JPH08183997A - Detergent composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a composition capable of stabilizing hinokitiol contained in a detergent composition in an effective state during storage or during use without any harmful effect. [Structure] It is characterized by containing hinokitiol as an essential component and a metal soap made of a metal other than an alkali metal. [Effect] The hinokitiol contained in the cleaning composition is maintained in a stable state not only during storage including once used but also during use. Therefore, the characteristics of hinokitiol are always effectively exhibited during use. Further, the foaming property, color tone and the like of the detergent composition are maintained in the initial state. It can also be configured in various forms.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improved composition of a detergent composition containing hinokitiol. For more information,
The present invention relates to a novel composition for stabilizing the contained hinokitiol by light, heat or chemically.

[0002]

BACKGROUND OF THE INVENTION Hinokitiol can be obtained by extracting it from natural products such as hinoki oil, hiba oil, etc., or by synthesis, and its chemical name is 4-isopropyl-2-hydroxy-cyclopenta-2,4,6-triene. -1-on. It is known that this hinokitiol is excellent in effects such as sterilization, antibacterial and antiseptic and has extremely low skin irritation (International Publication WO92 / 05240, JP-A-5-214364).
Issue).

From these effects, hinokitiol is
Prophylactic / therapeutic agent for periodontal disease (Japanese Patent Laid-Open No. 63-188619),
Cosmetics such as lotion, emulsion, cream, pack
1-199908, Japanese Patent Application Laid-Open No. 2-69411), skin cleansing agents (Japanese Patent Application Laid-Open No. 3-63216), and the like have been incorporated as components.

[0004]

However, hinokitiol is originally extremely unstable to light, heat and the like, and in this respect, even when it is contained as a component of the above-mentioned cosmetics and detergents. It is the same. Further, when hinokitiol is decomposed in such a detergent, not only the effect of sterilization, antiseptic, etc. is lost, but also discoloration of the detergent itself and other adverse effects such as deterioration of quality may occur. .

Therefore, a composition for stabilizing hinokitiol contained as a component has been invented in the past. For example, it is a composition in which a compound having a sterin nucleus such as cholesterin is blended (Japanese Patent Laid-Open No. 63-63115)
-188619 publication).

[0006] However, this conventional technique relates to a composition for the oral cavity, and because of its characteristics such as its use form and storage form, it is likely to be exposed to light and heat from the outside, and further, it is economical. In view of the property, this conventional composition cannot be directly used for the detergent composition. Further, even in this conventional composition, the stabilizing effect on the contained hinokitiol is not sufficient.

Therefore, the present invention provides a detergent composition which is relatively exposed to light, heat, etc. during storage or during use, and contains the hinokitiol contained therein in an effective state and is stabilized over time. The object of the present invention is to provide a composition composition that can be obtained.

[0008]

In order to achieve the above object, the present invention has the following composition for a detergent composition. That is, it is characterized by containing hinokitiol and a metal soap made of a metal other than an alkali metal as essential components.

In the composition of the present invention, metal soaps include lauric acid, myristic acid, palmitic acid, stearic acid, and metal salts of mixed fatty acids thereof, as well as N-.
Acyl glutamic acid, N-acyl sarcosinic acid, N-acyl-N-methyl taurine metal, metal alkyl sulfosuccinate, polyoxyethylene alkyl sulfosuccinic acid,
Alkyl ether carboxylic acid, polyoxyethylene alkyl ether carboxylic acid, alkyl phosphate ester, alkyl sulfate ester, polyoxyethylene alkyl sulfate ester, α-olefin sulfonic acid, alkyl-β-
Examples thereof include metal salts such as methylalaninic acid, but are not limited thereto.

Various metals other than alkali metals can be applied as the metal of the metal soap, but aluminum, calcium, from the viewpoints of the effectiveness of stabilizing the contained hinokitiol, the skin irritation, the harmlessness, etc. It is preferably one selected from magnesium, barium, copper, iron, cobalt and silver. More preferably, it is aluminum because it can retain its colorless and transparent properties.

The following are specific examples of the metal soap. Aluminum monostearate, aluminum distearate, aluminum tristearate, calcium stearate, magnesium stearate, magnesium myristate, aluminum N-lauroyl acylglutamate, copper N-lauroyl glutamate, cobalt N-myristoyl acyl glutamate, polyoxyethylene (10) Aluminum lauryl ether carboxylate, polyoxyethylene (10)
Examples include magnesium lauryl ether carboxylate, magnesium N-lauroyl sarcosinate, silver N-lauroyl sarcosinate, aluminum lauroyl-β-methylalaninate, calcium lauroyl-β-methylalaninate, and the like.

