JP3684144B2 - Cleaning composition - Google Patents

Description

製法：各成分を水に添加し攪拌する。
【００４０】
「表４」の結果より実施例４の洗浄剤組成物は、希釈時の界面活性剤が低濃度の場合においても洗浄効果が高い優れた洗浄剤であることがわかる。
【００４３】
【表６】

製法：各成分を水に添加し攪拌する。
【００４４】
「表６」の結果より実施例６の洗浄剤組成物は、希釈時の界面活性剤が低濃度の場合においても洗浄効果が高い優れた洗浄剤であることがわかる。
【００４５】
「生分解率」
実施例６の洗浄剤組成物の生分解率を、化学審議会法により規定されているBOD法にて求めた。その結果、洗浄剤組成物の5日間の生分解率は６２％であり、生分解性が高く環境に対して十分に配慮した洗浄剤であることが分かった。
【００４６】
「界面張力」
実施例６で用いた両性界面活性剤とアニオン界面活性剤を混合した水溶液のデカンに対する界面張力を測定した。総界面活性剤濃度を１質量％としスピニングドロップ法にて測定を行なった。図２に両性界面活性剤とアニオン界面活性剤の混合比とデカンに対する界面張力の関係を示す。図２より両性界面活性剤とアニオン界面活性剤を混合することによりデカンに対する界面張力が低下し、洗浄に適した状態に変化することが分かる。
【００４７】
「電気伝導度」
実施例６で用いた両性界面活性剤とアニオン界面活性剤の混合物にオレイン酸を添加したときの電気伝導度の変化を測定した。図３にオレイン酸の添加による電気伝導度の変化を示す。図３より両性界面活性剤とアニオン界面活性剤の混合物にオレイン酸を添加したときに電気伝導度が低下し、会合状態の秩序度が上昇し、洗浄に適した状態に変化することがわかる。
【００４８】
【発明の効果】
本発明によれば、優れた洗浄力を有し、少量の使用によっても充分な洗浄力を有するので環境に対して十分に配慮可能であって、安全性が高く、身体に対しても使用でき、生分解性にも優れた洗浄剤組成物を提供出来る。
【図面の簡単な説明】
【図１】 ヘキサノールとの含有量をパラメーターとした場合における等方性界面活性剤連続相を有する領域を表わした図である。
【図２】 両性界面活性剤とアニオン界面活性剤の混合比とデカンに対する界面張力の関係を表わした図である。
【図３】 オレイン酸の添加による電気伝導度の変化を表わした図である。BACKGROUND OF THE INVENTION
[0001]
The present invention relates to a cleaning composition. More specifically, the present invention relates to a cleaning composition suitable for cleaning hair and skin, cleaning glass such as tableware, cleaning homes, etc., having excellent cleaning power and sufficiently considering the influence on the environment.
[0002]
[Prior art]
As detergents for hair and skin, glass such as tableware, and dwelling, surfactant-type detergents mainly utilizing emulsification, dispersion, solubilization and the like, which are the characteristics of surfactants, have been used.
[0003]
In addition, some dish cleaners and residential cleaners use alkaline agents, and these alkaline cleaners saponify fatty acids generated by the transformation of fats and oils contained in dirt. Soap is made and washed. On the other hand, an acid-type cleaning agent is used for dirt in a bathroom or the like, and decomposes and cleans fatty acid calcium which is a main component of dirt. Furthermore, a solvent-type cleaning agent using a solvent such as trichlorethylene may be used for a cleaning agent having a special purpose that requires a very high cleaning power.
[0004]
[Problems to be solved by the invention]
However, solvent-type cleaning agents have problems such as toxicity and adverse effects on the environment. Alkali-type cleaners and acid-type cleaners are dangerous to the skin and eyes, corrode metals, and have problems such as environmental impact. Furthermore, the surfactant type has mild properties that can be used with skin and hair cleansing agents. However, if a large amount of surfactant is used, there is a concern about the environmental impact of the waste liquid. In addition, there is a demand for a surfactant-type detergent having a high detergency.
