JP5663183B2 - Toilet cleaning composition - Google Patents

Description

The present invention relates to a toilet cleaning composition in which the antibacterial activity of polyhexamethylene biguanide hydrochloride is improved by a specific nonionic surfactant.

In general, in an environment where water flows temporarily, such as inside a toilet bowl, inorganic and organic substances form insoluble salts and become dirty as they are, or dark stains derived from bacteria and mold occur using them as a substrate. . Therefore, it is generally performed to give antibacterial and bactericidal action to a toilet cleaning composition in which washing water is automatically poured into a water tank using hand-washing water in a flush toilet tank. A quaternary ammonium salt compound is used.
However, since quaternary ammonium salt compounds have almost no antibacterial activity at low concentrations, they are derived from bacteria and molds in applications such as toilet cleaning compositions that are diluted in a large excess of water. It was difficult to obtain a satisfactory antibacterial and bactericidal action for the effect of suppressing darkening stains.

Patent Document 1 discloses a solid sterilization detergent composition for hard surfaces as a sterilization detergent that can be used for floors and appliances such as toilets.
This hard sterilization detergent composition for hard surfaces is a non-foaming solid sterilization detergent for hard surfaces containing 0.05 to 20% by weight of a cationic fungicide and 0.5 to 30% by weight of a nonionic surfactant. In Patent Document 1, the permeability of the biguanide fungicide that is a cationic fungicide is improved by containing polyoxyethylene alkyl (C12-18) ether that is a nonionic surfactant in Patent Document 1, It is described that the bactericidal action is improved.
However, the effect of improving the bactericidal action of the biguanide fungicide by the nonionic surfactant is only about twice, and the effect of suppressing dark stains could not be expected.

Patent Document 2 discloses a toilet wash water additive composition containing a biguanide fungicide containing polyhexamethylene biguanide hydrochloride and an addition polymer of an alkylphenol compound and ethylene oxide.
However, this toilet cleaning water additive composition has insufficient bactericidal activity when the concentration of the biguanide fungicide is less than 3% by weight (60 ppm when diluted), and it is difficult to use the fungicide at a low concentration. Met.

JP-A-11-124594 JP-A-7-150194

The present invention improves the antibacterial and bactericidal action of polyhexamethylene biguanide hydrochloride having antibacterial and bactericidal action, realizes an effective antibacterial and bactericidal action at a low concentration, and can suppress dark stains An object is to provide a cleaning composition.

In order to solve the above problems, polyhexamethylene biguanide hydrochloride can be combined with a specific nonionic surfactant to improve the antibacterial and bactericidal action of polyhexamethylene biguanide hydrochloride. It was found that it can be used and is effective in preventing darkening stains on the toilet.

（式中ｍおよびｎは任意の整数である。）
で表され、式中Ｒ^１で表される置換基が、直鎖又は分岐状の炭素数１６〜１８のアルキル基である化合物を含有することを特徴とするトイレ洗浄用組成物に関する。 That is, the present invention
Polyhexamethylene biguanide hydrochloride, and
The following general formula (1):

(In the formula, m and n are arbitrary integers.)
And a substituent represented by R ¹ in the formula contains a linear or branched compound having a carbon number of 16 to 18 and a toilet cleaning composition.

In the present invention, the compound represented by the general formula (1) is preferably a polyoxyethylene alkyl ether in which R ¹ has 16 to 18 carbon atoms.
Moreover, it is preferable that the compound represented by General formula (1) has HLB 5-18.

In the present invention, the weight concentration of polyhexamethylene biguanide hydrochloride is preferably 0.3 to 3.0 ppm.

Moreover, in this invention, it is preferable that the compound represented by General formula (1) is 5 to 50 weight part with respect to 1 weight part of polyhexamethylene biguanide hydrochloride.

