JP2002020791A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an eco-friendly detergent composition having excellent cleaning power and high safety applicable even to human body. SOLUTION: The detergent composition is composed of (A) an ampholytic surfactant, (B) an anionic surfactant, (C) a liquid alcohol and/or a liquid fatty acid and (D) water. The mixing ratio of the component (A) and the component (B) is adjusted to satisfy the formula x<y-1 wherein (x) mN.m-1 is the interfacial tension of the 1 wt.% aqueous solution of the component (A) and the component (B) to decane and (y) mN.m-1 is the smaller one between the interfacial tension of the 1 wt.% aqueous solution of the component (A) and that of the component (B). The detergent composition is a continuous isotropic phase of the surfactant at 25 deg.C or a multiphase system containing a continuous isotropic phase of the surfactant and other phase.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates to a cleaning composition. More specifically, the present invention relates to a cleaning composition which is suitable for cleaning hair and skin, cleaning glass such as tableware, cleaning a house, etc., has excellent detergency and sufficiently considers the effect on the environment.

[0002]

2. Description of the Related Art As a cleaning agent for glasses such as hair, skin, tableware, etc., and a cleaning agent for a house, a surfactant-type cleaning agent mainly utilizing emulsifying, dispersing and solubilizing properties of a surfactant is used. Has been used.

[0003] Some dishwashing detergents and residential detergents include a type using an alkaline agent. Such an alkaline type detergent is a fatty acid produced by denaturation of oils and fats contained in dirt. To produce soap and wash it. On the other hand, acid stains are used for stains in bathrooms and the like, in which fatty acid calcium, which is a main component of the stains, is decomposed and washed. Further, a solvent-type cleaning agent using a solvent such as trichloroethylene may be used as a cleaning agent having a special use requiring an extremely high detergency.

[0004]

However, the solvent-type detergent has problems such as toxicity and adverse effects on the environment. In addition, the alkali type cleaning agent and the acid type cleaning agent are dangerous for skin and eyes, corrode metals, and have problems such as influence on the environment. In addition, the surfactant type has mild properties that can be used with skin and hair cleansing agents, but if a large amount of surfactant is used, there is a concern that the waste liquid will affect the environment. There is a demand for a surfactant type detergent having a high detergency.

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a surfactant-type detergent containing a specific component can be used as an isotropic surfactant continuous phase. The present invention was completed by finding that a detergent composition having excellent detergency and sufficient consideration for the environment can be obtained by adjusting to a multiphase system in which a surfactant continuous phase and another phase coexist. I came to.

An object of the present invention is to provide a detergent composition which has excellent detergency, is safe enough to be used on the body, and is sufficiently environmentally friendly.

[0007]

That is, the present invention relates to a cleaning composition containing the following components (A), (B), (C) and (D), wherein 1% of the components (A) and (B) is used. The interfacial tension of the ¹ % aqueous solution with respect to decane is defined as x (mN · m ⁻¹ ), and the smaller one of the interfacial tensions of the 1% aqueous solution of component (A) and component (B) with decane is defined as y (mN · m− ¹ ).
m ^-1 ), the detergent composition has a mixing ratio of the component (A) and the component (B) so as to satisfy the following formula (1), and the detergent composition has an isotropic surfactant at 25 ° C. It is intended to provide a detergent composition characterized by being a continuous phase or a multiphase system in which a continuous phase of an isotropic surfactant and another phase coexist. (A) amphoteric surfactant (B) anionic surfactant (C) liquid alcohol and / or liquid fatty acid (D) water

[Formula 3] x <y-1 (1)

The present invention also provides the above detergent composition, wherein the component (C) is a liquid alcohol and / or a liquid fatty acid having 4 to 8 carbon atoms.

Further, the present invention provides the above-mentioned detergent composition, wherein the mass ratio of the component (A) to the component (B) is in the range of 1: 9 to 9: 1.

