JPH03126798A - Liquid detergent composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific nonionic surfactant mixture, an enzyme and an amino alcohol at specific ratios, exhibiting powerful cleaning effect against oil and protein stain, having excellent foam- breaking property and storage stability and useful as a detergent for automatic dish washer. CONSTITUTION:The objective composition having a pH of 8-9.5 in the state of 0.2% aqueous solution contains (A) 0.5-10wt.% of a nonionic surfactant of formula I (n) and (m) are 2-8; (n+m) is 4-6; l is 7-19), (B) 0. 5-20wt.% of a nonionic surfactant of formula II and/or formula III (R is 10-20C alkyl; (P) is 2-15;(q) is 1-20; x1 and x2 are 1-30; x1+x2 is 2-60; (y) is 5-50). (C) 0. 01-5wt.% of an enzyme and (D) 0. 1-10wt.% of an amino alcohol of formula IV (R<1> is 1-4C hydroxyalkyl; R<2> and R<3> are H or 1-4C hydroxyalkyl).

Description

[Detailed Description of the Invention] The present invention is an automatic cleaner that is resistant to oil stains and protein stains, has high detergency, has excellent foam removal properties, and has good storage stability. The present invention relates to liquid cleaning compositions suitable for use in dishwashers.

Conventionally, in order to increase the detergency of liquid detergent compositions and improve the foam breaking properties, a method using an alkoxy ether of lower alcohol as a surfactant (Japanese Unexamined Patent Publication No. 58-147) has been proposed.
500), a method using ethoxylate of random secondary alcohol (Japanese Unexamined Patent Publication No. 49-41405)
In addition, a liquid detergent composition in which a silicone antifoaming agent is added to improve the foam breaking property is also known (Japanese Unexamined Patent Publication No. 18591/1983).

However, although the above-mentioned liquid detergent composition has some improvement effects on various performances such as cleaning power and foam removal, these performances are not sufficient. It has the disadvantage that it does not have sufficient cleaning power against oil stains and egg (particularly egg yolk) stickiness.

Recently, cleaning agents containing inorganic alkalis such as silicate and sodium carbonate have also been commercially available, but it is difficult to say that these are easy-to-use low-viscosity liquid cleaning compositions, and their cleaning effects are not sufficient. It's something that doesn't exist.

Therefore, a liquid detergent composition with high detergency and good foam removal properties has been desired.

The present invention has been made in view of the above circumstances, and has high detergency, can sufficiently clean oil stains, protein stains, etc. from items to be washed, has excellent foam removal properties, and is suitable for use in automatic dishwashers. An object of the present invention is to provide a liquid cleaning composition.

Means and Effects for Solving the Problem The inventor of the present invention, as a result of extensive studies in order to achieve the above object, has found the following general formula [I] (where n1m is a number from 2 to 8, respectively, and - n + m = 4 to 16, and the number 7 to 19 is 0.5 to 10 of the total composition.
% by weight, the following general formula (III H3 RO-(CH2CH20HCH2C:T(O←H-(I
r) ρ q (However, in the formula, R is an alkyl group having 10 to 20 carbon atoms, p is a number of 2 to 15, and q is a number of 1 to 20.) and the following general formula CIII) CH3 HO→ CH2CH2O←→CH2CH○HCH2CH,
○←H...(m) (However, in the formula, x is a number from 1 to 30, respectively, X □ 10x2 = 2 to 60, and y is a number from 5 to 50.) One or two selected from the nonionic surfactants represented by
0.5 to 20% by weight of the total composition, and 0.01 to 5% of the total composition of the enzyme, and the following general formula [IV) - 1 (wherein R1 is carbon It is a hydroxyalkyl group of number 1 to 4, and R2 and R3 are each a hydrogen atom or a carbon number 1.
-4 hydroxyalkyl group. ) When a liquid cleaning composition is prepared such that the amino alcohol represented by 0.1 to 10% by weight of the total composition is mixed and the pH of the 0.2% by weight aqueous solution is 8 to 9.5, automatic Even when used in a dishwasher, this liquid has high cleaning power that can cleanly remove heavy oil stains and protein (especially egg yolk) stains from the items being washed.It also has excellent foam removal properties and has good storage stability. It was discovered that a cleaning composition can be obtained, and the present invention was completed.

