KR20050119490A - Liquid detergent composition in the form of o/w microemulsion containing fabric softening agent - Google Patents

Abstract

The present invention relates to a liquid detergent composition for clothing, and more particularly to a liquid detergent composition in the form of O / W microemulsion having both washing power, fiber softening effect and antistatic effect. These microemulsions have a very low interfacial tension of 10 ⁻¹ to 10 ⁻³ dyn / cm and are thermodynamically stable, which is effective for nonpolar contamination and has excellent fiber flexibility. The microemulsion type liquid detergent composition according to the present invention comprises (a) 0.5 to 30% by weight of cationic surfactant, (b) 0.5 to 40% by weight of nonionic surfactant of HLB 4 to 20, and (c) 0.5 to alcohol as an adjuvant. 30% by weight, and (d) 0.5 to 30% by weight of oil, wherein the weight ratio of the oil and the nonionic surfactant is 0.01 to 1.5.

Description

Liquid detergent composition in the form of O / W microemulsion containing fabric softening agent

The present invention relates to a liquid detergent composition for clothing, and more particularly to a liquid detergent composition in the form of O / W microemulsion having both washing power, fiber softening effect and antistatic effect. These microemulsions have a very low interfacial tension of 10 ⁻¹ to 10 ⁻³ dyn / cm and are thermodynamically stable, which is effective for nonpolar contamination and has excellent fiber flexibility.

In general, as a softening method of the fiber, it is common to use a method of adding a softening agent at the last rinsing during the washing process of the garment, and the use of various compounds, especially cationic quaternary ammonium compounds, are used as the softening agent. It is well known. Cationic quaternary compounds require a separate addition of the fabric softener to the last rinse, since they are incompatible with anionic detergents. In addition, cationic quaternary compounds are relatively ineffective even in the presence of nonionic detergents. When the cationic quaternary ammonium antistatic softener is added together with the detergent, the removal of contaminants by the detergent is reduced, which hinders the detergent's cleanliness and consequently reduces the washing effect. Fabric flexibility of the ammonium compound is significantly reduced.

Accordingly, quaternary softeners have been enhanced with cleaning effects by mixing with or replacing other softeners with various compounds designed to counteract their detrimental cleaning properties. Examples of fabric softening compositions added to such wash cycles are disclosed in US Pat. Nos. 3,351,438, 3,660,286, and 3,703,480. Fabric softening compositions added to the wash cycle contain additional ingredients that make the cationic quaternary ammonium fabric softener and softening compound compatible with conventional laundry detergents. Efforts have been made to counteract this interference in detergent-softener compositions by using nonionic surfactants, higher amounts of brightener compounds, carboxymethylcellulose, yellowing inhibitors, bluing agents, etc. Almost no improvement has been made in the wash cycle flexible composition using various detergents which are anionic compounds.

There have been many technical publications regarding detergent compositions containing cationic softeners and nonionic surfactants, including quaternary ammonium compound softeners. Representative examples of such techniques include US Pat. Nos. 4,239,659, 4,222,905, 3,951,879, 3,351,483, and the like. US Pat. Nos. 3,537,993, 3,983,079 and 4,264,479 also disclose non-ionic surfactants, cationic fabric softeners and other ionic surfactants or modifiers such as zwitterionic and amphoteric surfactants. It is specifically described.

Many of these formulations of the prior art provide satisfactory cleansing and / or flexibility under a variety of different conditions, but have the disadvantage of not providing adequate flexibility compared to the softening agent added to the rinse cycle.

U.S. Patent No. 3,920,565 discloses a rinse cycle containing the cationic fabric softening agent and 2-15% C ₁₆ ~C ₂₂ fatty acid alkali metal salts (soaps), 0.5~4.0%, and optional components in non-ionic emulsifiers and a residual amount up to 2% of water Liquid fabric softeners are disclosed. Although di-higher alkyldimethylammonium chloride is the preferred cationic compound, mention is also made of mono-higher alkyl quaternary compounds. As is generally known in the art, relatively water soluble mono-higher alkyl quaternary ammonium compounds (e.g., stearyltrimethyl ammonium chloride) are less effective softeners than di-higher alkyl cationic quaternary softeners (US Pat. 4,236,965), and therefore it has been proposed to use them with anionic detergents (e.g. fatty acid soaps) which can form flexible composites with them for use as rinse cycle fabric softeners.