According to the toilet cleaning composition of the present invention, the antibacterial / bactericidal action of polyhexamethylene biguanide hydrochloride can be improved by blending a specific nonionic surfactant with polyhexamethylene biguanide hydrochloride. Therefore, an effective antibacterial and bactericidal action can be exhibited even at a low concentration.
In addition, the occurrence of dark stains can be suppressed.

（式中ｍおよびｎは任意の整数である。）
で表され、式中Ｒ^１で表される置換基が、直鎖又は分岐状の炭素数１６〜１８のアルキル基である化合物（以下、化合物Ａともいう）を含有する。 The toilet cleaning composition of the present invention comprises:
Polyhexamethylene biguanide hydrochloride (hereinafter also referred to as PHMB), and
The following general formula (1):

(In the formula, m and n are arbitrary integers.)
In which the substituent represented by R ¹ is a linear or branched alkyl group having 16 to 18 carbon atoms (hereinafter also referred to as compound A).

PHMB is one of the biguanide fungicides, and functions as an active ingredient having antibacterial and bactericidal action in the toilet cleaning composition.

The compound A is a nonionic surfactant, and R ¹ can be used in any of linear or branched (iso form).

In the general formula (1), R ¹ represents a linear or branched (isoform) alkyl group having 16 to 18 carbon atoms. When R ¹ is an alkyl group having 16 to 18 carbon atoms, the antibacterial and bactericidal action of PHMB can be preferably improved.

The compound A preferably has an HLB (Hydrophile-Lipophile Balance) of 5 to 18. When the HLB is in this range, the antibacterial and bactericidal action of PHMB can be preferably improved. The HLB of the compound A is more preferably 8-18, and further preferably 10-18.
Here, in Compound A, it is known that the addition mole number of ethylene oxide (EO) or propylene oxide (PO) and HLB are generally correlated, and the addition mole number of EO or PO is changed for the adjustment of HLB. This can be done by methods well known in the art. The HLB value can be calculated by several methods well known in the art. In the present invention, the HLB value was calculated by the Griffin method.

In the general formula (1), n and m are arbitrary integers. Particularly, when R ¹ is linear, n is preferably an integer of 2 to 17, and m is 0 to 24. preferable. Further, it is more preferable that n + m = 2 to 30 is satisfied. In compound A, ethylene oxide and propylene oxide may be either random or block adducts, and those in which propylene oxide is directly bonded to R ¹ are also included.

Specific examples of the compound A include, for example, POE cetyl ether, POE oleyl ether, POE stearyl ether, POE isocetyl ether, POE isooleyl ether, POE isostearyl ether, POE alkyl (C16-18) ether, POE · POP cetyl. Ether, POE / POP oleyl ether, POE / POP stearyl ether, POE / POP isocetyl ether, POE / POP isooleyl ether, POE / POP isostearyl ether, POP cetyl ether, POP oleyl ether, POP stearyl ether, POP isocetyl Examples include ether, POP isooleyl ether, and POP isostearyl ether.
Among these, POE cetyl ether, POE oleyl ether, POE stearyl ether, POE · POP cetyl ether, POE · POP oleyl ether, POE · POP stearyl ether are preferable in that the antibacterial and bactericidal action of PHMB is further improved.
POE cetyl ether, POE oleyl ether, and POE stearyl ether are particularly preferred.

Here, “POE” represents polyoxyethylene, and “POP” represents polyoxypropylene.

