JPH07292397A - Bactericidal liquid cleaning agent composition - Google Patents

Abstract

PURPOSE:To provide a bactericidal liquid cleaning agent composition having excellent cleaning power and frothing power. CONSTITUTION:This bactericidal liquid cleaning agent composition contains 0.05-30wt.% of an anionic surfactant and 0.02-20wt.% of at least one kind of >=3-valent metal salt. The composition contains at least one kind of anionic surfactant having sulfuric acid ester salt group, ethoxysulfuric acid ester salt group, sulfonic acid salt group or ethoxysulfonic acid salt group as a hydrophilic group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a germicidal liquid detergent composition, and more particularly to an anionic surfactant and 3
The present invention relates to a liquid detergent composition which contains a metal salt having a valency or more, is excellent in detergency and foaming power, and has bactericidal activity.

[0002]

2. Description of the Related Art Conventional liquid detergents mainly containing anionic surfactants, such as dishwashing detergents, have excellent foaming power and detergency, but the detergents themselves have no bactericidal power. . Cationic surfactants such as benzalkonium chloride and glycine-type amphoteric surfactants (for example, Tego 51 (trade name) manufactured by Gold Schmidt has strong bactericidal activity, but little detergency can be expected (Takehiko Fujimoto) Introducing the revised new surfactant, Sanyo Kasei Co., Ltd., 314
P. (1985)). As a method for improving this drawback, Japanese Patent Publication No. 47-29363 discloses that a cationic surfactant having a strong bactericidal power is blended with a nonionic surfactant to improve the cleaning power while maintaining the bactericidal power. The method of doing is described. JP-A-53-123409 also discloses a method of using an amphoteric surfactant and a nonionic surfactant in combination.

However, these cationic-nonionic surfactant mixed-system and amphoteric-nonionic surfactant-mixed liquid detergents are superior to conventional cationic surfactants and amphoteric surfactants alone. Although there are some improvements in foaming power and detergency, these properties are compared to liquid detergents containing anionic surfactant as a main component.
It was much worse.

[0004]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned conventional problems, and an object thereof is to contain an anionic surfactant as a main component and to have excellent foaming power and detergency and to be strong. It is intended to provide a germicidal liquid detergent composition having germicidal activity.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems in a detergent composition using an anionic surfactant, and as a result, have found that anionic surfactant and trivalent By using in combination with the above metal salts,
It was found that a bactericidal liquid detergent composition having a remarkably strong bactericidal power and excellent foaming power and detergency was obtained, and the present invention was completed.

The bactericidal liquid detergent composition of the present invention contains 0.05 to 30% by weight of an anionic surfactant and 0.02 to 20% by weight of at least one trivalent or higher valent metal salt. The surfactant is an anionic surface active agent having a sulfate group (sulfate) group, an ethoxy sulfate salt (ether sulfate) group, a sulfonate (sulfonate) group, or an ethoxysulfonate (ethersulfonate) group as its hydrophilic group. The bactericidal liquid detergent composition of the present invention contains at least one of the anionic surfactants, and thereby achieves the above object.

In a preferred embodiment, the metal salt is at least one selected from the group consisting of aluminum salt and iron salt.

[0008] In a preferred embodiment, the germicidal liquid detergent composition of the present invention further contains, as a solubilizer, a mixture of at least one lower alcohol or polyhydric alcohol.

In a preferred embodiment, the number of carbon atoms in the hydrocarbon chain contained in the anionic surfactant is 6-18.
Is.

In a preferred embodiment, the anionic surfactant is alkyl sulfate ester salt, alkyl ether sulfate ester salt, fatty acid amide ether sulfate ester salt, α-olefin sulfonate, alkylbenzene sulfonate, alkyl sulfonate. , An α-sulfo fatty acid ester salt, an acylmethyl taurine salt, and an alkyl ether sulfonate.

The present invention will be described in detail below.