[0010] The present invention also provides the above-mentioned detergent composition, wherein the mass ratio of the total mass of the components (A) and (B) to the component (C) is in the range of 5: 1 to 1: 2. Is what you do.

Further, the present invention relates to a method for preparing a 5% by mass aqueous solution of the components (A) and (B), wherein the electric conductivity is u (mS · cm ⁻¹ ) and the electric conductivity when the component (C) is further added. Degree v
(MS · cm ⁻¹ ), wherein the cleaning composition has a mass composition ratio of (C) to (A) and (B) so as to satisfy the following expression (2). To provide.

Equation 4 v <u (2)

Further, the present invention provides that the content of (A) and (B) is 1% by mass or less based on the total amount of the detergent composition, and the biodegradability of the detergent composition for 5 days is 50%. % Of the above-mentioned cleaning composition.

Further, the present invention provides the above-mentioned cleaning composition, wherein the cleaning composition is a skin or hair cleaning agent.

Further, the present invention provides the above-mentioned cleaning composition, wherein the cleaning composition is a cleaning agent for glass, ceramics or plastics.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

The amphoteric surfactant (A) used in the present invention has at least one cationic functional group and at least one anionic functional group.
It becomes anionic when alkaline, and has properties close to a nonionic surfactant near the isoelectric point. Amphoteric surfactants are classified into carboxylic acid type, sulfate ester type, sulfonic acid type and phosphate ester type depending on the type of anionic group. Preferred are carboxylic acid type, sulfate ester type and sulfonic acid type. 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 amido betaine.

The anionic surfactant (B) used in the present invention includes carboxylic acid salts such as fatty acid soaps and N-acyl glutamates, α-olefin sulfonates, alkane sulfonates, alkylbenzene sulfonic acids and the like. It is classified into sulfonic acid type, sulfate ester type such as higher alcohol sulfate ester salt, phosphate ester salt type and the like. Preferred are carboxylate type, sulfonic acid type and sulfate ester type, and particularly preferred are sulfate ester type. Specifically, for example, an alkyl ethoxy sulfate salt is mentioned.

Alkylbenzenesulfonic acid of the sulfonic acid salt type includes a branched-chain alkyl type and a straight-chain alkyl type, but these are not desirable in view of the effect on the environment (biodegradability). Particularly unfavorable are the branched-chain alkylbenzene sulfonates.

The amphoteric surfactant of component (A) and the anionic surfactant of component (B) are such that when mixed in an aqueous solution of the cleaning composition of the present invention, the interfacial tension with decane is reduced. , The type and the amount of the compound are selected. Interfacial tension is an important factor especially for washing oil, and in a solution with low interfacial tension with oil, the dirt spontaneously becomes spherical and detaches from the base material. Is known. In the present invention, specifically, the interfacial tension of a 1% by mass aqueous solution of the component (A) and the component (B) with respect to decane is x (mN · m
^-1 ), and the smaller one of the interfacial tensions with respect to decane of a 1% by mass aqueous solution of each of the component (A) and the component (B) is defined as y (mN · m ⁻¹ ). The mixing ratio of component (A) and component (B) is determined to be satisfactory. When the mixing ratio deviates from this, at 25 ° C., the composition is a continuous phase of an isotropic surfactant or a multiphase system in which a continuous phase of an isotropic surfactant and another phase coexist. It may not be a thing. A desirable mixing ratio of the amphoteric surfactant of the component (A) and the anionic surfactant of the component (B) is from 9: 1 to 1: 9. If the ratio is out of this range, the interfacial tension may not be sufficiently reduced and the cleaning effect may not be sufficient.

[Formula 5] x <y-1 (1)

In the present invention, the amphoteric surfactant of the component (A) and the anionic surfactant of the component (B) are mixed and used. Salt is formed and irritation to eyes and skin is greatly reduced.

