36 hours. Thereafter, the resultant was purified by drying, filtration, distillation under reduced pressure, and vacuum drying.

Molecular Weight: 256 g / mol

Phase: Oil Phase

¹ H NMR (CDCl ₃ , δ ppm): 0.91 (6H), 1.29 (8H), 1.42 (8H), 2.20 (6H), 2.32 (8H)

Mass (FAB +): m / e 257 [M + H] ⁺

Synthesis Example 5

1,6- ( N, N -Butylmethyl amineoxyl) hexane Synthesis

21.88 g (0.086 mol) of 1,6- ( N, N -butylmethyl amino) hexane was dissolved in 14 g of methanol, and then 24 g (0.215 mol; 30 wt% solution) of hydrogen peroxide was slowly added. After refluxing for 18 hours, the resultant was purified by distillation under reduced pressure and vacuum drying.

Molecular Weight: 288 g / mol

Phase: Yellow Oil Phase

¹ H NMR (CDCl ₃ , δ ppm): 0.97 (6H), 1.39 (8H), 1.77 (8H), 3.18 (6H), 3.32 (8H)

Mass (FAB +): m / e 289 [M + H] < + >, 170

Experimental Example 1

1-2. Evaluation of Changes in Anionic Surfactant Performance in a Mixture of Nonionic Compounds Containing Anionic Surfactants and Amineoxide Groups

Sodium lauryl sulfate (hereinafter referred to as 'SLS'; Aldrich's reagent; purity over 99%) was used as the anionic surfactant used for the physical property evaluation. The physical properties of SLS have kraft point of 2 ℃ (temperature drop) and 14 ℃ (temperature rise). A tension of 35.92 mN / m, 0.1% 25.19, 0.01% 57.18 was used. In addition, the hard water concentration was 310 ppm when measuring the hard water stability.

The kind and molecular weight of the nonionic compound used for physical property evaluation are shown in Table 1.

Nonionic Compound Type and Molecular Weight (g / mol) compound Synthesis Example 1 Synthesis Example 3 Synthesis Example 5 Molecular Weight 229 259 288

Choja used in the following experiment was immersed in a wash solution (KOH + IPA + water) for 4 hours or more, washed with distilled water and acetone, and then dried. Ultrapure water was used for the evaluation.

Changes in physical properties of the anionic surfactant were carried out for the kraft point, initial bubble, bubble stability, hard water stability, and surface tension.

1-2-1. Measurement of physical properties of nonionic compounds

1) Evaluation sample condition

1 g of the nonionic compounds of Synthesis Examples 1, 3, and 5 were dissolved in 99 g of water, respectively, to prepare a sample having a concentration of 1% by weight, and used for evaluation. Synthesis Example 1, 3, 5 samples all showed a transparent phase.

2) Kraft point measurement of nonionic compounds

The temperature at which the solution became cloudy was measured while cooling the transparent nonionic compound solutions of Synthesis Examples 1, 3, and 5 (conditions at the time of temperature drop). Moreover, the temperature which became transparent again by measuring the temperature of the turbid solution was measured (condition at the time of temperature increase).

At this time, the SLS showed a turbidity phenomenon in the temperature range of 2 to 3 ℃ at the temperature drop condition and became transparent again at 14 ℃ under the temperature rise condition. On the contrary, in all of Synthesis Examples 1, 3, and 5 of the present invention, no clouding occurred to 0 ° C under the conditions of temperature drop. Thus, when cloudiness did not arise at 0 degreeC, the experiment on the temperature rise was not performed.

3) Measurement of bubble power (initial bubble and bubble holding force)

The bubble-related experiments for Synthesis Examples 1, 3 and 5 were measured using a semi-micro TK method and the results are shown in Table 2 below. The experiment was repeated three times and then averaged. 1% aqueous solution was used for the experiment.

Classification (ml) 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Synthesis Example 1 210 55 - - - - Synthesis Example 3 230 228 228 225 223 223 Synthesis Example 5 - - - - - -

As shown in Table 2, Synthesis Example 3 shows a significant level of initial foaming power and bubble stability, while Synthesis Example 1 initially showed a relatively excellent level of foaming but low foaming stability is turned off soon. On the other hand, Synthesis Example 5 showed that no bubbles are generated. From the results of this experiment, Synthesis Examples 1 and 5 are considered to be applicable to a low-foam laundry detergent, etc. in which the generated bubbles should sink immediately, it is expected that the synthesis example 3 can be applied to a dish detergent that requires excellent foaming power.

4) Surface tension measurement

The surface tension of the nonionic compounds of Synthesis Examples 1, 3 and 5 was measured using a Kruss tensiometer k12. As a measuring method, a ring method was used. The concentrations of the nonionic compound samples of Synthesis Examples 1, 3, and 5 were 1%, 0.1%, 0.01%, and 0.001% by weight to prepare solutions. Surface tension results are shown in Table 3 below.

Surface tension measurement result of nonionic compound (unit: mN / m) division 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Synthesis Example 1 210 55 - - - - Partnership 3 230 228 228 225 223 223 Union example 5 - - - - - -

In Table 3, Synthesis Examples 1 and 3 showed relatively low surface tension results in the concentration range of the sample, but Synthesis Example 5 showed high surface tension values.

5) Hard water stability assessment

Hard water at a concentration of 10,000 ppm prepared by dissolving 11.69 g of CaCl ₂ · 2H ₂ O in 1 L of water was used for the experiment. Nonionic compounds of Synthesis Examples 1, 3 and 5 were evaluated for hard water stability using ml of hard water added until the time of the generation of pearl using a concentration of 0.5% (weight ratio) and 100 ml of sample, respectively. . The experiment took an average value after three iterations. As a result, all of the nonionic compounds of Synthesis Examples 1, 3, and 5 showed a small amount of negative charges, which resulted in no precipitation for hard water.

Measurement of physical property change of SLS in the mixture of 1-2-2 anionic surfactant (SLS) and nonionic compound of Synthesis Example 1

[Examples 1 to 6]

Anionic surfactant (SLS), the nonionic compound of Synthesis Example 1 was prepared in a molar ratio as shown in Table 4 below, all prepared sample solution was transparent. At this time, the quaternary ammonium salt, which is a cationic surfactant, was added in a molar ratio of 1: 0.001 relative to SLS.

Mixed system evaluation sample Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 SLS / Non-ion 0.56 / 0.44 0.63 / 0.37 0.72 / 0.28 0.83 / 0.17 0.93 / 0.07 0.993 / 0.007 Stability Transparency Transparency Transparency Transparency Transparency Transparency

Experimental Example 2

Measurement of physical properties of Examples 1 to 6

1) Kraft Point Measurement

Kraft points of Examples 1 to 6 (mixture of SLS and nonionic compounds) were measured, and the experimental results are shown in Table 5 below.

Kraft point measurement of the mixing system (unit ℃) division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 When temperature drops 0 < 0 < 0 < 0 < 0 2-3 When temperature rises - - - - 19 19-20

In Table 5, the kraft point (Krafft point) is lowered to 0 ℃ or less in Examples 1 to 4 where the mixing ratio of the nonionic additive is 1 / 0.25 or more. Examples 1 to 4 showed a result of maintaining a stable phase even at low temperatures compared with the case of using SLS alone. In addition, in the case of Examples 5 and 6, the solution turned cloudy in the temperature range of 0 to 3 ℃ under the conditions of temperature drop, and became transparent again at the temperature of 19 ℃ under the conditions of temperature rise.

2) Measurement of bubble power (initial bubble and bubble holding force)

The foaming force for Examples 1 to 6 was measured, and the results are shown in Table 6 below.