In the present invention, the metal soap includes not only those added as the metal soap itself but also those obtained as a reaction product in a mixed system with a detergent component. The reaction product is a cation exchange reaction (metathesis reaction) by mixing the metal salt of the specified metal, or a direct reaction by mixing the metal hydroxide.

Examples of the above-mentioned metal salts involved in the cation exchange reaction include aluminum chloride, calcium chloride, barium chloride, magnesium chloride, copper chloride, ferric chloride, cobalt chloride, silver chloride, silver nitrate, copper sulfate and the like. You can Further, examples of the metal hydroxide relating to the above direct reaction include aluminum hydroxide, magnesium hydroxide, calcium hydroxide and the like.

Next, in the present invention, when the metal soap is added as the metal soap itself, it can be added directly as a component in a general production process such as a frame kneading method.

In the case of the above-mentioned cation exchange reaction, the cation exchange reaction is carried out by mixing and dissolving the detergent component such as an alkali metal salt of fatty acid and the above metal salt under a temperature condition of, for example, about 70 ° C. And then mixing with hinokitiol.

In the case of the above-mentioned direct reaction, for example, a detergent component such as a fatty acid is mixed and dissolved under a temperature condition of, for example, about 60 ° C., and the above-mentioned metal hydroxide is mixed therein to directly react. It depends on the method. Since this reaction is a neutralization reaction, it is possible to mix a solution in which this hydroxide is mixed with another neutralizing agent.

Further, in the detergent composition according to the present invention, hinokitiol is used in an amount of 0.0
It can be blended in the range of 01 wt% or more and 10 wt% or less. This is because if the content is less than 0.001% by weight, the effects such as sterilization cannot be effectively obtained, and if it exceeds 10% by weight, the water-insoluble property causes the adverse effect of separation. .

The blending amount is preferably 0.01% by weight or more and 1.0% by weight or less. If the amount is within this range, the effects such as sterilization can be stably obtained,
Further, it is possible to use economically without causing the unique cypress odor.

Although the amount of the above-mentioned metal soap to be blended depends on the kind thereof, it is 0.1 part by weight or more per 1 part by weight of hinokitiol and 5.0% by weight or less in the detergent composition. be able to. If this ratio is less than 0.1 part by weight, stabilization against the contained hinokitiol cannot be effectively obtained, and if it exceeds 5.0% by weight, the composition has a reduced foaming property and is sometimes transparent. It becomes a cause of worsening the sex.

[0020]

[Function] In the detergent composition containing hinokitiol, the above-mentioned metal soap component blended therein is such that the hinokitiol contained therein may be chemically decomposed by light or heat, or may be chemically decomposed or changed with time. It acts to prevent and prevents the composition itself from being altered over a long period of time.

The composition of this metal soap does not impair the essential functions such as foaming property in the detergent composition, and in particular within a certain range, the colorless transparency of the composition is obtained. It is also possible to maintain.

[0022]

【Example】

Examples 1 to 5 Mixed fatty acids (lauric acid 15, myristic acid 30, palmitic acid 10, stearic acid 25 and oleic acid 20, wherein the numerical values are weight ratios) and 10% by weight of ethanol (hereinafter, simply “%”). Then, this was mixed in a reaction kettle at 50 to 70 ° C., and sodium hydroxide was added thereto for neutralization to obtain mixed fatty acid sodium.

Next, 45 of this mixed fatty acid sodium
% Equivalent amount was maintained at a temperature of 65 to 80 ° C., sorbitol 10%, purified sugar 10%, glycerin 5%, and hinokitiol and various kinds of metal soap powders were added as shown in Table 1 below. With the balance of deionized water to 100
% To form soap glue, which was poured into a frame, cooled, solidified, cut, dried and aged, and stamped to obtain a transparent solid soap.

[Table 1]

Table 1 shows the color tone, foamability and bactericidal effect of these solid soaps immediately after production, after light stability test and after high temperature stability test. Comparative Example 1 is a case where no metal soap other than alkali metal is blended, and Comparative Example 2 is a case where no hinokitiol is blended.

The color tone was judged by observing the appearance, and the color tone was shown by ◯ when there was no change at all, Δ when slight discoloration was observed, and × when the change was remarkable.

The foaming property is 1% of the target solid soap.
An aqueous solution was prepared by using artificial hard water containing 70 ppm of calcium carbonate, brought to a temperature state of 40 ° C., and stirred with a mixer to measure the amount of foaming generated. When the amount of foaming is 2200 ml or more, it is extremely good, ◎, when it is 2000 to 2200 ml, it is good, and when it is 1800 to 2000 ml, it is slightly inferior.
When it was 1800 ml or less, it was rated as ×.