The liquid alcohol (C) used in the present invention means a monohydric alcohol which is liquid at 25 ° C. Linear 1-alcohols include alcohols having 12 or less carbon atoms, and linear 2-alcohols include alcohols having 14 or less carbon atoms. Examples of the branched chain alcohol include isostearyl alcohol and 2-octyldodecanol. Oleyl alcohol is exemplified as one having a double bond. Preferably, they are a straight-chain 1-alcohol having 12 or less carbon atoms and oleyl alcohol. Particularly preferred are straight-chain 1-alcohols having 4 to 8 carbon atoms and oleyl alcohol. Alcohols having less than 4 carbon atoms are not desirable because they tend to require high blending. In addition, it is possible to use a mixture in which two or more alcohols are mixed at an appropriate mixing ratio to maintain a liquid state at 25 ° C.
That is, 25 in a state where two or more alcohols are mixed.
When it shows a liquid state at ° C, it is included in the liquid alcohol referred to in the present invention.

The liquid fatty acid (C) used in the present invention means a fatty acid which is liquid at 25 ° C. Straight-chain fatty acids include fatty acids having 9 or less carbon atoms, branched-chain fatty acids include isostearic acid, and those having a double bond include oleic acid. Even if it is a straight-chain fatty acid having 10 or more carbon atoms, it is possible to use a mixture that maintains a liquid state at 25 ° C. by mixing several kinds at an appropriate mixing ratio. That is, a case where two or more kinds of fatty acids are liquid at 25 ° C. in a mixed state is included in the liquid fatty acids according to the present invention. Preferably, it is a straight-chain fatty acid having 9 or less carbon atoms and oleic acid. Particularly preferred are straight-chain fatty acids having 4 to 9 carbon atoms and oleic acid.

In the present invention, when one or a combination of two or more selected from liquid alcohols and / or liquid fatty acids of component (C) is added to a mixed aqueous solution of components (A) and (B). In addition, it is desirable that the electric conductivity of the solution be reduced. A decrease in electrical conductivity means that the order of the aggregate formed by the surfactant increases. Salts in the solution contributing to the electrical conductivity have an increased order and are taken into the aggregates with an increased number of associations, so that the conductivity decreases.
Specifically, 5% by mass containing components (A) and (B)
Assuming that the electric conductivity of the aqueous solution is u (mS · cm ⁻¹ ) and the electric conductivity when the component (C) is further added to the aqueous solution is v (mS · cm ⁻¹ ), the following formula (2) It is preferable to have a mass composition ratio of (C) to (A) and (B) so as to satisfy the above condition.
In some cases, the cleaning composition may not be characterized by being a continuous phase of an isotropic surfactant or a multiphase system in which a continuous phase of an isotropic surfactant and another phase coexist. The total mass of the components (A) and (B) and the mass ratio of the component (C) are 5:
It is desirable to be in the range of 1-1: 2. When the ratio is less than 5: 1, the cleaning power is not sufficiently improved, and when the ratio exceeds 1: 2, (C)
Components may separate, which is not desirable.

[Formula 6] v <u (2)

The cleaning composition of the present invention satisfies the above requirements and is a continuous phase of an isotropic surfactant at 25 ° C. or a multiphase in which the continuous phase of an isotropic surfactant and another phase coexist. Must be phased. The 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. And the cleaning effect is extremely excellent as a cleaning composition.

