KR20070102867A - Solid/liquid phase transfer type laundry detergent - Google Patents

Abstract

A solid/liquid phase change type laundry detergent is provided to obtain a detergent that is easy to use, leaves no residue after washing, allows stable application of various functional materials, and maintains its cleaning/softening properties for a long time. A solid/liquid phase change type laundry detergent is obtained by melting a surfactant that is present in a solid phase at room temperature and in a liquid phase at 50 deg.C or higher, mixing the molten surfactant with a detergent; and cooling and formulating the mixture. The surfactant is at least one nonionic surfactant selected from the group consisting of aliphatic alcohol derivative, fatty acid derivatives and nonylphenol ethoxylate.

Description

Solid / liquid phase transfer type laundry detergent

The present invention relates to a new laundry detergent utilizing the solid / liquid phase transition phenomenon.

More than 100 years ago, many people began to use powdered laundry detergents. In the early 1900s, powdered laundry detergents using fatty acids, the main ingredients of soap, as the main ingredients of surfactants, and soda ash as alkaline ingredients, grew rapidly in Europe. These powdered laundry detergents have been steadily developed and are currently being developed and sold as products with various performances, and are the most widely used laundry detergents in Korea. Powder laundry detergents have a great advantage in the form of a product that can stably maintain various functional materials such as enzymes, functional polymers, and bleaching ingredients used in laundry washing. However, the powder-type laundry detergent has a difference in the quality difference felt by users according to the flow of the powder and the size of the powder particles after manufacturing the detergent, and when it is put into the washing machine, the powder is blown and the fine powder powder remains on the clothes after washing. have.

Recently, tablet type laundry detergents have been developed. Tablet laundry detergent is a product that prevents dusting and improves usability by agglomerating powder laundry detergent in a lump.

In contrast, liquid detergents have been growing in the detergent market in the US and Europe recently, and the US market share is more than 50%. The reason for this growth is considered to be that the liquid laundry detergent is highly soluble in the wash water and there is no residue after washing. However, liquid detergents are very difficult to ensure the stability of many other laundry ingredients (functional materials) that can be included to improve the washing effect due to the nature of the solvent, such as water (H ₂ O) contained in the liquid detergents, and thus various It is disadvantageous to provide a laundry detergent with improved washing effect as well as performance.

Meanwhile, efforts have been made to develop laundry detergents that can give flexibility to clothing at the same time as washing. Surfactants added to impart a softening effect to the laundry detergent are usually cationic surfactants in the form of quaternary ammonium salts, and organosilicon compounds such as amino modified silicones are also used. In general, cationic surfactants and anionic surfactants cannot be added to a laundry detergent at the same time. This is because cationic surfactants and anionic surfactants are difficult to dissolve in water because they are changed into a form of a large hydrophobic molecule by saponification by ionic bonds, and thus, detergency is lowered. In addition, in order to give a softening effect on clothes, cations or organosilicon compounds must be present in the wash water, so that they must be adsorbed on the clothes during washing and rinsing processes.

Therefore, the technical problem to be achieved by the present invention is to provide a laundry detergent that overcomes the disadvantages of each laundry detergent while maintaining the advantages of the conventional powder, tablet and liquid laundry detergent. More specifically, it has a certain form as a tablet laundry detergent, so it is very convenient to use. There is no residue after washing like a liquid laundry detergent, and there is no solvent such as powder laundry detergent, so there are no enzymes, polymers, and bleaching ingredients. It is to provide a phase-transfer type laundry detergent that can stably use a variety of functional materials, such as.

Another technical problem to be achieved by the present invention is to provide a phase-transfer type laundry detergent having a fiber softening effect that does not reduce the cleaning power and the softness, which is convenient to use because it contains a fiber softening component so that a softener does not need to be used separately. will be.

In order to achieve the above technical problem, the present invention melts the surfactant in the solid phase at room temperature (liquid phase) and liquid phase (liquid phase) at 50 ℃ or more, and then mixed with the laundry ingredients, the mixture is cooled to form a It provides a phase-transfer-type laundry detergent, characterized in that the formulation.