Bubble force measurement result (unit mL) of mixture system division 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Example 1 200 200 200 200 200 200 Example 2 248 245 245 245 245 245 Example 3 245 245 245 245 245 245 Example 4 245 245 245 245 245 245 Example 5 250 248 248 245 245 245 Example 6 250 250 250 250 250 250

In Table 6, as shown in Example 6, the lower the mixing ratio of the nonionic compound showed a similar tendency of the initial bubble and the foam retaining force to the SLS. In addition, as the mixing ratio of the nonionic additive was lower, the initial bubble level was increased, but the bubble formed once showed excellent bubble holding power that was maintained fairly stable. From the results of the above bubble power, it is considered that it can be applied to products requiring abundant bubbles during cleaning such as shampoo or body cleanser.

3) Surface tension measurement

Surface tension measurement results are shown in Table 7 below.

Measurement result of surface tension change of mixing system (room temperature) division density One% 0.1% 0.01% 0.001% Example 1 26.13 23.36 23.46 41.90 Example 2 26.10 23.34 23.56 43.33 Example 3 26.56 23.51 23.80 46.79 Example 4 27.13 23.33 26.26 48.25 Example 5 28.37 23.11 29.02 52.65 Example 6 31.06 24.05 34.05 60.81

As shown in Table 7, Example 6 showed a surface tension value almost similar to that of SLS, but the surface tension value tended to decrease as the mixing ratio of the nonionic compound increased. As in the above results, the surface tension is lowered and showing a constant value even at low concentrations means that the cmc is low, and from this result, it is possible to exhibit excellent cleaning power even with a small amount.

4) Measurement of Hard Water Stability Change

The results of measuring the hard water stability of the mixed system are shown in Table 8 below.

Measurement of Hard Water Stability Change division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 1 time 6.10 6.70 6.55 3.60 2.90 3.15 Episode 2 6.10 6.60 7.20 5.15 2.95 3.35 Average 6.10 6.65 6.88 4.38 2.93 3.25 Hard water concentration (ppm) 575 624 644 420 285 315

In Table 7, the amount of hard water added increased as the mixing ratio of the nonionic compound increased. The mixed system of SLS and nonionic compound showed about 2 times better hard water stability than SLS.

1-2-3. Measurement of physical property change of SLS in mixed system of SLS and nonionic compound of Synthesis Example 5

[Examples 7 to 12]

Anionic surfactant (SLS), a nonionic compound of Synthesis Example 5 was prepared in a molar ratio as shown in Table 9 below, all prepared sample solution was transparent. At this time, the quaternary ammonium salt, which is a cationic surfactant, was added in a molar ratio of 1: 0.001 relative to SLS.

Mixed system evaluation sample Example Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 SLS / Non-ion 0.67 / 0.33 0.73 / 0.27 0.8 / 0.2 0.89 / 0.11 0.95 / 0.05 0.995 / 0.005 Stability Transparency Transparency Transparency Transparency Transparency Transparency

Experimental Example 3

Measurement of physical properties of Examples 7 to 12

1) Kraft Point Measurement

The kraft point of the mixed system of SLS and a nonionic compound was measured. The experimental results are shown in Table 10 below.

Kraft point measurement of the mixing system (unit ℃) Example Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 When temperature drops 0 < 0 < 0 < 0 < 0 One When temperature rises - - - - 11-12 13

In Table 10, in Examples 7 to 10 where the mixing ratio of the nonionic additive is 1 / 0.25 or more, the kraft point is lowered to 0 ° C or less. In Examples 11 and 12, the solution turned cloudy at a temperature of 0 to 1 ° C. under the temperature drop condition, and became transparent again at a temperature of 11 to 13 ° C. at the temperature rise condition. In this example, it can be seen that it has a low level of low temperature stability than SLS.

2) Measurement of bubble power (initial bubble and bubble holding force)

Foaming force measurement results for Examples 7 to 12 are shown in Table 11 below.

Bubble force measurement result (unit mL) of mixture system division 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Example 7 183 160 143 125 113 105 Example 8 190 160 153 145 145 138 Example 9 200 190 183 178 175 173 Example 10 200 200 198 195 195 195 Example 11 223 218 213 210 203 198 Example 12 233 228 228 225 225 223

In Table 11, the lower the mixing ratio of the nonionic compound showed a tendency of the initial bubble and bubble retention similar to the SLS. In addition, as the mixing ratio of the nonionic additives was lower, the initial bubble level was increased, and the formed bubbles gradually decreased as time went by. Applicable to laundry detergents.

3) Surface tension measurement

Surface tension measurement results are shown in Table 12 below.

Measurement result of surface tension change of mixing system (room temperature) division density One% 0.1% 0.01% 0.001% Example 7 34.31 31.64 39.67 61.51 Example 8 35.15 31.72 39.08 60.73 Example 9 33.74 32.16 41.13 61.68 Example 10 36.18 32.17 43.40 62.94 Example 11 36.55 31.87 47.51 64.63 Example 12 37.07 33.48 56.61 64.20

In Table 12, Examples 11 and 12 showed almost similar surface tension values as SLS, but the surface tension values tended to decrease as the mixing ratio of the nonionic compound increased. As in the above results, low surface tension and having a constant value even at low concentrations means that cmc is low, and from this result, it is possible to exhibit excellent cleaning power even with a small amount.

4) Measurement of Hard Water Stability Change

The results of measuring the hard water stability of the mixed system are shown in Table 13 below.

Measurement of Hard Water Stability Change division Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 1 time 5.80 5.50 4.35 3.60 3.65 3.10 Episode 2 5.80 5.80 4.35 3.70 3.60 3.15 Average 5.80 5.65 4.35 3.65 3.63 3.13 Hard water concentration (ppm) 548 535 417 352 350 309

As a result, the hard water stability increased about 2 times as the mixing ratio of the nonionic compound increased.

2-1. Cationic compounds in mono-type quaternary ammonium form

Among the cationic compounds which will change the properties of the anionic surfactant in a mixed system with the anionic surfactant, five mono-types including one quaternary ammonium group as a representative cationic group, and a mono-type 2 compounds which added ethylene oxide (EO) as a nonionic hydrophilic group to the hydroxy group of the compound were synthesize | combined by the following method.

2-1-1. Synthesis of Cationic Compounds in Mono-type Quaternary Ammonium Form

Synthesis Example 6

Synthesis of N- (dimethyldodecylamino) ethanol

In a three-necked flask, isopropyl alcohol (IPA; 40 g), dodecyl chloride (153 g; 0.75 mol), 2- (dimethyl amino) ethanol (44.6 g; 0.5 mol) were added, followed by sodium iodide (sodium) as a catalyst. iodide) (2.4 g) was added followed by reflux. The reaction progress was checked by measuring the amine%. After raising the temperature of the reactor to 120 ℃ reaction proceeded 95% in 5 hours. The reaction product was mixed with acetone and then cooled and recrystallized. After recrystallization, the resultant obtained by manure was vacuum dried immediately.

Molecular Weight: 293 g / mol

Yield: 67%, white solid

Solubility: Very hygroscopic. Insoluble in acetone

Mass spectrometry (FAB +, m / e): 551, 258 [M-Cl] ⁺ , 265

¹ H NMR (solvent; D ₂ O, ppm): 0.8620 [3H], 1.2832 [18H], 1.6276 [2H], 3.1601 [6H], 3.3645 [2H], 3.4859 [2H], 4.0124 [2H]

Elemental Analysis: C ₁₆ H ₃₆ ONCl

Theory; C 65.38%, H 12.35%, N 4.77%

Found; C 64.00%, H 12.80%, N 5.60%

Synthesis Example 7

Synthesis of N- (dimethyloctylamino) ethanol

IPA (18.7 g), octyl chloride (66.9 g; 0.45 mol), 2- (dimethyl amino) ethanol (26.74 g; 0.3 mol) were added to a three necked flask, and the reactor was warmed to reflux. The reaction progress was checked by measuring the amine%. After raising the temperature of the reactor to 110 ° C, the reaction proceeded 97% in 6 hours. The reaction product was mixed with acetone, cooled and recrystallized. The recrystallized product was filtered and dried in vacuo immediately.