U.S. Patent No. 4,239,659 discloses a weight ratio of nonionic surfactant to cationic surfactant in the range of about 1: 1 to 40: 1, and the nonionic surfactant has a hydrophilic-lipophilic balance of about 5 to 17. Nonionic / cationic mixed surfactant detergent compositions in which the cationic surfactant is limited to a mono-higher alkyl quaternary ammonium compound (where the higher alkyl has about 20-30 carbon atoms) is described. have. The patent discloses that other auxiliary ingredients may be included in their usual amounts of use (about 0-40%). An extensive list of auxiliary ingredients is described including semi-polar nonions, anions, zwitterions and amphoteric surfactants, enhancers, dyes, fillers, enzymes, bleaches and the like. Examples using anionic surfactants and no reference thereto are described, but it is stated that auxiliary surfactants must be compatible with nonionic and cationic surfactants and that any of the anionic surfactants described in US Pat. No. 4,259,217 can be used.

As described above, the conventional liquid detergent is composed of an anionic surfactant and a nonionic surfactant, and when the cationic surfactants having a fiber softening effect are simultaneously added to the detergent composition, the anionic surfactant and the cationic surfactant are combined and washed. You will lose both effects and suppleness. Therefore, non-ionic surfactants should be prepared, but there is a problem in compatibility between the non-ionic surfactant and the cationic surfactant. For cationic surfactants containing dialkyl dimethyl ammonium salts, dialkylamidoimidazolinium salts, or quaternary ammonium salts of polyalkylamidoamines as the main component, the water solubility and emulsion dispersibility are poor, so that they may be mixed with nonionic surfactants. Uneasy.

Accordingly, the present invention is to solve the above problems, non-ionic surfactant, water, cationic surfactant stably form the O / W microemulsion form while showing a high washing effect and at the same time excellent fiber flexibility effect It provides a microemulsion type liquid detergent composition.

The present invention were using the first oil and the surfactant (added auxiliary surfactant, if necessary) to form a microemulsion in order to provide a superior liquid detergent composition has a phase stability indicating excellent detergency and fabric softener effect at the same time, in particular 10 ^-1 Due to the very low interfacial tension of ˜10 ⁻³ dyn / cm, microemulsions with excellent cleaning power and thermodynamically stable were prepared. A cationic surfactant was solubilized in this microemulsion to prepare a liquid detergent. This microemulsion has a form in which oil and cationic surfactants are dispersed in a continuous phase of water, and a non-ionic surfactant and anionic surfactant maintain micelle form on the surface of the dispersed phase consisting of oil and cationic surfactants so that a stable phase exists. do.

Phase-dependent phase behavior of a system consisting of three components of nonpolar oils such as nonionic surfactants, water and hydrocarbons is the equilibrium between the lower phase microemulsion and the excess of two phases of excess oil at low temperatures. In two phases there is an equilibrium between an upper phase microemulsion and excess water. In addition, the temperature at which the middle-phase microemulsion contains the same volume of water and oil in the middle region in which the two phases exist is called a phase inversion temperature (hereinafter referred to as 'PIT'). It is known that in PIT conditions, the system is hydrophobic-hydrophilic in balance, so that oils can be most solubilized in mesophase microemulsions due to the presence of very low interfacial tension, typically 10 ^-2 to 10 ^-4 dyn / cm [KH Raney, WJ Benton, and CAMiller, J. Colloid Interface Sci. , 117 , 282 (1987), CAMiller, and KHRaney, Colloid Suf. A. , 74 , 169 (1993)].