More preferably, the present invention provides a phase change type laundry detergent characterized in that the surfactant is at least one nonionic surfactant selected from the group consisting of fatty alcohol derivatives, fatty acid derivatives and nonylphenolethoxylates.

More preferably, the present invention provides a phase-transfer type laundry detergent, characterized in that the surfactant is an alkyl polyethylene glycol ether having the following formula.

alkyl-O- (CH ₂ CH ₂ O) _n H

More preferably, the alkyl of Formula 1 is any one selected from capryl, lauryl, myristyl, palmityl and stearyl, and n is It provides a phase-transfer type laundry detergent, which is an integer of 7 to 36.

More preferably, the present invention provides a phase change type laundry detergent, characterized in that it further comprises a fiber softening component in the phase change type laundry detergent.

More preferably, the present invention provides a phase-transfer type laundry detergent characterized in that the fibrous flexible component is a cationic surfactant or amino modified silicone in the form of a quaternary ammonium salt.

More preferably, the present invention provides a phase change type laundry detergent comprising a hole in the phase change type laundry detergent or containing a foamable material composed of an acid component and a base component.

More preferably, the present invention is any one or more laundry components selected from the group consisting of an enzyme, a fluorescent brightener, a cationic surfactant, an anionic surfactant, a peroxide, and a peroxide activator, wherein the phase-transfer type laundry detergent is aimed at improving the performance of the laundry detergent. It provides a phase-transfer type laundry detergent characterized in that it further comprises.

The invention also

(S1) melting the surfactant in a solid phase at room temperature and in a liquid phase at 50 ° C. or higher;

(S2) mixing the molten surfactant with a predetermined laundry component;

It provides a phase-transfer type laundry detergent manufacturing method comprising the; (S3) to cool the mixture of step (S2) to prepare a laundry detergent of the tablet type (tablet type).

More preferably, the present invention provides a phase-transfer type laundry detergent manufacturing method comprising the step of forming a hole in the tablet to generate a bubble during the manufacturing of the step (S3).

Hereinafter, the phase-transfer type laundry detergent of the present invention will be described in more detail.

The present invention is a solid state at room temperature but a liquid state at a high temperature, and when used in the water as a main component of the surfactant that can be liquefied in tablet form can be arbitrarily controlled in the form of laundry detergent, it is necessary to use a solvent such as water It is based on the surprising discovery that it is possible to ensure the stability of various laundry ingredients (eg, functional materials) and to produce laundry detergents with no residue after washing.

The phase-transfer type laundry detergent of the present invention is a solid state at room temperature but a liquid state at high temperature, and contains a surfactant as a main component which can be liquefied in water. More preferably, the surfactant is at least one nonionic surfactant selected from the group consisting of fatty alcohol derivatives, fatty acid derivatives and nonylphenolethoxylates, and more preferably, the surfactant is an alkyl polyethylene represented by the following Chemical Formula 1 Glycol ethers.

<Formula 1>

alkyl-O- (CH ₂ CH ₂ O) _n H

In addition, the surfactant of Formula 1 may vary the formulation and solubility in the wash water, such as melting temperature, depending on the type of alkyl and the number of n. Considering the ease of manufacture of the laundry detergent and solubility in the wash water alkyl in the formula (1) is Capryl (Capryl), lauryl (Myryl), Myristyl (palmityl), stearyl (stearyl) It is most preferably any one selected, n means the degree of polymerization of ethylene oxide, an integer of 7 to 20 is most preferred in terms of formulation and solubility.

The phase change laundry detergent of the present invention may be prepared, for example, as follows. The surfactant is liquefied at a high temperature to mix laundry ingredients (functional powder material or liquid material) such as enzymes, bleaches, bleach activators, alkali agents, fluorescent dyes, and the mixture is poured into a mold having a certain shape and gradually cooled. The phase change type laundry detergent of the present invention is completed.

One of the important points to achieve the purpose of the phase-change laundry detergent of the present invention is to ensure solubility in the wash water. Thus, more preferably, the present invention provides a phase change laundry detergent comprising a hole in the formulation to increase the contact area with the wash water. The laundry detergent having a large number of holes has a merit in that solubility is higher than that of the laundry detergent having no holes or fewer, so that the laundry detergent remains less in the garment after washing. Most preferred is a honeycomb-type laundry detergent in which these pores are distributed throughout the detergent formulation. Laundry detergents containing such pores can be made using a preformed mold to form the pores. In addition, it is possible to prepare a laundry detergent formulation having many holes by forcibly generating bubbles in the laundry detergent formulation while the surfactant is cooled using nitrogen gas or a bubble generator.

