JP5483852B2 - Bathroom cleaner composition and bathroom cleaner using the same - Google Patents

Description

  The present invention relates to a bathroom cleaning composition suitable for removing dirt adhering to a bathtub, a bathtub, a stool, a bath lid, and a washing place in a bathroom, and more specifically, while incorporating a surfactant as a main agent. The present invention relates to a bathroom cleaner composition having excellent sterilizing effect, good foaming, good foam retention, and excellent moisturizing effect.

  Conventionally, bathroom cleaners remove scale stains and soap debris generated by bathing, but it has been extremely labor intensive to remove particularly sticky stains. These bathroom stains are considered to be composed of protein stains, fatty acid soaps (mainly calcium salts), organic substances such as free fatty acids, and inorganic substances such as mud, and in particular, sticky stains are strongly combined with these organic and inorganic substances. Because it was attached, it was supposed to be hard to fall off.

  As a method for removing these stains, a surfactant composition having a high penetrating power or a detergent composition in which a water-soluble solvent and a metal chelating agent are combined is used to penetrate these stains and remove them. It was. Under such circumstances, polyoxyalkylene alkyl ethers, which are surfactants with high penetrating power and low foaming properties, have been widely used as bathroom cleaners, but have the disadvantage of low foaming and foam retention. In addition, there has been a problem of rough hands such as a dry hand after use.

  In addition, it is common to add antibacterial agents to bathroom cleaners, but in the actual use, protein stains such as scale stains are affected, and so much antibacterial activity is not recognized. Was also requested.

  The present invention solves the above-mentioned problems, and in a bathroom cleaning composition containing a surfactant having a high penetrating ability as a main agent, it has a drawback of low foaming and foaminess, which has been a conventional drawback, and an antibacterial activity. An object of the present invention is to solve the problem that it is not so high and to provide a bathroom cleaner excellent in moisture retention.

  As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by using a bathroom detergent composition obtained by combining a polyhexamethylene guanidine salt with a surfactant, In addition, the present inventors have found that if a water-soluble solvent or a chelating agent is further contained, a better bathroom cleaning composition can be obtained.

That is, the present invention comprises the following components (a) and (b)
(A) Surfactant 1-30% by mass
(B) Polyhexamethylene guanidine salt 0.01 to 1% by mass
It is the cleaning composition for bathrooms characterized by containing.

  In addition, the present invention is a bathroom cleaner composition comprising the bathroom cleaner composition further containing 1 to 15% by mass of a water-soluble solvent as a component (c).

  Furthermore, the present invention is a bathroom cleaner characterized by filling the above-mentioned bathroom cleaner composition in a spray container and using it in the form of foam.

  The bathroom cleaner composition of the present invention has better foaming, better foaming, and higher antibacterial activity than conventional products of the same type. Furthermore, when used, the skin has excellent moisture retention.

  Therefore, the bathroom cleaner composition of the present invention can be advantageously used as a bathroom cleaner, in particular, as a bathroom cleaner used by filling a spray container and discharging it in the form of foam.

  The surfactant which is the component (a) of the bathroom cleaner of the present invention is not particularly limited as long as it has high penetrating power and exhibits a cleaning effect. As this component (a), a nonionic surfactant, an anionic surfactant, or an amphoteric surfactant is used, but the nonionic surfactant is less likely to reduce the disinfection effect of the polyhexamethylene guanidine salt. Is preferable. Examples of the nonionic surfactant include polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene oleyl ether, polyoxyethylene polyoxypropylene decyl ether, and polyoxyethylene polyoxypropylene lauryl. Examples include ether, polyoxyethylene polyoxypropylene myristyl ether, polyoxyethylene polyoxypropylene oleyl ether, and mixtures thereof. These are more preferably those in which the number of added moles of polyoxyethylene (hereinafter also referred to as POE) is 5 to 25.

  The compounding quantity of this component (a) is 1-30 mass% in a cleaning composition, Preferably it is 1-15 mass%. When the amount of the surfactant is less than 1% by mass, the effect of penetrating and peeling off the dirt is poor. On the other hand, when the amount is more than 30% by mass, these effects are not improved and the bubble breakage is deteriorated.

  In addition, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant can be used as the component (a). Among these, an anionic surfactant and an amphoteric surfactant are components when they are blended at a high concentration. A complex is formed with the polyhexamethylene guanidine salt (b), and precipitation tends to occur over time. For this reason, it is necessary to suppress these compounding quantities, and specifically, it is preferable that the compounding quantity of an anionic surfactant or an amphoteric surfactant shall be 5 mass% or less.