Therefore, in the present invention, (1) the nonionic surfactant of formula CI) is
．． 5 to 10% by weight, (2) 0.5 to 10% of the total composition of one or more nonionic surfactants selected from the above (III and (II) formula 1)
20% by weight, (3) # element 0.01 to 5% by weight of the total composition, (4) Amino alcohol of the above formula (IV) 0.1 to 10% of the total composition
% by weight, and the pH of the 0.2% by weight aqueous solution is 8 to 9.
5 is provided.

The present invention will be explained in more detail below.

First, in the composition of the present invention, as described above, as a nonionic surfactant, the following general formula CI) (wherein n1m is a number of 2 to 8, respectively, n0m = 4 to 16, and the sentence is 7 to 19) and the following general formula (II) CH.

RO→CH2CH,○)-(CH2CH○←H...(I
I) P q (However, in the formula, R is an alkyl group having 10 to 20 carbon atoms, p is a number of 2 to 15, and q is a number of 1 to 2o.) Oxyethylene polyoxypropylene ether and the following general formula (III
) CH3 HO-(CH2CH20 gate CH2CHO)-(CH2C
H20←H...(III) (However, in the formula, x1.x2 are each a number from 1 to 30, x□+x, = 2-60, and y is a number from 5 to 50.) One or more nonionic surfactants selected from pluronic type nonionic surfactants are used in combination.

That is, the secondary alcohol ethoxylate type nonionic surfactant represented by the above formula CI) has excellent detergency, phosphorization-free property, resistance to hard water, compatibility, easy solubility, low temperature stability, Although it is known to be excellent in terms of foam removal and rinsing properties, its performance cannot be said to be fully satisfactory, and it does not necessarily satisfy liquid stability in cold regions. However, in the present invention, C
General formula (n), (nI) to the nonionic surfactant of formula I)
A liquid detergent composition that exhibits excellent foam-breaking properties and excellent liquid stability even in cold regions, by incorporating at least one type of nonionic surfactant represented by the formula and in a specific amount. It is something that can be obtained.

Here, the nonionic surfactant represented by formula (1) is a conventionally known one, and n is 2 to 8, preferably 4 to 7,
m is 2-8, preferably 4-7, n+m is 4-16, preferably 8-14, a is 7-19, preferably 10-1
5 is used.

The amount of the nonionic surfactant represented by formula (1) is 0.5 to 10% by weight, preferably 2.5 to 9.5% by weight based on the total composition of the liquid cleaning composition. . If the blending amount is less than 0.5% by weight, sufficient detergency against oil stains will not be exhibited, and if it exceeds 10% by weight, too much foaming will result, resulting in poor foam removal during rinsing.

Furthermore, as the polyoxyethylene polyoxypropylene ethyl of the higher aliphatic alcohol represented by the formula [■], conventionally known polyoxyethylene polyoxypropylene ethyl is used, but R has 10 to 2 carbon atoms.
0, preferably 11 to 18 alkyl group, p is 2 to 5
, preferably 3-12, q is l-20, preferably 3-12
18 are used. In addition, as the above-mentioned higher aliphatic alcohol, not only a higher alcohol but also a secondary alcohol can be used.

Furthermore, as a pluronic type nonionic surfactant represented by formula [III), X□ and X2 are each 1 to 30
, preferably 5 to 20, and the sum of X engineering and X2 is 2 to
60, preferably 10 to 40, 5 to 50, preferably 10 to 40.

The blending amount of the nonionic surfactant of formulas [■] and [■] is 0.5 to 20% by weight based on the total amount of the liquid cleaning composition.
, preferably 2 to 15% by weight.

If the amount is less than 0.5% by weight, the ability to remove foam during rinsing will be poor, and storage stability in cold regions will be lacking.If it exceeds 20%, there will be too much foaming during rinsing. Deterioration of foam removal properties.

Next, as for the enzyme used in the composition of the present invention, there is no particular limitation on its type, and various enzymes can be used, but from the point of view of dishwashing, amylase, which is a starch-degrading enzyme (for example, Termamil manufactured by Novo), ), proteolytic U
(e.g. Alcalase manufactured by Novo) and lipolytic enzymes are effective.

The amount of enzyme blended is 0.01 to 5% by weight, preferably 0.2 to 2% by weight. If the blending amount is less than 0.01%, it is too small to exhibit its effect, and if it exceeds 5%, the performance is saturated and the aroma becomes bad, which is not preferable.