As the anionic surfactant used in the present invention, alkyl sulfate ester salt, alkyl ether sulfate ester salt, fatty acid amide ether sulfate ester salt (for example, Sanamide CF-3, NOF Corporation), α
-Olefin sulfonate, alkylbenzene sulfonate, alkyl sulfonate, α-sulfo fatty acid ester salt, acylmethyl taurine salt (for example, Diapon K, NOF Corporation), alkyl ether sulfonate (for example, Avanel S) -70, PPG Indu
stories) and the like. Generally, the number of carbon atoms in the hydrocarbon chain of the anionic surfactant is 6 to 1.
It is preferably 8. If the number of carbon atoms in the hydrocarbon chain is less than 6, the sterilizing power of the resulting detergent composition may be insufficient, and if it exceeds 18, the solubility in water may decrease. Among the above-mentioned anionic surfactants, those having an ether bond (for example, alkyl ether sulfate ester salt, fatty acid amide ether sulfate ester salt, alkyl ether sulfonate salt, etc.) have ethylene oxide in the structure of the anionic surfactant. The average number of added moles of is preferably 7 or less. The average number of moles of ethylene oxide added in the anionic surfactant is 7
If it exceeds the range, the sterilizing power may decrease. In the present specification, the average addition mole number of ethylene oxide is, for example, (3EO) when the average addition mole number is 3.
Express. The anionic surfactant is usually provided as an alkali metal salt (eg, sodium salt, potassium salt, etc.), but may be another salt (eg, magnesium salt, aluminum salt, etc.).

In the present invention, as the metal salt used in combination with the anionic surfactant, a metal salt having a valence of 3 or more is used. Examples of such trivalent or higher metal salts include chlorides such as aluminum, iron, chromium and lanthanum, sulfates, acetates and nitrates. Examples of the chloride include aluminum chloride, ferric chloride, chromium chloride, lanthanum chloride and the like. Particularly preferred metal salts include aluminum salts and iron salts. It is also possible to use a trivalent or higher valent metal salt of an anionic surfactant.

Even when monovalent and divalent metal salts are used, some bactericidal power can be obtained. However, since the effect is weak, when an attempt is made to obtain a liquid detergent composition having a sufficient bactericidal activity, the concentration of the monovalent and divalent metal salts in the composition becomes very high and salting out occurs. , Not practical. On the other hand, when a metal salt having a valence of 3 or more is used, the obtained liquid detergent composition has a sufficient bactericidal activity with about half the amount of the anionic surfactant, and does not salt out.

When the content of the anionic surfactant in the liquid detergent composition of the present invention is relatively high, it is obtained by adding the above-mentioned trivalent or higher metal salt which is usually used in about half the amount of the anionic surfactant. The viscosity of the resulting solution of the liquid detergent composition increases. Further, if the content of the metal salt having a valence of 3 or more is too large, the obtained liquid detergent composition may cause gelation or become cloudy / separated. High-viscosity or gel-like products are extremely difficult to use in practice, not only significantly impairing their commercial value, but also in the production of the liquid detergent composition of the present invention, operability deteriorates, for example, filling into a container is difficult. It causes problems such as

As described above, gelation occurs, white turbidity,
In order to obtain sufficient bactericidal activity without separation, usually, in the liquid detergent composition of the present invention, 0.05 to 30% by weight of the anionic surfactant and at least one trivalent or more of the above are used. 0.02 to 20% by weight of the metal salt is contained. When the liquid detergent composition of the present invention is used as a detergent for, for example, dishes, it is usually about 15 to 30% by weight of anionic surfactant and about 5 to 15 of a metal salt having a valence of 3 or more.
Prepared to contain wt%. The liquid detergent composition having such an anionic surfactant concentration is usually used by diluting it so that the anionic surfactant concentration becomes 0.05 to less than 10% by weight.