  The polyhexamethylene guanidine salt, which is the component (b) of the present invention, has the three effects of improving the foaming and foaming of the cleaning composition of the present invention, the moisturizing effect on the skin during use, and the sterilizing effect. It is what you play.

（ｎは１〜１００の整数であり、Ｘは無機酸または有機酸を表す） This component (b) polyhexamethylene guanidine salt is a compound represented by the following formula (II), and is already commercially available as an antibacterial agent.

(N is an integer of 1 to 100, and X represents an inorganic acid or an organic acid)

  The polyhexamethylene guanidine salts include nitrate, formate, acetate, benzoate, dehydroacetate, propionate, gluconate, sorbate, phosphate, fumarate, maleate, carbonate Examples thereof include salts, sulfates, and paratoluene sulfonates.

  The compounding quantity of this component (b) is 0.01-1 mass% in a cleaning composition, Preferably it is 0.01-0.5 mass%. When the blending ratio of the polyhexamethylene guanidine salt is less than 0.01% by mass, the foaming and foaming effects and the moisturizing effect are not sufficiently exhibited, and even if the blending amount exceeds 1% by mass, the effect is not improved.

  The polyhexamethylene guanidine salt of the component (b) has a disinfecting effect in addition to the effect of improving foaming and foam retention as described above, and the moisturizing effect on the skin during use. Although it is already known that this polyhexamethylene guanidine salt itself has a sterilizing effect, it can be said that the sterilizing effect exerted in the bathroom cleaning composition of the present invention is within a range that can be expected from now. It is not a thing.

  That is, generally, whether or not a compound has a sterilizing action is determined using a microorganism growing in a medium. And if it shows an antibacterial action with respect to this microorganism, it will be evaluated that it has a disinfection effect. The polyhexamethylene guanidine salt used in the present invention also exhibits a sterilizing action in a test in a medium, like other sterilizing agents.

  However, even a normal disinfectant that exhibits a disinfecting action in a medium has not been known so far when it is included in a bathroom cleaner. For example, benzalkonium chloride, which is widely known as having a sterilizing action, did not show a sterilizing action against, for example, S. aureus, when formulated in a bathroom cleaner. The reason for this is that, unlike microorganisms that grow in the culture medium, microorganisms that coexist with bathroom stains, especially Staphylococcus aureus, are protected by protein stains such as scale stains and are difficult to disinfect.

  On the other hand, the polyhexamethylene guanidine salt used in the present invention is effective against this Staphylococcus aureus and exhibits a sterilizing action even when formulated in a bathroom cleaner. The main effect is that it cannot be predicted at all in the present situation in which most sterilizing agents do not show sterilizing action when mixed in a bathroom cleaner.

  The bathroom cleaner of the present invention comprises the above components (a) and (b) as essential components, but other components can be blended as necessary. Examples of such components include water-soluble solvents (component (c)). This component (c) is blended in order to have the effect of removing dirt and foaming, and examples thereof include alcohol solvents, glycol solvents, glycol ether solvents and the like.

（式中、Ｒ¹は直鎖もしくは分岐鎖の炭素数３〜６のアルキル基、Ｒ²は水素又はメ
チル基を示し、ｎは１〜６の数を示す） Among these components (c), preferred examples include glycol ether solvents represented by the following formula (I).

(In the formula, R ¹ represents a linear or branched alkyl group having 3 to 6 carbon atoms, R ² represents hydrogen or a methyl group, and n represents a number of 1 to 6)

  Among the above glycol ether solvents, particularly preferred are ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, erylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, hexaethylene. Examples include glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, triethylene glycol hexyl ether, and tetraethylene glycol hexyl ether.

The compounding quantity of this component (c) is 1-15 mass% in a cleaning composition, Preferably it is 2-10 mass%. If the blending amount of the water-soluble solvent is less than 1% by mass, the effect of removing stains is not sufficiently exhibited, and even if blending exceeds 15% by mass, the effect is not improved. Furthermore, when a glycol ether solvent is used, the number of carbon atoms (length of the alkyl chain) of the alkyl group (R ¹ ) in the above formula is preferably 3-6. When the number of carbon atoms in the alkyl group is less than 3, the effect of removing dirt, foaming and foaming cannot be sufficiently exhibited, and even if the number exceeds 6, the effect is not improved.

  Moreover, a metal chelating agent can be mentioned as another example of the well-known arbitrary component mix | blended. This metal chelating agent is blended for facilitating removal of dirt existing on the bathtub or bathroom floor, especially dirt centered on calcium. Specific examples of the chelating agent include, but are not limited to, ethylenediaminetetraacetic acid (hereinafter also referred to as EDTA), hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonic acid. , Ethylene glycol bis (2-aminoethyl ether) tetraacetic acid and salts thereof, and ethylenediamine tetraacetate which is inexpensive and has a high metal sequestering ability is particularly preferable.

  The blending amount of the chelating agent is 0.1 to 10% by mass, preferably 0.5 to 5% by mass in the cleaning composition. If the blending amount of the chelating agent is less than 0.1% by mass, effects such as dissolution of soap residue will not be sufficiently exhibited, and even if it exceeds 10% by mass, the effect will not be improved.

  In the production of the bathroom cleaning composition of the present invention, as known optional components blended in addition to the water-soluble solvent and the chelating agent, inorganic components, water-soluble polymers, viscosity modifiers, humectants, pH adjusters, Examples include antiseptics, antioxidants, ultraviolet absorbers, fragrances, and pigments.

  The bathroom cleaning composition of the present invention is, for example, in accordance with an ordinary method, the essential components (a) and (b) described above, and further, if necessary, a water-soluble solvent, a chelating agent or other known optional components are mixed. It can be produced by stirring and making it uniform.

  The bathroom cleaning composition of the present invention described above may be used as a liquid bathroom cleaning agent as it is, but it should be used as a bathroom cleaning agent filled in a spray container and discharged in the form of foam. Is preferred.

  EXAMPLES Hereinafter, although an Example and a test example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

Example 1
The cleaning agent base having the composition shown in Table 1 was mixed with the sterilizing components shown in Table 2 so as to have the blending amounts shown in the same table, and stirred until uniform to obtain a cleaning composition. Next, the obtained composition was subjected to a sterilization activity test by the following method. The results are also shown in Table 2. The amount of each disinfectant was determined with reference to the effective amount of each catalog.

<Bactericidal activity test>
The tests were conducted in accordance with the “Method for testing the disinfection activity of residential detergents and soaps” established in the “Disinfection” labeling standard established by the Fair Trade Commission on September 1, 2006. That is, a mixture (test bacterial solution) of dirt (predetermined bovine serum albumin; 1.5%) and bacteria (Staphylococcus aureus or E. coli; 1.25 to 6.25 × 10 ⁸ cfu / mL) was used as a test piece ( 20 mm diameter stainless steel disc) is inoculated so that the bacteria become 0.01 mL / test piece, and is allowed to dry until it looks dry, and then the test piece is inoculated with 0.1 mL / test piece. For 5 minutes. Thereafter, an inactivating agent was poured to inactivate the effect of the test sample on bacteria, and then the number of viable bacteria on the test piece was quantified. In addition, the sterilization activity value is defined as "the difference between the common logarithm of the number of viable bacteria of the test specimen inoculated with the test sample inoculated with the common logarithm of the viable count of the test specimen inoculated with the control sample" and the evaluation standard is The following criteria were used according to the sterilization display criteria.
(Criteria)
Bactericidal activity value 0 to 1.5
１．５ 1.5-2 ... △
〃 2-3
以上 3 or more ◎◎

<Result>

  From the results shown in Table 2, Composition 1, which combines a nonionic surfactant and a polyhexamethylene guanidine salt, was superior in sterilizing activity against Staphylococcus aureus as compared with other sterilizing agents. Further, for Escherichia coli, all the disinfectants showed a disinfection activity value of 2 or more.

Example 2
To the detergent base having the composition shown in Table 3, the sterilizing components shown in Table 4 were mixed so as to have the blending amounts shown in the same table, and stirred until uniform to obtain a detergent composition. Next, the sterilization activity test was performed on the obtained composition in the same manner as in the above method. The results are shown in Table 4.

<Result>

  From the results in Table 4, the compositions 2 to 5 in which polyhexamethylene guanidine phosphate was blended in various blending amounts into a detergent base containing a nonionic surfactant were all sterilizing activities against Staphylococcus aureus. The value was high. Further, for Escherichia coli, all the disinfectants showed a disinfection activity value of 2 or more.