In the present invention, whether or not the detergent composition is a continuous phase of an isotropic surfactant is determined by appearance, preparation of a phase equilibrium diagram, measurement of electric conductivity, measurement of self-diffusion coefficient by NMR, freeze fracture. It is determined by electron microscopic observation of the replica prepared by the method. In terms of appearance, the continuous phase of an isotropic surfactant is a transparent low-viscosity one-phase region and is optically isotropic. The optically anisotropic liquid crystal phase can be distinguished from the liquid crystal phase 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 isotropic one-phase region, ie, aqueous micelle solution and reverse micelle oil solution. On a phase equilibrium diagram of a three-component system composed of water / oil / surfactant (including cosurfactant), it is an isotropic transparent low-viscosity one-phase region and is not a region that is continuous from either the water or oil top. Although it can be identified by having such features as above, this feature differs depending on the system to be configured. It is known that the conductivity of the continuous phase of the isotropic surfactant obtained by the measurement of the electrical conductivity is about ／ of that of the aqueous micelle phase obtained in the same system. The self-diffusion coefficient measurement by NMR is described by Lindman et al. In J. C.
olloid Interface Sci. 1981, 83, 569 and the like. According to the electron microscopic observation of the 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.

FIG. 1 shows (A) 5% by mass of 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine as an amphoteric surfactant, and (B) polyoxyethylene (3 mol) as an anionic surfactant. Lauryl ether sulfate Na
5% by mass, (C) 1 to 10% by mass of hexanol as liquid alcohol and / or liquid fatty acid, and (D) the temperature of the detergent composition when water is used as the residue and the content of hexanol as parameters. FIG. 3 is a diagram showing a region having an isotropic surfactant continuous phase in the case where the process is performed. L ₁ represents a micelle aqueous phase, L _α represents a lamellar liquid crystal phase, D represents a continuous phase of an isotropic surfactant, and O represents an oil phase (hexanol phase). The present invention is an area where D (isotropic surfactant continuous phase) exists at 25 ° C.

The various components to be blended in the present invention are required to have good biodegradability so as to have little effect on the environment. In the case of an alkyl group, those having a double bond have the best biodegradability, followed by linear alkyl. Among the linear types, those having a short alkyl chain length are considered to be good. Branched-chain alkyls are not considered to have good biodegradability. Also, the benzene ring has a problem in biodegradability. It is desirable to use a biodegradable material that has little effect on the environment. The method for obtaining the rate of biodegradation (biodegradation rate) is specified by the Chemical Council Law. Actually, the amount of oxygen consumed by aerobic decomposition by activated mud rich in aerobic bacteria (BOD: Biologi
TOD (Theological Oxygen Demand) obtained by theoretically calculating cal Oxygen Demand from the chemical structure of the detergent:
Calculated by dividing by the theoretical oxygen demand). The branched-chain alkylbenzenesulfonate and the straight-chain alkylbenzenesulfonate allegedly having a problem in biodegradability have a biodegradation rate of less than 5% for 5 days. The cleaning composition of the present invention, with due consideration of the environment,
It is preferable that the content of (A) and (B) is 1% by mass or less based on the total amount of the detergent composition, and that the biodegradability of the detergent composition for 5 days is 50% or more.

The cleaning composition of the present invention is obtained by mixing the above essential components (A), (B), and (C) with water of the component (D), and blending it with a detergent or a cosmetic as required. Is appropriately added within a range that does not impair the effects of the present invention, and is produced by a conventional method according to the desired dosage form.

The cleansing composition of the present invention is preferably used as a cleansing agent for skin or hair, glass, ceramics or plastics.

[0030]

Next, the present invention will be described in more detail with reference to examples. Note that the present invention is not limited to this. The compounding amount represents mass%.

The following test was conducted to confirm the cleaning effect of the cleaning composition of the present invention. "Cleaning effect evaluation method" A region of 2 cm x 2 cm was set in advance on a slide glass for microscope observation,
1 g was uniformly applied. The washing solution was diluted with ion-exchanged water to a certain surfactant concentration, filled in a 200 ml beaker, and heated to 60 ° C. in a constant temperature aqueous phase. The slide glass coated with Vaseline was gently immersed in the cleaning solution, gently pulled up after 5 minutes had elapsed, and immediately the amount of Vaseline remaining on the glass was visually determined. "Criteria for determining cleaning effect" ：: Vaseline residual amount is 10% or less ：: Vaseline residual amount is 25% or less △: Vaseline residual amount is 50% or less ×: Vaseline residual amount exceeds 50%

Each table shows the evaluation results of the cleaning agents of the examples and comparative examples, and the cleaning agents obtained by diluting the examples and the comparative examples by 10 times, 100 times, and 200 times, respectively.