In the liquid detergent composition of the present invention, together with the nonionic surfactant and enzyme, the following general formula (rV) (wherein R1
is a hydroxyalkyl group having 1 to 4 carbon atoms, R, 2, R3
are each a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms. ), and the pH of the aqueous solution in which the composition is dissolved is adjusted to a specific range at the time of use. In this case, although the combination of nonionic surfactant and enzyme can provide sufficient cleaning power for ordinary dirt, it is not sufficient for cleaning heavily oily dirt or egg (particularly egg yolk) stickiness. However, if the amino alcohol of the above formula (IV) is combined and the pH of the 0.2% by weight aqueous solution is adjusted to 8.
By setting the ratio to 9.5, it is possible to obtain a liquid detergent composition that exhibits sufficient cleaning power against items with a lot of oil stains and egg (particularly egg yolk) stickiness.

Here, in the CIVI formula, R1 is a hydroxyalkyl group having 1 to 4 carbon atoms, R2 and R3 are each a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms, and the hydroxyalkyl group is, for example, a hydroxymethyl group,
Examples include hydroxyethyl group. Like this [■]
Specifically, the amino alcohol in the formula is monoethanolamine.

Jetanolamine, triethanolamine, etc. are preferably used.

The blending amount of the amino alcohol of formula (IV) is 0.1 to ↓0% by weight, preferably 0.5 to 8% by weight of the entire composition. The amount of amino alcohol blended is 0.1% by weight.
If it is less than 0.2% by weight, the pH of the 0.2% aqueous solution is too low.
pH cannot be increased to 8 or higher, and the pH cannot be maintained during washing. On the other hand, if it exceeds 10% by weight, the amount of acid required for neutralization will increase, the foaming will be too large during washing, the foam removal performance during rinsing will be poor, and the color tone will deteriorate during high temperature storage.

When the composition of the present invention is dissolved in water at the time of use, a 0.2 wt.
5, preferably 8.2 to 9.3.

If the pH of the 0.2% by weight aqueous solution is lower than 8, sufficient cleaning power will not be exerted on items with a lot of oil stains or on sticky eggs (particularly egg yolks).

If pH and H exceed 9.5, the enzyme is saturated in terms of performance, and if the alkali is too strong, glass and aluminum products may lose their luster, and the storage stability of the enzyme may deteriorate.

In addition, pH of the composition is toluenesulfonic acid, 13 It can be adjusted with acids such as citric acid and sulfuric acid.

The liquid detergent composition of the present invention has the above-mentioned specific nonionic surfactant combination system, enzyme, and amino alcohol as essential components, but if desired, it may contain other components that are commonly used in this type of detergent composition. Various auxiliary ingredients can also be added. As such auxiliary ingredients, for example, fragrances, pigments, bleaching agents, disinfectants, etc. can be added, and furthermore, common hydrotropes such as ethanol, propylene glycol, polyethylene glycol, 1-luenesulfonate, etc. In addition, clenching agents such as citrate, CMC, gluconate, water-soluble polymers, etc. can also be added.

The liquid cleaning composition of the present invention comprises a nonionic surfactant represented by the general formula CI), and a nonionic surfactant represented by the general formula [IT] or [IT
At least one nonionic surfactant represented by I), an enzyme and an amino alcohol represented by general formula (IV) are blended in specific amounts, and the pH at the time of use (0.2% by weight aqueous solution) is By setting the ratio to 8 to 9.54, it exhibits sufficient cleaning power for items with a lot of oil stains and stuck eggs (especially egg yolk), and has good foam removal properties during rinsing. Moreover, since it has excellent storage stability, its commercial value is extremely high.

EXAMPLES Hereinafter, the present invention will be specifically explained 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 cleaning compositions having the compositions shown in Table 1 were prepared and tested for oil stain cleaning ability, egg yolk stain cleaning ability, foam suppressing effect, and color tone change (stored at 50°C for 12 weeks). I did it. The results are shown in Table ↓. The test method and evaluation method are as follows.