Example 3
Components having the composition shown in Table 5 were mixed and stirred until uniform to obtain a cleaning composition. Next, the obtained composition was subjected to a sterilization activity test in the same manner as described above, and the foaming power and cleaning power were examined by the following methods.

<Foaming power test>
In accordance with the method described in JIS-3362, the foaming force and the foam stability were evaluated using a Ross Miles foaming force measuring device. That is, the height of the foam of the 0.25 mass% aqueous solution prepared using the tap water (25 degreeC) was measured using the Ross Miles foaming power measuring apparatus immediately after throwing in and after leaving for 2 minutes. The value of the foam height was shown by averaging the results of five foaming tests.

<Detergency test>
Detergency was evaluated by a modified method of the peanut test. First, the surface of an FRP (glass fiber reinforced plastic) test piece having a certain size is rubbed with a paper file to uniformly make fine scratches. The surface color tone (L ₀ * a ₀ * b ₀ *) of this test piece is measured with a color difference meter. Next, artificial dirt (containing 0.5% Sudan III) is prepared by the following method, and a substantially constant amount of artificial dirt is uniformly adhered on the FRP test piece and dried. The surface color tone (L ₁ * a ₁ * b ₁ *) of the FRP test piece with the dirt adhered was measured with a color difference meter, and ΔE ₁ (= [(L ₁ * −L ₀ *) ² + (a ₁ * ^{_{-a 0 *) 2 + (b}} 1 * -b 0 *) 2 ] ^1/2) is calculated. Further, the test piece is set in a peanut tester, and a detergency test is performed in a 20% test solution (rotation speed: 250 rpm, 10 minutes, 40 ° C.). After the stirring is completed, the test piece is taken out and washed with water, and is further sandwiched with highly water-absorbing paper to remove moisture. The surface color tone (L ₂ * a ₂ * b ₂ *) of this test piece was measured with a color difference meter, and ΔE ₂ (= [(L ₂ * −L ₁ *) ² + (a ₂ * −a ₁ *) ² + (b ₂ * −b ₁ *) ² ] ^1/2 ). A cleaning rate (= ΔE ₂ / ΔE ₁ × 100) is obtained from ΔE ₁ and ΔE ₂ and used as an index of cleaning power (n = 6).
(Preparation of artificial dirt)
Triolein (0.8%), palmitic acid (0.7%), oleic acid (1%), palmitic acid Na (4%), stearic acid Na (3.5%), Sudan III (0.5%) ), And purified water (89.5%) is dissolved by heating to make it uniform. Further, a calcium chloride solution (2.862% as anhydrous calcium chloride) is added to this solution to prepare an artificial soil.

＊各成分の配合量は、質量％で示す。 <Result>

* The amount of each component is expressed in mass%.

From the results of Table 5, the composition 6 containing the surfactant and the polyhexamethylguanidine salt has a sterilizing effect, foaming and foaming as compared with the comparative 13 which does not contain the polyhexamethylguanidine salt and the water-soluble solvent. I found it excellent. Moreover, it turned out that the composition 7 which mix | blended the water-soluble solvent further with surfactant and polyhexamethylguanidine salt has foaming, a foam, and a detergency more excellent than the composition 6.

Example 4
Each component of the composition shown in Table 6 was mixed and stirred until uniform to obtain a cleaning composition. The resulting composition was then examined for foaming power in the same manner as in the foaming power test described above. The results are shown in Table 7.

＊各成分の配合量は、質量％で示す。

* The amount of each component is expressed in mass%.

<Result>

  From Table 7, it was found that compositions 8 and 9 in which a surfactant and polyhexamethylguanidine salt were further blended with a water-soluble solvent had better foaming and foaming compared to Comparative 13 in which no water-soluble solvent was blended. . Moreover, in the comparison of the composition 8 and 9 and the composition 10, it turned out that the length of the alkyl chain of the alkyl ether of the contained water-soluble solvent has an influence on foaming.

Example 5
Each component of the composition shown in Table 8 was mixed and stirred until uniform to obtain a cleaning composition. Next, the obtained composition was examined for moisture retention by the following method. The results are shown in Table 9.

＊各成分の配合量は、質量％で示す。

* The amount of each component is expressed in mass%.

<Moisture retention evaluation>
After applying each of the above two preparations to the test site by the cup method, the amount of horny water at the test site was measured over time to evaluate the moisture retention.