In the present invention, the combined use of PHMB and Compound A can improve the antibacterial / bactericidal action of PHMB.
Therefore, the weight concentration of PHMB is not particularly limited, but is preferably 0.3 to 3.0 ppm, and more preferably 0.3 to 2.0 ppm. The lower limit is more preferably 0.5 ppm. The upper limit is more preferably 1.0 ppm, and particularly preferably 0.8 ppm.
Within this range, the effect of improving the antibacterial / bactericidal action of PHMB when used in combination with Compound A is more remarkable. Conventionally, the antibacterial and bactericidal action of PHMB was not observed within this range, but when used in combination with Compound A, the toilet cleaning composition has excellent antibacterial and bactericidal action even within such a low concentration range. It can be. For this reason, even at a low concentration that has not been used in the past as having no antibacterial / bactericidal action, it can be used according to the present invention. And the amount of the antibacterial agent in the toilet cleaning composition is required to be as low as possible in consideration of the influence on the environment. An excellent toilet cleaning composition can be obtained.
Moreover, according to the toilet cleaning composition of the present invention, it is also possible to suppress the occurrence of dark stains on toilet toilets and the like. Black stains occur when bacteria adhere to organic or inorganic deposits attached to toilets, etc., and then these bacteria produce extracellular polymers and mold spores adhere to the extracellular polymer surface. Although it can be considered, in the present invention, the generation of extracellular polymer can be suppressed by removing bacteria attached on organic or inorganic deposits by antibacterial and bactericidal action. It is thought that you can.

Here, the concentration of PHMB is a concentration at the time of use. For example, in a toilet cleaning composition that is assumed to be diluted with water at the time of use, it means the concentration after dilution. For example, in the case of a so-called on-tank type toilet cleaning composition that is filled in a container and used in a hand-washing portion at the top of a tank of a flush toilet, when the water is flushed, A certain amount of the composition inside is discharged and collected in the tank together with water, which means the concentration in the tank at this time.

In the toilet cleaning composition of the present invention, compound A is preferably blended in an amount of 5 to 50 parts by weight per 1 part by weight of PHMB.
The lower limit is more preferably 10 parts by weight. On the other hand, the upper limit is more preferably 40 parts by weight, still more preferably 30 parts by weight, and particularly preferably 20 parts by weight.
When the concentration of Compound A exceeds 50 parts by weight, the toilet cleaning composition has an excellent antibacterial and bactericidal action, but the effect of improving the antibacterial and bactericidal action per compounding amount of Compound A tends to be suppressed. Specifically, when the concentration of PHMB is 0.5 ppm, it is preferable to add about 2.5 to 25 ppm of Compound A.

In the toilet cleaning composition of the present invention, a functional component, an anti-redeposition agent, a pH adjuster, a chelating agent, a viscosity adjuster, a suspending agent, an antiseptic, an antioxidant, and an ultraviolet absorber as necessary. In addition, components such as enzymes, pigments, and pigments such as dyes may be contained in appropriate amounts. Examples of the functional component include an aromatic component and a deodorizing component. Examples of the aromatic component include natural fragrances such as lavender, lemon, orange, jasmine and peppermint; synthetic fragrances such as limonene, terpinolene, geraniol, citronellol and ethyl acetate; and blended fragrances thereof. In addition, examples of the deodorant component include extracts from plants such as rice, pine, hinoki and cocoon; desalted betaine compounds; modified organic acid compounds; triethanolamine; stabilized chlorine dioxide; . These functional components may be used individually by 1 type, and may be used in combination of 2 or more type.

The toilet cleaning composition of the present invention is, for example, an on-tank liquid cleaning composition that is used by being filled in a container and installed in a hand-washing unit at the top of a tank of a flush toilet. It can be used as a suspended liquid cleaning composition that is used in preparation, an aerosol liquid cleaning composition that is used by filling a container together with a propellant, and the like.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

Example 1
A sterilized purified water (manufactured by Otsuka Pharmaceutical Co., Ltd.) was used to prepare a 5000 ppm aqueous solution of polyhexamethylene biguanide hydrochloride (manufactured by Arch Chemicals Japan, Proxel IB). The prepared 5000 ppm aqueous solution was diluted 100 times to a 50 ppm aqueous solution, and further diluted 100 times to prepare a 0.5 ppm aqueous solution. The polyoxyethylene cetyl ether described in Table 1 (R ¹ = cetyl group in the general formula (1)) (Brownon CH-310L, manufactured by Aoki Yushi Kogyo Co., Ltd.) in each aqueous solution was added at each concentration (6, 8, 10 ppm). ) Was added and stirred to prepare a toilet cleaning composition.

