JP3326052B2 - Liquid detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition having excellent detergency for hard surfaces, especially for scum and sebum stains in bathrooms and the like, and rinsing after washing. The present invention relates to a liquid detergent composition having good properties.

[0002]

2. Description of the Related Art Nonionic surfactants, anionic surfactants, and the like are used as cleaning agents for hard surfaces, especially for bathrooms and bathtubs.
An acidic detergent mainly composed of an organic acid and a solvent; a neutral detergent combining a nonionic surfactant and an anionic surfactant; and a nonionic surfactant, an anionic surfactant and a sequestering agent Alkaline cleaning agents and the like mainly using are widely used.

[0003] However, dirt from bathrooms and bathtubs is different from other residential dirt in that its dirt components are mainly metal soap, especially fatty acid calcium salts, to which oils such as proteins, nucleic acids and lipids are bound. However, such a conventional cleaning agent is not always satisfactory in detergency. In addition, since it is mainly composed of a nonionic surfactant and an anionic surfactant, the foaming property at the time of washing is insufficient or even if foaming is good, the rinsing property after washing is not good. Was something.

[0004] From such a viewpoint, a detergent which is neutral and has an excellent detergency against metal stone scum has been developed. No. 61-283696); a detergent comprising a combination of a cationic surfactant, a nonionic surfactant and a water-soluble solvent (JP-A-61-283699).
No.); a detergent comprising a combination of a cationic surfactant, a nonionic surfactant and maleic acid (JP-A-61-283).
No. 700) has been reported. However, even with these cleaning agents, it cannot be said that they are still sufficiently satisfactory with respect to metal stone canscum stains, especially with respect to stains accumulated over a long period of time. He did not have the power.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a foaming power at the time of washing and a good rinsing property after washing. Another object of the present invention is to provide a liquid detergent composition exhibiting excellent detergency.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of various studies on the combined effect of surfactants, interaction with solvents and chelating agents, on the detergency and foaming power during cleaning and rinsing after cleaning for metal stone canscum and sebum dirt, specific cation activity It has been found that by using a combination of an agent, an amphoteric surfactant and soap, a detergent having excellent foaming power and rinsing properties, and exhibiting a good detergency for scum stains and sebum stains can be obtained. ,
It has been found that a detergent composition having more excellent foaming power and detergency can be obtained by using a chelating agent in combination, and the present invention has been completed.

That is, the present invention provides the following component (a):
(B) and (c): (a) General formula (2)

[0008]

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[In the formula , R ³ represents a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and X represents a halogen atom or an alkyl sulfate residue.]

[0010]

[0011]

[0012]

[0013]

[0014]

A cationic surfactant selected from quaternary ammonium salts represented by the formula:

(B) General formulas (4), (5), (6) and (7)

[0017]

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[0018] wherein, R ⁷ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, R ⁸ and R
⁹ represents an alkyl group having 1 to 5 carbon atoms which may be the same or different and may be substituted by a hydroxyl group; R ¹⁰ represents a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms;
Represents a hydrogen atom or a hydroxyl group, r, s and t each represent an integer of 1 to 3, u represents an integer of 1 to 5, v represents an integer of 1 or more, and w and x are 0 ≦ w + x ≦ An amphoteric surfactant selected from betaines represented by the formula:

(C) General formula (8)

Embedded image R ¹¹ COOM (8) (wherein, R ¹¹ represents a linear or branched alkyl or alkenyl group of 7 to 17 carbon atoms, M represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine A) a fatty acid or a salt thereof;

[0020]

DETAILED DESCRIPTION OF THE INVENTION The cationic surfactant of the component (a) itself causes a substitution reaction with the metal ion of the fatty acid metal salt to decompose the metal stone scum, and a specific amphoteric surfactant is used in combination. When it does, the effect is remarkably improved. Further, by combining soap, a high cleaning effect can be obtained not only for metal soap scum but also for sebum stains. It is considered that this is because the cationic surfactant and the soap form a complex to efficiently adsorb to the soil interface, thereby lowering the interfacial tension with the soil. In addition, by using soap in combination with the mixed system of the cationic surfactant and the amphoteric surfactant, the foaming power at the time of washing and the rinsing property after washing can also be improved. In the present invention, the general formula
1 selected from quaternary ammonium salts represented by (2)
Species or two or more are used.