The bactericidal effect was based on the paper disk method. That is, the sample is an aqueous solution (8: 2 of ethanol and water).
It was prepared as a solution having a concentration of 20% by weight in a solution mixed at a ratio of 1 part by weight and used as a preparation sample. On the other hand, Staphylococcus aureus was dispersed in sterilized water so as to be 10 ⁶ CFU / ml, 0.5 ml of this was inoculated into 5 ml of broth BA agar medium, and then the inoculated medium was pre-solidified BA agar medium (15 ml). ) Overlaid. Next, a paper disc (8 mmφ, filter paper made by Toyo Roshi Co., Ltd.) was made to contain 50 μl of the above-mentioned adjusted sample, which was placed in the central part of the above-mentioned layered medium, and after culturing at 30 ° C. for 24 hours, the paper disc By measuring the diameter of the stop band that occurs on the surface.

Further, the light stability is 3000 L by a fluorescent lamp.
The target sample was exposed under the illumination of ux and left for 300 hours.

The high temperature stability was determined by leaving the target sample at 37 ° C. for 30 days.

From the results shown in Table 1, the soap compositions of Examples 1 to 5 according to the present invention have excellent bactericidal effects, and the effects are almost stable to light and heat. You can check that. Further, the original foaming property, that is, the cleaning performance is maintained as it is, and the color tone is hardly changed. Also, Examples 1 to 3
It is also found that the transparency in the colorless state is retained when the metal of the metal soap is aluminum, as described above.

(Examples 6 to 12) Ethanol 15% was added to a mixed fatty acid (myristic acid 60, palmitic acid 20, stearic acid 10, oleic acid 5 and ricinoleic acid 5, the numerical values being the weight ratios), and the same as above. Obtained mixed fatty acid sodium, and added sorbitol 15%, glycerin 5%, diglycerin 5%, purified sugar 10%, hinokitiol and aluminum tristearate in the amounts shown in the following Table 2 in the same manner as above, and ion-exchanged water was added. Was mixed as 100% and was treated in the same manner as above to obtain solid soap.

[Table 2]

The same characteristics as described above are shown in Table 2 above for these solid soaps.

Regarding the transparency, a sample with a thickness of 1 mm was used as a sample, and the transmittance of visible light of this sample was measured. When the transmittance was 40% or more, it was considered to be extremely good, and when it was 30 to 40%. Good: Good, 20 ~ 30, poor: △, 20%
When the following cases or the occurrence of crystals were evaluated as x.
The criteria such as color tone are the same as above.

From the results shown in Table 2, when the content of the metal compound exceeds 0.01%, the bactericidal effect can effectively maintain the stability over time against light and heat, and the foamability. With respect to the above, the compounding amount can be effectively maintained when the compounding amount is 5.0 or less, but it tends to be slightly decreased when the compounding amount is 3.0 or more, and the color tone is colored (yellow) when the compounding amount is 0.01 or less. It can be seen that when it is 0% or more, it becomes cloudy and becomes opaque.

Therefore, as the compounding amount of the metal soap,
It is effective for the stability of hinokitiol and the like in the range of 0.01 or more and 5.0% or less, but it is confirmed that the compounding amount in the range of more than 0.01% and less than 3.0 is particularly preferable. be able to.

(Examples 13 to 16) Mixed fatty acids (palm kernel fatty acid 40, palm fatty acid 60, numerical values are weight ratios)
Ethanol (15%) was added to the mixture to obtain mixed fatty acid sodium in the same manner as above, to which sorbitol (15%) was added.
Glycerin 5%, purified sugar 10%, and, as shown in Table 3 below, hinokitiol and metal soap were added, and mixed with ion-exchanged water to make 100%, and treated in the same manner as above to obtain solid soap. .

[Table 3]

The characteristics similar to those described above are shown in Table 3 for these solid soaps. The criteria are the same as above.

From the results shown in Table 3, the metal soap was N-
It can be confirmed that even if the metal salt of acylglutamic acid or the metal salt of carboxylic acid type anionic surfactant is used, the same stabilizing effect and the like as described above can be obtained.

(Examples 17 to 25) N-coconut oil fatty acid dipotassium acylglutamate and dipotassium N-stearoyl acylglutamate were mixed in a weight ratio of 1: 1 and
50% of this mixture was mixed with 5% of sorbitol and 10% of glycerin.
% And ethanol 15% were mixed in, and this was heated to 70 ° C. and dissolved. Then, a metal salt shown in the following Table 4 as a 30% aqueous solution is added to this solution so that the amount shown therein is added to cause a metathesis reaction, and then a high-speed mixer (3
5,000 rpm for 15 minutes) to uniformly mix and disperse. Next, hinokitiol was added to this in an amount shown in Table 4, and it was adjusted to 100% with ion-exchanged water, and this was treated in the same manner as above to obtain a solid soap.