On the other hand, nonionic surfactant systems containing polar oils such as fatty acids and fatty alcohols have been found to remove large amounts of polar components by the lamellar liquid crystal phase formed in the intermediate phase [JCLim, and CAMiller, Prog. Colloid Polym. Sci. , 83 , 29 (1990), HSKilman and PHFvan Steen, "Surface Active Agents", Society Chemical Industry , 191 , London (1979).

Mesophase microemulsions that can dissolve and remove large amounts of oil are not present in the initial aqueous surfactant solution, but are mostly produced by interdiffusion between the oil phase and the aqueous surfactant solution phase and are rich in these surfactants. Predicting the formation of layers is an important key to predicting the cleansing results of the system in question. For this purpose, the prediction of the phase equilibrium for the surfactant system is essential.

In this situation, the inventors conducted phase equilibrium experiments on non-ionic surfactants, anionic surfactants, water, oils and cationic surfactants to find the optimum blending ratio, thereby inventing the O / W microemulsion system according to the present invention. It was completed.

The microemulsion type liquid detergent composition of the present invention for achieving the above object,

(a) 0.5 to 30% by weight of cationic surfactant,

(b) 0.5 to 40% by weight of nonionic surfactant of HLB 4 to 20,

(c) 0.5 to 30% by weight of alcohols as adjuvants, and

(d) 0.5 to 30% by weight of oil,

It is characterized in that the weight ratio of the oil and the nonionic surfactant is 0.01 to 1.5.

Examples of the cationic surfactant of component (a) include dialkyl dimethyl ammonium chloride represented by Chemical Formula 1, dialkylimidazolinium salt represented by Chemical Formula 2, and the following Chemical Formula 3. Dialkylamido quaternary ammonium salt, ester quat type and the like, these may be used alone or in combination of two or more. As for content in these compositions, 1-30 weight% is preferable.

Wherein R is an alkyl or alkenyl group of C ₁₄ ~C ₁₈ straight-chain or branched-chain.

In the formula, R is the same as in the general formula (1).

In the above formula, R is the same as in formula (1).

Dialkyldimethylammonium chloride and ester quart type cationic surfactants are preferred in view of the flexibility of the fibers. The content of the cationic surfactant is 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 3 to 10% by weight, based on the composition.

The nonionic surfactants of component (b) are on average HLB 4 to 20 and are used not only for microemulsion of oil components and cationic surfactants, but also for increasing cleanability and improving phase stability of products.

Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene aryl phenol ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene alkyls Amines, sorbitan fatty acid esters, alkylalcoholamines, or arylalcoholamines and the like may be used, preferably polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, alkylalcoholamines, more preferably polyoxyalkyl Lene alkyl ethers are used.

The content of the nonionic surfactant is 0.5 to 40% by weight, preferably 5 to 35% by weight, more preferably 15 to 30% by weight based on the composition.

Alcohols of component (c) are added to increase the phase stability of the microemulsions produced in the four-component systems of oils, cationic surfactants, nonionic surfactants and water, which also helps to maintain the microemulsion over a wide temperature range. To contribute to phase stability.

Alcohols include ethanol, propanol, butanol, hexanol, octanol, decanol, isopropanol, isohexanol, isooctanol, isodecanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol methyl ether, diethylene glycol Methyl ether, triethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monobutyl Ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, or In triethylene glycol monohexyl Le and the like may be used. Preferably, propanol, butanol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene Glycol monohexyl ether and triethylene glycol monohexyl ether are used, More preferably, propanol, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether are used.

The content of alcohol is 0.5 to 30% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight, based on the composition.

Here, the mixing ratio of the alcohol / nonionic surfactant is mixed in a ratio of 0.01 to 1.5, preferably 0.05 to 1.2, more preferably 0.1 to 1.

As the oil component of component (d), both natural and non-natural systems may be used, and D-limonene, L-limonene, D / L-limonene, α-terpineol, β-terpineol, terpentine terpentine, terpenol, pine oil, α-pinene, β-pinene, liquid paraffin, isohexadecane and the like can be used. Of these, natural limonene and liquid paraffin are preferred in consideration of environmental stability and human safety.

