JP2581231B2 - Liquid detergent composition - Google Patents

Description

The present invention relates to an automatic dishwasher which is resistant to oil stains and protein stains, has a high detergency, has excellent defoaming properties, and has good storage stability. It relates to a suitable liquid detergent composition.

2. Description of the Related Art Conventionally, in order to enhance the detergency of a liquid detergent composition and to improve the foam-removing property, a method using a lower alcohol and an alkoxy ether as a surfactant (Japanese Patent Application Laid-Open No. 58-147500
JP-A-49-41405) and a method using a random secondary alcohol ethoxylate (JP-A-49-41405), and adding a silicone-based defoaming agent to a liquid detergent composition to form a foam. With improved sharpness (Japanese Unexamined Patent Publication No.
18591) is also known.

However, the liquid detergent composition has some effects of improving various properties such as detergency and foam removal, but the performance is not sufficient.For example, when the composition is applied to an automatic dishwashing machine, the subject to be washed is severe. It has a drawback that sufficient detergency cannot be exerted against sticking of oil stains and eggs (especially egg yolk).

Recently, detergents containing an inorganic alkali such as silicate or sodium carbonate have also been marketed, but none of them are easy-to-use low-viscosity liquid detergent compositions, and their washing effects are not sufficient. is there.

Accordingly, there has been a demand for a liquid detergent composition having a high detergency and good bubble elimination.

The present invention has been made in view of the above circumstances, and has a high detergency, can sufficiently wash oil stains, protein stains, and the like of an object to be washed, and has excellent foam removing properties, and is suitable for automatic dishwashing machines. It is an object to provide a liquid cleaning composition.

Means and Action for Solving the Problems The present inventor has conducted intensive studies to achieve the above object, and as a result, the following general formula [I] (Where n and m are respectively 2 to 8 and n + m = 4
1616, and l is a number of 7〜19. The nonionic surfactant represented by the formula: 0.5 to 10% by weight of the total composition, the following general formula [II] (Where R is an alkyl group having 10 to 20 carbon atoms;
Is a number of 2 to 15, and q is a number of 1 to 20. ) And the following general formula [III] (Where x ₁ and x ₂ are each a number from 1 to 30, and x ₁ + x ₂ =
2 to 60, and y is a number of 5 to 50. One or two selected from nonionic surfactants represented by
At least 0.5% to 20% by weight of the total composition and at least 0.01% to 5% by weight of the enzyme are blended in the general formula [IV] Wherein R ¹ is a hydroxyalkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms. 0.1-10% by weight of the composition
When a liquid detergent composition is prepared so that the pH of a 0.2% by weight aqueous solution is 8 to 9.5, even if the composition is applied to an automatic dishwasher, severe oil stains and proteins (particularly Egg yolk) It has been found that a liquid detergent composition having a high detergency capable of washing off dirt cleanly, having good foam elimination properties, and having good storage stability can be obtained. Was.

Therefore, the present invention provides (1) a nonionic surfactant of the above formula (I) having a total composition of 0.1%;
5 to 10% by weight, (2) 0.5 to 20% by weight of the total composition of one or more selected from the nonionic surfactants of the above formulas (II) and (III), (3) Enzyme of the entire composition (4) 0.1 to 5% by weight of the amino alcohol of the above formula (IV)
1010% by weight of a 0.2% by weight aqueous solution having a pH of 8 to 9.5.

 Hereinafter, the present invention will be described in more detail.

First, in the composition of the present invention, as described above, as a nonionic surfactant, the following general formula (I) (Where n and m are respectively 2 to 8 and n + m = 4
1616, and l is a number of 7〜19. A nonionic surfactant of the secondary alcohol ethoxylate type represented by the following general formula [II] (Where R is an alkyl group having 10 to 20 carbon atoms;
Is a number of 2 to 15, and q is a number of 1 to 20. A polyoxyethylene polyoxypropylene ether of a higher aliphatic alcohol represented by the following general formula [III]: (Where x ₁ and x ₂ are each a number from 1 to 30, and x ₁ + x ₂ =
2 to 60, and y is a number of 5 to 50. ) Is used in combination with one or more nonionic surfactants selected from the Pluronic type nonionic surfactants.

