JPH11335700A - Detergent composition for bathroom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition for a bathroom, capable of manifesting an excellent detergent activities against a metal salt of a fatty acid in the bathroom, excellent in foamability and rinsing properties, and further excellent in long term preservation stability at a low temperature. SOLUTION: This detergent composition comprises (A) 0.1-20 wt.% anionic surfactant or nonionic surfactant, having a polyoxyalkylene group having 2-9 average number of added moles, (B) 0.01-5 wt.% fatty acid or a salt thereof, (C) 0.1-30 wt.% solvent, and (D) 0.1-20 wt.% sequestering agent, and the weight ratio of the components A to B is regulated so as to be (3/7)-(49/1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bathroom cleaning composition.

[0002]

2. Description of the Related Art In general, stains on floors, walls and utensils in bathtubs and bathrooms are caused by organic substances such as fatty acid metal salts (mainly calcium salts), free fatty acids, glycerides, nitrogen-containing compounds, etc., and mud. It consists of a mixture of inorganic substances.

Hitherto, as a cleaning agent for removing such stains, for example, an acidic cleaning agent containing a hydroxycarboxylic acid as an acidic substance, a surfactant, and a water-soluble solvent has been known (Japanese Patent Application Laid-Open No. HEI 9-163,881). 52-77111). However, although such an acidic cleaning agent has a cleaning effect, there is a problem in that it damages joint materials such as tile joints and aluminum sashes.

On the other hand, a detergent which is neutral and has excellent detergency against fatty acid metal salt stains has been developed.
JP-A-61-283696 discloses a neutral detergent containing a combination of a cationic surfactant and a nonionic surfactant, and JP-A-61-283699 discloses a cationic detergent and a nonionic surfactant. Japanese Unexamined Patent Publication (Kokai) No. 61-283700 discloses a detergent comprising a combination of a surfactant and a water-soluble solvent, and a detergent comprising a combination of a cationic surfactant, a nonionic surfactant and maleic acid.
No. 97 discloses a bathroom detergent and the like in which a cationic surfactant, a nonionic surfactant, an aminocarboxylic acid and a solvent are combined. However, the detergents and the like described in these publications are still insufficient in detergency and foaming property for fatty acid metal salt stains, and simultaneously satisfy rinsing properties and long-term storage stability at low temperatures. It was not something.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has as its object to solve the above problems. It is an object of the present invention to provide a bathroom cleaning composition which is excellent in rinsing properties and also has excellent long-term storage stability at low temperatures.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have found that a bathroom having an excellent washing effect on fatty acid metal salt stains, excellent foaming and rinsing properties, and excellent long-term storage stability at low temperatures. As a result of diligent research to develop a detergent composition for use, an anionic or nonionic surfactant having a specific polyoxyalkylene group, a fatty acid and its salt, a solvent, and a sequestering agent are required. By quantitatively combining them, the above-mentioned bathroom detergent composition was successfully obtained, and the present invention was completed. That is, the bathroom detergent composition of the present invention comprises (A) an anionic surfactant or a nonionic surfactant having an average addition mole number of 2 to 9 and having a polyoxyalkylene group of 0.1 to 2;
0% by weight, (B) 0.01 to 5% by weight of a fatty acid or a salt thereof, (C) 0.1 to 30% by weight of a solvent, and (D) 0.1 to 20% by weight of a sequestering agent. (A)
The component / (B) component is characterized in that the weight ratio is 3/7 to 49/1.

[0007]

Embodiments of the present invention will be described below in detail. The bathroom cleaning composition of the present invention (hereinafter simply referred to as “cleaning composition”) comprises (A) an anionic surfactant having a polyoxyalkylene group having an average addition mole number of 2 to 9 or a nonionic surfactant. Activator 0.1-20% by weight
And (B) 0.01 to 5% by weight of a fatty acid or a salt thereof,
(C) 0.1 to 30% by weight of a solvent and (D) 0.1 to 20% by weight of a sequestering agent.
(B) The component is characterized in that the weight ratio is 3/7 to 49/1.

The anionic or nonionic surfactant (A) used in the present invention must have a polyoxyalkylene group having an average addition mole number (p) of 2 to 9. . If the average number of added moles (p) of the polyoxyalkylene group is less than 2, the storage stability at low temperatures is not sufficient, while if it exceeds 9, the foam removal and rinsing properties are undesirably deteriorated. Examples of the polyoxyalkylene group include a polyoxyethylene, a polyoxypropylene, and a polyoxybutylene group, and a polyoxyethylene group is particularly preferable. Examples of the anionic surfactant or nonionic surfactant having a polyoxyalkylene group having an average addition mole number (p) of 2 to 9 include:
Preferably, it has a linear or branched alkyl or alkenyl group having an average carbon number of 4 to 26, more preferably 8 to 24.