The present invention also provides a phase-transfer type laundry detergent containing an acid component and an alkaline component together with components having the property of foaming when dissolved in the wash water. Such foaming material can quickly dissolve the laundry detergent in the wash water, thereby greatly improving the clothing residual phenomenon after washing. Citric acid and the like may be used as the acid component, and sodium hydroxide (NaHCO ₃ ), soda ash (Na ₂ CO ₃ ), etc. may be used as the alkali component, and these components may have foaming characteristics through neutralization reaction when dissolved in washing water. And partially exothermic, which is thought to also play a role in promoting dissolution of the surfactant.

The present invention also provides a phase-transfer type laundry detergent capable of including a fiber softening component having a softening effect therein by not using an anionic surfactant. More preferably, cationic surfactants or amino modified silicone components in the form of quaternary ammonium salts may be used as the fiber flexible component.

For example, a phase-transfer type laundry detergent containing a fiber flexible component therein may be prepared as follows. First, the core portion is made of cationic quaternary ammonium salt or amino modified silicone which is commonly used as a fabric softener therein. Subsequently, the surfactant of the present invention, which is solid at room temperature but liquid at high temperature, is liquefied at high temperature to mix laundry ingredients (functional powder material or liquid material) such as enzymes, bleaches, bleach activators, alkali agents, fluorescent dyes, and the like. do. Put the core made of the fiber softening component in the center of the prepared standardized mold, wrap the core portion by pouring the mixture of the surfactant and the laundry ingredients, and then gradually cool to complete the phase change type laundry detergent with the fiber softening effect. .

The present invention may include laundry ingredients of various functional powders or liquid materials for the purpose of improving the performance of the laundry detergent in addition to the surfactant and the fiber softener of the present invention described above. Such laundry components may include, but are not limited to, enzymes, optical brighteners, cationic surfactants, anionic surfactants, peroxides, peroxide activators, and the like. However, when the anionic surfactant is added to the phase change type laundry detergent having the fiber softening effect of the present invention, care should be taken not to impair the purpose of the present invention by combining the anionic surfactant and the cationic fiber softening component.

Hereinafter, examples will be described in detail to help understand the present invention. However, the embodiments according to the present invention may be modified in many different forms, and the scope of the present invention should not be construed as being limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Example 1 Evaluation of Formation of Surfactant

The formulation of the surfactant present in the solid state at room temperature and in the liquid state at 50 ° C. or higher was examined. The surfactant used was nonionic alkyl polyethyleneglycol ether, which changed the length of the alkyl chain and the addition amount of ethylene oxide. The mold of the formulation used a metal mold made for ease of desorption. To prepare a phase-transfer type laundry detergent with the ingredients and contents shown in Table 1 below, and evaluated the formulation.

Example 1-1 Example 1-2 Example 1-3 Example 1-4 C12EO07 100 - - - C16EO14 - 100 - - C18EO14 - - 100 - C18EO30 - - - 100

The number after C in Table 1 indicates the length of the alkyl chain, and the number after EO indicates the amount of ethylene oxide added. For example, C18 means that alkyl is stearyl and EO7 indicates that 7 mole of ethylene oxide was added. In all four examples, the phase-transfer type laundry detergent could be easily prepared.

Experimental Example 1 Evaluation of Phase Stability and Solubility

The sample prepared in Example 1 was used to examine phase stability at room temperature and solubility in wash water. The room stability was evaluated to maintain the dosage form after 48 hours at room temperature, the solubility was filled with 5 Kg of laundry in a general washing machine and 40 g of each washing detergent prepared in Example 1 was added to wash water at 20 ℃ It was measured by the amount of residue remaining after washing at.

