JPS6356280B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-soluble aromatic detergent composition that utilizes the properties of carrageenan, particularly lambda-type carrageenan, and that dissolves into water after solidifying into a gel to provide a cleaning effect. Traditionally, carrageenan has been used as a gelling agent and thickening agent in all fields. For example, JP-A No. 49-12046 discloses a volatile solid deodorant fragrance using carrageenan as a gelling agent, and JP-A No. 52-70035 and JP-A No. 53- No. 145932 describes an example of blending with a surfactant. However, these are all compositions for volatilizing fragrances and the like into the air together with moisture after gelling, and in compositions containing carrageenan as a gelling agent, once heated to gel, they are evaporated into water. There is no concept of using it by dissolving it, and no such gel composition is known. Usually commercially available carrageenan is an extract of chondrus crispus, and is composed of about 60% katsupa-type carrageenan and about 40% lambda-type carrageenan, and has excellent gelling properties and swells in cold water, but hardly any The main ingredient is Katsupa-type carrageenan, which does not dissolve easily. In the above-mentioned fragrances, carrageenan is used simply as a holding base for fragrances, etc., and gel strength is also required, so it is natural that carrageenan mainly composed of katsupa-type carrageenan is used. considered to be a thing. However, when such a carrageenan mainly having a Katsupa type is used, it is difficult to obtain a gel composition that is slowly soluble in water after gel solidification. On the other hand, water-soluble compositions generally available on the market include colored toilet cleaners that use polyethylene glycol as a solidifying agent, but these have low concentrations of active ingredients and can be blended with any substance. However, it also has the disadvantage that the dissolution rate cannot be adjusted freely. In view of the above circumstances, the present inventors have conducted intensive research on gel compositions in the form of dosage forms that are used by dissolving them in water after gel solidification.
60 lambda type carrageenan from 7 types of theta
It has been found that when carrageenan containing % or more is used as a gelling agent, active ingredients such as detergents can be blended at a high concentration, and a gel composition that is slowly soluble in water is obtained after gel solidification. It has been discovered that the dissolution rate of the water-soluble gel and the active ingredients contained in the gel composition can be freely adjusted by incorporating a fast-dissolving substance and/or a slow-dissolving substance as described below into the gel composition. It has come to completion. That is, the present invention provides lambda-type carrageenan 60
% or more of carrageenan, a detergent, and a fragrance, and provides a water-soluble aromatic detergent composition that slowly dissolves in water after solidifying into a gel and exhibits a detergent effect. Furthermore, the present invention provides a water-soluble aromatic cleaning gel composition whose dissolution rate is controlled by incorporating a fast-dissolving substance and/or a slow-dissolving substance into the gel composition. The essential feature of the present invention is to use carrageenan containing 60% or more of lambda type carrageenan as a gelling agent. Although lambda-type carrageenan has a slightly weak gelling ability, it has good solubility in cold water. Taking these properties of lambda-type carrageenan into consideration, we conducted extensive research and found that carrageenan containing 60% or more of lambda-type carrageenan has good gelation and good cold water solubility after gelation. Therefore, in the present invention, carrageenan containing 60% or more of lambda type carrageenan is used, and if the lambda type in the carrageenan is less than 60%, a gel composition with good slowly solubility in water after gel solidification is obtained. That is difficult. The content of the carrageenan is preferably 1 to 5% by weight of the gel composition. Since it is possible to mix 10 times the amount of detergent to the above carrageenan, it is meaningless to mix more than 5% by weight of the above carrageenan, and considering the solubility in water,
It may be selected within the above range depending on the amount of cleaning agent to be mixed. The cleaning agents used in the present invention include n-paraffin-based, higher alcohol-based, α-olefin-based,
There are anionic detergents such as fatty acid-based, sulfosuccinic acid-based, and resin acid-based detergents, and nonionic detergents such as higher alcohol-based, alkanolamide-based, and fatty acid-based detergents, and at least one of these is blended. The blending amount is preferably 1 to 25% by weight, and may be selected within this range depending on the application. Here, the relationship between the content ratio of lambda-type carrageenan and the dissolution rate is shown in Table 1-1.