In the present invention, examples of the anionic surfactant having a polyoxyalkylene group include:
Polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl aryl ether sulfate, polyoxyalkylene alkenyl aryl ether sulfate, polyoxyalkylene mono- or di-alkyl ether phosphate, polyoxy Alkylene mono- or di-alkenyl ether phosphate, polyoxyalkylene mono- or diphenyl ether phosphate, polyoxyalkylene alkyl ether carboxylate, polyoxyalkylene alkenyl ether carboxylate, polyoxyalkylene alkyl ether acetate, poly Oxyalkylene alkenyl ether acetate and the like can be mentioned, and among them, polyoxyalkylene alkyl ether sulfate is preferable.
Further, as the salts, alkali metal salts such as sodium and potassium, ammonium salts, mono-, di- or tri-
Alkanolamine salts such as ethanolamine are exemplified.

In the present invention, the nonionic surfactant having a polyoxyalkylene group includes, for example,
Compounds represented by the following general formulas (I) or (II), polyoxyalkylenealkyl ( _C8-22 ) ethers, polyoxyalkylenealkyl ( _C8-22 ) phenyl ethers, polyoxyalkylene polyoxypropylene block polymers, etc. Is mentioned.

[0011]

Embedded image [R ¹ in the formula (I) represents an alkyl group having 2 to 3 carbon atoms, m + n represents 7 to 11, and x represents 2 to 9. ]

Embedded image [R ² in the formula (II) represents an alkyl group having 10 to 18 carbon atoms, and y + z represents 2 to 9. Note that these anionic surfactants and nonionic surfactants may be used alone or in combination of two or more.

In the present invention, the amount of the component (A) is from 0.1 to 20% by weight based on the total amount of the detergent composition.
Preferably, it is 1 to 10% by weight. If the amount is less than 0.1% by weight, the storage stability at low temperatures is not sufficient. On the other hand, if the amount exceeds 20% by weight, there is no particular improvement effect on the detergency, and the foaming and rinsing properties are rather improved. Deteriorates, which is not preferable.

The fatty acid or salt thereof as the component (B) used in the present invention includes, for example, a fatty acid having a linear or branched alkyl or alkenyl group having an average carbon number of 8 to 26, an alkali metal salt thereof, and ammonium. Salts, or alkanol-substituted ammonium salts such as mono, di, and tri are exemplified. Specific examples include lauric acid, palmitic acid, oleic acid, myristic acid, stearic acid, coco fatty acid, tallow acid (tallow hydrolyzed fatty acid), or alkali metal salts or alkanolamine salts thereof. Among these, alkali metal salts or alkanolamine salts of lauric acid, coconut fatty acid and myristic acid are particularly preferred. These fatty acids or salts thereof may be used alone or in combination of two or more.

In the present invention, the compounding amount of the component (B) is
It is 0.01 to 5% by weight, preferably 0.01 to 3% by weight, based on the total amount of the detergent composition. The amount is 0.01
If the amount is less than 5% by weight, the foaming power and the rinsing property are not sufficient.

In the present invention, the mixing ratio of the above components (A) and (B) [component (A) / component (B)].
Is from 3/7 to 49/1 by weight ratio, preferably from 4/6 to
20/1 is desirable. If this ratio is less than 3/7, the storage stability at low temperatures is not sufficient, while 49 /
If it exceeds 1, the rinsing property is not sufficient, which is not preferable.

As the solvent that is the component (C) used in the present invention, generally used solvents can be used and are not particularly limited. For example, the following general formulas (III) to
1 selected from the compound represented by (V), a dihydric alcohol having 4 to 12 carbon atoms and a monohydric alcohol having 1 to 5 carbon atoms
Species or two or more are preferred.

[0017]

Embedded image [R ³ and R ⁴ in the formula (III) each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic group;
And u are each 0 to 10 and do not become 0 at the same time, and in {}, when t and u are larger than 0, the oxyethylene group and the oxypropylene group are in a random state and / or
Or a polyoxyalkylene chain bonded in a block shape. ]

Embedded image [R ⁵ and R ⁶ in the formula (IV) represent an alkyl group having 1 to 3 carbon atoms. ]

Embedded image [R ⁷ in the formula (V) represents an alkyl group having 1 to 3 carbon atoms. ]

In the solvent represented by the above general formula (III), when R ³ and R ⁴ are alkyl groups, the number of carbon atoms is 1 to 4.
Is particularly preferred. In the general formula (III), ethylene oxide (EO) and propylene oxide (P.
O. ) Are 0 to 1 respectively.
0 is used, but the order of addition is not particularly limited, and may be randomly added. Specific examples of the solvent represented by the general formula (III) include ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, triethylene glycol monophenyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Butyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, polyoxyethylene (p = 2-5) polyoxypropylene (p = 2-3) glycol dimethyl ether, polyoxyethylene (p =
3) Glycol phenyl ether, phenyl carbitol, phenyl cellosolve, benzyl carbitol and the like. Among these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, and polyoxyethylene (p = 2 to 5) glycol phenyl ether are preferred from the viewpoint of storage stability and detergency.