  Specifically, first, 8 healthy men were used as subjects. The subject entered the artificial climate room (25 ° C., 50% RH) and acclimated for 1 hour. After acclimatization, the skin horny moisture content in the left and right forearms was measured (equipment used; skin surface horny layer moisture content measuring device, SKICON-200, manufactured by IBI S Co., Ltd.). The amount of horny water was used.

  Next, a 10% aqueous solution of the above formulation was prepared, and 10 mL each was placed in a glass cup having a diameter of 3 cm. This glass cup was mounted so that the aforementioned 10% aqueous solution was in contact with the inner skin of the left and right forearms and left for 15 minutes.

  Thereafter, the glass cup was removed, and the test site was washed thoroughly with distilled water, and then the moisture was gently wiped off with a towel. After resting in an artificial climate chamber for 30 minutes, the amount of horny water at the test site was measured, and the amount of horny water after 30 minutes was determined.

  Furthermore, after resting in an artificial climate room for 1 hour, the keratin water content was measured in the same manner, and the keratin water content after 90 minutes was obtained. Each of the above keratin water content values is an average of 5 points measured at the test site.

<Result>

  From Table 9, it turned out that the composition 11 which mix | blended the polyhexamethylene guanidine salt had high moisture retention and the improvement effect of the moisture content compared with the comparison 14 which is not mix | blended.

Example 6
Each component of the composition shown in Table 10 was mixed and stirred until uniform to obtain a cleaning composition. Next, the actual feeling of use of the obtained composition was monitored and evaluated by the following method. The results are shown in Table 11.

＊ 各成分の配合量は、質量％で示す。

* The amount of each component is expressed in mass%.

<Evaluation of actual monitor>
The above-mentioned two preparations and a cleaning tool (soft urethane sponge) were distributed to 12 panelists, and they were actually used in each home, and the usability of the two preparations was compared and evaluated. In the evaluation, each question item was evaluated according to the following evaluation criteria, and the answer results were scored and tabulated.

Evaluation criteria:
(Bubbling; 5-level evaluation)
Evaluation contents Score Very good 5
Good 4
Normal 3
Bad 2
Very bad 1

(Foam mochi; 5-level evaluation)
Evaluation contents Score Very good 5
Good 4
Normal 3
Bad 2
Very bad 1

(Moisturizing feeling after use; 5-grade evaluation)
Evaluation contents Points Moist feeling 5
Somewhat moist 4
Normal 3
There is some feeling of bulkiness 2
There is a feeling of roughness 1

<Result>

  From the results of Table 11, it was found that the composition 12 containing the polyhexamethylene guanidine salt had higher use evaluation such as foaming, foaming, moisturizing feeling, etc., compared to the comparison 15 in which the polyhexamethylene guanidine salt was not added.

Example 7
Each component of the composition shown in Table 12 was mixed and stirred until uniform to obtain a cleaning composition. About the obtained composition, the disinfection effect, bubble power, and detergency were investigated by the above-mentioned method. The results are shown in Table 12.

＊ 各組成の配合量は、質量％で示す。

* The amount of each composition is expressed in mass%.

From the results of Table 12, it had excellent sterilizing effect against Escherichia coli and Staphylococcus aureus, had good foam, and excellent detergency.

  The bathroom cleaning composition of the present invention has better foaming and foaming properties, higher antibacterial activity, and better moisture retention on the skin than conventional similar products.

Therefore, the bathroom cleaning composition of the present invention can be advantageously used as a bathroom cleaning agent. Particularly, when this is filled in a spray container and discharged in the form of foam, it is rich in foaming. Become an excellent bathroom cleaner.

that's all

Claims (5)

The following components (a) and (b)
(A) Alkylene oxide addition type nonionic surfactant 1-30 mass%
(B) Polyhexamethylene guanidine salt 0.01 to 1% by mass
A cleaning composition for bathrooms, comprising: The bathroom cleaner composition according to claim 1, wherein the alkylene oxide addition-type nonionic surfactant is one or two selected from polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene alkyl ether .   Furthermore, the cleaning composition for bathrooms of Claim 1 or 2 which contains 1-15 mass% of water-soluble solvents as a component (c). 4. The bathroom cleaning composition according to claim 3, wherein the water-soluble solvent of component (c) is a glycol ether solvent represented by the following formula (I).

(In the formula, R ¹ represents a linear or branched alkyl group having 3 to 6 carbon atoms, R ² represents hydrogen or a methyl group, and n represents a number of 1 to 6)   A bathroom cleaning composition according to any one of claims 1 to 4, which is filled in a spray container and used in the form of foam.