JP7128504B1 - Method for producing cleaning composition - Google Patents

Abstract

An object of the present invention is to provide a detergent composition having both stable detergency and antibacterial activity and excellent stability over time, and a method for producing the same. According to the method, 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b) polysaccharide thickener are added to a water-soluble continuous phase containing citric acid to form a uniform layer. After that, 2 to 20% by weight of (c) fine silicon dioxide is added to provide a micro-dispersed gel detergent composition and an optimal manufacturing method thereof, which has excellent detergency and antibacterial properties against stubborn stains. It has stability without force separation for a long period of time. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to a method for producing a gel-like detergent composition having a specific composition that has both a cleaning effect and a bactericidal effect and is excellent in stability over time.
More specifically, 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b) thickening polysaccharide are added to a water-soluble continuous phase containing citric acid, and a uniform layer is formed. After forming, 2 to 20% by weight of nano-sized fine silicon dioxide (c) is added, and the interface has excellent balance between oil removal and polishing, stability over time, and antibacterial activity. The present invention relates to a method for producing a microemulsion-type gel detergent composition that does not use an active agent and is transparent in appearance .

The emergence of the new coronavirus has caused the spread of infection, and the world has changed completely. The balance of economic activities has collapsed, and lifestyles have changed dramatically. Human beings are struggling in the so-called new normal, a world with no end in sight, without finding an effective solution to the corona crisis, which is facing an unprecedented human crisis.

However, as long as there is life, economic activity and social life are inevitable even if daily infection control and prevention are taken. rice field.

Under such circumstances, of course, the so-called antibacterial business is in the spotlight from the public health perspective of keeping viruses at bay. Wearing a mask has become a common sense act in daily life, and the practice of gargling and washing hands has almost become a part of the daily life cycle. In addition, antibacterial agents are widely used not only outdoors but also at home.

Furthermore, personal hygiene concept extends to the details of lifestyle, and sufficient antibacterial maintenance is required for, for example, daily necessities, fixtures, and materials for flooring and furniture.

In the recent corona crisis, domestic infections have increased rapidly and become a major social problem, and it goes without saying that daily hygiene management continues to be important. The importance of total care for the entire lifestyle centered on is increasing, and a series of antibacterial and antiviral measures will continue to be a very important issue.

There are various causes of COVID-19 infection, but many of them have not yet been identified and clarified. However, it is an unquestionable empirical fact that the drastic countermeasure is maintenance of daily cleaning and sterilization effects.

In this regard, the applicant attempted to develop a cleaning agent based on his accumulated technology, made an invention, and acquired a patent for this finding (Japanese Patent No. 6752479; Patent Document 1).
The technology according to Patent Document 1 has achieved considerable results in the implementation of sanitation projects, but in the course of formulation design, depending on the blending composition adopted, there are cases where the surfactant is used at a high concentration, and environmental measures in SDGs In view of the above, the need for further improvements has arisen.
In addition, from the viewpoint of prevention of domestic infections and antibacterial care, there is a need to expand functionality.

Here, the technology according to Patent Document 1 is a so-called cream cleanser type, and silicon dioxide is an essential functional ingredient for maintaining detergency.
It is convenient to add a known antibacterial agent in order to add antibacterial power while maintaining detergency. As a result, there is a problem that it is difficult to sufficiently exhibit the antibacterial effect. This problem is faced as long as a surfactant is used, and one of the development conditions is ideally not to use a surfactant in formulation design.

Another important development condition is maintaining uniformity of the silicon dioxide used. Since it is an inorganic substance, precipitation occurs depending on the composition of the base, especially when no surfactant is used, and this hinders the cleaning effect. This problem is significant when the formulation contains a large amount of water.

Therefore, it is extremely important to consider the balance between these factors and to select an effective detergent composition. However, according to the prior art, no useful detergent composition has been provided that focuses on this point. It is the actual situation.

Patent Literature 2 discloses a transparent gel-like detergent with excellent stability and sterilizing power, which is obtained by selecting specific ingredients that cause little skin irritation. The above problem has not been resolved. In addition, it lacks general versatility.

Patent Document 3 discloses a gel-like hand sterilizing detergent composition that has both a sterilizing effect and a cleansing effect and is easy to handle. There is no difference from the technique according to Patent Document 2 in that it is a composition to be blended and no consideration is given to the environment.