Example Formulation Retention Amount of residue after washing [g] Example 1-1 Bad - Example 1-2 Great 6.8 Example 1-3 Great 6.5 Example 1-4 Great 9.3

As can be seen from the results in Table 2 above, when the surfactants used in Examples 1-2 and 1-3 consider both the formulation retention after 2 days and the amount of residue after washing, Examples 1-1 and 1- It was preferred over the surfactant used in 4.

<Example 2 and Experimental Example 2> Evaluation of the solubility of the phase change type laundry detergent according to the physical structure

Formulation retention and solubility The surfactant of Example 1-3 (Stearyl polyethylene glycol ether / C18EO20) showing the most preferable results was evaluated the solubility of the phase-transfer type laundry detergent according to the physical structure. After preparing the surfactant into a cube having a predetermined thickness, the solubility according to its shape was examined by changing the number of holes in the cube. Solubility was evaluated in the same manner as in Experiment 1. The results are shown in Table 3.

Example Number of holes Cuboid size [mm] Residual amount after washing [g] horizontal Vertical Height 2-1 0 40 30 10 7.5 2-2 One 40 30 10 7.3 2-3 8 40 30 10 6.1 2-4 16 40 30 10 3.2

As shown in Table 3, it can be seen that the solubility increases as the number of holes increases in the rectangular parallelepiped. This honeycomb form is thought to increase solubility because it greatly increases the contact area with water, which plays an important role in solubility.

Example 3 Comparison of Phase Transfer Type Laundry Detergent and Conventional Powder Type Laundry Detergent

The powder-type laundry detergent most commonly used with the phase-transfer type laundry detergent of the present invention was prepared with the ingredients and contents of Table 4. The unit is weight percent.

Furtherance Example 3 Comparative Example 1 Comparative Example 2 Sodium carbonate 47 35 10 Sodium sulfate - 25 - Straight chain alkylbenzenesulfonate - 5 5 Alpha olefin sulfonate 10 5 5 Zeolite 4A - 20 - Sodium hydroxide - - 5 Polyoxyethylene Stearyl Ether (EO 20 mol) 40 - - Polyoxyethylene Stearyl Ether (EO 7 mol) 2 9 9 Powder Fluorescent Dye ¹⁾ 0.5 0.5 - Powder enzyme ²⁾ 0.5 0.5 - water - - 66 ¹⁾ Tinopal CBS-X (Ciba Specialty Chemical, Switzerland) ²⁾ Savinase 12.0T (Novozymes, Denmark)

In Table 4, Comparative Example 1 is a powder laundry detergent widely used, and Comparative Example 2 is a liquid laundry detergent. In particular, Example 3 is a phase-transfer type laundry detergent having a honeycomb form of a rectangular parallelepiped having 16 holes therein.

<Experimental Example 3-1> Washing force evaluation experiment

The washing powers of Comparative Example 1 and Comparative Examples 1 and 2 were evaluated. To a tergo-o-tometer, water at 20 ° C. and hardness of 133 CaCO ₃ ppm and each laundry detergent are added at a rate of 1 g / L, which is contaminated by wfk 10D and wfk 20D. 8 x 8 cm 2 cotton cloth (2 sheets each) and 5 x 5 cm 2 Japanese Laundering Association (8 sheets) were added. It was washed for 10 minutes, rinsed for 3 minutes, and then dried naturally.

After measuring the whiteness of the contaminated cotton cloth before and after washing using a colorimeter, and substituted the Kubelka Munch equation of Equation 1 to calculate the washing power, the results are shown in Table 5 below.

Bleaching rate (%) = [(1-Rs) ² / 2Rs- (1-Rb) ² / 2Rb] / [(1-Rs) ² / 2Rs- (1-Ro) ² / 2Ro] × 100

In Equation 1, Rs is the surface reflectivity of the contaminated cotton cloth, Rb is the surface reflectivity of the cotton cloth after decontamination, and Ro is the surface reflectivity of the white cotton cloth.

division Example 3 Comparative Example 1 Comparative Example 2 WFK 10D 78% 82% 74% WFK 20D 82% 86% 83% Japan Laundry Science Association 88% 84% 83%

As shown in Table 5, the phase-change laundry detergent formulated according to the present invention showed a somewhat lower cleaning power in WFK 10D and 20D compared to the powder laundry detergent of Comparative Example 1, but for the contaminated cloth prepared by the Japan Laundry Science Association High cleaning power was shown. This can be said to be the result of the stronger cleaning power in the case of dirty stains in the laundry of the household, considering the characteristics of contaminated cloth. In addition, compared with the liquid laundry detergent of Comparative Example 2, it was confirmed that the performance is excellent in all contaminated cloths.