5g of salad oil, 5g of lard, 5g of butter (
(total of 1.5 g), egg yolk Log was used as the egg yolk stain, and to further compound the stain, rice grains were added at the same time as Log. In addition, the items to be washed include 3 rice bowls (ceramic), 3 soup bowls (resin painted), 3 small bowls (ceramic), 3 large plates (ceramic), and 3 small plates (ceramic).
One large plate (made of melamine resin) and three glass cups were used. Add oil and rice grains during the test, add 5g of egg yolk to one large plate and one small plate, and heat at 25°C ± 3°.
The sample was left in a constant temperature room at C150%RH±10% for 2 hours, washed in a dishwasher at a composition concentration of 0.2% under the following conditions, and then evaluated based on the following evaluation method.

(i) Washing condition 1, dishwasher: A fully automatic dishwasher (SW-Nl) in which a detergent solution is sprayed from a rotating nozzle to wash tableware placed on the spray trajectory.

(manufactured by Sharp Corporation) 2.Cleaning temperature: Tap water automatically supplied (3DH, 1
The temperature of the cleaning solution at the end of the cleaning (5°C) was set to 60°C.

3. Washing time: 20 minutes 4. Rinsing: A cycle of rinsing for 1 minute after water supply and draining was performed three times, and heating rinsing was performed twice while raising the temperature to 60'C.

16 5. Drying: After rinsing, set the temperature inside the dishwasher to 80℃.
It was dried for 1 hour while gradually raising the temperature to .

(ji) Cleaning power (oil, egg yolk stains), foam suppression effect, color tone evaluation method 1, oil stain cleaning power evaluation method: Oil red (0,
1% ethanol solution), and the degree of coloring was visually judged according to the following criteria (evaluated by the average score of the various dishes mentioned above).

0 point 2 The degree of coloring is extremely significant.

1 point: Color most of the time.

Color 2 points.

3 points: Slightly colored.

4 points: Hardly colored.

5 points: No coloring.

2. Egg yolk stain detergency evaluation method: After cleaning, the stains attached were visually judged according to the following criteria (evaluated by the average score of the various dishes mentioned above).

0 points: Almost no dirt has been removed.

1 point: Dirt remains (about 3/4 of the remaining area).

2 points: Dirt remains (residual area ↓/2 approx.).

3 points: Dirt remains (residual area ↓/about 4).

4 points: Dirt remains (residual area approximately 1/10).

5 points: All dirt has been removed.

3. Foaming evaluation method: clean, unwashed items with a composition concentration of 0.2%, washed in a dishwasher under the above washing conditions, and at the end of the first rinse cycle and drained. The state of the remaining foam was visually judged according to the following criteria.

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

△: Residual air bubbles are 3 to 10 cm ○: Residual air bubbles are 1 to 3 mm ◎: Residual air bubbles are less than ↑ m 4 Color tone evaluation method: After storing the liquid cleaning composition in a constant temperature room at 50 ° C for 2 weeks, the following Visual judgment was made according to standards.

×: Significantly colored.

△: Colored.

○: Not colored.

8- * Nonionic surfactant (1) Formula % Formula % (ITr) Formula H3 Amino alcohol (rV) Formula From the results of Table 1, it is found that the amount of nonionic surfactant of formula CT4 is outside the range of the present invention ( Comparative Example 5゜6), one with no amino alcohol added (Comparative Example 1゜4), one with a large amount of added amino alcohol (Comparative Example 2), and the pH of the aqueous solution at the time of use was within the range of the present invention 0-4. The other one (Comparative Example 3) does not have sufficient cleaning power and foam removal, but the liquid cleaning composition of the present invention has strong cleaning power, excellent foam removal, and also has good storage stability. was confirmed.

Claims (1)

[Claims] 1. (1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (However, in the formula, n and m are each a number from 2 to 8, n+m=
4 to 16, and l is a number from 7 to 19. ) Nonionic surfactant represented by 0.5 to 10 of the total composition
(2) The following general formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼... [II] (However, in the formula, R is an alkyl group having 10 to 20 carbon atoms, and p is 2 ~15, q is a number from 1 to 20) and the following general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [III] (However, x_1 and x_2 in the formula are each 1 -30, x_1+x_2=2-60, and y is a number of 5-50.) One or two selected from the following nonionic surfactants.
0.5 to 20% by weight of the total composition of the species or more, (3) 0.01 to 5% of the total composition of the enzyme, (4) the following general formula [I
V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[IV] (However, in the formula, 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. 5. A liquid cleaning composition characterized by: