JPH11217600A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition having high cleanup effect on scale stains and slightly affecting objects to be cleaned. SOLUTION: This detergent composition essentially comprises a surfactant and a solvent, and also contains total of 0.1-20 wt.% of (A) an aminocarboxylic acid, wherein at least a part thereof is in the form of one or more kinds of salts selected from potassium salt, ammonium salt and organic amine salt and (B) a carboxylic acid other than the above component A in the weight ratio A/B of >1 but <=10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cleaning composition, and more particularly, to a cleaning composition suitable for use in a bathroom or the like.

[0002]

2. Description of the Related Art In general, in bathroom dirt, mold dirt is stained on walls, ceilings, etc., and fatty acid metal salts (mainly calcium salts) called descaling are degraded on floors, bathtubs, basins, and the like.
A mixture of organic substances such as free fatty acids, glycerides and nitrogen-containing compounds and inorganic substances such as mud is attached.

[0003] Conventionally, as a cleaning agent for removing such mold stains, for example, bleach-washing is performed with a mold remover containing sodium hypochlorite as a main component. It is known to wash with an acidic detergent containing an acid, a surfactant and a water-soluble solvent (Japanese Patent Application Laid-Open Nos. 52-77111 and 57-28).
199).

[0004] However, the acidic cleaning agents described in these publications have a disadvantage that they damage the surface of tile joints, enamels, and fiber reinforced plastic bathtubs. Therefore, as a means for solving these drawbacks, a weakly acidic detergent has been proposed, but the decomposition rate of the fatty acid metal salt is slow, and time and labor are required to completely remove dirt. Although a cleanser containing an abrasive has been proposed, there have been problems such as damage to a bathtub made of stainless steel and fiber-reinforced plastic, and an abrasive remaining after washing and rinsing.

On the other hand, JP-A-52-76308, JP-A-53-35710, and JP-A-54-15840 have been disclosed.
No. 9, No. 56-22397, No. 63-193
No. 998 and No. 63-245499 disclose a bathroom detergent composition relating to a combination of a surfactant and a sequestering agent, or a combination of a surfactant, a sequestering agent and a solvent. ing. However,
The cleaning compositions disclosed in these publications have a problem that their cleaning power is not sufficient when actually used. Therefore, at present, there is a demand for the development of a detergent composition having excellent detergency and suitable for bathrooms and the like.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cleaning composition which has an excellent cleaning effect on hard scale stains and has little adverse effect on an object to be washed.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, in a detergent composition containing at least a surfactant and a solvent, a specific aminocarboxylic acid or By blending the salt and a carboxylic acid other than the aminocarboxylic acid or a salt thereof in a specific ratio, the fatty acid metal salt (mainly calcium salt), which is a main component of the scale, is quickly decomposed and solubilized. It has been found that the removal rate can be improved, light stains can be washed simply by spraying a cleaning agent and then left for a while and then showered, and that strong stains can be easily washed only by lightly rubbing, thereby completing the present invention. It was reached. The cleaning composition of the present invention resides in the following (1) and (2). (1) a detergent composition comprising at least a surfactant and a solvent,
(A) an aminocarboxylic acid at least one part of which is at least one salt selected from a potassium salt, an ammonium salt or an organic amine salt, and (B) a carboxylic acid other than the component (A), A cleaning agent characterized in that the weight ratio of component (A) / component (B) is greater than 1 and not more than 10, and the total amount of component (A) + component (B) is 0.1 to 20% by weight. Composition. (2) The cleaning composition according to claim 1, wherein at least a part of the component (B) is at least one salt selected from a potassium salt, an ammonium salt and an organic amine salt.

[0008]

Embodiments of the present invention will be described below in detail. The cleaning composition of the present invention is a cleaning composition containing at least a surfactant and a solvent, wherein (A)
(A) a component containing at least a part of an aminocarboxylic acid which is one or more salts selected from a potassium salt, an ammonium salt and an organic amine salt, and (B) a carboxylic acid other than the component (A); Wherein the weight ratio of component (B) is greater than 1 and not more than 10, and the total amount of component (A) + component (B) is 0.1 to 20% by weight.

The component (A) used in the present invention includes an aminocarboxylic acid or a salt thereof. At least a part of the aminocarboxylic acid is at least one salt selected from a potassium salt, an ammonium salt and an organic amine salt. It is necessary to be. As aminocarboxylic acids, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetrapropionic acid,
Triethylenetetramine hexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, cyclohexane-
1,2-diaminetetraacetic acid and the like. In addition, these are carboxylate (potassium salt, ammonium salt,
Organic amine salts), even in the form of an acid, potassium hydroxide, ammonium hydroxide and organic amines such as monoethanolamine, diethanolamine, and morpholine to neutralize some or all of the carboxyl groups to form water-soluble salts. It is also possible to mix.