The compounds represented by the above general formula (IV) include 1,3-dimethyl-2-imidazolidinone,
3-Diethyl-2-imidazolidinone is exemplified as a suitable compound, and as the compound represented by the above general formula (V), 3-methoxy-3-methylbutanol, 3-ethoxy-3-methylbutanol and the like are preferable. .

Examples of the dihydric alcohol having 4 to 12 carbon atoms include isopropylene glycol and 2,2,4-trimethyl-1,3-pentadiol. Further, examples of the monohydric alcohol having 1 to 5 carbon atoms include methanol, ethanol, and isopropyl alcohol. By blending these lower alcohols, etc.,
The low-temperature stability of the composition is further improved. These solvents may be used alone or in combination of two or more.

In the present invention, the amount of the component (C) is 0.1 to 30% by weight, preferably 1 to 15% by weight, more preferably 4 to 10% by weight, based on the total amount of the cleaning composition.
% By weight. When the amount is less than 0.1% by weight, the storage stability at low temperatures and the detergency are insufficient, and the interaction with the other components of the present invention, ie, a surfactant and a sequestering agent, is also sufficient. Results cannot be obtained.
On the other hand, when the amount exceeds 30% by weight, the effect of increasing the amount is not observed.

Examples of the metal ion sequestering agent (D) used in the present invention include a metal ion sequestering agent of an organic substance and a metal ion sequestering agent of an inorganic substance. Examples of the sequestering agent for an organic substance include an aminocarboxylic acid-based substance, an oxycarboxylic acid-based substance, and a carboxylic acid-based substance. Specific examples of aminocarboxylic acid-based substances include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, ethyleneglycoldietherdiaminetetraacetic acid, and cyclohexane-1. , 2-diaminetetraacetic acid and the like. Specific examples of the oxycarboxylic acid-based substance include glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and the like. Specific examples of the carboxylic acid-based substance include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, carboxymethylsuccinic acid, and carboxymethyloxysuccinic acid. These are not limited to the acid form, but they are neutralized with potassium hydroxide, sodium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, morpholine, etc. to neutralize some or all of the carboxyl groups and formulated as water-soluble salts. It is also possible.

Examples of the sequestering agent for inorganic substances include mainly condensed phosphoric acids such as pyrophosphoric acid, tripolyphosphoric acid and hexametaphosphoric acid, and alkali metal salts and zeolites thereof. These sequestering agents can be used alone or in combination of two or more.

In the present invention, the amount of component (D) is
It is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the detergent composition. When the amount is less than 0.1% by weight, the detergency is insufficient, and the interaction with the other two components of the liquid detergent composition of the present invention is also insufficient. On the other hand, when the amount exceeds 20% by weight, no remarkable effect is observed even if the amount is increased.

In the present invention, in order to further increase the detergency,
If necessary, a surfactant other than the components (A) and (B) can be blended. In this case, the total amount of the component (A) and the component (B) is required to be at least 10% by weight or more in all the surfactants. If the total amount is less than 10% by weight, the rinsing properties and / or the storage stability at low temperatures are inferior. It will be. As other surfactants that can be blended other than the above-mentioned components (A) and (B), surfactants used in ordinary cleaning agents can be blended. For example, the above-mentioned (A) and (B) components can be blended. Other anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like.

Further, in the present invention, other optional components can be appropriately blended as required. As optional components,
For example, a bactericide, an antiseptic or antifungal agent, a fragrance, a pigment, an antioxidant, a thickener, an ultraviolet absorber, a solubilizer, and the like can be added. In addition, these optional components are not particularly limited as long as they are generally used in cleaning agents. Further, the pH in the cleaning composition of the present invention,
Although not particularly limited, preferably, pH 5
The pH of the detergent composition is desirably 9, and the pH of the detergent composition can be adjusted with a pH adjuster or the like so as to fall within this range.