[0005]
As a result of intensive studies to solve the above problems, the present inventors have determined that a surfactant-type detergent containing a specific component is an isotropic surfactant continuous phase or an isotropic surfactant. It was found that when a multiphase system in which a continuous phase and other phases coexist is adjusted, a detergent composition having excellent detergency and sufficiently considering the influence on the environment can be obtained, and the present invention has been completed. It was.
[0006]
An object of the present invention is to provide a cleaning composition that has an excellent detergency, is safe enough to be used on the body, and has sufficient consideration for the environment.
[0007]
[Means for Solving the Problems]
That is, the present invention relates to a detergent composition containing the following components (A), (B), (C), and (D), wherein the interfacial tension with respect to decane of a 1% by mass aqueous solution of the components (A) and (B) is x (MN · m ⁻¹ ), and y (mN · m ⁻¹ ) is the smaller of the interfacial tensions of 1% by mass aqueous solution of component (A) or component (B) with respect to decane. A cleaning agent having a mixing ratio of component (A) and component (B) so as to satisfy (1), wherein the cleaning composition is an isotropic surfactant continuous phase at 25 ° C. It is a composition, Comprising: The cleaning composition whose mass ratio of the total mass of a component (A) and (B) and a component (C) is the range of 5: 1 to 1: 2 is provided.
(A) Amphoteric surfactant (B) Anionic surfactant (C) Liquid alcohol and / or liquid fatty acid (D) Water [Formula 3]
x <y-1 (1)
[0008]
The present invention also provides the above-mentioned cleaning composition, wherein the component (C) is a liquid alcohol and / or a liquid fatty acid having 4 to 8 carbon atoms.
[0009]
Furthermore, this invention provides the said cleaning composition whose mass ratio of a component (A) and a component (B) is the range of 1: 9-9: 1.
[0011]
Furthermore, in the present invention, the electrical conductivity of a 5 mass% aqueous solution of components (A) and (B) is u (mS · cm ⁻¹ ), and the electrical conductivity when component (C) is further added is v When the (mS · cm ⁻¹ ) is used, the above-described cleaning composition having a mass composition ratio of (C) to (A) and (B) so as to satisfy the following formula (2): It is to provide.
[Formula 4]
v <u (2)
[0013]
Furthermore, the present invention provides the above-described cleaning composition, wherein the cleaning composition is a skin or hair cleaning agent.
[0014]
The present invention also provides the above-described cleaning composition, wherein the cleaning composition is a cleaning agent for glass, ceramics or plastic.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of the present invention will be described in detail.
[0016]
The amphoteric surfactant of component (A) used in the present invention has at least one cationic functional group and one anionic functional group, becomes cationic when the solution is acidic, and anionic when the solution is alkaline, and has an isoelectric point. In the vicinity, it has a property close to that of a nonionic surfactant. Amphoteric surfactants are classified into carboxylic acid type, sulfuric acid ester type, sulfonic acid type and phosphoric acid ester type depending on the type of anionic group. Carboxylic acid type, sulfuric acid ester type and sulfonic acid type are preferred. The carboxylic acid type is further classified into an amino acid type and a betaine type, particularly preferably a betaine type. Specific examples include imidazolium betaine, alkyl betaine, and amide betaine.
[0017]
Component (B) anionic surfactant used in the present invention is a carboxylic acid type such as fatty acid soap or N-acyl glutamate, a sulfonic acid type such as α-olefin sulfonate, alkane sulfonate, or alkylbenzene sulfonic acid. And sulfate alcohol salt type such as higher alcohol sulfate ester salt, phosphate ester salt type and the like. Carboxylate type, sulfonic acid type and sulfate ester type are preferred, and sulfate ester type is particularly preferred. Specific examples include alkyl ethoxy sulfate salts.
[0018]
Of the sulfonate types, alkylbenzene sulfonic acids include branched-chain alkyl types and straight-chain alkyl types, which are undesirable in terms of environmental impact (biodegradability). Particularly preferred are branched alkylbenzene sulfonates.