The content of these oils is 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 3 to 10% by weight, based on the composition.

The present invention may not only provide a stable phase by increasing the polarity of the microemulsion, but may further add an anionic surfactant as necessary as an element to help the cleaning power.

Water is a component that occupies the continuous phase of the microemulsion, and 50 to 80% by weight, preferably 55 to 75% by weight, more preferably 65 to 75% by weight of the total composition is blended.

In addition to the above components, the composition of the present invention may contain anionic surfactants and other additives within the range where the phase stability of the microemulsion is not a problem, and within the range that does not impair washing power and flexibility or human and environmental safety.

The anionic surfactant may be alkyl ether sulfate, straight chain alkylbenzene sulfonate, alpha-olefin sulfonate, alkane sulfonate, alkyl sulfate, etc., preferably sodium decyl sulfate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium Hexadecyl sulfate, sodium octadecyl sulfate, sodium lauryl sulfate, sodium myristyl sulfate and sodium stearyl sulfate are used, most preferably sodium dodecyl sulfate.

As the additive, preservatives, chelating agents and antifoaming agents for removing the microemulsion liquid detergent and the like can be blended in an appropriate amount. The composition may contain 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 1% by weight, and its content may vary depending on the object, purpose and cleaning method of the object to be cleaned.

The microemulsion liquid detergent composition of the present invention may be prepared by mixing the above components by a conventional method for preparing an emulsion. When the additive is polar, it is preferable to first mix water with the nonionic surfactant, the anionic surfactant, and the alcohol, and then with the remaining component oil. In the case of nonpolarity, it is advisable to mix the additive in the oil and then to mix it with a mixture of the remaining components, nonionic surfactant, anionic surfactant, alcohol and water. When the microemulsion type detergent prepared in this way is used as a liquid laundry detergent, the cleaning power of the nonionic surfactant as the cleaning component, the antistatic property of the cationic surfactant, and the softening power can be simultaneously exhibited.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Examples 1-6, Comparative Examples 1 and 2

To prepare a liquid detergent composition of Examples 1 to 6, Comparative Examples 1 and 2 using a conventional manufacturing process according to the composition shown in Table 4.

Detergency Evaluation

Detergency evaluation was performed using a stirred mixed detergent tester (Tergotometer, United States Testing Co., Inc.) which is mainly used for laboratory use. The cleaning power measurement temperature was operated at a rotational RPM 120 at 25 ℃, the sample amount was used 1g of the sample in 1L of water, washing time was carried out twice for 10 minutes, rinsing 3 minutes each.

As the staining cloth used for the measurement, AS12 and Japanese wet staining cloth were used. Each contaminated cloth was cut into 4 x 4 cm in width and 9 pieces were used for one sample.

For each contaminated cloth before and after washing, the cleaning effect was determined by measuring the whiteness with a colorimeter (Japan testing Co., INC.), Calculating the washing power according to the following formula, and judging it according to the evaluation criteria shown in Table 1. Is shown in Table 4.

Detergency (%) = (C-B) / (A-B) * 100

Where A: whiteness of the white cloth

B: contaminant whiteness before cleaning

C: contaminant whiteness after washing

Cleaning power ◎ very good (more than 75% of washing power) ○: excellent (70-75% of washing power) (Triangle | delta): Medium (65-70% of washing power) X: Poor (less than 65%)

Flexibility evaluation

Commercially available 100% cotton towels were washed and naturally dried with the concentration of the liquid detergent composition prepared according to Examples 1 to 6 and Comparative Examples 1 and 2 at 35 g / 35 L. Then, sensory evaluation was performed on experienced subjects. The softness score for the touch degree was given from the lowest 1 point to the highest 5 points according to Table 2 below, and repeated 3 or more times to measure the softness effect by the average value. The results are shown in Table 4.