Patent Document 4 describes a powder containing photocatalyst, apatite and silicon dioxide, or composite particles of photocatalyst and apatite and silicon dioxide, or composite particles of photocatalyst and silicon dioxide, and cyclodextrin particles. Although the cleaning composition and its functionality are disclosed, according to the technology, it has a certain effect as a functional material that can be used for various purposes, but it focuses on the effectiveness of the photocatalyst. , and there are problems with powder sedimentation and uniformity in formulation design. In particular, the interaction with the water-based base tends to cause aggregation, and there are many restrictions on formulation.
If the stability of the functional powder is impaired, it is a natural result that the desired effects such as cleaning effect and sterilization and sterilization effects cannot be exhibited stably.

As described above, it has not yet been realized to provide a cleansing agent composition which has a stable constitution without segregation over time, etc., while having a constant cleansing effect and an antibacterial effect, while considering the environmental aspect. In particular, the actual situation is that no major studies have been made on the improvement of formulation development that follows the trend of cream cleansers.

Japanese Patent No. 6752479 JP-A-59-232194 JP-A-2001-2615550 JP 2010-95676 A

The present invention has been made in view of the above unattained problems, and selects raw materials while considering the environment, and is essential for exhibiting particularly stable detergency and antibacterial properties. An object of the present invention is to provide a detergent composition excellent in stability and a method for producing the same.

In order to solve the above problems, the present inventors have adjusted the balance of ingredients that have good stability over time by selecting materials that do not reduce the detergency and have antibacterial properties. The present invention was completed based on the discovery that the detergent composition thus constituted exhibits the desired effects. Specifically, it is as follows.

The inventors of the present invention searched for materials that are derived from natural products and expected to have cleaning and antibacterial effects in consideration of the environment and versatility. As a result, they focused on citric acid.
In addition, from the viewpoint of technical improvement according to Patent Document 1, silicon dioxide is used, but no surfactant is used, so in order to ensure stable dispersibility and uniformity in the formulation, gel formulations are adopted. Arrived.

Here, the silicon dioxide used has been finely treated to improve its dispersibility, but for stability over time, it is effective to use a specific polyhydric alcohol and a polysaccharide thickener together. was found to be effective, and was selected as an essential component in the present invention.
Propylene glycol and/or glycerin are the most suitable polyhydric alcohols, and xanthan gum and/or guar gum are the most suitable polysaccharide thickeners.

That is, according to the present invention, 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b) polysaccharide thickener are added to a water-soluble continuous phase containing citric acid. , after forming a uniform layer, 2 to 20% by weight of (c) fine silicon dioxide treated to nanosize is added to the microemulsion type gel detergent composition. be.

As described above, the detergent composition of the present invention is prepared by adding specific amounts of (a) polyhydric alcohol and (b) polysaccharide thickener to a water-soluble continuous phase containing citric acid, and forming a uniform layer. , a microemulsion-type gel-like detergent composition containing a specific amount of fine silicon dioxide (c) added, and a combination of these specific component types and amounts to provide strong oil stains. However, it exhibits sufficient detergency and antibacterial power, and can exhibit a stable detergency effect for a long period of time.

The cleaning composition of the present invention also has a notable feature in its manufacturing method.
That is, in the method for producing a detergent composition of the present invention, as the first step, a continuous layer of citric acid gel is formed in advance by adding citric acid in a weight ratio of 0.3 to 0.5 to 1 part of purified water. , As a second step, a separately prepared mixture of 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b) thickening polysaccharide is added to the continuous phase of the citric acid gel. After stirring to form a uniform layer, in the third step, 2 to 20% by weight of (c) nano-sized fine silicon dioxide is added and stirred to obtain the desired surfactant most suitable for solving the problem. To provide a microemulsion type gel detergent composition which is transparent in appearance when not used . This surfactant-free, transparent microemulsion-type gel detergent composition forms a thermodynamically stable continuous layer, so it is expected to always have stable detergency and antibacterial activity even after long-term storage. It is possible.