[0019]
The type of amphoteric surfactant of component (A) and anionic surfactant of component (B) is such that when mixed in an aqueous solution of the cleaning composition of the present invention, the interfacial tension against decane is reduced. And the amount is selected. Interfacial tension is an important factor especially for cleaning oil, and in a solution with low interfacial tension with oil, the oil stain spontaneously becomes spherical and detaches from the base. Are known. In the present invention, specifically, the interfacial tension with respect to decane of the 1% by mass aqueous solution of component (A) and component (B) is x (mN · m ⁻¹ ), and each of component (A) or component (B) When the smaller one of the interfacial tensions with respect to decane of the 1 mass% aqueous solution of y is m (mN · m ⁻¹ ), the components (A) and (B) The mixing ratio is determined. A detergent composition characterized in that if it deviates from this mixing ratio, it is an isotropic surfactant continuous phase at 25 ° C. or a multiphase system in which an isotropic surfactant continuous phase and other phases coexist. It may not be a thing. A desirable mixing ratio of the amphoteric surfactant of component (A) to the anionic surfactant of component (B) is 9: 1 to 1: 9. When this range is deviated, the interfacial tension is not sufficiently lowered and the cleaning effect may not be sufficient.
[Formula 5]
x <y-1 (1)
[0020]
In the present invention, the amphoteric surfactant of component (A) and the anionic surfactant of component (B) are mixed and used, but when mixed in an aqueous solution, a salt is generated in both by electrostatic interaction. , Eyes and skin irritation is greatly reduced.
[0021]
The liquid alcohol of component (C) used in the present invention means a monohydric alcohol that is liquid at 25 ° C. Examples of the linear 1-alcohol include alcohols having 12 or less carbon atoms, and examples of the linear 2-alcohol include alcohols having 14 or less carbon atoms. Examples of the branched chain alcohol include isostearyl alcohol and 2-octyldodecanol. An oleyl alcohol is mentioned as what has a double bond. Preferred are linear 1-alcohols having 12 or less carbon atoms and oleyl alcohol. Particularly preferred are linear 1-alcohols and oleyl alcohols having 4 to 8 carbon atoms. Alcohols having less than 4 carbon atoms are not desirable because they tend to require high blending. In addition, the mixture which kept liquid state at 25 degreeC by mixing two or more types of alcohol with a suitable mixing ratio can be utilized. That is, in the case where two or more kinds of alcohols are mixed and exhibit a liquid state at 25 ° C., they are included in the liquid alcohol referred to in the present invention.
[0022]
The liquid fatty acid (C) used in the present invention means a fatty acid that is liquid at 25 ° C. Examples of the straight chain fatty acid include fatty acids having 9 or less carbon atoms, examples of the branched chain fatty acid include isostearic acid, and examples of those having a double bond include oleic acid. Moreover, even if it is a linear fatty acid having 10 or more carbon atoms, it is possible to use a mixture which is kept in a liquid state at 25 ° C. by mixing several kinds at an appropriate mixing ratio. That is, when it is liquid at 25 ° C. with two or more fatty acids mixed, it is included in the liquid fatty acid referred to in the present invention. Preferred are linear fatty acids having 9 or less carbon atoms and oleic acid. Particularly preferred are linear fatty acids having 4 to 9 carbon atoms and oleic acid.
[0023]
In the present invention, when one or a combination of two or more selected from the liquid alcohol and / or liquid fatty acid of component (C) is added to the mixed aqueous solution of component (A) and component (B), It is desirable for the electrical conductivity of the to decrease. A decrease in electrical conductivity means an increase in the order of the aggregate formed by the surfactant. Since the salts in the solution that contribute to the electrical conductivity are taken into the aggregate with an increased degree of order and an increased number of associations, the conductivity decreases. Specifically, the electrical conductivity of a 5% by mass aqueous solution containing components (A) and (B) is u (mS · cm ⁻¹ ), and component (C) is further added to this aqueous solution. When the electric conductivity is v (mS · cm ⁻¹ ), it is preferable to have a mass composition ratio of (C) to (A) and (B) so as to satisfy the following formula (2), and deviates from this. Then, when it is not a detergent composition characterized by being an isotropic surfactant continuous phase at 25 ° C. or a multiphase system in which an isotropic surfactant continuous phase and other phases coexist is there. Further, the total mass of the components (A) and (B) and the mass ratio of the component (C) is preferably in the range of 5: 1 to 1: 2. If the ratio is less than 5: 1, the detergency is not sufficiently improved. If the ratio exceeds 1: 2, component (C) may be separated.