Generally, when the viscosity of the liquid detergent composition becomes high, a solubilizer is further added to adjust the viscosity. Such solubilizers include lower alcohols and polyhydric alcohols. The lower alcohol (for example, ethanol, isopropyl alcohol, etc.) and the polyhydric alcohol (for example, hexylene glycol, butylene glycol, etc.) effectively act as a solubilizer (that is, a viscosity adjusting agent, a viscosity reducing agent),
It is desirable as a solubilizer used in the present invention because it does not reduce the sterilizing power of the detergent. A particularly preferred solubilizer is
Hexylene glycol. Usually, as the solubilizer, in addition to the above lower alcohol and polyhydric alcohol,
Although sodium toluene sulfonate, sodium xylene sulfonate, urea and the like are also used, these are not preferable in the present invention because they significantly reduce the sterilizing power of the detergent.

The bactericidal liquid detergent composition of the present invention contains, in addition to the above-mentioned components, components generally added to liquid detergents, if necessary, such as non-ionic compounds such as polyoxyethylene alkyl ether. Surfactants, oily ingredients such as higher alcohols, moisturizing ingredients such as glycerin, pigments, solvents,
Fragrances, thickeners (water-soluble polymers, etc.) and the like can be added.

Examples of preferable combinations as components used for obtaining the bactericidal liquid detergent composition of the present invention include, but are not limited to, the combinations shown in Table 1 below. In Table 1, the amount of each component is represented by weight% when the sterilizing liquid detergent composition is 100% by weight.

[0020]

[Table 1]

The bactericidal liquid detergent composition of the present invention is prepared by dissolving or dispersing the above-mentioned anionic surfactant, trivalent or higher valent metal salt and, if necessary, additives such as a solubilizer in water. Can be obtained by As a solvent other than water, a water-soluble solvent such as a lower alcohol or a polyhydric alcohol may be contained.

[0022]

The details of the mechanism by which the bactericidal liquid detergent composition of the present invention exhibits excellent bactericidal activity are unknown, but the following reasons can be considered, for example.

The bactericidal liquid detergent composition of the present invention contains a specific anionic surfactant and a metal salt having a valence of 3 or more, and the hydrophilic group of the anionic surfactant reacts with the cation of the metal salt. As a result, the hydrophobicity is increased, which makes it easier for the anionic surfactant bound with the metal cation to be adsorbed on the cells. At this time, since the metal salt needs to sufficiently react with the hydrophilic group portion of the anionic surfactant, a metal salt having a valence of 3 or more is used. In order to make the monovalent and divalent metal salts sufficiently hydrophobic, it is necessary to use the monovalent and divalent metal salts in a high concentration, in which case salting out is not suitable for practical use.

When a metal salt is used, the surface of the bacterial cell, which is normally negatively charged, reacts with the cation of the metal salt to neutralize the charge on the surface of the bacterial cell. It is conceivable that the anionic surfactant contained in the composition becomes accessible and sterilized.

[0025]

The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
The effect was determined by the following test method.

(1) Bactericidal activity 4.5 ml of the test solution was added to the test bacterial solution (about 1% in broth liquid medium).
E. coli cultured for 6 hours. The culture solution of E. coli (ATCC No.25922) was washed by centrifugation twice with sterile distilled water and then resuspended in sterile distilled water (E. coli (ATCC No.25922): about 10 ⁵ to 10 ⁶⁾
/ Ml)) 0.5 ml and stir well. 10
After a minute, 0.5 ml of this mixture was mixed with 4.5 ml of an inactivating agent (polysorbate 804 4% + lecithin 0.3% + 0.1 M sodium citrate (adjusted to about pH 7)) to sterilize the test solution. Stopped. This mixed solution was further diluted stepwise with an inactivating agent, and a fixed amount was pour-cultured on ordinary agar medium to determine the number of surviving bacteria per 0.5 ml of the test solution. The ratio of the number of dead sterilization to the number of test bacteria was evaluated as follows. ⊚: Death sterilization number 99% or more ○: Death sterilization number 90% or more and less than 99% ×: Death sterilization number less than 90% xx: Not killed at all

(2) Viscosity The viscosity of the test liquid was evaluated according to the following criteria. ○: Appropriate fluidity ×: Gelation or almost no fluidity.