Molecular Weight: 238 g / mol

Yield: 42%, white solid

Solubility: Very hygroscopic. Insoluble in acetone

Mass spectrometry (FAB +, m / e): 439, 202 [M-Cl], 200

Synthesis Example 8

Synthesis of N- (butyldimethylamino) ethanol

IPA (29 g), 1-chlorobutane (70 g; 0.75 mol), 2- (dimethyl amino) ethanol (44.6 g; 0.5 mol) were added to a three necked flask, and NaI (1.4 g) was added as a catalyst. The reactor was warmed to reflux. The reaction progress was checked by measuring the amine%. The reaction proceeded for 21 hours. The reaction product was mixed with acetone and then cooled and recrystallized. The recrystallized product was filtered and dried in vacuo immediately.

Molecular Weight: 182 g / mol

Yield: 85%, white solid

Solubility: Very hygroscopic. Insoluble in acetone

Mass spectrometry (FAB +, m / e): 327, 146 [M-Cl] ⁺

¹ H NMR (solvent; D ₂ O, ppm): 0.9657 [3H], 1.3837 [2H], 1.7449 [2H], 3.1427 [6H], 3.3831 [2H], 3.4904 [2H], 4.0445 [2H]

Elemental Analysis: C ₈ H ₂₀ ONCl

Theory; C 52.88%, H 11.09%, N 7.71%

Found; C 52.20%, H 11.70%, N 7.30%

Synthesis Example 9

Synthesis of N- (dimethylethylamino) ethanol

Into a three-necked flask, IPA (40 g), iodine-ethane ((117 g; 0.75 mol), 2- (dimethylamino) ethanol (44.6 g; 0.5 mol) were added, followed by NaI (2 g) as a catalyst. The reaction product was poured into n-hexane, cooled and recrystallized, and the resultant was filtered and dried in vacuo immediately.

Molecular Weight: 245 g / mol

Yield: 110 g (90%) yellow solid

Solubility: Very hygroscopic. Recording in acetone. Insoluble in n-hexane.

Mass spectrometry (FAB +, m / e): 363, 118 [MI] ⁺

¹ H NMR (solvent; D ₂ O, ppm): 1.3763 [3H], 3.1266 [6H], 3.4672 [2H + 2H], 4.0457 [2H]

Elemental Analysis: C ₆ H ₁₆ ONI

Theory; C 29.4%, H 6.6%, N 5.7%

Found; C 28.8%, H 6.9%, N 5.2%

Synthesis Example 10

Synthesis of N- (trimethylamino) ethanol

IPA (37 g), iodine-methane (142 g; 1.0 mol), 2- (dimethyl amino) ethanol (44.6 g; 0.5 mol) were added to a three neck flask, and the reaction was completed at the same time. At this time, the reaction was completed while adding an reactant and an exothermic reaction occurred. The reaction product was poured into acetone, cooled and recrystallized. The recrystallized product was filtered and dried in vacuo immediately.

Molecular Weight: 231 g / mol

Yield: 76%; White solid

Solubility: Very hygroscopic. Insoluble in acetone

Mass spectrometry (FAB +, m / e): 335, 154, 104 [MI] ⁺

¹ H NMR (solvent; D ₂ O, ppm): 3.1876 [9H], 3.5024 [2H], 4.0540 [2H]

Elemental Analysis: C ₅ H ₁₄ ONI

Theory; C 25.99%, H 6.11%, N 6.11%

Found; C 26.19%, H 6.27%, N 5.64%

2-1-2. Synthesis of Compounds Containing Nonionic Groups (EO) to Mono-type Cationic Compounds

Synthesis Example 11

N- (dimethyldodecylamino) ethanol (EO) ₂ Synthesis of

Into a three-necked flask, add IPA, dodecyl chloride (91.8 g; 0.45 mol), 2- (dimethyl amino) ethanol (EO) 2 (79 g; 0.3 mol), add NaI (1.7 g) as a catalyst, and After raising the temperature to 110 ℃ 97% reaction proceeded in 7 hours. The resulting product was separated and purified using column chromatography using silica gel as a filler.

Molecular Weight: 382 g / mol

Yield: 26%; Transparent oil

Solubility: Very hygroscopic. Recording in acetone

Mass spectrometry (FAB +, m / e): 478 [EO = 5], 434 [EO = 4], 390 [EO = 3], 346 [EO = 2], 302 [EO = 1], 258 [EO = 0 ]

Synthesis Example 12

Synthesis of N- (dimethyldodecylamino) ethanol (EO) 4

Into a three-necked flask, add IPA (47.6 g), dodecyl chloride (92 g; 0.45 mol), 2- (dimethyl amino) ethanol (EO) 4 (143.7 g; 0.3 mol) and add NaI (2.4 g) as catalyst. After raising the temperature to 110 ℃ and proceeded for 12 hours. The reaction product was separated and purified by column chromatography using silica gel as a filler.

Molecular Weight: 507 g / mol

Yield: 21%; Light brown oil

Solubility: Very hygroscopic. Recording in acetone

Mass spectrometry (FAB +, m / e): 610 [EO = 8], 566 [EO = 7], 522 [EO = 6], 478 [EO = 5], 434 [EO = 4], 390 [EO = 3 ], 346 [EO = 2], 302 [EO = 1]

2-2. Mixing the cationic compound of the mono-type quaternary ammonium form (Synthesis Examples 6 to 10) and the cationic compound (Synthesis Examples 11 and 12) which combined the nonionic group to the mono-type (Synthesis Examples 11 and 12) Property change of SLS in the system

[Examples 13 to 18]

Sodium lauryl sulfate (SLS; Sigma reagent; molecular weight 288g / mol), the cationic compounds prepared in Synthesis Examples 6 to 12, and alkanolamide, respectively, in a molar ratio of 1: 1: 0.001 Mixed. The concentration of the mixed system was adjusted to 2% aqueous solution, and the mixing ratio of the SLS and the cationic compound was adjusted to be 1: 1 in molar ratio so as to show the change in physical properties (Table 14).

Sample conditions for measuring kraft points and bubble forces division Addition amount (g) to 100 ml of water, (SLS: molar ratio of cation compound = 1: 1) SLS Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Example 13 0.98 1.02 - - - - - - Example 14 1.10 - 0.90 - - - - - Example 15 1.22 - - 0.78 - - - - Example 16 1.07 - - - 0.93 - - - Example 17 1.10 - - - - 0.90 - - Example 18 0.86 - - - - - 1.14 - Example 19 0.76 - - - - - - 1.24

Experimental Example 4

In order to measure the change in physical properties in the mixing system of Examples 13 to 19, items such as kraft point, initial bubble, bubble retention, hard water stability, cmc, and surface tension were measured.

1) Kraft Point Measurement

Kraft point experiments measured the temperature at which the turbidity was started while lowering the temperature of the transparent mixed solution and the temperature at which the turbidity solution became transparent while increasing the temperature again. The cloudiness starts at low temperatures and becomes clear at low temperatures, indicating that the solution remains stable in aqueous solution. At this time, the samples of Examples 13, 14, 18, and 19, which showed turbidity when mixed, did not perform this experiment, and experiments were performed on Examples 15 to 17. The results of the experiment are shown in Table 15 below.