[Formula 6]
v <u (2)
[0024]
In the cleaning composition of the present invention, the above-described requirements are satisfied, and the isotropic surfactant continuous phase at 25 ° C. or a multiphase system in which the isotropic surfactant continuous phase and other phases coexist. There must be. An isotropic surfactant continuous phase is a bicontinuous phase in which surfactants are infinitely associated. Both water and oil are continuous, and an optically isotropic transparent low-viscosity solution. The cleaning effect is extremely excellent as a cleaning agent composition.
[0025]
In the present invention, whether the detergent composition is an isotropic surfactant continuous phase is determined by appearance, creation of phase equilibrium diagram, electrical conductivity measurement, measurement of self-diffusion coefficient by NMR, freeze fracture method. It is determined by observation with an electron microscope of the replica prepared. In terms of appearance, the isotropic surfactant continuous phase is a transparent low-viscosity one-phase region and is optically isotropic. The optically anisotropic liquid crystal phase can be distinguished by holding the sample while combining two polarizing plates with a phase difference of 90 degrees and confirming that there is no light transmission. The following method is further effective for distinguishing between the isotropic surfactant continuous phase and the other micelle aqueous solution and reverse micelle oil solution which are other isotropic one-phase regions. In the three-component phase equilibrium diagram composed of water / oil / surfactant (including cosurfactant), it is an isotropic transparent low-viscosity one-phase region, and it is not a continuous region from either water or oil apex. However, this feature varies depending on the system to be constructed. It is known that the conductivity of the isotropic surfactant continuous phase obtained by measuring the electric conductivity takes about 2/3 of the aqueous micelle phase obtained in the same system. The self-diffusion coefficient measurement by NMR is a method described in detail by Lindman et al. In J. Colloid Interface Sci. 1981, 83, 569 and the like. According to electron microscope observation of an isotropic surfactant continuous phase sample prepared using the freeze fracture method, it is possible to obtain an image in which both water and oil are continuous. According to this image, water or oil can be easily distinguished from a spherical aggregate image obtained in a continuous micelle aqueous solution phase.
[0026]
FIG. 1 shows (A) amphoteric surfactant with 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine 5% by mass, (B) anionic surfactant with polyoxyethylene (3 mol) lauryl ether sulfate. 5% by mass of Na, (C) 1-10% by mass of hexanol is used for liquid alcohol and / or liquid fatty acid, and (D) the temperature of the cleaning composition when water is used as the residue and the content of hexanol as parameters. It is a figure showing the area | region which has an isotropic surfactant continuous phase in the case where it did. L ₁ represents a micellar aqueous phase, L _α represents a lamellar liquid crystal phase, D represents an isotropic surfactant continuous phase, and O represents an oil phase (hexanol phase). The present invention is a region where D (isotropic surfactant continuous phase) exists at 25 ° C.
[0027]
Various components to be blended in the present invention are required to have good biodegradability so as not to affect the environment. In the case of an alkyl group, those having a double bond have the best biodegradability, followed by linear alkyl. Among the straight-chain types, those having a short alkyl chain length are considered good. Branched alkyls are not considered biodegradable. Also, the benzene ring has a problem in biodegradability. A highly biodegradable material that has little environmental impact is desirable. The method for obtaining the degradation rate (biodegradation rate) by microorganisms is regulated by the Chemical Council Law. In fact, TOD (Theological Oxygen Demand) obtained by theoretically calculating the amount of oxygen consumed by aerobic decomposition (BOD: Biological Oxygen Demand) from the chemical structure of the cleaning agent due to the activated mud rich in aerobic bacteria: Calculated by dividing by the theoretical oxygen demand). Both the branched alkylbenzene sulfonate and the linear alkylbenzene sulfonate, which are considered to have problems in biodegradability, have a 5-day biodegradation rate of less than 5%. In the cleaning composition of the present invention, in consideration of the environment, the contents of (A) and (B) are 1% by mass or less based on the total amount of the cleaning composition, and The 5-day biodegradation rate is preferably 50% or more.