Experimental Example 3-2 Solubility Evaluation Experiment

The solubility of each was evaluated using the laundry detergent of Example 3 and Comparative Examples 1 and 2. 5 g of the standard sample of each laundry detergent was taken in a beaker, and then dissolved by stirring for 10 minutes with 1 liter of 20 ° C washing water. Thereafter, the amount of remaining insoluble components was measured. The results are shown in Table 6.

division Example 4 Comparative Example 1 Comparative Example 2 Amount of insoluble ingredient 0 1.0 g (20%) 0

As shown in Table 6, the conventional powdered laundry detergent can be confirmed that the zeolite remains insoluble in water. On the other hand, the phase-transfer type laundry detergent prepared according to the present invention does not contain zeolite, which is an insoluble ingredient of water, in the same manner as the liquid laundry detergent of Comparative Example 2, and thus, residues do not remain in the wash water.

<Example 4> Comparison of the phase-transfer type laundry detergent and the conventional powder laundry detergent with softening effect

The phase-transfer type laundry detergent of the present invention to which the fiber flexible component was added, and the powder type laundry detergent generally used were prepared in the ingredients and contents of Table 7. The unit is weight percent.

Furtherance Example 4 Comparative Example 3 Comparative Example 4 Sodium carbonate 50 30 10 Sodium sulfate - 20 - Straight chain alkylbenzenesulfonate - 5 5 Alpha olefin sulfonate - 5 5 Zeolite 4A - 20 - Sodium hydroxide - - 5 Polyoxyethylene Stearyl Ether (EO 14 mol) 29 - - Polyoxyethylene Stearyl Ether (EO 7 mol) 3 9 9 Quaternary Ammonium Salts 8 5 5 Amino modified silicone 8.5 5 5 Powder Fluorescent Dye ¹⁾ 0.7 0.5 - Powder enzyme ²⁾ 0.8 0.5 - water - - 61 ¹⁾ Tinopal CBS-X (Ciba Specialty Chemical, Switzerland) ²⁾ Savinase 12.0T (Novozymes, Denmark)

In Table 7, Example 4 is an example of a phase-transfer type laundry detergent provided with a softening effect, Comparative Example 3 is a laundry detergent added a flexible component to the most widely used powder type laundry detergent, Comparative Example 4 is a flexible powder It is a liquid laundry detergent which added. In particular, Example 4 is a phase-transfer type laundry detergent in the form of a cuboid in which a fiber flexible component is contained in a core of a product.

<Experimental Example 4-1> Washing force evaluation experiment

Washing power was compared and evaluated using the washing agents of Example 4, Comparative Examples 3 and 4, and the following method was used. 0.6 g / L of water having a hardness of 133 CaCO ₃ ppm and a laundry detergent of Example 4, 0.6 g / L, and 1 g / L of the laundry detergents of Comparative Examples 3 and 4, respectively, in a Terg-o-tometer. In each case, 8 × 8 cm 2 cotton cloth (2 sheets each) and 5 × 5 cm 2 contaminant cloth (8 sheets) were contaminated with wfk 10D and wfk 20D. It was washed for 10 minutes, rinsed for 3 minutes, and then dried naturally.

After measuring the whiteness of the contaminated cotton cloth before and after washing using a colorimeter, the washing force was calculated by substituting the Kubelka Munch equation of Equation 1, and the results are shown in Table 7 below.

division Example Comparative Example 3 Comparative Example 4 WFK 10D 76% 75% 68% WFK 20D 81% 80% 70% Japan Laundry Science Association 87% 82% 75%

As shown in Table 8, the phase-change laundry detergent formulated according to the present invention showed somewhat superior washing power in WFK 10D and 20D compared to the powder detergent of Comparative Example 3, and for the contaminated cloth prepared by the Japan Laundry Science Association. It showed higher cleaning power. Considering the characteristics of the contaminated cloth, this can be said to be the result of stronger cleaning power in case of dirty contamination of general household laundry. In addition, it was confirmed that the performance in all the contaminated cloth compared to the liquid laundry detergent of Comparative Example 4.