Flexibility ◎ very good (3.5 or more) ○: excellent (3.0 to 3.5) △: normal (2.5 to 3.0 X: Poor (2.5 or less)

Phase safety assessment

After storing the liquid detergent composition prepared according to Examples 1 to 6 and Comparative Examples 1 and 2 for 4 weeks at room temperature and high temperature (40 ° C.), the stability of the composition was evaluated according to Table 3 below. The results are shown in Table 4.

Stability Stable: Overall transparent state without sedimentation or clouding Instability: Overall blurring and lack of transparency Phase separation: suspended or precipitated

Ingredient (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Polyoxyethylene (7) Lauryl Ether 25 30 30 29.5 29.5 25 25 25 Sodium Dodecyl Sulfate 0.5 0.5 Dialkyldimethylammonium Chloride 4 4 Esterquat Type Surfactant 7 7 7 5 7 7 Liquid paraffin 5 7 7 5 Isoparaffin 7 7 5 5 water 46 33 33 33 33 47 46.5 46 ethanol 10 15 Propanol 15 21 21 21 21 17 7 additive 2 2 2 2 2 2 2 2 Sum 100 100 100 100 100 100 100 100 Emulsion form μE μE μE μE μE μE E E Alcohol / nonionic surfactants 0.6 0.7 0.7 0.7 0.7 0.68 0.68 0.6 Stability Room temperature stability stability stability stability stability stability Instability detach 40 ℃ stability stability stability stability stability stability Instability Instability evaluation Cleaning power ○ ◎ ◎ ○ ◎ ○ △ X Flexibility ◎ ◎ ◎ ◎ ◎ ◎ ○ △

Note) μE: microemulsion, E: emulsion

As described above, the present invention provides a microemulsion type liquid detergent composition which can have both washing, fiber softening effect, antistatic effect and the like. In particular, O / W microemulsions prepared using nonionic surfactants, anionic surfactants, cationic surfactants, and oils have very low interfacial tensions of 10 ⁻¹ to 10 ⁻³ dyn / cm and are thermodynamically stable to prevent nonpolar contamination. It is effective and has good fiber flexibility.

Claims (5)

(a) 0.5 to 30% by weight of cationic surfactant, (b) 0.5 to 40% by weight of nonionic surfactant of HLB 4 to 20, (c) 0.5 to 30% by weight of alcohols as adjuvants, and (d) 0.5 to 30% by weight of oil, Micro-emulsion liquid detergent composition, characterized in that the weight ratio of the oil and the nonionic surfactant is 0.01 to 1.5. The cationic surfactant according to claim 1, wherein the cationic surfactant is a dialkyldimethylammonium chloride represented by Formula 1, a dialkylimidazolinium salt represented by Formula 2, a dialkylamido quaternary ammonium salt represented by Formula 3, ester quart type Microemulsion type liquid detergent composition characterized in that the mixture of one or two or more selected from the group consisting of. <Formula 1> (Wherein R is a straight or branched chain alkyl or alkenyl group having from C ₁₄ to C ₁₈ ) <Formula 2> (Wherein R is the same as formula 1) <Formula 3> (Wherein R is the same as formula 1) The nonionic surfactant according to claim 1, wherein the nonionic surfactant is selected from polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenol ether, polyoxyalkylene aryl phenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, A microemulsion type liquid detergent composition, characterized in that at least one selected from the group consisting of polyoxyalkylene alkyl amine, sorbitan fatty acid ester, alkyl alcohol amine, and aryl alcohol amine. The alcohol according to claim 1, wherein the alcohols are ethanol, propanol, butanol, hexanol, octanol, decanol, isopropanol, isohexanol, isooctanol, isodecanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol Methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, ethylene glycol monohexyl ether, diethylene Glycol monohexyl ether, and triethylene glycol From the group consisting of mono-hexyl ether type micro-emulsion, it characterized in that the selected one or more liquid detergent compositions. The oil of claim 1, wherein the oil is D-limonene, L-limonene, D / L-limonene, α-terpineol, β-terpineol, terpentin, terpenol, pine oil, α-pinene, β-pinene Microfluidic liquid detergent composition, characterized in that at least one selected from the group consisting of, liquid paraffin, and isohexadecane.