[0028]
The cleaning composition of the present invention is a mixture of the essential components (A), (B), (C) and the water of the component (D), and other components blended in the cleaning agent or cosmetic as necessary. It adds suitably in the range which does not impair the effect of this invention, and is manufactured by a conventional method according to the target dosage form.
[0029]
The cleaning composition of the present invention is preferably used as a cleaning agent for skin or hair cleaning agents, glass, ceramics or plastics.
[0030]
【Example】
Next, the present invention will be described in more detail with reference to examples. Note that the present invention is not limited to this. A compounding quantity represents the mass%.
[0031]
In order to confirm the cleaning effect of the cleaning composition of the present invention, the following tests were conducted.
"Cleaning effect evaluation method"
An area of 2 cm × 2 cm was set in advance on a slide glass for microscopic observation, and 0.1 g of petrolatum was uniformly applied. The cleaning liquid was diluted with ion-exchanged water so as to have a constant surfactant concentration, filled in a 200 ml beaker, and heated to 60 ° C. in a constant temperature aqueous phase. The slide glass coated with petrolatum was gently immersed in the washing solution and gently lifted after 5 minutes, and immediately the residual amount of petrolatum on the glass was visually determined.
"Criteria for cleaning effectiveness"
◎: Vaseline residual amount is 10% or less ○: Petrolatum residual amount is 25% or less Δ: Petrolatum residual amount is 50% or less ×: Petrolatum residual amount exceeds 50%
Each table shows the evaluation results for the cleaning materials of Examples and Comparative Examples, and the cleaning materials diluted by 10 times, 100 times, and 200 times of Examples and Comparative Examples, respectively.
[0033]
[Table 1]
Ingredients Comparative Example 1 Comparative Example 2
Palm Fatty Acid Amidopropyl Betaine 10
POE (3 mol) lauryl ether sulfate Na-10
Oleic acid 2 2
Detergent effect test surfactant 10% pure by weight ◎ ◎
Surfactant 1% by mass: 10-fold dilution ○ ○
Surfactant 0.1% by mass: 100-fold dilution × ×
Surfactant 0.05% by mass: 200-fold dilution × ×
Manufacturing method: Each component is added to water and stirred.
[0035]
[Table 2]
Ingredients Comparative Example 3 Comparative Example 4
2-Alkyl-N-carboxymethyl 9 9
-N-hydroxyethyl
Imidazolium betaine
POE (5 mol) lauryl ether sulfuric acid 1 1
Triethanolamine 1-butanol--
Deionized water Residual Residual cleaning effect test Surfactant pure 10% by mass ◎ ◎
Surfactant pure 1% by mass: 10-fold dilution △ △
Surfactant 0.1% by mass: 100-fold dilution × ×
Surfactant 0.05% by mass: 200-fold dilution × ×
Manufacturing method: Each component is added to water and stirred.
[0037]
[Table 3]
Ingredients Example 3
Lauryldimethylaminoacetic acid betaine 1
N-myristoyl-L-glutamate Na 9
1-Hexanol 5
Ion exchange water Residual cleaning effect test Surfactant pure 10% by mass ◎
Surfactant 1% by mass: 10 times dilution ◎
Surfactant 0.1% by mass: 100-fold dilution ○
Surfactant 0.05% by mass: 200-fold dilution ○
Manufacturing method: Each component is added to water and stirred.
[0038]
From the results in Table 3, it can be seen that the cleaning composition of Example 3 is an excellent cleaning agent having a high cleaning effect even when the surfactant at the time of dilution is at a low concentration.
[0039]
[Table 4]

Manufacturing method: Each component is added to water and stirred.
[0040]
From the results of “Table 4”, it can be seen that the detergent composition of Example 4 is an excellent detergent having a high cleaning effect even when the surfactant at the time of dilution is at a low concentration.