[0033]

Ingredients Example 1 Comparative Example 1 Comparative Example 2 Coconut fatty acid amidopropyl betaine 510 POE (3 mol) lauryl ether sulfate Na 5-10 oleic acid 222 Detergent effect test Surfactant pure content 10% by mass ◎ ◎ ◎ Surfactant pure content 1% by mass: 10-fold dilution ◎ ○ ○ Surfactant pure content 0.1% by mass: 100-fold dilution ○ × × Surfactant pure content 0.05% by mass: 200-fold dilution ○ × × Production method: Add each component to water and stir.

From the results shown in Table 1, it can be seen that the detergent composition of Example 1 is an excellent detergent having a high cleaning effect even when the concentration of the surfactant at the time of dilution is low.

[0035]

Ingredients Example 2 Comparative Example 3 Comparative Example 4 2-Alkyl-N-carboxymethyl 999-N-hydroxyethyl imidazolium betaine POE (5 mol) lauryl ether sulfate 111 Triethanolamine 1- Butanol 20--Ion-exchange water Residue Residue Residue Residue Cleaning test 10% by mass of pure surfactant ◎ ◎ ◎ 1% by mass of pure surfactant: 10 times dilution ◎ △ △ 0.1% by mass of pure surfactant: 100 times Dilution ○ × × 0.05% by mass of pure surfactant: 200 times dilution ○ × × Production method: Add each component to water and stir.

From the results shown in Table 2, it can be seen that the detergent composition of Example 2 is an excellent detergent having a high cleaning effect even when the concentration of the surfactant at the time of dilution is low.

[0037]

Ingredients Example 3 Betaine lauryl dimethylaminoacetate 1 N-myristoyl-L-glutamate Na 9 1-hexanol 5 Deionized water Residue Cleaning effect test Surfactant pure content 10% by mass ◎ Surfactant pure content 1 Mass%: 10-fold dilution ◎ Pure surfactant 0.1 mass%: 100-fold dilution ○ Surfactant pure content 0.05 mass%: 200-fold dilution ○ Production method: Add each component to water and stir.

From the results shown in Table 3, it can be seen that the detergent composition of Example 3 is an excellent detergent having a high cleaning effect even when the concentration of the surfactant at the time of dilution is low.

[0039]

Table 4 Ingredients Example 4 N-palmityl N, N-dimethylaminopropyl 6 sulfonic acid coconut fatty acid methyltaurine Na 4 caprylic acid 3 ion-exchanged water Residual cleaning effect test Surfactant pure content 10% by mass ◎ Surfactant Pure content 1 mass%: 10-fold dilution ◎ Surfactant pure content 0.1 mass%: 100-fold dilution ○ Surfactant pure content 0.05 mass%: 200-fold dilution ○ Production method: Add each component to water and stir.

From the results shown in Table 4, it can be seen that the cleaning composition of Example 4 is an excellent cleaning agent having a high cleaning effect even when the concentration of the surfactant at the time of dilution is low.

[0041]

Ingredients Example 5 Lecithin 6 Na 4 Lauric acid 2-butanol 15 Deionized water Residue Production method: After dissolving lecithin in 2-butanol, add it to water with other components and stir.

From the results shown in Table 5, it can be seen that the detergent composition of Example 5 is an excellent detergent having a high cleaning effect even when the concentration of the surfactant at the time of dilution is low.

[0043]

Ingredients Example 6 2-Alkyl-N-carboxymethyl 9-N-hydroxyethylimidazolium betaine POE (3 mol) lauryl ether sulfate Na 0.7 POE (3 mol) lauryl ether sulfate 0.3 tri Ethanolamine Oleic acid 5 Deionized water Residual Production method: Add each component to water and stir.