That is, the secondary alcohol ethoxylate type nonionic surfactant represented by the above formula [I] is itself a detergency, easy to dephosphorize, hard water-based, compatible, easy to dissolve, low-temperature stability. It is known that it is excellent in terms of foam elimination property and rinsing property, but its performance cannot be said to be sufficiently satisfactory, and it does not necessarily satisfy liquid stability in cold districts and the like. However, in the present invention,
The nonionic surfactants of the formula (I) include the general formulas (II) and (II)
Liquid washing showing excellent foam removal properties and excellent liquid stability even in cold regions by blending at least one of the nonionic surfactants represented by the formula (I) and a specific blending amount. Agent composition can be obtained.

Here, the nonionic surfactant represented by the formula (I) is
It is conventionally known, and n is 2 to 8, preferably 4 to
7, m is 2 to 8, preferably 4 to 7, n + m is 4 to 16,
Preferably, those having 8 to 14 and 1 to 7 to 19, preferably 10 to 15 are used.

The compounding amount of the nonionic surfactant represented by the formula [I] is 0.5 to 10% by weight, preferably 2.5 to 9.5% by weight, based on the whole composition of the detergent composition. The compounding amount is 0.
If the amount is less than 5% by weight, sufficient detergency against oil stains will not be exerted. If the amount exceeds 10% by weight, foaming will be too large, and the foam-removing property during rinsing will be reduced.

Further, as the polyoxyethylene polyoxypropylene ether of the higher aliphatic alcohol represented by the formula (II), conventionally known ones are used, wherein R has 10 to 2 carbon atoms.
An alkyl group having 0, preferably 11 to 18, p is 2 to 15, preferably 3 to 12, and q is 1 to 20, preferably 3 to 18 are used. In addition, as the higher aliphatic alcohol, not only a primary alcohol but also a secondary alcohol can be used.

Further, as the pluronic type nonionic surfactant represented by the formula (III), x ₁ and x ₂ are each 1 to 30, preferably 5 to 20, and the sum of x ₁ and x ₂ is 2 to 60, Preferably 10 to 40, y is 5 to 50, preferably 10 to 40 are used.

The compounding amount of the nonionic surfactants of the formulas [II] and [III] is 0.5 to 20% by weight, preferably 2 to 15% by weight, based on the entire liquid detergent composition. The amount is 0.5
When the amount is less than 10% by weight, the foam-removing property at the time of rinsing is inferior, and the storage stability in a cold region is lacking.

Next, the type of the enzyme used in the composition of the present invention is not particularly limited, and various enzymes can be used. However, from the viewpoint of dishwashing, an amylase that is a starch-degrading enzyme (for example, Termamyl manufactured by Novo Corporation) Proteolytic enzymes (for example, Alcalase manufactured by Novo) and lipolytic enzymes are effective.

The amount of the enzyme is 0.01 to 5% by weight, preferably 0.1%.
2 to 2% by weight. If the compounding amount is less than 0.01%, the effect is too small to exhibit its effect, and if it exceeds 5%, the performance is saturated, and the fragrance deteriorates, which is not preferable.

In the liquid detergent composition of the present invention, together with the nonionic surfactant and the enzyme, the following general formula (IV) (Wherein, R ¹ is a hydroxyalkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms). In addition, the pH of the aqueous solution in which the composition is dissolved during use is adjusted to a specific range. In this case, even if a combination of a nonionic surfactant and an enzyme is used, it is possible to obtain a sufficiently satisfactory detergency with ordinary stains, but it is sufficiently effective against a lot of oil stains and eggs (especially egg yolk). Detergency is not exhibited, but combined with the amino alcohol of the above formula (IV), and,
By adjusting the pH of the 0.2% by weight aqueous solution to 8 to 9.5, it is possible to obtain a liquid detergent composition exhibiting sufficient detergency against a lot of oily stains and eggs (especially egg yolk).