Examples 2 to 10 and Comparative Examples 1 to 5
Instead of Braunone CH-310L, the compound represented by the general formula (1) described in Table 1 (nonionic surfactant, R ¹ is linear) was used (Examples 2 to 5, 9 to 10). Comparative Examples 1 and 2) or a compound represented by the general formula (1) described in Table 1 (nonionic surfactant, R ¹ is branched) (Examples 6 to 8, Comparative Examples) A toilet cleaning composition was prepared in the same manner as in Example 1 except for 3 to 5).

(Evaluation method)
The sterilizing effect of the obtained toilet cleaning composition was evaluated by the following method.

(1) Staphylococcus aureus NBRC12732 is used as a test strain, and this strain is streaked on a SCD agar medium (Soybean-Casein Digest Agar, manufactured by Nippon Pharmaceutical Co., Ltd.) with a platinum ear, Pre-cultured for 24 hours.

(2) The pre-cultured test strain was suspended in a Nutrient broth medium (manufactured by Nippon Becton Dickinson Co., Ltd.) so as to be about 10 ⁸ cfu / ml (hereinafter referred to as a bacterial solution).

(3) 9.9 ml of each of the following solutions A to D was dispensed into a 50 ml sterile centrifuge tube (manufactured by Nippon Becton Dickinson Co., Ltd.). Thereafter, 0.1 ml of the bacterial solution was inoculated into each centrifuge tube to make 10 ml, and statically cultured at 25 ° C. for 3 hours.
Solution A: Only sterile physiological saline (Otsuka Pharmaceutical Co., Ltd.) (blank)
Solution B: Aqueous solution of 0.5 ppm polyhexamethylene biguanide hydrochloride (PHMB) only C solution: Aqueous solution D of various nonionic surfactants (compounds represented by the above general formula (1)) of various concentrations: Implementation Aqueous solutions of Examples 1-10 and Comparative Examples 1-5

(4) 0.1 ml is taken from each of the solutions A to D 3 hours after inoculation, and a dilution series is appropriately prepared using phosphate buffered saline (manufactured by Wako Pure Chemical Industries, Ltd.), and then the stock solution Each 0.1 ml of the diluted solution was smeared on an SCDLP agar medium (Soybean-Casein Digest Agar with Lecithin & Polysorbate 80, manufactured by Nippon Pharmaceutical Co., Ltd.), and cultured at 35 ° C. for 18 hours to measure the number of viable cells.

(5) The antibacterial activity value of each of the solutions B to D was calculated according to the following formula. In each solution, the larger the antibacterial activity value, that is, the greater the decrease in the number of viable bacteria relative to the blank A, the higher the antibacterial property.
Antibacterial activity value = log [number of bacteria in A (sterilized physiological saline only)]-log [number of bacteria in each solution of BD]

Using the calculated antibacterial activity value of each of the solutions B to D, the effect of improving the antibacterial / bactericidal action of PHMB by the combined use with the compound represented by the general formula (1) was calculated. A value (db) obtained by subtracting the antibacterial activity value b of the B solution (aqueous solution containing only PHMB) from the antibacterial activity value d of the D solution (aqueous solution containing PHMB and the compound represented by the general formula (1)) "Improvement effect value" was obtained, and the obtained improvement effect value was evaluated according to the following criteria.

Judgment criteria for improvement effect values:
Less than 1: ×
1 or more and less than 1.5: △
1.5 or more and less than 2.0: 〇2.0 or more: ◎

Further, the “improvement effect value” was divided by the concentration of the compound represented by the general formula (1) in the D solution to calculate the “antibacterial activity value per 1 ppm of the compound represented by the general formula (1)”. .