[Table 4]

The properties similar to those described above are shown in Table 4 for these solid soaps. The criteria are the same as above.

From the results shown in Table 4, it can be confirmed that the same effects as described above for stabilizing hinokitiol are exhibited even when the composition of the metallic soap produced in the mixed system with the detergent component is the same.

(Example 26) Mixed fatty acid (lauric acid 2
Ethanol 15%, sorbitol 5%, and glycerin 5% were added to 0, myristic acid 30, palmitic acid 20, stearic acid 30, and the numerical values are weight ratios, and heated and dissolved at 60 ° C. Then add 48% sodium hydroxide 8.
By adding 7% and calcium hydroxide 0.5% and mixing, mixed fatty acid calcium is produced together with mixed fatty acid sodium, sugar 10%, diglycerin 5
%, And 0.1% of hinokitiol was further added to adjust the amount to 100% with ion-exchanged water, and this was treated in the same manner as above to obtain a solid soap.

The same light stability test and high temperature stability test as described above were conducted on this solid soap, and as a result, no change in color tone was observed in any of the tests, and good foaming property and bactericidal effect were maintained. It was confirmed to do.

[0044]

INDUSTRIAL APPLICABILITY According to the present invention, the hinokitiol contained in the detergent composition is stable with respect to external light, heat, etc. over time even during storage including during use or during use. Since the hinokitiol is retained in the state, the properties of hinokitiol such as sterilization and antiseptic are always effectively exhibited during use.

Further, appearances such as foamability and color tone are maintained almost unchanged from the initial state, so that usability as a cleaning agent can be improved.

In addition, when the cleaning agent is made of a transparent material, it is possible to maintain its characteristics as it is, so that the cleaning agent can be made in various forms, and the higher the product value is, the higher the price. High-value products can also be obtained.

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[Procedure amendment]

[Submission date] February 10, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

BACKGROUND ART hinokitiol, cypress oil, by extracting from natural products such as cedarwood oil, or even obtained by synthesis, chemical name is 4-isopropyl-2-hydroxy - cyclo hepta-2,4,6 It is trien-1-one. It is known that this hinokitiol is excellent in effects such as sterilization, antibacterial and antiseptic properties, and has extremely low skin irritation (International Publication WO92 / 05240, JP-A No. 5/05240).
-214364).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

In the composition of the present invention, the metallic soap includes lauric acid, myristic acid, palmitic acid, stearic acid, a metal salt of a mixed fatty acid thereof, and N-.
Acyl glutamic acid, N- acyl sarcosinates, N- acyl -N- Mechirutauri down, alkyl sulfosuccinates,
Polyoxyethylene alkyl sulfosuccinic acid, alkyl ether carboxylic acid, polyoxyethylene alkyl ether carboxylic acid, alkyl phosphate ester, alkyl sulfate ester, polyoxyethylene alkyl sulfate ester, α-olefin sulfonic acid, alkyl-β-methylalaninic acid, etc. Examples of the metal salts thereof include, but are not limited to:

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

Next, 45% of this mixed fatty acid sodium
While maintaining a considerable amount at a temperature of 65 to 80 ° C, sorbitol 10%, purified sugar 10%, glycerin 5%, and hinokitiol and various kinds of metal soap powders are added as shown in Table 1 below. 100% with the rest of ion-exchanged water
The mixture was mixed to form a soap glue, which was poured into a frame, cooled, solidified, cut, dried and aged, and stamped to obtain a transparent solid soap.

[Table 1]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046] When configured as detergents transparent nature, since it is also possible to maintain the characteristics thereof, can also be configured as a variety of forms, much High level You can get high value with.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Daiji Nagahama, 2-13-26, Himejima, Nishiyodogawa-ku, Osaka-shi, Osaka Prefecture P & P F Co., Ltd. (72) Tetsuo Nishina 2-chome, Himejima, Nishiyodogawa-ku, Osaka-shi, Osaka No.26 P & P Co., Ltd.

Claims (2)

[Claims] 1. A cleaning composition comprising hinokitiol as an essential component and a metal soap made of a metal other than an alkali metal. 2. The detergent composition according to claim 1, wherein the metal of the metallic soap is one selected from aluminum, calcium, magnesium, barium, copper, iron and silver.