[0021]

The linear or branched alkyl or alkenyl group represented by R ³ in the general formula (2) has a preferred chain length of 6 to 20, more preferably 6 to 14, and still more preferably 6 to 14. To 12, particularly preferably 6 to 10.
Further, among the R ³ , a linear or branched alkyl group is preferable, a linear alkyl group is particularly preferable, more preferably 6 to 14 carbon atoms, further 6 to 12 carbon atoms, particularly 6 to 10 carbon atoms. Are preferred.

[0023]

[0024]

[0025]

[0026]

[0027]

Among Xs which represent counter ions of these cationic surfactants, halogen atoms include bromine, iodine and chlorine atoms, and alkylsulfuric acid residues include methanesulfonic acid and ethanesulfonic acid. And the like, and among them, a halogen atom, particularly a bromine atom or a chlorine atom is preferable.

These components (a) are contained in the liquid detergent of the present invention in an amount of 0.1 to 30% by weight (hereinafter simply referred to as%), more preferably 0.3 to 15%, from the viewpoint of detergency. Particularly preferably, the content is 0.5 to 10%.

The amphoteric surfactant of the component (b) is used in combination with the cationic surfactant of the component (a) to significantly improve the detergency against metal stone scum stain. Equations (4), (5),
1 selected from betaines represented by (6) and (7)
Species or two or more are used.

In the general formula (4), R ⁷ is preferably a saturated alkyl group having 8 to 18 carbon atoms from the viewpoint of detergency, more preferably 10 to 1
Six saturated alkyl groups are preferred. For similar reasons, R ⁸ , R
⁹ is preferably a methyl group, an ethyl group or a hydroxyethyl group, and r is preferably 1. In formula (5), R ⁷ is preferably a saturated alkyl group having 8 to 18 carbon atoms, and more preferably a saturated alkyl group having 10 to 16 carbon atoms, from the viewpoint of detergency. For the same reason, R ⁸ and R ⁹ are each preferably a methyl group, an ethyl group or a hydroxyethyl group, s is preferably 1 and t is preferably 1.

In the amidobetaine type amphoteric surfactants (6) and (7) used in the present invention, R ¹⁰ is preferably a saturated alkyl group having 9 to 15 carbon atoms from the viewpoint of detergency. For the same reason, R ⁸ and R ⁹ are each a methyl, ethyl or hydroxyethyl group, u is 2 or 3, v is 1,
w is preferably 1, and x is preferably 1. Specific examples of these include alkylamidopropyl-N, N-dimethylacetate betaine, alkylamidopropyl-N, N-dimethyl-
Examples thereof include 2-hydroxypropylsulfobetaine and alkylamidopropyl-N, N-dimethyl-propylsulfobetaine. In terms of detergency and foaming power, lauric amidepropyl-N, N-dimethylacetate betaine, myristin Acid amide propyl-N, N-dimethyl acetate betaine, cocamido amide propyl-N, N-dimethyl acetate betaine, hydroxysulfobetaine, laurate amide propyl-N, N-dimethyl-2-hydroxypropyl betaine and the like are preferred.

The amount of the component (b) is preferably from 0.1 to 30% from the viewpoint of detergency and foaming power, and from 0.3 to 15%.
% Is more preferable, and 0.5 to 10% is particularly preferable.

As the fatty acid represented by the formula (8) of the component (c) or a salt thereof, a fatty acid having 7 to 17 linear or branched alkyl or alkenyl groups, or an alkali metal salt or an ammonium salt or a monovalent thereof. And alkanol-substituted ammonium salts such as di, tri and the like.
As specific examples, “Emazol 871” and “Emazol 875” (manufactured by Emery Co., Ltd.) which are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, cocoic acid, palm nucleic acid, tallow acid, and methyl branched acid )
Or a water-soluble salt thereof.