Measurement result of kraft point change in mixing system division Temperature drop (℃) Temperature rise (℃) Example 15 <0 - Example 16 <0 - Example 17 <0 -

In Table 15, in Examples 15 to 17, compared to SLS alone, the performance of the kraft point (krafft point) below 0 ° C. was improved. This shows that most of the aqueous phase can maintain a stable solution state without precipitation of surfactant even at low temperature in the liquid detergent.

2) Measurement of initial bubble and bubble holding force of mixed system

Samples used for initial bubble and bubble stability measurement were prepared under the same conditions as those used for measuring kraft points (Table 14). However, the samples of Examples 13, 14, 18, and 19, which showed turbidity when mixed, did not perform this experiment, and only Examples 15 to 17 were used. This experiment was measured by semi-micro TK method, and the average value was taken after 3 measurements. Foaming force measurement results are shown in Table 16 below.

Initial bubble level and bubble holding force measurement result (unit; mL) division 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Example 15 115 38 10 10 10 10 Example 16 140 65 35 10 10 10 Example 17 155 95 60 50 40 40

As shown in Table 16, initial bubble levels of Examples 15 to 17 showed almost the same level of results compared to SLS alone. However, in the bubble stability measurement experiment, the mixing system of Examples 15 to 17 showed a result that bubbles were turned off in 2 minutes. And as the alkyl group of the cationic compound is longer, the bubble retention was lowered.

From the above results, it can be seen that the mixed system of Examples 15 to 17 of the present invention maintains the initial bubble level of the anionic surfactant, while the generated bubbles can be removed in a short time. It turns out that it has very excellent performance as this bubble retention inhibitor.

3) Hard water stability assessment

11.69 g of CaCl ₂ ㆍ 2H ₂ O was dissolved in 1 L of water to prepare 10,000 ppm of hard water, and then slowly added to a 0.5% aqueous solution sample to add hard water stability (ml) to the point where turbidity was added. Evaluated. The results of the above experiments are shown in Table 17 below. In this case, the evaluation was not performed in Examples 13, 14, 18, and 19, which showed turbidity when mixed.

Hard water stability evaluation result Sample (0.5% aqueous solution) 10,000 ppm hard water addition amount (ml) Hard water concentration (ppm) Example 15 6.6 619 Example 16 2.8 272 Example 17 3.0 291

In Table 17, only the sample mixed with Example 15 showed about 2 times improvement in hard water stability compared to SLS alone, and Examples 16 and 17 showed hard water stability almost similar to that of SLS.

4) Measurement of surface tension and cmc change in the mixing system

Surface tension and cmc change in the mixing system of Examples 13 to 19 were measured using a processor tensiometer K12 manufactured by Kruss. The sample to measure the surface tension was prepared by mixing SLS and cationic compound in a molar ratio of 1: 1. The water used was ultrapure water. It was used after drying in an oven. The results of measuring surface tension and cmc change are shown in Table 18 below.

Surface tension and cmc change measurement result (25 ℃) division cmc (10 ^-3 M) Surface tension (mN / m) Example 13 0.06 25 Example 14 0.84 29 Example 15 3.3 35 Example 16 3.8 38 Example 17 5.8 39 Example 18 0.11 26 Example 19 0.2 36

As can be seen in Table 18, the surface tension of the mixed system in which the SLS and the cationic compound of Examples 13 to 19 was mixed showed a result of decreasing the SLS by 13 to 44%. In particular, in the case of the mixed system of Examples 12, 13, 18 and 19, cmc was diluted from 10 to 100 times. This means that even a small amount can be used to exhibit excellent surfactant.

3-1. Bis-type cationic compound containing two intramolecular cationic groups

3-1-1. Synthesis of Cationic Compounds

As in Schemes 3, 4 and 5, a suitable cationic compound was selected according to the length of the linker and the length of the alkyl group to prepare the desired cationic compound.

Synthesis Example 13

1,6- [2- ( N -Methyl amino) ethanol] Synthesis of Hexane

45 g (0.6 mol) of 2- (methyl amino) ethanol, 46.5 g (0.3 mol) of 1,6-dichlorohexane, and 48 g of Na ₂ CO ₃ were mixed with 40 g of IPA, followed by reflux for 25 hours. Thereafter, the resultant was purified through filtration, distillation under reduced pressure, and vacuum drying.

Molecular Weight: 232 g / mol

Phase: Oil Phase

¹ H NMR (CDCl ₃ , δ ppm): 1.07 (4H), 1.28 (4H), 2.20 (6H), 2.37 (4H), 2.47 (4H), 3.41 (4H)

Mass (FAB +): m / e 233 [M + H] ⁺

Synthesis Example 14

1,6- [2- ( N, N -Dimethyl amino) ethanol] hexane synthesis using Scheme 1

20 g of IPA was mixed with 23.2 g (0.1 mol) of 1,6- [2- ( N -methylamino) ethanol] hexane, 42.6 g (0.3 mol) of iodomethane, and 5 g of NaI, followed by 2 hours at room temperature. The reaction proceeded. Thereafter, the resultant was purified through filtration, vacuum distillation, vacuum drying, and acetone recrystallization.

Molecular weight: 262 g / mol

Phase: yellow powder (hygroscopic)

¹ H NMR (D ₂ O, δ ppm): 1.20 (4H), 1.83 (4H), 3.16 (12H), 3.38-3.55 (8H), 4.06 (4H)

Mass (FAB +): m / e 389 [M2 ++ I -] +, 297, 261, 247, 217

Synthesis Example 15

1,6- [2- ( N, N -Ethylmethyl amino) ethanol] Synthesis of Hexane (Scheme 1)

20 g of IPA was mixed with 15.11 g (0.065 mol) of 1,6- [2- ( N -methylamino) ethanol] hexane, 30.5 g (0.195 mol) of iodineethane and 3 g of NaI, followed by reflux for 9 hours. It was. Thereafter, the resultant was purified through filtration, vacuum distillation, vacuum drying, and acetone recrystallization.

Molecular Weight: 290 g / mol

Phase: yellow powder (hygroscopic)

¹ H MR (D ₂ O, δ ppm): 1.35 (4H), 1.45 (4H), 2.97 (6H), 3.37 (10H), 3.47 (8H), 4.04 (4H)

Mass (FAB +): m / e 417 [M2 ++ I -] +

Synthesis Example 16

1,6- [2- ( N, N -Butylmethyl amino) ethanol] Synthesis of Hexane (Scheme 2)

To 11 g of IPA , 20.5 g (0.156 mol) of 2- ( N, N -butylmethyl amino) ethanol, 12.1 g (0.078 mol) of 1,6-dichlorohexane, 33 g of Na ₂ CO ₃ and 5 g of NaI were mixed. Reflux for 14 hours. Then, the result was purified by filtration, distillation under reduced pressure, vacuum drying.

Molecular Weight: 346 g / mol

Phase: Oil Phase

¹ H NMR (D ₂ O, δ ppm): 1.00 (6H), 1.41 (8H), 1.75 (8H), 3.10 (6H), 3.34-3.51 (12H), 4.04 (4H)

Mass (FAB +): m / e 381 [M ⁺⁺ ₂ Cl ^{-] +}

Synthesis Example 17

1,6- [2- ( N, N -Methyloctyl amino) ethanol] hexane synthesis (using Scheme 2)

6 g of IPA was mixed with 18.76 g (0.1 mol) of 2- ( N, N -methyloctyl amino) ethanol, 7.8 g (0.05 mol) of 1,6-dichlorohexane, 2.2 g of Na ₂ CO ₃ and 2.5 g of NaI, Reflux for 22 hours. Thereafter, the resultant was purified through filtration, distillation under reduced pressure, and vacuum drying.