As mentioned above, the present invention exhibits detergency and antibacterial power that can be adapted to all life scenes by a specific component composition / formulation composition, and realizes a uniform formulation that is stable over a long period of time. To provide a detergent composition capable of stably exhibiting both antibacterial and antibacterial effects, and a method for producing the same.

Thus, according to the present invention, firstly, in an aqueous continuous phase containing citric acid, preferably 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b ) After adding a polysaccharide thickener to form a uniform layer, 2 to 20% by weight of (c) fine silicon dioxide treated to nanosize is added to create a surfactant-free, transparent microemulsion. Secondly, preferably in the first step, 0.3 to 0.5 by weight of citric acid is added to 1 part of purified water in advance. A continuous layer of citric acid gel is formed, and as a second step, separately prepared 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b ) After adding and stirring the thickening polysaccharide mixture to form a uniform layer, in the third step, 2 to 20% by weight of (c) nano-sized fine silicon dioxide is added and stirred to solve the problem A method for producing the desired surfactant-free, clear, stable, microemulsion-type , gel-like cleaning composition is provided.

Citric acid in the present invention is an organic compound contained in citrus fruits and the like, and is one of hydroxy acids. many included. Due to its refreshing acidity, it is often used as a flavor-adjusting ingredient in processed foods. The sourness of citrus fruits is mostly due to the taste of citric acid.
As it easily dissolves calcium carbonate, it is also used to clean urinary stones in toilet bowls, bathrooms, electric pots, and limescale accumulated inside humidifiers. , the use of sterilization products is expanding.
As described above, it is a useful material that is widely acceptable from an environmental point of view because it is mainly derived from natural products.
In the present invention, 0.3 to 0.5 weight ratio is preferably added to 1 part of purified water.

Since the polyhydric alcohol of the basic configuration (a) has good permeability to the object to be cleaned, the composition of the present invention enhances the cleaning effect of the cleaning material, while the present invention does not use a surfactant. , plays a major role as an aid to improve the dispersion stability of fine silicon dioxide. From the viewpoint of compatibility with citric acid, ethylene glycol, propylene glycol, 1-3-butylene glycol, and glycerin can be used as ingredients to be blended, and propylene glycol and glycerin are most preferable. is preferably 2 to 10% by weight.

The thickener of basic configuration (b) plays a major role as a base for gel formation in the water-soluble continuous phase containing citric acid of the present invention, and compatibility with polyhydric alcohols is also important. In this regard, from a functional point of view, a thickener that can include the role of a polyhydric alcohol can be selected without using the above surfactant, but xanthan gum and / or guar gum can be preferably used. . The usual blending amount is 0.1 to 10% by weight, preferably 0.5 to 5% by weight in order to maintain the compatibility with each component constituting the detergent of the present invention and the stability of the formulation as a whole. used.

The fine silicon dioxide of the basic configuration (c) is powdered into nano-sized particles by a known method, and is added in the range of 2 to 20% by weight to the finished product manufactured according to the application. .

Purified water is balanced within a range for the blending amounts of (a), (b) and (c) above. In particular, a pharmaceutical feature of the present invention is that it constitutes a thermodynamically stable microemulsion, which can be prepared by simple mixing and stirring at room temperature without complicated steps such as homogenization under reduced pressure. However, in order to obtain a continuous layer that is more stable over time, the final stirring time should be at least 3 hours.

In addition, the microemulsion of the present invention has a suitable order of addition and stirring in order to maintain stable properties both in appearance and over time.
In mixing (a) a polyhydric alcohol and (b) a thickener to be prepared as premix raw materials, it is also an essential condition in the manufacturing process that water should not be mixed.

That is, according to the present invention, preferably in the first step, a continuous layer of citric acid gel is formed in advance by adding citric acid in a weight ratio of 0.3 to 0.5 to 1 part of purified water, and As a step, a separately prepared mixture of 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b) thickening polysaccharide is added to the continuous phase of the citric acid gel and stirred, After forming a uniform layer, in the third step, 2 to 20% by weight of (c) fine silicon dioxide is added and stirred to obtain a microemulsion preparation capable of exhibiting desired effects.
Especially in the third step, if (c) is added and mixed at once or added and mixed for a short period of time, the nano-sized fine silicon dioxide cannot be dispersed in the continuous layer and aggregation occurs, resulting in a translucent or suspended layer. will occur, so be careful.

