JPH10183182A - Whitening of detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for whitening a detergent composition, capable of increasing the whitening degree of a polishing cream, a detergent paste, a powdery detergent or soap by using a specific stilbene type whitening agent. SOLUTION: This method for whitening a detergent composition comprises adding 0.0001-1wt.% of one or more kinds of compounds of the formula (R, R1 are each H, CH3 , CH2 CH3 , CH2 CH2 OH; X is Na, K, ammonium cation, an amine, an alkanolamine) to a detergent composition. The compound of the formula is preferably 2,2'-[1,2-ethendiyl-bis[5-[[4-[bis(2-hydroxyethyl)amino]-6-[(4- sulfophenyl) amino]-1,3,5-triazin-4,2-yl]amino]]bis-1,4-benzenedisulfonic acid tetrasodium salt. Thereby, the whitening degree of the detergent paste can be enhanced so as to cover the non-aesthetic brown, gray or yellow color caused by the original natural color of a raw material substance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the use of highly hydrophilic stilbene-type clarifiers for increasing the whiteness of final detergent products or slurry intermediates in the form of pastes. More specifically, the purpose of the added clarifying agent is to increase the whiteness of such detergent pastes by a non-aesthetic browning caused by the natural coloring of the raw materials,
It is to increase the color to cover gray coloration or yellowing.

[0002]

The use of optical brighteners in detergents is well known in the art. However, their use is mainly linked to the effect of the optical brightener on the surface to be cleaned by the cleaning agent. In fact, during the cleaning action, the optical brightener tends to adsorb to its surface,
It covers it more completely or incompletely. The effect of the clarifying agent is to absorb the ultraviolet portion of the sun's rays and subsequently emit visible light (by well-known mechanisms:
For example, Kirk-Othmer's Encyclopedia of ChemicalTec
hnology, 4th ed., p. 222) provides a distinct increase in the whiteness of the background.

[0003] However, optical clarifiers exhibit their effect not only when they are adsorbed on solids, but also in aqueous solutions. For this reason, a second effect of its use relates to the possibility of whitening the detergent itself. In other words, optical brighteners are also useful for whitening detergents. The established use in the market described above has only esthetic reasons, which are linked to the fact that consumers associate high detergent performance with the white color of the detergent. This requirement has prompted the use of optical brighteners to enhance the fluorescence of the detergent itself. A classic example is a clarifier such as sodium biphenyl-4,4'-bis (styryl-2-sulfonate), which is used in small quantities but is very expensive.

[0004]

It is therefore conceivable to introduce a very water-soluble stilbene-type optical brightener in order to bleach detergent powders, pastes or intermediate product slurries.

[0005] The highly water-soluble stilbene-type clarifiers used hitherto in the paper and textile industries have been surprisingly found to be effective in whitening various detergent products. Was issued.

Accordingly, one of the objects of the present invention is to provide a method for whitening abrasive creams, detergent pastes, powdered detergents and soaps, ie a method for increasing its whiteness.

[0007]

The method comprises the following formula (I):

[0008]

Embedded image

(Wherein R and R₁Are the same but different
Each may be -H, -CH_Three, -CH _TwoCH_Three, -CH_Two
-CH_TwoOH and X is sodium, potassium or
With ammonium cation, amine or alkanolamine
is there. One or more compounds of formula (I)
And then added in an amount of 0.0001 to 1% by weight.
You.

Another object of the present invention is a detergent composition having improved whiteness comprising one or more compounds of the formula (I).

[0011] These and other objects of the invention, in some preferred embodiments, and by way of example,
Will be shown in detail.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Various compounds of formula (I) are known in the chemical literature and are commercially available;
Alternatively, it can be obtained according to a known method.