Molecular Weight: 458 g / mol

Phase: Oil Phase

¹ H NMR (D ₂ O, δ ppm): 0.89 (6H), 1.31 (24H), 1.77 (8H), 3.10 (6H), 3.36 (8H), 4.49 (4H), 4.04 (4H)

Mass (FAB +): m / e 493 [M2 ++ Cl -] +

Synthesis Example 18

1,6- [2- ( N, N Dodecylmethyl amino) ethanol] synthesis of hexane (Scheme 2)

To 10 g of IPA , 18.69 g (0.077 mol) of 2- ( N, N -dodecylmethyl amino) ethanol, 6 g (.0.39 mol) of 1,6-dichlorohexane and 3 g of NaI were mixed and refluxed for 20 hours. . Thereafter, the reaction product was purified through filtration, distillation under reduced pressure, and vacuum drying.

Molecular Weight: 570 g / mol

Phase: Oil Phase

¹ H NMR (D ₂ O, δ ppm): 0.94 (6H), 1.20 (40H), 1.82 (8H), 3.20 (6H), 3.59 (8H), 3.69 (4H), 4.09 (4H)

Mass (FAB +): m / e 605 [M2 ++ Cl -] +

Experimental Example 6

3-2. Evaluation of Changes in Anionic Surfactant Performance in a Mixture of Anionic Surfactants and Cationic Compounds

Sodium lauryl sulfate (hereinafter referred to as 'SLS'; Aldrich's reagent; purity above 99%) was used as the anionic surfactant used for the physical property evaluation.

In addition, as the cationic compound, n having a value of 6 in the cationic compound of Formula 1a was used (Table 19).

[Formula 1a]

In Formula 1a, R is an alkyl group of C ₁ to C ₁₂ , R ₅ is hydrogen, n is 6.

Cationic Compound Type and Molecular Weight (n = 6) division Synthesis Example 14 Synthesis Example 16 Synthesis Example 18 Compound (R / X) C ₁ / I C ₄ / Cl C ₁₂ / Cl Molecular Weight (g / mol) 516 374 598

Choja used in the following experiment was immersed in a wash solution (KOH + IPA + water) for 4 hours or more, washed with distilled water and acetone, and then dried. Ultrapure water was used for the evaluation.

Changes in physical properties of the anionic surfactant were carried out for the kraft point, initial bubble, bubble stability, hard water stability, and surface tension.

3-2-1. Measurement of physical properties of cationic compounds

1) Evaluation sample condition

1 g of cationic compounds of Synthesis Examples 14, 16, and 18 were dissolved in 99 g of water, and samples having a concentration of 1% by weight were used for evaluation. In this case, the sample having a C1, C2, C4 of the alkyl group is transparent, but the sample having an alkyl group of C8, C12 showed a cloudy appearance. The solution became clear at 0.1 wt% for C8 and 0.01 wt% for C12.

2) Kraft Point Measurement of Cationic Compounds

The temperature at which the solution became cloudy was measured while cooling the clear cationic compound solution (conditions during temperature drop). Moreover, the temperature which became transparent again by measuring the temperature of the turbid solution was measured (condition at the time of temperature increase).

At this time, SLS showed a turbidity phenomenon at 2 to 3 ° C. when the temperature was lowered and became transparent again at 14 ° C. at the temperature rise. On the contrary, the cationic compounds of the present invention did not appear cloudy even at 0 ° C when the temperature was lowered. Thus, when the cloudy phenomenon did not occur at 0 degreeC, the experiment at the time of temperature rise was not performed.

3) Measurement of bubble power (initial bubble and bubble holding force)

Bubble-related experiments were measured using the semi-micro TK method and the results are shown in Table 20 below. The experiment was repeated three times and then averaged. A 1% solution was used for the experiment, and in the case of Synthesis Example 18, a cloudy solution was used for the evaluation.

Result of bubble measurement measurement of cationic compound (unit ml) Classification (ml) 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Synthesis Example 14 No bubbles are generated Synthesis Example 16 No bubbles are generated Synthesis Example 18 213 203 190 128 120 105

As shown in Table 20, bubbles were not generated in Synthesis Examples 14 and 16, which are cationic compounds having alkyl groups, but in Synthesis Example 18, initial bubbles were also generated at 213 ml and 105 ml after 5 minutes. Showed results.

4) Surface tension measurement

Surface tension of the cationic compounds of Synthesis Examples 14, 16, and 18 was measured using a teniometer k12 manufactured by Kruss. The Ring method was used and the average value was taken after 5 measurements. The concentration of each cationic compound sample was used in the experiment by preparing a solution of 1%, 0.1%, 0.01%, 0.001% by weight ratio. Surface tension results are shown in Table 21 below.

Surface tension measurement result of cationic compound (unit: mN / m) division density One% 0.1% 0.01% 0.001% Synthesis Example 14 59.49 70.04 71.41 - Synthesis Example 16 37.45 51.95 61.98 - Partnership 18 30.30 30.70 30.85 47.44

As shown in Table 21, Synthesis Example 18 showed a relatively low surface tension result in the range of the sample concentration to be tested, while other cationic compounds showed a high surface tension value.

Measurement of physical property change of SLS between 3-2-2 anionic surfactant (SLS) and cationic compound of Synthesis Example 14 (R = C1 / n = 6)

[Examples 20 to 25]

Anionic surfactant (SLS) and the cationic compound of Synthesis Example 14 were prepared in a molar ratio as shown in Table 22 below, and the prepared sample solutions were all transparent. At this time, alkanolamide, which is a nonionic surfactant, was added in a molar ratio of 1: 0.001 with respect to SLS.

Mixed system evaluation sample division Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Mixed amount / ratio 2 / 1.0 2 / 0.75 2 / 0.5 2 / 0.25 2 / 0.1 2 / 0.01 SLS / C1 (g) 0.53 / 0.47 0.60 / 0.40 0.69 / 0.31 0.82 / 0.18 0.92 / 0.08 0.991 / 0.009 Stability Transparency Transparency Transparency Transparency Transparency Transparency

Experimental Example 7

1) Kraft Point Measurement

Kraft points of Examples 20 to 25 (mixed system of SLS and cationic compound) were measured, and the results are shown in Table 23 below.

Kraft point measurement of the mixing system (unit ℃) division Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 When temperature drops <0 <0 <0 <0 <0 -0.5 When temperature rises - - - - - 13

As a result of the measurement, as shown in Table 23, the kraft point of all the samples was shown to be lowered below 0 ℃. However, in Example 25 having a mixing ratio of 2 / 0.01, the solution turned cloudy at −0.5 ° C. when the temperature was dropped, and became transparent again at 13 ° C. when the temperature was increased. It can be seen that the solubility (stability) is improved at low temperatures compared to SLS. In the case of other samples that maintained a transparent solution even below 0 ° C, the kraft point measurement could not be performed at the temperature rise.

2) Measurement of bubble power (initial bubble and bubble holding force)

Foaming force measurement results are shown in Table 24 below.

Bubble force measurement result (unit mL) of mixture system division 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Example 20 175 118 80 65 58 53 Example 21 193 160 128 100 85 78 Example 22 223 205 185 180 175 175 Example 23 218 210 210 205 203 195 Example 24 225 223 220 220 220 218 Example 25 238 233 230 230 230 223

In Table 24, the lower the mixing ratio of the cationic compound showed a similar tendency of the initial bubble and the foam retaining force to the SLS. In Example 20 and Example 21, the initial bubble was lowered and the bubble was easily turned off. At other mixing ratios, the initial bubble and bubble holding power slightly decreased as the mixing ratio of the cationic compound increased, but there was no significant difference.

3) Surface tension measurement

Surface tension measurement results are shown in Table 25 below.