<Experimental Example 4-2> Evaluation of fiber softness effect

Using the laundry detergents of Example 4, Comparative Examples 3 and 4 was compared and evaluated the fiber softening effect, the following method was used. Using a standard laundry detergent in the standard use amount of commercially available 100% cotton towels were repeatedly washed five times in a washing machine and then dehydrated. Then, the cotton towels were washed in a drum washing machine using a laundry detergent of Examples 4, Comparative Examples 3 and 4, respectively, in a standard course, dried, and then conditioned at 20 ° C. and 65% RH for 24 hours. I was. Thereafter, sensory evaluation was performed on experienced panelists to give the intensity of the fragrance as a score from 1 to 5, and the results were repeated three or more times, and the average values are shown in Table 10 below. At this time, the flexibility evaluation criteria are as shown in Table 9 below.

division Very good (◎) Excellent (○) Normal (△) Bad (×) Suppleness score 4.5 or more 3.5 to 4.5 2.5 to 3.5 Less than 2.5

division Example 4 Comparative Example 3 Comparative Example 4 Softening effect ◎ △ △

As shown in Table 10, the phase-transfer type laundry detergent containing the fiber softening component of the present invention can give excellent softening effect as compared to general powder type and liquid type laundry detergent containing the flexible component as in Comparative Examples 3 and 4. It can be confirmed that.

As described above, the present invention can arbitrarily prepare a form of a detergent like a tablet laundry detergent, and unlike a liquid laundry detergent, it is not necessary to use a solvent such as water, thereby ensuring the stability of various functional materials, and washing powder. Unlike detergents, it provides a phase-change laundry detergent that does not leave any residue after washing. The present invention also provides an easy-to-use phase-transfer type laundry detergent containing fiber softening component that does not require the use of a softening agent. The phase-transfer type laundry detergent containing the fiber softening component does not reduce the cleaning power and the softening effect even in long-term storage.

Claims (10)

The phase-transfer type laundry comprising melting the surfactant in the solid phase at room temperature and in the liquid phase at 50 ° C. or higher and mixing the laundry component, and then cooling the mixture to formulate it into a uniform form. Detergent. The phase-transfer type laundry detergent according to claim 1, wherein the surfactant is at least one nonionic surfactant selected from the group consisting of fatty alcohol derivatives, fatty acid derivatives and nonylphenolethoxylates. The phase-transfer type laundry detergent according to claim 2, wherein the surfactant is an alkyl polyethylene glycol ether represented by the following Chemical Formula 1. <Formula 1> alkyl-O- (CH ₂ CH ₂ O) _n H The method of claim 3, wherein the alkyl of Formula 1 is any one selected from the group consisting of Capryl, lauryl, Myristyl, palmityl and stearyl, n is an integer of 7 to 36, the phase-transfer type laundry detergent. The phase-transfer type laundry detergent according to claim 1, wherein the laundry detergent further contains a fiber softening component therein. 6. The phase change type laundry detergent according to claim 5, wherein the fibrous flexible component is a cationic surfactant or amino modified silicone in the form of a quaternary ammonium salt. The phase-transfer type laundry detergent according to claim 1, wherein the laundry detergent contains a hole therein or contains a foaming material composed of an acid component and a base component. According to claim 1, The washing component is a phase change, characterized in that any one or more selected from the group consisting of enzymes, optical brighteners, cationic surfactants, anionic surfactants, peroxides and peroxide activators for the purpose of improving the performance of the laundry detergent. Type laundry detergent. (S1) melting the surfactant in the solid phase (normal phase) at room temperature and the liquid phase (liquid phase) at 50 ℃ or more; (S2) mixing the molten surfactant with a predetermined laundry component; (S3) cooling the mixture of step (S2) to produce a tablet type laundry detergent; Phase transition type laundry detergent manufacturing method comprising a. The method of claim 9, further comprising forming a hole in the tablet by generating bubbles during manufacture of the step (S3). 11.