The most preferred fatty acid or salt thereof from the viewpoint of rinsing properties and ease of blending is a fatty acid having 11 to 15 carbon atoms in a saturated alkyl chain or a salt thereof. A specific example is linear or branched myristic acid, and the myristic acid content in the total fatty acid composition is more preferably 30% or more, and particularly preferably 60% or more.

The fatty acid or its salt (c) is preferably present in the composition of the present invention in an amount of 0.1 to 10%, more preferably 0.3 to 10%.
-5%, particularly preferably 0.5-3%.

As the component (c), fatty acids may be used alone or in combination of two or more.

The sum of the contents of the components (a), (b) and (c) in the composition of the present invention is 0.3 to 30%, and the weight ratio of the components (a) and (b) is ( a) / (b) = 9/1 to 1
/ 9 and the sum of the contents of components (a) and (b) and (c)
Is more preferably (a + b) / (c) = 20/1 to 1/1.

The mixing ratio of the components (a) and (b) is preferably a / b = 9/1 to 1/9 by weight, preferably 7/3 to 1/9.
More preferably, it is 5 / 8.5. This ratio is 9/1
If it exceeds or is less than 1/9, the detergency against the soap scum may be reduced. As described above, the addition of the component (c) is not limited to the improvement of the foaming power and the rinsing property when used in combination with the components (a) and (b). Bring power.
When the mixing ratio of (a) + (b) / (c) exceeds 20/1, the foaming power and the rinsing property may be deteriorated, and when it is less than 1/1, the cleaning power and the foaming power are reduced. Sometimes.

Furthermore, in order to further improve the detergency of sebum dirt and metal stone scumming dirt, especially to impart excellent detergency to dirt accumulated for a long period of time, (d)
It is more preferable to mix a water-soluble solvent as a component and a sequestering agent as a component (e).

Although the water-soluble solvent of the component (d) used in the present invention is not particularly limited, the following general formula (9)
One or two or more compounds selected from the compounds represented by formulas (11) to (11), dihydric alcohols having 4 to 12 carbon atoms and monohydric alcohols having 1 to 5 carbon atoms are preferable.

[0042]

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(Wherein, R ¹² and R ¹³ each represent a hydrogen atom, an alkyl, phenyl or benzyl group having 1 to 8 carbon atoms, except when both R ¹² and R ¹³ are hydrogen atoms). a represents an integer of 0 to 10 and b represents an integer of 0 to 10, except when both a and b are 0. R ¹⁴ and R
¹⁵ represents an alkyl group having 1 to 3 carbon atoms. R ¹⁶ has 1 carbon atom
Represents an alkyl group of 3 to 3)

In the water-soluble solvent represented by the general formula (9), when R ¹² and R ¹³ are an alkyl group, the number of carbon atoms is particularly preferably 1 to 4. In the formula (9), ethylene oxide (EO) and propylene oxide (P.
O. A) and b of the average number of moles added 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 this compound (9) include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Polyoxyethylene (p = 2-3) polyoxypropylene (p
= 2 to 3) glycol dimethyl ether (p indicates the average number of moles added), 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, polyoxyethylene (p = 1 to 4) glycol phenyl ether, and dipropylene glycol monobutyl ether are preferred from the viewpoints of detergency and usability.

The compounds represented by the general formula (10) include 1,3-dimethyl-2-imidazolidinone,
Examples of suitable compounds include 1,3-diethyl-2-imidazolidinone, and compounds represented by the general formula (11) include 3-methoxy-3-methylbutanol, 3-ethoxy-3-methylbutanol, , 8-octanediol and the like are preferred.

Examples of the dihydric alcohol having 4 to 12 carbon atoms include isoprene glycol, 2,2,4-trimethyl-1,3-pentadiol, and 1,8-octanediol.

Further, examples of the monohydric alcohol having 1 to 5 carbon atoms include methanol, ethanol and isopropyl alcohol. By blending these lower alcohols, the low-temperature stability of the composition is improved.