Here, in the formula (IV), R ¹ is a hydroxyalkyl group having 1 to 4 carbon atoms, R ² and R ³ are each a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms, and as the hydroxyalkyl group, Examples include a hydroxymethyl group and a hydroxyethyl group. Specifically, monoethanolamine, diethanolamine, triethanolamine and the like are preferably used as the amino alcohol of the formula [IV].

The amount of the amino alcohol of the formula [IV] is 0.1 to 10% by weight, preferably 0.5 to 8% by weight of the whole composition. When the amount of the amino alcohol is less than 0.1% by weight, the pH of the 0.2% by weight aqueous solution cannot be adjusted to 8 or more because it is too small, and the pH cannot be maintained during washing. On the other hand, if the content exceeds 10% by weight, the amount of acid required for neutralization increases, and foaming during washing is too much, so that foam elimination during rinsing is inferior and color tone deteriorates during high-temperature storage.

When the composition of the present invention is dissolved in water at the time of use, the pH of a 0.2% by weight aqueous solution thereof is 8 to 9.5, preferably
Adjust to be 8.2 to 9.3. PH of 0.2% by weight aqueous solution
If the value is lower than 8, oily stains and eggs (especially egg yolk)
Sufficient detergency is not exhibited against sticking. On the other hand, when the pH exceeds 9.5, the performance is saturated, and when the alkali is too strong, gloss of glass and aluminum products is lost and the storage stability of the enzyme is deteriorated.

The pH of the composition is toluenesulfonic acid, citric acid,
It can be adjusted with an acid such as sulfur.

The liquid detergent composition of the present invention contains the above-mentioned specific nonionic activator combination system, an enzyme, and an amino alcohol as essential components, and is optionally used as a further component in this type of detergent composition as desired. Various auxiliary components described above can also be added. As such auxiliary components, for example, fragrances, pigments, bleaching agents, bactericides and the like can be added,
Further, general hydrotrope agents such as ethanol, propylene glycol, polyethylene glycol, and toluenesulfonate, and chelates such as citrate, CMC, glyconate, and water-soluble polymer can also be added. .

Effect of the Invention The liquid detergent composition of the present invention comprises a nonionic surfactant represented by the above general formula [I], and a general formula [II], [III]
At least one nonionic surfactant represented by the formula, an enzyme and an amino alcohol represented by the general formula [IV] are blended in specific amounts, and the pH at the time of use (0.2% by weight aqueous solution) is adjusted to 8 to 9.5. As a result, it has sufficient detergency against washings with lots of oil stains and sticking of eggs (especially egg yolks), and has good foam elimination properties during rinsing, and excellent storage stability. Therefore, its commercial value is extremely high.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 6, Comparative Examples 1 to 6] Various liquid detergent compositions having the compositions shown in Table 1 were prepared, and the oil stain cleaning power, egg yolk cleaning power, foam suppressing effect, color tone change (50 ° C) , Two weeks). The results are shown in Table 1. In addition, the test method and the evaluation method are as follows.

Test method and evaluation method 5 g of salad oil, 5 g of lard, 5 g of butter (15 g in total)
g), 10 g of egg yolk was used as egg yolk stain, and 10 g of rice grains were added at the same time to further compound the stain. In addition, three bowls of rice bowl (pottery), three soup bowls (resin coating),
3 small bowls (porcelain), 3 large plates (porcelain), 3 small plates (porcelain)
Sheets, one large plate (made of melamine resin), and three glass cups. Oil and rice grains are added at the time of testing, and egg yolk is on a large plate 1
5g each per plate and small plate, then 25 ℃ ± 3
℃, 50% RH ± 10% in a constant temperature room for 2 hours, composition concentration
After washing in a dishwasher under the following conditions at 0.2%, evaluation was made based on the following evaluation method.