In the present invention, the following compounds are particularly preferred: 2,2 '-[1,2-ethenediyl-bis [(3-sulfo-4,1-phenylene) imino- [6- [bis (2-
(Hydroxyethyl) amino-1,3,5-triazine-
4,2-diyl] imino]] hexa sodium salt of bis 1,4-benzenedisulfonic acid (CAS 68971-
49-3) 2,2 ′-[1,2-ethenediyl-bis [(3-sulfo-4,1-phenylene) imino- [6- (2-diethylamino) -1,3,5-triazine-4, 2-Diyl] imino]] hexa sodium salt of bis 1,4-benzenedisulfonic acid (CAS 41098-56-0) 2,2 ′-[1,2-ethenediyl-bis [5-[[4
-[Bis (2-hydroxyethyl) amino] -6
Tetrasodium salt of [(4-sulfophenyl) amino] -1,3,5-triazin-4,2-yl] amino] bis 1,4-benzenedisulfonic acid (CAS 1647
0-24-9) These compounds are well known and have long been used in different technical fields such as the paper and textile industries.

The salts of the stilbenes are very soluble in water and water / glycol mixtures and have a tendency to remain readily in solution during the washing process. Thus, they do not compete with other types of optical brighteners for adsorption on any type of surface. They do not interfere with the actually experienced systems of optical brighteners for the textile industry or have a tendency to deposit on solid surfaces or on the skin.

[0015] Nevertheless, their specific ability to emit visible light parts is outstanding, so that even very small amounts of these substances in solution give a high overall brightness. In addition, they provide complete compatibility with many common compounding ingredients used in the detergent industry and are stable to temperature changes.

According to the invention, the optical brightener of formula (I) is added during the formulation of the detergent product, preferably at the end of the formulation.

The process according to the invention is also applied to formulated detergents which are well known on the market and improves their whiteness.

The compositions according to the invention which comprise one or more compounds of the formula (I) are, for example, abrasive creams, detergent pastes, powdered detergents (including those obtained by atomization) and soaps. .

These compositions, together with common ingredients, are prepared by techniques well known to those skilled in the art.

In a preferred embodiment, the liquid detergent composition according to the invention comprises up to 70% by weight of a group consisting of ionic surfactants, nonionic surfactants, alkali metal salts of fatty acids and mixtures thereof. 0.0001 to 1% by weight, preferably 0.001 to 1% by weight of the selected surfactant
One or more clarifying agents of the formula (I) in the range of 0.5% by weight and often used for whitening washed textiles, for example 4,4-bis {[( 4-anilino) -6- (di-N-2-hydroxyethyl) amino-1,3,5-triazin-2-yl] amino {stilbene-2,2′-disulfonic acid and 4-bis} [(4
-Anilino) -6-morpholino-1,3,5-triazin-2-yl] amino {stilbene-2,2'-disulfonic acid and other well-known organic auxiliaries such as optical clarifiers. Including.

In the case of laundry detergents, the abovementioned optical clarifiers are of the same kind but are more hydrophobic and conversely have a stronger clarifier action on the fibers. Can be combined effectively. Using chemically identical stilbene / triazine family optical brighteners can reduce the number and type of impurities present in the final product. In addition, reducing the total amount of optical brightener present in the formulation is achieved because the glittering effect of the powder is solely due to the particular brightener that does not interact with others. .

In the case of polishing pastes, the use of an optical brightening agent allows effective whitening of the formulation, but this whitening can only be obtained with difficulty by the choice of the polishing powder.

[0023]

The following examples further illustrate the present invention. Unless stated otherwise, all percentages are by weight.

Example 1 An abrasive cream having the following composition was prepared: 2% of a nonionic surfactant (alkyl ethoxylated alcohol: C14, E07) 1% of an anionic surfactant (sodium lauryl sulfate) Suspension [acrylic vinyl copolymer: 3V SIGMA
“Polygel W30” (registered trademark)] 0.
5% ・ Abrasive powder (calcium carbonate) 40% ・ Water to 100% ・ pH 9-10

This formulation was prepared by first dissolving each surfactant in water and then dissolving the polymer. After neutralizing with soda and adjusting the pH to the specified value, the abrasive powder was added slowly. 2000
A cream having a viscosity between cps and 5000 cps was obtained. 0.06% of 2,2 'in this base formulation
-[1,2-ethenediyl-bis [(3-sulfo-4,
1-phenylene) imino- [6- [bis (2-hydroxyethyl) amino-1,3,5-triazine-4,2-
Hexasodium salt of diyl [imino]] bis 1,4-benzenedisulfonic acid was added (in particular, a 0.5% aqueous solution having an extinction coefficient of 75 was used).