The water-soluble solvent of the component (d) is preferably contained in the composition of the present invention in an amount of 0.1 to 2 from the viewpoint of the cleaning ability against sebum stains.
-30%, more preferably 1-15%, particularly preferably 5-10%.

As the sequestering agent of component (e),
There is no particular limitation as long as it has the ability to chelate and block metal ions, and examples thereof include hydroxycarboxylic acids or salts thereof, and aminocarboxylic acids or salts thereof. Specifically, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonic acids, tripolyphosphoric acid,
Ethylene glycol bis (2-aminoethyl ether)
Tetraacetic acid, citric acid, maleic acid, polyacrylic acid,
Examples include isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzylimidinoacetic acid, imidinoacetic acid and salts thereof. Of these, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, citric acid and salts thereof are particularly preferred.

The component (e) is preferably incorporated in the composition of the present invention in an amount of 0.1 to 20% from the viewpoint of scum cleaning ability.
It is more preferable to mix 0.5 to 10%, and it is particularly preferable to mix 1 to 5%.

The liquid detergent composition of the present invention further contains a nonionic surfactant and / or an anionic surfactant in an amount of 0.1 to improve the detergency of sebum stains.
1-15% can be blended.

The nonionic surfactant used in the present invention is not particularly limited, but includes polyoxyethylene alkyl ethers or polyoxyethylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers,
Polyoxypropylene alkyl ethers, polyoxypropylene alkenyl ethers, polyoxybutylene alkyl ethers, polyoxybutylene alkenyl ethers, alkylene oxide-added alkyl or alkenyl group-containing nonionic surfactant mixture, sucrose fatty acid esters, One or more selected from aliphatic alkanolamides, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensed surfactants and alkyl glycosides are preferred.

The anionic surfactant used in the present invention is not particularly limited, but preferably has a polyoxyalkylene group from the viewpoint of blending stability.

Examples of the anionic surfactant having a polyoxyalkylene group include polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl aryl ether sulfate, and polyoxyalkylene alkenyl aryl ether sulfate. , Polyoxyalkylene mono- or di-alkyl ether phosphate, polyoxyalkylene mono- or di-alkenyl ether phosphate, polyoxyalkylene mono- or diphenyl ether phosphate, polyoxyalkylene alkyl ether carboxylate, poly Oxyalkylene alkenyl ether carboxylate,
Polyoxyalkylene alkyl ether acetate, polyoxyalkylene alkenyl ether acetate and the like, among which polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl ether acetate and polyoxyalkylene Alkenyl ether acetates are particularly preferred.

The composition of the present invention contains an alkali agent such as an alkanolamine (0.1 to 15%), a thickener, a pigment, a colorant, a fragrance, a bactericide, a preservative and a total weight of the composition of 100%. % Of water or the like can be added.

The composition of the present invention is produced by mixing the above components according to a conventional method, and the pH is preferably 3 to
It is preferably in the range of 12, more preferably 5 to 10, particularly preferably 6 to 8. Outside of this range, problems such as rough hands may occur.

The composition of the present invention is used for cleaning bathtubs and bathtubs made of tiles, ceramics, enamels, reinforced plastics (FRP), stainless steel, wood, and the like, that is, hardeners for bathroom cleaners, washstands, sinks, and the like. It is suitable as a surface cleaning agent.

[0058]

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

Examples 1 to 5 Liquid detergent compositions having the compositions shown in Table 1 were prepared, and their dirt removing power, foaming power, and rinsing properties were evaluated. The numbers in the table indicate% by weight. Examples 1, 2, 4, and 5
This is a reference example.

At ordinary households, the dirt in the sink of the wash basin that has not been washed for about two months is scrubbed with a sponge,
The cleaning power, the foaming power during cleaning, and the rinsing property were evaluated. The evaluation points are as follows.

<Stain Removal> The following five levels were visually evaluated, and the average value of n = 5 was used as a score. 5: Very good stain removal. 4: Good dirt removal. 3: There is unevenness in dirt removal. 2: Degree of dirt being slightly removed. 1: Almost no dirt is removed.