From the results shown in 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 concentration of the surfactant at the time of dilution is low.

"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, the biodegradability of the detergent composition for 5 days was 62%, indicating that the detergent was highly biodegradable and had sufficient consideration for the environment.

"Interfacial tension" The interfacial tension of decane of the aqueous solution obtained by mixing the amphoteric surfactant and the anionic surfactant used in Example 6 was measured. The measurement was performed by the spinning drop method with the total surfactant concentration being 1% by mass. FIG.
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 mixing the amphoteric surfactant and the anionic surfactant lowers the interfacial tension with respect to decane and changes to a state suitable for washing.

"Electrical Conductivity" The change in electric 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 the change in electric 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 electric conductivity decreases, the degree of order in the associated state increases, and the state changes to a state suitable for washing.

[0048]

According to the present invention, it has excellent detergency,
Providing a detergent composition that has sufficient detergency even when used in small quantities, is fully environmentally friendly, is safe, can be used on the body, and has excellent biodegradability. I can do it.

[Brief description of the drawings]

FIG. 1 is a diagram showing a region having a continuous phase of an isotropic surfactant when the content with hexanol is used as a parameter.

FIG. 2 is a diagram showing a relationship between a mixing ratio of an amphoteric surfactant and an anionic surfactant and an interfacial tension with respect to decane.

FIG. 3 is a diagram showing a change in electric conductivity due to addition of oleic acid.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C11D 17/00 C11D 17/00 17/08 17/08 F term (reference) 4C083 AB051 AB052 AC061 AC101 AC102 AC241 AC242 AC252 AC582 AC712 AC792 AD572 BB05 BB07 CC23 CC38 DD27 EE03 EE09 4H003 AB03 AB31 AD04 BA12 DA02 DA05 DA12 DA17 EB04 EB07 ED02 FA02 FA03

Claims (8)

[Claims] In a detergent composition containing the following components (A), (B), (C) and (D), the interfacial tension of a 1% by mass aqueous solution of the components (A) and (B) with respect to decane is x
(MN · m ⁻¹ ), and the smaller one of the interfacial tensions with respect to decane of a 1% by mass aqueous solution of each of the component (A) and the component (B) is defined as y (mN · m ⁻¹ ). The detergent composition has a mixing ratio of component (A) and component (B) so as to satisfy (1), and the cleaning composition is an isotropic surfactant continuous phase at 25 ° C. or isotropic surfactant A cleaning composition comprising a multiphase system in which a continuous phase and another phase coexist. (A) amphoteric surfactant (B) anionic surfactant (C) liquid alcohol and / or liquid fatty acid (D) water Formula 1 x <y-1 (1) 2. 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. 3. The cleaning composition according to claim 1, wherein the mass ratio of component (A) to component (B) is in the range of 1: 9 to 9: 1. 4. The cleaning composition according to claim 1, wherein the total mass of the components (A) and (B) and the mass ratio of the component (C) are in the range of 5: 1 to 1: 2. object. 5. The electric conductivity of a 5% by mass aqueous solution of the components (A) and (B) is u (mS · cm ⁻¹ ), and the electric conductivity when the component (C) is further added is v ( (mS · cm ⁻¹ ), the composition has a mass composition ratio of (C) to (A) and (B) so as to satisfy the following expression (2). 5. The cleaning composition according to item 4. [Formula 2] v <u (2) 6. The content of (A) and (B) is 1% by mass or less based on the total amount of the cleaning composition, and the 5-day biodegradation rate of the cleaning composition is 50% or more. Claims 1, 2,
The cleaning composition according to 3, 4 or 5. 7. The cleaning composition according to claim 1, 2, 3, 4, 5, or 6, wherein the cleaning composition is a skin or hair cleansing agent. 8. The cleaning composition according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the cleaning composition is a cleaning agent for glass, ceramics, or plastics.