As shown in Table 1, when used in combination with Compound A, the antibacterial / bactericidal action of PHMB could be improved.
In addition, when 10 ppm of Compound A was added to 0.5 ppm of PHMB, the “antibacterial activity value per 1 ppm of compound” tended to be suppressed, but particularly when the concentration of Compound A was 2.5 to 25 ppm. Excellent antibacterial and bactericidal activity was demonstrated. That is, it was particularly preferred when the compound A was 5 to 50 parts by weight relative to 1 part by weight of PHMB.
The “improvement effect value” indicates an antibacterial activity value per 1 ppm of the compound represented by the general formula (1).

In addition, 35 monitors were selected, a group using nothing, a group using only PHMB (concentration 0.5 ppm), a group using only compound A (concentration 10 ppm), and the toilet cleaning composition of Example 1 A group using (the concentration of Compound A is 10 ppm), a group using the toilet cleaning composition of Example 4 (the concentration of Compound A is 10 ppm), and the toilet cleaning composition of Example 7 (the concentration of Compound A is 5 groups each were divided into 7 groups: a group using 10 ppm) and a group using the toilet cleaning composition of Example 9 (compound A concentration of 10 ppm). The toilet was used twice a day for each monitor, and the effect of suppressing darkening stains was confirmed by comparing the number of days until darkening stains were generated on the toilet bowl.
As a result, the group using only the PHMB and the group using only the compound A showed the same result as the group not using anything, whereas the group using the cleaning composition according to the example Was able to significantly suppress darkening stains in toilet bowls.
In addition, the toilet cleaning compositions of other examples also showed the same effect on dark stains.

About the toilet cleaning composition of this invention, the prescription examples other than the Example mentioned above are shown below as prescription examples 1-39. The unit of each component in the table is ppm.

In Formulation Examples 1 to 39, PHMB and various compounds A were mixed at a ratio of 1: 5 to 1:50 to prepare a toilet cleaning composition. Furthermore, about the density | concentration of PHMB, it is set as 0.3 ppm, 0.8 ppm, 1.0 ppm, 2.0 ppm, and 3.0 ppm so that it may become a ratio of 1: 5 to 1:50 with the compound A described in Tables 2-4. A toilet cleaning composition was also prepared.

In any case, the antibacterial activity was the same as that of the example, and particularly when the PHMB concentration was 0.3 to 0.8 ppm, the antibacterial / bactericidal action was improved by the combined use with Compound A.
Moreover, all show the effect similar to an Example about the darkening stain | pollution | contamination suppression effect in a toilet bowl, especially when the density | concentration of PHMB is 0.3-0.8 ppm, it is in the darkening stain | pollution | contamination suppression effect by combined use with the compound A It was excellent.

Claims (5)

Polyhexamethylene biguanide hydrochloride, and
The following general formula (1):

(In the formula, m and n are arbitrary integers.)
And a polyoxyalkylene alkyl ether having a linear or branched alkyl group having 16 to 18 carbon atoms, wherein the substituent represented by R ¹ is a linear or branched alkyl group. Cleaning composition. 2. The toilet cleaning composition according to claim 1, wherein the polyoxyalkylene alkyl ether represented by the general formula (1) is a polyoxyethylene alkyl ether in which R ¹ has 16 to 18 carbon atoms. The toilet cleaning composition according to claim 1 or 2, wherein the polyoxyalkylene alkyl ether represented by the general formula (1) has an HLB of 5 to 18. The toilet cleaning composition according to any one of claims 1 to 3, wherein the weight concentration after dilution when polyhexamethylene biguanide hydrochloride is used is 0.3 to 3.0 ppm. The toilet according to any one of claims 1 to 4, wherein the polyoxyalkylene alkyl ether represented by the general formula (1) is 5 parts by weight or more and 50 parts by weight or less with respect to 1 part by weight of the polyhexamethylene biguanide hydrochloride. Cleaning composition.