(3) Stability Immediately after preparation of the test solution and after storage at room temperature for 1 month, the appearance of the sample was visually evaluated according to the following criteria. ◯: Transparent, no abnormality ×: White turbidity, separation or gelation occurred.

(4) Foaming power 20 ml of each test solution (600-fold diluted solution of each composition or commercial detergent) is placed in a graduated cylinder with a 100 ml capacity stopper.
Was charged, shaken up and down for 15 seconds, and the volume of foam after standing for 30 seconds was measured.

(5) Detergency A polypropylene cap (diameter 59 mm × height 13)
100 ml of the test liquid and 5 stainless steel balls having a diameter of 4 mm were placed in a polypropylene wide-mouthed bottle (diameter 62 mm × height 111 mm, capacity 225 ml) having a polypropylene (mm). On the inside of the cap, 0.5 ml of beef tallow previously kept at about 70 ° C. was dropped and uniformly applied. The jar was sealed with this cap and kept at 37 ° C.
Set this on the round odometer and rotate at 40 rpm
After washing with water for 3 minutes, remove the cap and store it in water (2
(000 ml) and air dried. The detergency was evaluated by obtaining the detergency rate from the following formula.

[0031]

[Equation 1]

W _a : Weight of the cap before washing W _b : Weight of the cap after washing W _o : Weight of the cap before attaching dirt.

Example 1 Various anionic surfactants (A) to (J) shown in Table 2 were sterilized so that the surfactants were 0.1% by weight and aluminum chloride was 0.1% by weight. It was dissolved in distilled water to obtain a liquid detergent composition, and the bactericidal activity was examined by the above method. The obtained results are shown in Table 2.
The results of Comparative Examples 1 to 5 below are also shown in Table 2.

(Comparative Example 1) A liquid detergent composition was prepared by using the various anionic surfactants (A) to (J) in the same manner as in Example 1 except that aluminum chloride was not added. The sterilizing power was examined.

(Comparative Example 2) Anionic surfactants (A) to (J)
Instead of various anionic surfactants (K) shown in Table 2 ~
A liquid detergent composition was obtained in the same manner as in Example 1 except that (O) was used, and the bactericidal activity was examined in the same manner.

(Comparative Example 3) A liquid detergent composition was prepared by using the various anionic surfactants (K) to (O) in the same manner as in Comparative Example 2 except that aluminum chloride was not added. The sterilizing power was examined.

(Comparative Example 4) Anionic surfactants (A) to (J)
Instead of various nonionic surfactants (P) shown in Table 2
A liquid detergent composition was obtained in the same manner as in Example 1 except that (U) was used, and the bactericidal activity was examined in the same manner.

(Comparative Example 5) A liquid detergent composition was obtained by using the various nonionic surfactants (P) to (U) in the same manner as in Comparative Example 4 except that aluminum chloride was not added. Then, the sterilizing power was examined.

[0039]

[Table 2]

As is apparent from Table 2, the bactericidal activity of the liquid detergent composition containing the anionic surfactants (A) to (J) and aluminum chloride obtained in Example 1 was excellent. . The liquid detergent composition obtained in Comparative Example 1, which did not contain aluminum chloride as a metal salt, had no bactericidal activity. The liquid detergent composition using a nonionic surfactant and an anionic surfactant such as an alkyl ether carboxylate having a carboxyl group as a hydrophilic group did not show bactericidal activity with or without aluminum chloride. .

Example 2 Various metal salts (a) -shown in Table 3
Using (d), 0.4% by weight of sodium octanesulfonate and 0.1% by weight of a metal salt are dissolved in sterile distilled water to obtain a liquid detergent composition, and the sterilizing power is obtained by the above method. I checked. The results obtained are shown in Table 3. The results of Comparative Examples 6 to 8 below are also shown in Table 3.

(Comparative Example 6) A liquid detergent composition was obtained by using the various metal salts (a) to (d) in the same manner as in Example 2 except that sodium octanesulfonate was not added. The sterilizing power was examined.