[0043]
[Table 6]

Manufacturing method: Each component is added to water and stirred.
[0044]
From the results of “Table 6”, it can be seen that the cleaning composition of Example 6 is an excellent cleaning agent having a high cleaning effect even when the surfactant upon dilution has a low concentration.
[0045]
"Biodegradation rate"
The biodegradation rate of the cleaning composition of Example 6 was determined by the BOD method defined by the Chemical Council Law. As a result, it was found that the 5-day biodegradation rate of the detergent composition was 62%, and it was a detergent with high biodegradability and sufficient consideration for the environment.
[0046]
"Interfacial tension"
The interfacial tension with respect to decane of the aqueous solution in which the amphoteric surfactant and the anionic surfactant used in Example 6 were mixed was measured. The total surfactant concentration was 1% by mass, and the measurement was performed by the spinning drop method. FIG. 2 shows the relationship between the mixing ratio of the amphoteric surfactant and the anionic surfactant and the interfacial tension with respect to decane. From FIG. 2, it can be seen that by mixing the amphoteric surfactant and the anionic surfactant, the interfacial tension with respect to decane is lowered and changes to a state suitable for cleaning.
[0047]
"Electric conductivity"
The change in electrical conductivity when oleic acid was added to the mixture of the amphoteric surfactant and the anionic surfactant used in Example 6 was measured. FIG. 3 shows changes in electrical conductivity due to the addition of oleic acid. FIG. 3 shows that when oleic acid is added to the mixture of the amphoteric surfactant and the anionic surfactant, the electrical conductivity decreases, the order of the associated state increases, and the state changes to a state suitable for washing.
[0048]
【The invention's effect】
According to the present invention, it has excellent detergency, and even with a small amount of use, it has sufficient detergency, so it can be fully considered for the environment, is highly safe and can be used on the body. In addition, a cleaning composition excellent in biodegradability can be provided.
[Brief description of the drawings]
FIG. 1 is a diagram showing a region having a continuous isotropic surfactant phase when the content of hexanol is used as a parameter.
FIG. 2 is a graph showing the relationship between the mixing ratio of amphoteric surfactant and anionic surfactant and the interfacial tension with respect to decane.
FIG. 3 is a graph showing a change in electrical conductivity due to the addition of oleic acid.

Claims (6)

In the detergent composition containing the following components (A), (B), (C), and (D), the interfacial tension with respect to decane of 1% by mass aqueous solutions of the components (A) and (B) is expressed as x (mN · m ⁻¹ ), And when y (mN · m ⁻¹ ) is the smaller of the interfacial tensions with respect to decane of each 1% by mass aqueous solution of component (A) or component (B), the following formula (1) is satisfied. A cleaning composition characterized in that it has a mixing ratio of component (A) and component (B), and the cleaning composition is an isotropic surfactant continuous phase at 25 ° C., A cleaning composition in which the mass ratio of the total mass of components (A) and (B) to component (C) is in the range of 5: 1 to 1: 2.
(A) Amphoteric surfactant (B) Anionic surfactant (C) Liquid alcohol and / or liquid fatty acid (D) Water [Formula 1]

  The cleaning composition according to claim 1, wherein the component (C) is a liquid alcohol and / or a liquid fatty acid having 4 to 8 carbon atoms.   The cleaning composition according to claim 1 or 2, wherein the mass ratio of the component (A) to the component (B) is in the range of 1: 9 to 9: 1. The electrical conductivity of a 5 mass% aqueous solution of the components (A) and (B) is u (mS · cm ⁻¹ ), and the electrical conductivity when the component (C) is further added is v (mS · cm ^−1). The cleaning composition according to claim 1, 2 or 3, wherein the composition has a mass composition ratio of (C) to (A) and (B) so as to satisfy the following formula (2): .
[Formula 2]

The cleaning composition according to claim 1, 2, 3 or 4, wherein the cleaning composition is a skin or hair cleaning agent. The cleaning composition according to claim 1, 2, 3 or 4, wherein the cleaning composition is a cleaning agent for glass, ceramics or plastic.

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