Measurement result of surface tension change of mixing system (room temperature) division density One% 0.1% 0.01% Example 20 35.04 36.24 36.45 Example 21 33.12 36.27 36.32 Example 22 36.8 37.08 36.6 Example 23 35.43 37.29 36.11 Example 24 35.47 31.76 45.66 Example 25 35.7 25.86 48.12

In Table 25, Example 25 showed almost the same surface tension value as SLS, but the surface tension value tended to decrease as the mixing ratio of the cationic compound increased. As in the above results, the lower surface tension and no change at low concentrations mean that the cmc is low, which means that even a small amount of the compound can exhibit excellent cleaning power.

4) Measurement of Hard Water Stability Change

The results of measuring the hard water stability of the mixed system are shown in Table 26 below.

Measurement of Hard Water Stability Change division Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 2 / 1.0 2 / 0.75 2 / 0.5 2 / 0.25 2 / 0.1 2 / 0.01 1 time 8.6 5.1 3.2 2.3 2.0 2.4 Episode 2 8.4 5.2 3.4 2.3 1.9 2.4 Average (ml) 8.5 5.15 3.3 2.3 1.95 2.4 Hard water concentration (ppm) 780 490 320 220 190 230

As shown in Table 26, the amount of hard water added increased as the mixing ratio of the cationic compound increased. However, the difference in hard water stability between Example 20 and Example 25 was about 2 times.

3-2-3. Measurement of SLS Property Changes in a Mixture of SLS and Cationic Compounds of Synthesis Example 16 (R = C4 / n = 6)

[Examples 26 to 31]

The mixing conditions of the samples for physical property evaluation are shown in Table 27 below. As a result of mixing system, all samples showed a transparent phase in 1% aqueous solution. At this time, alkanolamide, which is a nonionic surfactant, was added in a molar ratio of 1: 0.001 with respect to SLS.

division Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Molar ratio 2 / 1.0 2 / 0.75 2 / 0.5 2 / 0.25 2 / 0.1 2 / 0.01 SLS / C4 (g) 0.61 / 0.39 0.67 / 0.33 0.75 / 0.25 0.86 / 0.14 0.92 / 0.08 0.994 / 0.006

1) Measurement of Kraft Point Change of Mixing System

Kraft points were measured for Examples 26 to 31, and the results are shown in Table 28 below.

Measurement result of kraft point change of mixing system division Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 When temperature drops <0 <0 <0 <0 -One -0.5 When temperature rises - - - - 10 to 12 11-13

As shown in Table 28, the kraft point was lowered to 0 ° C. or less even when a small amount of the cationic compound was mixed as in Example 31. This means that the mixing system remains stable in water even at low temperatures.

2) Measurement of change of bubble power of mixing system

The measurement results of the bubble force are shown in Table 29 below.

Measurement result of bubble change of mixed system division 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Example 26 180 133 63 58 55 45 Example 27 178 113 73 43 38 35 Example 28 218 213 213 213 213 213 Example 29 223 218 218 215 215 213 Example 30 223 223 223 220 220 218 Example 31 235 230 230 230 225 225

In Table 29, the initial bubble was decreased from the sample having a mixing ratio of 2 / 0.75 or more of the cationic compounds, such as Examples 26 and 27, the bubble was suddenly turned off after 2 minutes. Therefore, the bubble retention lowering ability of the cationic compound having 4 carbon atoms is considered to be superior to that of the cationic compound having a short alkyl group.

3) Measurement of surface tension change of mixing system

The measurement results of the surface tension are shown in Table 30 below.

Measurement result of surface tension change of mixing system division density One% 0.1% 0.01% Example 26 32.75 32.57 31.98 Example 27 32.51 32.48 35.09 Example 28 33.56 32.89 33.37 Example 29 33.65 32.72 32.87 Example 30 34.64 31.70 37.60 Example 31 35.11 26.19 48.02

In Table 30, when the mixing ratio of the cationic compound of Example 31 is 2 / 0.01, the surface tension value is almost the same as that of SLS, but when the mixing ratio of Examples 26 to 30 is 2 / 0.1 or more, 1% solution. As the mixing ratio of the cationic compound was increased, the surface tension was decreased. And it can be seen that it has a lower cmc than SLS from the results showing a constant surface tension value up to 0.01%. This is the result showing the possibility of having excellent cleaning power even at low concentrations.

4) Measurement of Hard Water Stability Change

The measurement results of hard water stability are shown in Table 31 below.

Measurement of Hard Water Stability Change division Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 1 time 55 38 8.45 3.60 2.95 3.40 Episode 2 58 38.7 8.75 3.75 2.90 3.50 Average 56.5 38.35 8.60 3.68 2.93 3.45 Hard water concentration 3610 2772 792 355 285 352

As shown in Table 31, when the mixing ratio of the cationic compounds of Examples 29 to 31 is 2 / 0.25 or less, the hard water stability was not improved much compared to SLS, but the mixing ratio of 2 / 0.5 or more of Examples 26 to 28 was significantly improved. The results were shown. Based on the experimental results, it is considered that it can be applied to products that can maintain excellent cleaning power and phase stability under the conditions of using hard water.

3-2-4. Measurement of SLS Property Changes in a Mixture of SLS and Cationic Compounds of Synthesis Example 18 (R = C12 / n = 6)

[Examples 32 to 37]

Evaluation samples were prepared under the conditions shown in Table 32 below. Turbidity was observed at a mixing ratio of 2 / 0.5 or more of Examples 32 to 34. Example 34 The sample became clear in 0.01% aqueous solution and the remaining sample became clear at 0.001% concentration. At this time, alkanolamide, which is a nonionic surfactant, was added in a molar ratio of 1: 0.001 with respect to SLS.

division Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 SLS / Reaction Example 18 0.47 / 0.53 0.55 / 0.45 0.64 / 0.36 0.78 / 0.22 0.90 / 0.10 0.989 / 0.011 Stability White cloud White cloud White cloud Transparency Transparency Transparency 0.001% 0.001% 0.01% Transparency Transparency Transparency

1) Measurement of Kraft Point Change of Mixing System

The change of the kraft point of the mixing system was measured for Examples 25 to 30, and the measurement results are shown in Table 33 below. At this time, Examples 25 and 26 used a 0.001% solution, and Example 27 used a 0.01% solution.

Measurement result of kraft point change of mixing system division Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 When temperature drops <0 <0 <0 <0 <0 -One When temperature rises - - - - - 12 to 13

As shown in Table 33, the experimental results showed that the kraft point (Krafft point) is lowered below 0 ℃ as the cationic compounds are mixed in all the samples.

2) Measurement of change of bubble power of mixing system

Foaming force measurement results are shown in Table 34 below.

Measurement result of bubble change of mixed system division Molar ratio 0 min 1 minute 2 minutes 3 minutes 4 minutes 5 minutes Example 25 2 / 1.0 20 0 0 0 0 0 Example 26 2 / 0.75 30 0 0 0 0 0 Example 27 2 / 0.5 193 190 190 190 190 190 Example 28 2 / 0.25 243 240 240 240 240 240 Example 29 2 / 0.1 243 240 238 238 238 238 Example 30 2 / 0.01 218 215 215 215 215 215

As a result of the measurement, the samples of Examples 25 and 26 showed a phenomenon in which bubbles were hardly generated. According to the results of this experiment, in the case of a cationic compound having 12 carbon atoms, it can be expected to play a role as an antifoaming agent.

3) Measurement of surface tension change of mixing system

The measurement results of the surface tension are shown in Table 35 below.