Here, a microemulsion is generally a type of dispersion system similar to an emulsion, but the micelle diameter is as small as about 100 nanometers or less, and it is thermodynamically stable and strong. It is easily formed without stirring. Since the micelles formed are small, they scatter less visible light and are characterized by being visually transparent or translucent.

As mentioned above, microemulsions have a transparent appearance, do not separate, and have the property of easily dissolving substances that have affinity for both hydrophilic and hydrophobic components. Therefore, it is used for many purposes.

In the present invention, the advantage of using a microemulsion formulation is based on the following theory of cleaning functionality, although the details are not clear.

That is, as a result of the citric acid mixed with the polyhydric alcohol and thickener quickly permeating the object to be cleaned, it is compatible with oil stains and removes the stains. Secondary cleaning is initiated by physical rubbing and polishing of the nano-sized silicon dioxide. It is presumed that the synergistic effect of the cleansing action with citric acid accelerates the removal of dirt.

The polyhydric alcohol and the thickener improve the affinity of citric acid to the object to be washed in the washing process, and the antibacterial power of citric acid coats the surface of the object to be washed after washing.

In this way, after finishing, the effect of citric acid that permeates and adsorbs to the object to be washed continues and can also be imparted with antibacterial properties. It is possible.

In addition, in order to strengthen the surface coating power on the object to be washed, it is optional to add a small amount of a coating agent within the range that does not impair the effects of the present invention.

In addition, moisturizers, softeners, solvents, antibacterial agents, fragrances, and the like can be added to the detergent composition of the present invention, if necessary, as long as they do not impair the effects of the present invention.

EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to the examples.

<Test Example 1> Stability test over time (test method)
The composition shown in Table 1 was filled in a wide-mouthed standard bottle, capped, and stored in a constant temperature bath at -5°C to 40°C for 1 year, and the external appearance of the formulation was visually evaluated every 3 months.
At the same time, the cleaning effect was evaluated after one year had passed.
There are three evaluation items: removal of dirt from the object to be washed, comparison of the surface (property) condition, and usability.
The stain removal and surface (property) of the object to be washed were evaluated by the degree of recovery to the original state, and the usability was sensorily evaluated using the surface wettability and the degree of load of stain removal as indicators.
The compositions (test samples) in Table 1 were all obtained by the following production methods found according to the present invention.
That is, as a first step, a continuous layer of citric acid gel is formed by adding citric acid in a weight ratio of 0.3 to 0.5 to 1 part of purified water in advance, and as a second step, the continuous layer of the citric acid gel is formed. A separately prepared mixture of 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b) polysaccharide thickener is added to the phase and stirred to form a uniform layer. As a process, 2 to 20% by weight of (c) nano-sized fine silicon dioxide is added and stirred.

(Results and discussion)
As shown below, the product of the present invention did not change over time and maintained its functionality. In addition, stain removal from the surface of the object to be washed, finishing properties, and usability are also good, and it is clear that the microemulsion composition composed of the components specified in the present invention has excellent commercial value. .

Table 2 shows that all compositions conforming to the microemulsion type of the present invention have the desired effect by performing a stability test obtained by the same manufacturing method as above.

Claims (3)

As a first step, a water-soluble continuous layer of citric acid gel is formed in advance by adding citric acid in a weight ratio of 0.3 to 0.5 to 1 part of purified water, and as a second step, the citric acid gel is added. After adding and stirring a separately prepared mixture of 2 to 10% by weight of (a) polyhydric alcohol and 0.5 to 5% by weight of (b) thickening polysaccharide to the water-soluble continuous phase to form a uniform layer In the third step, 2 to 20% by weight of (c) nano-sized fine silicon dioxide is added and stirred to prepare a surfactant-free, transparent microemulsion-type gel detergent composition. Production method. 2. The method for producing a microemulsion-type gel detergent composition that does not contain a surfactant and has a transparent appearance according to claim 1, wherein the polyhydric alcohol is propylene glycol and/or glycerin. 3. The method for producing a surfactant-free microemulsion-type gel detergent composition having a transparent appearance according to any one of claims 1 and 2, wherein the thickening polysaccharide is xanthan gum and/or guar gum.