(Comparative Example 7) Instead of the metal salts (a) to (d),
A liquid detergent composition was obtained in the same manner as in Example 2 except that the various metal salts (e) to (l) shown in Table 3 were used, and the bactericidal activity was examined in the same manner. (Comparative Example 8) Various metal salts (e) were prepared in the same manner as in Comparative Example 7 except that sodium octanesulfonate was not added.
Liquid detergent compositions were obtained by using ~ (l), and the bactericidal activity was examined in the same manner.

[0044]

[Table 3]

As is apparent from Table 3, the liquid detergent containing the anionic surfactant sodium octanesulfonate obtained in Example 2 and the trivalent metal salts (a) to (d). The bactericidal activity of the composition was excellent. However, the liquid detergent composition of Comparative Example 5 containing no anionic surfactant showed almost no germicidal activity. 1 price or 2
The liquid detergent composition using a valent metal salt showed almost no bactericidal activity regardless of the presence or absence of the anionic surfactant.

Example 3 The stability and viscosity of the liquid detergent compositions 1 to 23 having the compositions shown in Table 4 were examined by the above method, and the compositions 1 to 23 were tested for anionic surfactant concentration. A test solution was prepared by diluting it with sterilized distilled water so as to have a concentration of 0.05% by weight, and its sterilizing power was examined by the above method. The results are shown in Table 4. The amount of each component in Table 4 is
It is expressed in% by weight when the sterilizing liquid detergent composition is 100% by weight.

[0047]

[Table 4]

Liquid detergent compositions 1 to 23 were excellent in bactericidal activity, stability and viscosity.

Example 4 With respect to the liquid detergent compositions 4, 6 and 7 in Table 4, the foaming power and the cleaning power were measured by the above-mentioned methods. The results obtained are shown in Table 5. The results of Comparative Example 9 below are also shown in Table 5.

Comparative Example 9 The following commercially available kitchen detergent I,
For II and III, the foaming power and detergency were measured by the above method. Kitchen Detergent I: Lauryl Ether (3EO) Sulfate-
It contains Na as a main component and does not contain a metal salt having a valence of 3 or more. Kitchen Detergent II: Lauryl Ether (3EO) Sulfate-
It contains Na and betaine-based surfactants as main components and does not contain trivalent or higher valent metal salts. Kitchen detergent III: lauryl glycoside as the main component, 3
It does not contain metal salts with a valency or higher.

[0051]

[Table 5]

As can be seen from Table 5, the liquid detergent composition of the present invention was found to have foaming power and detergency equal to or higher than that of a commercial kitchen detergent.

[0053]

According to the present invention, it is possible to obtain a liquid detergent composition which is excellent in detergency and foaming power and has bactericidal activity. The germicidal liquid detergent of the present invention is useful as a dish detergent.

Claims (5)

[Claims] 1. Anion surfactant 0.05 to 30% by weight and at least one trivalent or higher valent metal salt 0.02.
An antiseptic liquid detergent composition containing 20% by weight, wherein the anionic surfactant has a sulfate group, an ethoxy sulfate group, a sulfonate group or an ethoxysulfonate group as its hydrophilic group. A germicidal liquid detergent composition which is a surfactant and contains at least one of the anionic surfactants. 2. The germicidal liquid detergent composition according to claim 1, wherein the metal salt is at least one selected from the group consisting of aluminum salts and iron salts. 3. The germicidal liquid detergent composition according to claim 1, further comprising a mixture of at least one lower alcohol or polyhydric alcohol as a solubilizing agent. 4. The germicidal liquid detergent composition according to claim 1, wherein the hydrocarbon chain of the anionic surfactant has 6 to 18 carbon atoms. 5. The anionic surfactant is an alkyl sulfate ester salt, an alkyl ether sulfate ester salt, a fatty acid amide ether sulfate ester salt, an α-olefin sulfonate, an alkylbenzene sulfonate, an alkyl sulfonate, or an α-sulfo. The germicidal liquid detergent composition according to claim 1, which is selected from the group consisting of a fatty acid ester salt, an acylmethyl taurine salt, and an alkyl ether sulfonate.