<Foaming Power> The foaming power during scrubbing with a sponge was visually evaluated. ：: Very good foaming power. Δ: Slightly good foaming power. X: The foaming power is not so good.

<Rinseability> After rubbing with a sponge, rinsing with a shower, the rinsing property (foam removal property) near the drain port at that time was visually evaluated. ：: Very good rinsing properties. Δ: Rinsing properties are slightly good. X: Rinsing is not so good.

[0064]

[Table 1]

From Table 1, the components (a), (b) and (c)
The composition of the present invention in which is blended is excellent in detergency, foaming power and rinsing properties, and it can be seen that the composition in which the component (d) is blended further improves the cleaning power.

Examples 6 to 10 Liquid detergent compositions having the compositions shown in Table 2 were prepared, and their dirt-removing power, foaming properties, and rinsing properties were evaluated. The numbers in the table indicate% by weight. Examples 6 and 7 are reference examples.
is there.

The polypropylene wash basin and bath chair stains which had been used for three months in an ordinary household and were stained with a bath were scrubbed with a sponge containing a detergent composition to evaluate the detergency. Detergency A). In addition, the cleaning performance was evaluated when four adults bathed in a FRP bathtub, allowed to stand overnight, and then drained and air-dried for about one week. (Detergency B). At the same time, the evaluation of the foaming power and the rinsing property was also performed in Example 1.
Was performed in the same manner as described above. The evaluation points are as follows.

<Detergency> A: Very good stain removal. C: Slight removal slightly good. ×: Soil removal is not so good.

[0069]

[Table 2]

Table 2 shows that the composition of the present invention has excellent detergency against dirt to which both soap and sebum adhered, and also has good foaming and rinsing properties.

[0071]

Industrial Applicability The liquid detergent composition of the present invention has an extremely strong detergency against stone canscum and sebum dirt, has good foaming power and good rinsing properties, and is used for cleaning hard surfaces such as bathrooms and sinks. Useful for

Continuation of the front page (72) Inventor Masaki Tosaka 2606 Akabane, Kaiga-cho, Haga-gun, Tochigi Prefecture Kao Corporation Research Institute (56) References JP-A-7-82593 (JP, A) JP-A-6-322398 (JP, A) ) WO 95/14757 (WO, A1) WO 93/15173 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-1/94

Claims (4)

(57) [Claims] 1. The following components (a), (b) and (c): (a) general formula (2) Wherein R ³ represents a straight-chain or branched-chain alkyl or alkenyl group having 6 to 20 carbon atoms, and X represents a halogen atom or an alkyl sulfate residue. (B) a cationic surfactant; (b) general formulas (4), (5), (6) and (7) [Wherein, R ⁷ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and R ⁸ and R ⁹ may be the same or different and have 1 to 5 carbon atoms which may be substituted with a hydroxyl group. Represents an alkyl group, R ¹⁰ represents a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms, Y represents a hydrogen atom or a hydroxyl group, r, s and t represent an integer of 1 to 3,
u represents an integer of 1 to 5, v represents an integer of 1 or more, w
And x are integers satisfying 0 ≦ w + x ≦ 4], and (c) an amphoteric surfactant selected from betaines represented by the following general formula (8): (Wherein, R ¹¹ represents a linear or branched alkyl or alkenyl group having 7 to 17 carbon atoms, and M represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine) or a fatty acid salt thereof; And the weight ratio of components (a) and (b) is (a) /
(B) = 7/3 to 1.5 / 8.5, and with component (a)
The weight ratio of the sum of the contents of (b) to the component (c) is (a + b)
/ (C) = 20/1 to 1/1, a liquid detergent composition. Wherein components (a), (b) and liquid detergent composition of the sum according to claim 1, wherein Ru 0.3 to 30 wt% der content of (c). 3. The liquid detergent composition according to claim 1, further comprising a water-soluble solvent (d). 4. The liquid detergent composition according to claim 1, further comprising a sequestering agent (e).