[0027]

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Examples 1 to 8 and Comparative Examples 1 to 9
And the cleaning composition of the compounding composition shown in Table 2 was prepared. In addition, the pH of the cleaning composition was all adjusted to 7.5. With respect to the obtained detergent compositions of Examples 1 to 8 and Comparative Examples 1 to 9, the detergency against foam stain, foaming property, rinsing property and storage stability were evaluated by the following test methods. The results are shown in Tables 1 and 2 below.

(1) Detergency test for scale stain A liquid bath composition (stock solution) was impregnated with a polypropylene bathtub (used for one month) to which scale stains which cannot be easily removed by rubbing were adhered. Rubbing was performed five times with a urethane sponge, and the stain removal state was visually judged based on the following criteria. The criteria are as follows. 5 points: Very good dirt removal 4 points: Good dirt removal 3 points: There is unevenness in dirt removal 2 points: Some extent of dirt removal 1 point: Almost no dirt removal

(2) Bubbling test A stainless steel tub was impregnated with a urethane sponge impregnated with a 10% diluted liquid detergent composition (stock solution).
The state of rubbing and foaming was evaluated visually based on the following criteria. The criteria are as follows. 5 points: very good bubbling 4 points: good bubbling 3 points: uneven bubbling 2 points: slightly bubbling 1 point: almost no bubbling

(3) Rinse test Detergent concentration 0.25% (Temperature 20 ° C, German hardness 4 ° D
100 cc of the detergent aqueous solution of H) was collected in a 500 cc separating funnel and shaken a certain number of times. Thereafter, the liquid was poured out, and then, 500 cc of rinsing water (temperature: 20 ° C., German hardness: 4 ° DH) was poured, and the separating funnel was slowly poured into 10 minutes.
After the rotation, the liquid was poured out, and this was repeated, and the number of times until the bubbles disappeared was determined, which was used as the evaluation value of the rinsing property (defoaming property).

(4) Storage stability test The liquid detergent composition (100 ml) to be each sample was put in a container (100 ml) and stored at -5 ° C for 7 days.
Visual judgment was made according to the following criteria. The criteria are as follows. ：: no change in appearance △: slight precipitation X: clear white precipitation

[0033]

[Table 1]

[0034]

[Table 2]

(Consideration of Tables 1 and 2) As is clear from Table 1, the cleaning composition of the present invention containing a predetermined amount of the four components (A) to (D) is effective in reducing the scale stain. It turns out that all have excellent performance with respect to detergency, foaming property, rinsing property and storage stability. On the other hand, as is clear from Table 2, the detergent composition containing no A component (Comparative Example 1) is inferior in detergency, foaming property and storage stability, and contains the B component. The detergent composition without Comparative Example 2 (Comparative Example 2) was inferior in detergency, lathering and rinsing properties, and the detergent composition containing no C component (Comparative Example 3) showed detergency, lathering and rinsing. It can be seen that the detergent composition containing no D component (Comparative Example 4) was inferior in detergency and storage stability (Comparative Example 4). Further, the detergent composition in which the blending amount of the component A is less than (A) / (B) = 3/7 (Comparative Example 5) is inferior in storage stability, and the blending amount of the component A is (A) / (B) It can be seen that the detergent composition with more than 49/1 (Comparative Example 6) is inferior in rinsing properties. Furthermore, when the polyoxyalkylene group of the component A is less than 2 mol (Comparative Example 7), storage stability is inferior, and when it exceeds 9 mol (Comparative Example 8), rinsing properties are inferior. Furthermore, the detergent composition falling within the scope of the present invention has excellent storage stability as compared with the case where a combination of an anionic surfactant having no polyoxyalkylene group and a fatty acid salt is added (Comparative Example 9). It turns out that it has. When the results of Tables 1 and 2 are combined, Comparative Examples 1 to 9 which are out of the scope of the present invention in which any one of the above four components (A) to (D) is missing and combined are out of the scope of the present invention. The effects of the present invention appear for the first time in Examples 1 to 8 in which the effects are not exhibited and the four components are mixed in a predetermined amount.

[0036]

According to the present invention, a bathtub, a bathtub,
Bathroom cleaning, which has an excellent cleaning effect on stools, sand saws, and scales adhering to a washing place, has excellent foaming and rinsing properties, and has excellent long-term storage stability at low temperatures. An agent composition is provided.

Claims (1)

[Claims] (1) 0.1 to 20% by weight of an anionic or nonionic surfactant having a polyoxyalkylene group having an average number of moles of addition of 2 to 9, and (B) a fatty acid or a salt thereof. 0.01 to 5% by weight and (C) solvent 0.1 to 3
0% by weight and (D) 0.1 to 20% by weight of a sequestering agent, wherein the component (A) / component (B) has a weight ratio of 3/7 to 49/1. Bathroom cleaning composition.