Measurement result of surface tension change of mixing system division density One% 0.1% 0.01% 0.001% Example 25 24.35 25.79 30.80 40.31 Example 26 24.74 26.86 31.90 39.93 Example 27 25.38 26.41 32.20 41.45 Example 28 26.15 27.76 33.36 45.65 Example 29 27.82 29.76 35.02 50.05 Example 30 36.33 31.59 48.09 -

As a result, the surface tension decreases as the mixing ratio of the cationic compound increases at a concentration of 1%, and the surface tension increases slightly as the concentration decreases. However, in the aqueous solution of 1% concentration, the surface tension was lowered as the mixing ratio of the cationic compound was increased.

4) Measurement of Hard Water Stability Change

Hard water stability measurement results are shown in Table 36 below.

Measurement result of change of hard water stability of mixed system division Example 28 Example 29 Example 30 1 time 6.10 3.45 3.35 Episode 2 6.10 3.45 3.50 Average 6.10 3.45 3.43 Hard water concentration 575 333 332

As shown in Table 36, the hard water stability of the mixed system was not evaluated because the 1% aqueous solution showed a turbidity at 2 / 0.5 or more cationic compound mixing ratio as in Examples 25 to 27, and in Examples 28 to 30, The stability was slightly improved.

As described above, the mixed surfactant system according to the present invention includes the compound of Formula 1 having a structure including at least one nonionic group or a cationic group to increase the cleaning power of the anionic surfactant and to increase initial bubble and bubbles. It can control holding power, increase hard water stability and lower surface tension and cmc, so it can be applied to solid, liquid, gel, paste detergent such as laundry detergent, shampoo, rinse, dish detergent, hair dye, fabric softener, soap, etc. Effective in

Claims (16)