[Table] In Table 1-1 above, each gel contains carrageenan 3.2 containing lambda-type carrageenan in the various proportions mentioned above.
% by weight, 0.3% by weight of potassium chloride, and other water. Further, quick solubility and gel strength were determined by the method described below (described in connection with Table 5). As is clear from the above results, when the carrageenan used contains less than 60% of the lambda type carrageenan, the formed gel does not dissolve in water at all. Therefore, in the aromatic cleaning composition of the present invention in which the formed gel is slowly dissolved in water, the proportion of lambda-type carrageenan in carrageenan of 60% or more is a critical value. In addition, if the proportion of water-soluble lambda-type carrageenan is too high, for example, 100
%, the duration of the gel will be short and it will dissolve quickly, so it is preferable to add a slowly soluble substance as described below. Next, we investigated the effects of various detergents on the gel obtained using carrageenan containing 65% lambda-type carrageenan, and the results are shown in Table 1-2.
Shown below.

【table】

[Dissolution rate test]

In this device, tap water is poured into a cylinder with a diameter of 10 cm and a height of 50 cm from the bottom, and when a certain capacity is reached, the tap water flows down in a siphon style. Five gels are fixed in the cylinder at intervals of 6 cm from the bottom using wire mesh. do. A reference gel is placed at the bottom, and the decrease in gel due to dissolution in tap water is measured over time using a gravimetric method. The dissolution rate is expressed as the logarithm of the weight ratio of the sample gel to the reference gel when the weight of the reference gel is halved. That is, dissolution rate=log Msampl/M _STD , where M _STD is the weight (g) reduced by half of the reference gel after a certain period of time, and Msampl is the weight (g) of the sample gel after the same period of time. In addition,
Msampl is placed at the top of the cylinder. A gel-like substance is formed by dissolving the carrageenan containing 60% or more of the lambda-type carrageenan mentioned above and a detergent together with an appropriate amount of fragrance or other additives such as pigments in water and then heating. can get. In other embodiments of the invention, fast-dissolving substances, slow-dissolving substances, or both are included in order to control the dissolution rate of active ingredients (mainly detergents and fragrances). The amount of each is 1~
It is preferably 15% by weight, and is appropriately selected within this range depending on the desired dissolution rate. Fast-soluble substances include sodium nitrate, ammonium sulfate, sodium sulfate, sodium chloride, boric acid, and sodium organic acids; slow-soluble substances include aluminum sulfate, calcium sulfate, potassium sulfate, and dibasic sulfate.
These include iron, magnesium sulfate, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, potassium ferricyanide and potassium organic acids. The effects of these fast-dissolving substances and slow-dissolving substances on the dissolution rate of the gel in the presence of higher alcohol anions are shown in Tables 2 and 3.
The dissolution rate test was performed using the method described above, and the reference gel was placed at the bottom when it was a fast-dissolving gel (Table 2), and at the top when it was a slow-dissolving gel (Table 3). did.

【table】

[Table] is the value when added to the comparative formulation.

[Table] is the value when added to the comparative formulation.
As described above, according to the present invention, by using carrageenan containing 60% or more of lambda-type carrageenan as a gelling agent, it is possible to make a cleaning gel that dissolves in water, and it is clear from the examples described below. In addition to the advantage of being able to obtain a water-soluble aromatic cleansing composition in which the active ingredient is eluted in water at a constant concentration, there is also the advantage that the active ingredient can be blended at an extremely high concentration as a water-soluble composition. For example, for 1.5g of lambda-type carrageenan,
About 10 times as much detergent can be included. Furthermore, by incorporating a fast-dissolving substance and/or a slow-dissolving substance, the dissolution rate of the gel, that is, the dissolution rate of the active ingredient, can be adjusted as desired. Furthermore, the most characteristic feature of the water-soluble aromatic cleaning composition according to the present invention is that it always provides a fresh surface when releasing active ingredients (mainly cleaning agents and fragrances) in water. This means that when conventional volatile solid fragrances volatilize their active ingredients (mainly fragrances) into the air, as the water evaporates, a carrageenan film is formed on the surface, and the active ingredients are removed. This is in contrast to the negative effect on volatilization, and clearly shows how useful the water-soluble aromatic detergent composition according to the present invention is for use with carrageenan. In addition, carrageenan is safe enough to be eaten, is non-polluting, does not pollute the environment, and does not affect activated sludge. Moreover, it is extremely easy to transport and store, has excellent resilience even if a small amount of moisture evaporates into the air, and there is no risk of fire. Therefore, the water-soluble aromatic cleaner composition according to the present invention also has the above-mentioned effects. By having the above-mentioned advantages or effects, the water-soluble aromatic cleaning composition according to the present invention can be used for various purposes. for example,
It can be applied to commercial dish detergents and bathtub detergents that utilize the discharge pressure of tap water. Furthermore, as a slowly soluble detergent, it can be applied as a pipe clogging prevention agent, a substitute for toilet bowls, and even a colored detergent for toilets. EXAMPLES The present invention will be explained in more detail with reference to Examples below. Example 1 Table 4 shows formulation examples for fast-dissolving detergents.
These detergents are mainly applied to commercial dishwashing detergents, bath detergents that utilize the discharge pressure of tap water, and dishwashing detergents.