(I) Washing conditions 1. Dishwasher: Fully automatic dishwasher (SW-N1, manufactured by Sharp Corporation) in which a detergent solution is sprayed from a rotating nozzle and the dishes set on the spray track are washed. Washing temperature: Tap water supplied automatically (3DH, 15 ℃)
The washing liquid temperature at the end of washing was 60 ° C.

3. Rinse time: 20 minutes 4. Rinse: Rinse for 1 minute after water supply, drain three times, and heat-rinse once with heating to 60 ° C.

5. Drying: After rinsing, drying was performed for 1 hour while gradually increasing the temperature in the dishwasher cabinet to 80 ° C.

(Ii) Detergency (oil, yolk stain), defoaming effect, color tone evaluation method 1. Oil stain detergency evaluation method: Oil red (0.1
% Ethanol solution), and the degree of coloring was visually determined according to the following criteria (evaluated by the average score of the above-mentioned various dishes).

0 point: The degree of coloring is extremely remarkable.

1 point: Almost colored.

2 points: colored.

3 points: Colored slightly.

4 points: Almost no coloring.

5 points: no coloring.

2. Egg yolk cleaning power evaluation method: Dirt adhering after cleaning was visually determined according to the following criteria (evaluated by the average score of the above-mentioned various dishes).

0 point: Dirt is hardly removed.

1 point: Dirt remains (residual area: about 3/4).

2 points: dirt remains (remaining area about 1/2).

3 points: Stain remains (residual area about 1/4).

4 points: Stain remains (residual area about 1/10).

5 points: All dirt is removed.

3. Foaming evaluation method: Non-stained, non-washed, with a composition concentration of 0.2%, washed with a dishwasher under the above washing conditions, the first rinsing cycle was completed, and remained when drained. The state of the foam was visually determined based on the following criteria.

×: Residual bubbles exceed 10 mm from the liquid surface.

△: Residual air bubbles 3 to 10 mm ○: Residual air bubbles 1 to 3 mm ◎: Residual air bubbles less than 1 mm 4. Color table evaluation method: After storing the liquid detergent composition in a 50 ° C. constant temperature room for 2 weeks, the following criteria Was visually determined.

×: markedly colored.

Δ: Colored.

：: Not colored.

From the results in Table 1, it can be seen that the addition amount of the nonionic surfactant of the formula [I] is out of the range of the present invention (Comparative Examples 5 and 6), the amino acid-free one (Comparative Examples 1 and 4), the amino alcohol Those having a large amount of addition (Comparative Example 2) and those having a pH of the aqueous solution during use outside the range of the present invention (Comparative Example 3),
Although the foam removal was not sufficient, it was confirmed that the liquid detergent composition of the present invention has strong detergency, excellent foam removal, and good storage stability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication C11D 3:26 3: 386)

Claims (1)

(57) [Claims] (1) The following general formula [I] (Where n and m are respectively 2 to 8 and n + m = 4
1616, and l is a number of 7〜19. (2) 0.5 to 10% by weight of the total composition of the nonionic surfactant represented by the following formula (II): (Where R is an alkyl group having 10 to 20 carbon atoms;
Is a number of 2 to 15, and q is a number of 1 to 20. ) And the following general formula [III] (Where x ₁ and x ₂ are each a number from 1 to 30, and x ₁ + x ₂ =
2 to 60, and y is a number of 5 to 50. One or two selected from nonionic surfactants represented by
At least 0.5% to 20% by weight of the total composition; and (3) 0.01% to 5% by weight of the enzyme, (4) the following general formula [IV] Wherein R ¹ is a hydroxyalkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms. 0.1-10% by weight of the composition
Wherein the pH of the 0.2% by weight aqueous solution is from 8 to 9.5.