In a surfactant system, a) anionic surfactants; And b) a compound represented by formula (1) Surfactant systems comprising: [Formula 1] In the formula of Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are each independently or simultaneously a hydroxide having 1 to 20 carbon atoms, saturated or unsaturated chain group, benzyl group, hydroxyethyl group, ethylene oxide group or propylene oxide group added. Hydroxyethyl group; R ₅ is an alkyl group having 1 to 20 carbon atoms, an ethylene oxide group or propylene oxide group, an alkyl group having at least one hydroxyl group bonded thereto, an alkyl group having at least one hydroxyl group bonded thereto, or at least one alkyl group or ether group containing at least one double bond; It is an alkyl group contained above; A ₁ and A ₂ each independently or simultaneously represent a hydroxy ethyl group or an oxygen anion having 1 to 20 carbon atoms, a saturated or unsaturated chain group, a benzyl group, a hydroxy ethyl group, an ethylene oxide group or a propylene oxide group. O ^-), and; n is an integer from 0 to 20; X is a halogen group element, a sulfate group, a methyl sulfate group, or an acetate group. The surfactant system according to claim 1, wherein the mixing ratio of the a) anionic surfactant and b) the compound of the formula (1) is 1: 0.0001 to 1: 1.0 in molar ratio. In a surfactant system, a) anionic surfactants; b) a compound represented by Formula 1; And c) nonionic surfactants, cationic surfactants, or mixtures thereof Surfactant systems comprising: [Formula 1] In the formula of Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are each independently or simultaneously a hydroxide having 1 to 20 carbon atoms, saturated or unsaturated chain group, benzyl group, hydroxyethyl group, ethylene oxide group or propylene oxide group added. Hydroxyethyl group; R ₅ is an alkyl group having 1 to 20 carbon atoms, an ethylene oxide group or propylene oxide group, an alkyl group having at least one hydroxyl group bonded thereto, an alkyl group having at least one hydroxyl group bonded thereto, or at least one alkyl group or ether group containing at least one double bond; It is an alkyl group contained above; A ₁ and A ₂ each independently or simultaneously represent a hydroxy ethyl group or an oxygen anion in which 1 to 20 carbon atoms are saturated or unsaturated chain group, benzyl group, hydroxy ethyl group, ethylene oxide group or propylene oxide group. O ^-), and; n is an integer from 0 to 20; X is a halogen group element, a sulfate group, a methyl sulfate group, or an acetate group. The interface according to claim 3, wherein the mixing ratio of a) the anionic surfactant, b) the compound of Formula 1, and c) the nonionic surfactant is in a molar ratio of 1: 0.0001: 0.0001-1: 1.0: 0.5. Activator system. The interface according to claim 3, wherein the mixing ratio of a) the anionic surfactant, b) the compound of Formula 1, and c) the cationic surfactant is in a molar ratio of 1: 0.0001: 0.0001-1: 1.0: 0.5. Activator system. The method of claim 3, wherein The mixing ratio of the a) anionic surfactant, b) the compound of formula 1, c) nonionic surfactant, and cationic surfactant is 1: 0.0001: 0.0001: 0.0001 to 1: 1.0: 0.5: 0.5 in a molar ratio Surfactant system. According to claim 1 or 3, wherein the compound of formula N, N , N -dimethyl lauryl amine oxide; N, N, N -ethyl methyl lauryl amine oxide; N, N , N -dimethyl dodecyl amine oxide; N, N , N -butyl methyl lauryl amine oxide; N, N , N -dimethyl hexadecyl amine oxide; N, N , N -dibutyl lauryl amine oxide; N, N , N- (2-hydroxyethyl lauryl methyl) amine oxide; N, N , N- (di-2-hydroxyethyl lauryl) amine oxide; N, N , N- (2-hydroxyethyl lauryl butyl) amine oxide; N, N , N- (2-hydroxy (EO) ₅ ethyl lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (PO) ₅ lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (EO) ₅ (PO) ₅ lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (EO) ₁₀ lauryl methyl) amine oxide; N, N , N- (2-hydroxyethyl (EO) ₁₅ lauryl methyl) amine oxide; 1,6- ( N, N -butylmethyl amineoxyl) hexane; 1,6- ( N, N -butylmethyl amineoxyl) dipropyl ether; 1,6- ( N, N -butylmethyl amineoxyl) -3-hydroxyhexane; 1,6- ( N, N -butylmethyl amineoxyl) butane; 1,6- ( N, N -butylmethyl amineoxyl) octane; 1,6- ( N, N -butylmethyl amineoxyl) -2-hydroxypropane; 1,6- [2- ( N -methyl amineoxyl) ethanol] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (EO) ₅ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (PO) ₅ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (EO) ₅ (PO) ₅ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol (EO) ₁₀ ] hexane; 1,6- [2- ( N -methyl amineoxyl) ethanol] dipropyl ether; 1,6- [2- ( N -methyl amineoxyl) ethanol] -2-hydroxypropane; 1,6- [2- ( N -methyl amineoxyl) ethanol] butane; And 1,6- [2- ( N -methyl amineoxyl) ethanol] octane; a surfactant system, characterized in that at least one non-ionic compound selected from the group consisting of: 8. The surfactant system of claim 7, wherein the nonionic compound is prepared by reacting hydrogen peroxide with a tertiary amine. The surfactant system according to claim 7, wherein the nonionic compound is prepared by combining a linker represented by the following formula (2) with a secondary amine to obtain a tertiary amine and then reacting with hydrogen peroxide solution: [Formula 2] In formula 2, n is an integer of 1 to 20; X 'is a halogen group element; R ₅ is hydrogen or an alkyl or allyl group having 1 to 20 carbon atoms including at least one double bond, a hydroxy group, or an ether group. According to claim 1 or 3, wherein the compound of formula Dimethyl octyl ethanol ammonium, dimethyl decyl ethanol ammonium, dimethyl lauryl ethanol ammonium, dimethyl octyl ethanol (EO) ₅ ammonium, dimethyl decyl ethanol (EO) ₅ ammonium, dimethyl lauryl ethanol (EO) ₅ ammonium, dimethyl octyl ethanol (EO) ₁₀ Ammonium, Dimethyl Decyl Ethanol (EO) ₁₀ Ammonium, Dimethyl Lauryl Ethanol (EO) ₁₀ Ammonium, Dimethyl Octyl Ethanol (EO) ₁₅ , Dimethyl Decyl Ethanol (EO) ₁₅ , Dimethyl Lauryl Ethanol Ammonium (EO) ₁₅ , Trimethyl Octyl Ammonium, tridecyl lauryl ammonium, trimethyl lauryl ammonium, 1,6- [2- ( N -dimethyl amino) ethanol] hexane, 1,6- [2- ( N, N -ethylmenyl amino) ethanol] hexane, 1,6- [2- ( N, N -butylmethyl amino) ethanol] hexane, 1,6- [2- ( N, N -methyloctyl amino) ethanol] hexane, 1,6- [2- ( N, N -dodecylmethyl amino) ethanol] hexane, 1,8- [2- ( N -dimethyl amino) ethanol] octane, 1,8- [2- ( N, N -ethylmethyl amino) ethanol] octane, 1, 8-[ 2- ( N, N -butylmethyl amino) ethanol] octane, 1,8- [2- ( N, N -methyloctyl amino) ethanol] octane, 1,8- [2- ( N, N -dodecylmethyl Amino) ethanol] octane, 1,6- [2- ( N -dimethylamino) ethanol (EO) ₂ ] hexane, 1,6- [2- ( N, N -ethylmethyl amino) ethanol (EO) ₂ ] hexane , 1,6- [2- ( N, N- butylmethyl amino) ethanol (EO) ₂ ] hexane, 1,6- [2- ( N, N -methyloctyl amino) ethanol (EO) ₂ ] hexane, 1 , 6- [2- ( N, N -dodecylmethyl amino) ethanol (EO) ₂ ] hexane, 1,6- [2- ( N -dimethylamino) ethanol (EO) ₄ ] hexane, 1,6- [ 2- ( N, N -ethylmethyl amino) ethanol (EO) ₄ ] hexane, 1,6- [2- ( N, N -butylmethyl amino) ethanol (EO) ₄ ] hexane, 1,6- [2- ( N, N -methyloctylamino) ethanol (EO) ₄ ] hexane, 1,6- [2- ( N, N -dodecylmethyl amino) ethanol (EO) ₄ ] hexane, 1,8- [2- ( N -dimethylamino) ethanol (EO) ₂ ] octane, 1,8- [2- ( N, N -ethylmethyl amino) ethanol (EO) ₂ ] octane, 1,8- [2- ( N, N -butyl methylamino) ethanol (EO) _2] octane, 1,8- [2- (N, N - methyl-octanoic Amino) ethanol (EO) _2] octane, 1,8- [2- (N, N - dodecyl-methylamino) ethanol (EO) _2] octane, 1,8- [2- (N - dimethyl amino) ethanol ( EO) ₄ ] Octane, 1,8- [2- ( N, N -ethylmethylamino) ethanol (EO) ₄ ] Octane, 1,8- [2- ( N, N -butylmethyl amino) ethanol (EO) ₄ ] Octane, 1,8- [2- ( N, N -methyloctylamino) ethanol (EO) ₄ ] Octane, 1,8- [2- ( N, N -dodecylmethyl amino) ethanol (EO) ₄ ] Octane, 1,6- [2- ( N -dimethylamino) ethanol (PO) ₂ ] Hexane, 1,6- [2- ( N, N -ethylmethyl amino) ethanol (PO) ₂ ] Hexane, 1, 6- [2- ( N, N -Butylmethyl amino) ethanol (PO) ₂ ] Hexane, 1,6- [2- ( N, N -methyloctyl amino) ethanol (PO) ₂ ] Hexane, 1,6- [2- ( N, N -dodecylmethyl amino) ethanol (PO) ₂ ] Hexane, 1,6- [2- ( N -dimethylamino) ethanol (PO) ₄ ] Hexane, 1,6- [2- ( N, N -ethylmethyl amino) ethanol (PO) ₄ ] hexane, 1,6- [2- ( N, N -butylmethyl amino) ethanol (PO) ₄ ] hexane, 1,6- [2- ( N, N -methyloctyl amino) ethanol (PO) ₄ ] hexane, 1,6- [2- ( N, N -dodecyl Methyl amino) ethanol (PO) ₄ ] hexane, 1,8- [2- ( N -dimethylamino) ethanol (PO) ₂ ] octane, 1,8- [2- ( N, N -ethylmethyl amino) ethanol ( PO) ₂ ] octane, 1,8- [2- ( N, N -butylmethylamino) ethanol (PO) ₂ ] octane, 1,8- [2- ( N, N -methyloctylamino) ethanol (PO) ₂ ] octane, 1,8- [2- ( N, N -dodecylmethyl amino) ethanol (PO) ₂ ] octane, 1,8- [2- ( N -dimethylamino) ethanol (PO) ₄ ] octane, 1,8- [2- ( N, N -ethylmethyl amino) ethanol (PO) ₄ ] octane, 1,8- [2- ( N, N -butylmethyl amino) ethanol (PO) ₄ ] octane, 1, Group consisting of 8- [2- ( N, N -methyloctylamino) ethanol (PO) ₄ ] octane, and 1,8- [2- ( N, N -dodecylmethyl amino) ethanol (PO) ₄ ] octane Surfactant system, characterized in that the cationic compound selected from at least one member. The method of claim 10 wherein the cationic compound is Iii) reacting the secondary amine with a compound represented by the following Chemical Formula 2 under alkaline conditions to prepare a tertiary amine; And ii) a compound comprising a saturated or unsaturated chain group having 1 to 20 carbon atoms, a benzyl group, a hydroxy ethyl group or a hydroxy ethyl group having 1 to 20 ethylene oxide groups or propylene oxide groups added to the tertiary amine. Surfactant system, characterized in that prepared by a method comprising the step of quaternizing: [Formula 2] In formula 2, n is an integer of 1 to 20; X 'is a halogen group element; R ₅ is hydrogen or an alkyl or allyl group having 1 to 20 carbon atoms including at least one double bond, a hydroxy group, or an ether group. The method of claim 10 wherein the cationic compound is (Iii) combining secondary amines with compounds containing from 1 to 20 carbon atoms, saturated or unsaturated chain groups, benzyl groups, hydroxy ethyl groups, or hydroxy ethyl groups added with 1 to 20 ethylene oxide groups or propylene oxide groups; Preparing a tertiary amine; And ii) quaternizing the tertiary amine with the compound of formula (2). The method according to claim 1 or 3, The anionic surfactant is sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), linear alkylbenzenesulfonate (LAS), monoalkyl phosphate (MAP), acyl isethionate (SCI), Surfactant system, characterized in that at least one selected from the group consisting of alkyl glyceryl ether sulfonate (AGES), acyl glutamate, acyl taurate, and fatty acid metal salts . 4. The nonionic surfactant of claim 3, wherein the nonionic surfactant is an alcohol alkoxylate, alkylphenol ethoxylate, alkylpolyglycosides, amine oxide, and alkanolamide. alkanolamide) surfactant system, characterized in that at least one selected from the group consisting of. 4. The method of claim 3, wherein the cationic surfactant is a compound in the form of an amine salt, a compound comprising quaternary ammonium, a monoalkyl dimethyl amine derivative, a dialkyl monomethyl amine derivative, an imidazoline derivative, a quaternary ammonium Surfactant system, characterized in that at least one selected from the group consisting of a compound, and a cationic surfactant in the quaternary ammonium form of the oligomeric type. A solid, liquid, gel, or paste phase detergent composition comprising the surfactant system as claimed in claim 1.