[Table] Many types of cleaning agents other than those listed in the above table were also tested, but they are omitted here. Table 5 shows the results of measuring the dissolution rate, quick solubility, and gel strength of the detergents shown in Table 4.

[Fast dissolution test]

For each formulation, make a total amount of 50g in a 100ml beaker and heat it to gel. Next, pour 150 ml of tap water into a 300 ml beaker so that the entire gel is immersed.
The weight is measured every day, and the number of days required for the weight of the gel to reach O is determined from the graph, and this is defined as the rapid dissolution (unit: days). [Gel strength test] Measured using a model M-30/AR card meter manufactured by Iio Electric Co., Ltd. It is shown as a comparative value when the control is set as 1.00. The weight was 400g and the measurement was performed using a pressure-sensitive axis of 3φ. Next, Table 6 shows the results of measuring the amount of elution over time for the anionic surfactant of the No. 2 formulation and the nonionic surfactant of the No. 4 formulation shown in Table 4. In addition, the analysis of surfactants is based on JIS K.
Pursuant to Law 3362.

[Table] As is clear from Table 6 above, the elution of the surfactant is approximately constant, indicating that the active ingredient is dissolved in a constant amount. This is a major feature of the formulation of the present invention. Example 2 Table 7 shows formulation examples for slowly soluble detergents.
These detergents are primarily suitable for use as pipe anti-clogging detergents.

【table】

[Table] Table 8 shows the dissolution rate, quick solubility, and gel strength of the detergents shown in Table 7.

[Table] Yes.
Table 9 shows prescriptions No. 7 and No. 9 shown in Table 7.
The amount of elution of anionic surfactant measured every number of days is shown. In addition, the analysis of surfactant is
This was done in accordance with JIS K3362 method. Regarding the analysis of nonionic surfactants, we also confirmed the method of quantifying ethylene oxide groups and spectrophotometry.

【table】

[Table] From Table 9 above, it can be seen that the surfactant, which is an active ingredient, is eluted in a constant amount, regardless of the decrease in gel. Example 3 Table 10 shows formulation examples of colored aromatic detergents for flush toilets.

【table】

[Table] Table 11 shows the dissolution rate and quick solubility of the detergents shown in Table 10.

[Table] Yes.
Table 12 shows the anionic surfactant (cleaning agent) and pigment (coloring agent) in formulation No. 12 and No. 14 in Table 10.
The amount of elution of was measured for each elapsed number of days is shown.
The analysis of the cleaning agent was conducted according to JIS K3362 method. The colorant was quantified by spectrophotometry.

【table】

[Table] As shown above, the elution of the detergent into water is extremely smooth, and although there are some differences depending on the type of detergent, the amount of detergent eluted as the gel decreases is constant. It has been found that, unlike conventional systems that release active ingredients into the air, extremely good water-soluble compositions can be obtained.

Claims (1)

[Scope of Claims] 1 1 to 5% by weight of carrageenan containing 60% or more of lambda type carrageenan, n-paraffin type, higher alcohol type, α-olefin type, fatty acid type,
Contains 1 to 25% by weight of at least one detergent selected from sulfosuccinic acid-based and resin acid-based anionic detergents, higher alcohol-based, alkanolamide-based and fatty acid-based nonionic detergents, and fragrance. A gel-like water-soluble aromatic cleaning composition. 2 1 to 5% by weight carrageenan containing 60% or more of lambda type carrageenan, n-paraffin type, higher alcohol type, α-olefin type, fatty acid type,
1 to 25% by weight of at least one detergent selected from sulfosuccinic acid-based and resin acid-based anionic detergents and higher alcohol-based, alkanolamide-based and fatty acid-based nonionic detergents, rapidly soluble substances, and A gel-like water-soluble aromatic cleaning composition comprising a slow-soluble substance and/or a fragrance. 3. The water-soluble aromatic cleaner composition according to claim 2, wherein the rapidly soluble substances are sodium nitrate, ammonium sulfate, sodium sulfate, sodium chloride, boric acid, and sodium organic acid, and are blended in an amount of 1 to 15% by weight. thing. 4. The slowly soluble substances are aluminum sulfate, calcium sulfate, potassium sulfate, ferrous sulfate, magnesium sulfate, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, potassium ferricyanide, and potassium organic acid, and are blended in an amount of 1 to 15% by weight. The water-soluble aromatic cleaning composition according to claim 2 or 3.