In the present invention, at least a part of the above-mentioned various aminocarboxylic acids is required to be at least one salt selected from potassium salts, ammonium salts and organic amine salts from the viewpoint of the effect of cleaning the scale. In the case of other salts, for example, sodium salts of the above-mentioned various aminocarboxylic acids, a remarkable effect of compounding is not recognized, which is not preferable.
These aminocarboxylic acids or salts thereof may be used alone or in combination of two or more. In the component (A) used in the present invention, the amount of the aminocarboxylic acid in which at least one part is at least one salt selected from a potassium salt, an ammonium salt and an organic amine salt is based on the total amount of the component (A). It is desirable that the content be 1 to 100% by weight (total amount of the component (A)), more preferably 10 to 100% by weight. When the amount of the aminocarboxylic acid of the potassium salt, ammonium salt or organic amine salt is less than 1% by weight, the washing effect becomes insufficient, which is not preferable.

The component (B) used in the present invention comprises the component (A)
A carboxylic acid other than the component or a salt thereof is exemplified. Examples of the carboxylic acid of the component (B) include glycolic acid, malic acid, citric acid, diglycolic acid, succinic acid,
Tartaric acid, succinic acid, fumaric acid, phthalic acid, 2,2′-oxydiacetic acid, gluconic acid, etc., and preferably, malic acid, citric acid, succinic acid, succinic acid, tartaric acid,
2'-oxydiacetic acid. These may be used in the form of an acid in the form of a carboxylate (sodium salt, potassium salt, ammonium salt, organic amine salt, etc.), and sodium hydroxide, potassium hydroxide, ammonium hydroxide and monoethanolamine, diethanolamine, It is also possible to neutralize a part or all of the carboxyl group with an organic amine such as morpholine and blend it as a water-soluble salt. These carboxylic acids or salts thereof may be used alone or in combination of two or more. More preferably, the component (B) is the above-mentioned various carboxylic acids, at least one part of which is one or more salts selected from potassium salts, ammonium salts and organic amine salts. By using these carboxylate (potassium salt, ammonium salt or organic amine salt), it is possible to exhibit a more excellent descaling effect. In addition, the amount of these carboxylate is (B)
It is preferably from 0 to 100% by weight [total amount of the component (B)], more preferably from 10 to 100% by weight, based on the total amount of the components.

Further, counter ions of the above components (A) and (B) include calcium, ammonium and organic amine salts. In particular, aminocarboxylic acids and salts thereof are
It is very important that the solubility of the fatty acid salt formed by the reaction of the fatty acid metal salt (mainly calcium salt), which is the main component of the scale, with the aminocarboxylate affects the washing rate. Therefore, it is more effective to use an anionic surfactant, a chelating agent, an ionic hydrotrope or the like contained in the detergent composition as the above counter ion.

In the present invention, the component (A) and the component (B)
The amount of the component is greater than 1 and 10 or less, preferably 1.1 to 5 by weight ratio of the component (A) / the component (B), and is the total amount of the component (A) + the component (B). It is desirably in the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the composition. If the weight ratio of the component (A) and the component (B) is out of the above range, the effects on the detergency and the object to be washed cannot be satisfied at the same time. In particular, if the weight ratio of the component (A) to the component (B) is 1 or less, the influence on the object to be washed is increased, which is not preferable (this point will be further described in Examples and the like which will be described later). On the other hand, if the total amount is less than 0.1% by weight, the rate of decomposition of the fatty acid metal salt is low, and a sufficient cleaning effect cannot be exerted. On the other hand, if the amount exceeds 20% by weight, there is no special improvement effect, and the object to be washed may be damaged.

Although the surfactant contained in the present invention is not particularly limited, examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant. . Specific representative examples are as follows, and these surfactants can be used alone or in combination of two or more.

Examples of the anionic surfactant include alkyl sulfate (C8 to C22) salts and alkyl sulfate (C8 to C22).
C22) polyoxyethylene (p = 1-6) salt, alkyl (C8-22) benzenesulfonate, α-olefin (C8-C22) sulfonate, monoalkyl (C8
To C22) phosphate, and the like. The counter ion (cation) of these anionic surfactants is an alkali metal, an alkaline earth metal, an alkanolamine, an ammonium ion or the like. Of these, alkyl polyoxyethylene sulfate, alkyl benzene sulfonate, α-olefin sulfonate and the like are preferable.

Examples of the cationic surfactant include an alkyl (C8-C22) trimethylammonium salt, a dialkyl (C8-22) dimethylammonium salt, an alkyl (C8-C22) ammonium salt, and an alkyl (C8-C22) ammonium salt.
To C22) benzyldimethylammonium salt and the like. Counter ions (anions) of these cationic surfactants include chlorine and bromine elements.

Examples of the nonionic surfactant include polyoxyethylene (p = 1-20) alkyl (C8-C)
22) Ether, polyoxyethylene (p = 1-20)
Nonylphenyl ether, fatty acid diethanolamide,
Alkyl (C8-C22) dimethylamine oxide and the like can be mentioned.

Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants such as alkylcarboxybetaine and alkylsulfobetaine;
An imidazoline type amphoteric surfactant can be mentioned.

The amount of the surfactant (A) is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 20% by weight, based on the total amount of the composition. 10
It is desirably in the range of weight%. If the amount of the component (A) is less than 0.1% by weight, the interaction with other components is weak, so that the dispersing and solubilizing effects on soil are weak, and the detergency is insufficient. On the other hand, when the content exceeds 20% by weight, no special improvement effect is brought about for the detergency, and instead the foam runs out,
It is not preferable in use because the rustiness is deteriorated.

Although the solvent contained in the present invention is not particularly limited, the following general formulas (I) and (I)
Compounds represented by I) and (III) are preferred. R ₁ O ｛C ₂ H ₄ O) m (C ₃ H ₆ O) n｝ R ₂ (I) [In the formula (I), R ₁ and R ₂ are a hydrogen atom, and have 1 to 8 carbon atoms. Represents an alkyl group, a phenyl group or a benzyl group, m and n are each 0 to 5, and are not 0 at the same time,
{} Indicates a polyoxyalkylene chain in which, when m and n are larger than 0, an oxyethylene group and an oxypropylene group are bonded in a random and / or block manner. ]

Embedded image [R ₃ and R ₄ in the formula (II) represent an alkyl group having 1 to 3 carbon atoms. R ₅ OC (CH ₃ ) ₂ CH ₂ CH ₂ OH (III) [R ₅ in the formula (III) represents an alkyl group having 1 to 3 carbon atoms. )

Examples of the solvent of the general formula (I) include ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol diethyl ether, dipropylene glymonomethyl ether, and propylene glycol monoethyl ether. Ethyl ether, dipropylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether,
Propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethylene glycol monobutyl ether, dipropylene glycol ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polypropylene glycol (P = 8 to 15), and the like. it can. Further, as the solvent represented by the general formula (II), for example,
Suitable examples include 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone. Further, as the solvent represented by the general formula (III), for example, 3-methyl-3-methoxybutanol,
3-Methyl-3-ethoxybutanol and the like are preferred. These solvents may be used alone or in combination of two or more.

The amount of the solvent is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the total amount of the composition. If the amount is less than 0.1% by weight, the detergency is insufficient, and
Interaction with other components is not sufficient. On the other hand, when the amount is more than 20% by weight, no remarkable effect is observed.

[0023] The pH of the cleaning composition of the present invention is not particularly limited.
Preferably, it is in the range of 5 to 11, more preferably 6 to 8. When the pH of the composition is less than 5 or more than 11, a cleaning composition having excellent detergency and having no adverse effect on the object to be cleaned cannot be obtained. In order to keep the pH of the cleaning composition of the present invention within the above range, the pH is adjusted with an alkali agent such as potassium hydroxide, ammonium hydroxide, and organic amine, and an acidic substance such as sulfuric acid, hydrochloric acid, citric acid, and sulfonic acid. can do.

Further, the cleaning composition of the present invention may optionally contain other optional components as needed. Optional components include, for example, a lower alcohol, a lower alkylbenzene sulfonic acid or a salt thereof, a hydrotrope such as ethylene glycol, a bactericide, a preservative and a preservative, which are blended to maintain the liquidity at a low or high temperature. Fungicides, fragrances, dyes, antioxidants, thickeners, ultraviolet absorbers. The compound used for these optional components may be any compound as long as it is generally used for a detergent, and is not particularly limited.

In the present invention, for the first time, a cleaning composition containing at least a surfactant and a solvent contains the above-mentioned components (A) and (B) in the above-mentioned specific weight ratio and weight range. A detergent composition suitable for bathrooms, etc., that is, quickly decomposes and solubilizes fatty acid metal salts (mainly calcium salts), which are main components of descaling, etc., improves the removal rate, and light stains remove detergent. After spraying, it can be washed simply by leaving it for a while and then flowing in a shower, and it is possible to obtain a detergent composition that can be easily washed by rubbing strong dirt lightly.

[0026]

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 6 and Comparative Examples 1 to 8] A cleaning composition having the composition shown in Table 1 below was prepared, and the cleaning power against scale stains (light scale stains, strong scale stains) and the object to be washed. Was evaluated by the following method. In addition, potassium hydroxide (KOH), sodium hydroxide (NaOH), and ammonium hydroxide (N
H ₄ OH) and monoethanolamine (MEA), the aminocarboxylic acid or carboxylic acid of the component (A) or (B) in the composition contains these salts (potassium salt, sodium salt, Ammonium salt, monoethanolamine salt). The results are shown in Table 1 below.

(1) Detergency against scale 1) Detergency against light scale Dirt is used in a bathroom at home for about one month, and a polypropylene wash basin with scale is attached with a commercially available trigger spray. The cleaning composition was sprayed, left for a while (about 1 minute), rinsed with a shower, and the state of removal of stains was visually judged according to the following criteria. The criteria are as follows. Judgment criteria: ◎: Very good stain removal ○: Good stain removal △: Uneven stain removal ×: Almost no stain removal

2) Detergency for strong scale stains A wash basin made of polypropylene which has been used in a bathroom at home for about three months and has stains which cannot be easily removed is washed with a urethane sponge (50 × 50 mm). 5 g of the composition (stock solution) was rubbed with a load of about 20 g / cm ² five times, and the state of removal of stains was visually judged according to the following criteria. The criteria are as follows. Judgment criteria: ◎: Very good stain removal ○: Good stain removal △: Uneven stain removal ×: Almost no stain removal

(2) Influence test on the object to be washed A joint (with a diameter of about 30 m) was placed in 100 ml of the bathroom detergent composition.
m, thickness 5 m, and weight 5 g) were immersed for 12 hours, and the state of the surface was visually judged according to the following criteria. The criteria are as follows. Judgment criteria: ：: No change is observed at all ○: Very slight change is observed △: Slight change is observed ×: Clear change is observed

[0031]

[Table 1]

(Consideration of Table 1) Example 1 within the scope of the present invention
-6 are compared with Comparative Examples 1 to 8 which are out of the range of the present invention.
It has been found that the composition is a cleaning composition which can be quickly washed with light scale by spray cleaning, has an excellent cleaning effect on strong scale, and has little adverse effect on the object to be washed. Looking at the comparative examples individually, Comparative Example 1
Contains the component (A) and the component (B), but the weight ratio of the component (A) / the component (B) is out of the range of 0.4.
Therefore, it can be seen that the cleaning power for the descaling is low, and that the cleaning object is adversely affected. Comparative Examples 2 to 4 are cases in which the component (A) or the component (B) is not contained, respectively. In these cases, it can be seen that both the detergency against the scale and the effect on the object to be washed cannot be satisfied. . Comparative Example 5 contains the component (A) and the component (B). However, since the weight ratio of the component (A) / the component (B) is out of the range of 0.6, it is difficult to remove strong scale stains. It turns out that it has low detergency. Comparative Examples 6 and 7
It contains the component (A) and the component (B),
The weight ratio of component (A) / component (B) is 1.0 out of the range.
[Weight ratio of component (A) and component (B) is the same], 0.5
In these cases, it is found that there is an adverse effect on the object to be washed. Comparative Example 8 contains the component (A) and the component (B), but since the total amount of the component (A) is contained in the form of a sodium salt, it can be seen that the detergency against scale is inferior.

[0033]

According to the present invention, there is provided a detergent composition which can quickly remove scale stains, has an excellent cleaning effect, and has little adverse effect on an object to be washed.

Claims (2)

[Claims] 1. A detergent composition comprising at least a surfactant and a solvent, wherein (A) an aminocarboxylic acid wherein at least one part is at least one salt selected from a potassium salt, an ammonium salt and an organic amine salt. An acid and (B) the above (A)
A carboxylic acid other than the component;
A cleaning composition, wherein the weight ratio of the component (B) is more than 1 and 10 or less, and the total amount of the component (A) + the component (B) is 0.1 to 20% by weight. 2. The cleaning composition according to claim 1, wherein at least a part of the component (B) is at least one salt selected from a potassium salt, an ammonium salt and an organic amine salt.