Example 2 The same abrasive cream as in Example 1 was prepared. 0.06% of 2,2 ′-[1,2-ethenediyl-bis [(3-sulfo-4,1-phenylene) imino- [6- (2-diethylamino) -1,3 , 5-Triazine-4,2-diyl] imino]] bis 1,4-benzenedisulfonate hexasodium salt (in particular, a 0.5% aqueous solution having an extinction coefficient of 75 was used).

Example 3 The same abrasive cream as that of Example 1 was prepared. 0.06% of 2,2 ′-[1,2-ethenediyl-bis [5-[[4- [bis (2-hydroxyethyl) amino] -6-[(4-sulfophenyl) ) Amino] -1,3,5-triazin-4,2-yl] amino] bis-1,4-benzenedisulphonic acid tetrasodium salt (in particular, a 0.3% aqueous solution having an extinction coefficient of 120 was used). .

The increase in whiteness between the formulations with and without the optical brightener according to the invention is evident to the naked eye. Spectrophotometer for various surfaces (Zeiss
Evaluation by the company "Elrepho 2000" (trade name) gave the following results:

[0029]

[Table 1]

It can be seen that the increase in whiteness obtained in this cream is appropriate given the strongly reduced yellowness.

Example 4 A similar evaluation of the effectiveness of the method of the present invention was made on an end product abrasive cream present on the European market.
The composition of this cream was not determined. Each cream is indicated by its trade name.

2,2 '-[1,2-ethenediyl-bis [(3-sulfo-4,1-phenylene) imino- [6-
[Bis (2-hydroxyethyl) amino-1,3,5-
Triazine-4,2-diyl] imino]] bis1,4-
The hexasodium salt of benzenedisulfonic acid was used.

The clarifying agent was added in the amounts listed above, but the clarifying agent was now added after compounding. The table below reports that all pastes achieved the following whiteness / brightness:

[0034]

[Table 2]

These results show the general applicability of the process according to the invention, irrespective of the type and composition of the detergent product.

Example 5 A detergent paste having the following composition was prepared: 40% anionic surfactant (alkyl ethoxy sulfate: C14, E02, S04, 28% solution) 40% anionic surfactant (sodium lauryl sulfate) 10% Chelating agent (sodium tripolyphosphate) 25% Water until 100% pH 9-10 Solutions of each surfactant were prepared with slight heating of the paste.

The base formulation had 0.06% of 2,2 ′
-[1,2-ethenediyl-bis [(3-sulfo-4,
1-phenylene) imino- [6- [bis (2-hydroxyethyl) amino-1,3,5-triazine-4,2-
Hexasodium salt of diyl [imino]] bis 1,4-benzenedisulfonic acid was added (in particular, a 0.5% aqueous solution having an extinction coefficient of 75 was used).

Example 6 The same detergent paste as in Example 5 was prepared. 0.06% of 2,2 ′-[1,2-ethenediyl-bis [(3-sulfo-4,1-phenylene) imino- [6- (2-diethylamino) -1,3 , 5-Triazine-4,2-diyl] imino]] bis 1,4-benzenedisulfonate hexasodium salt (in particular, a 0.5% aqueous solution having an extinction coefficient of 75 was used).

Example 7 The same detergent paste as in Example 5 was prepared. 0.06% of 2,2 ′-[1,2-ethenediyl-bis [5-[[4- [bis (2-hydroxyethyl) amino] -6-[(4-sulfophenyl) ) Amino] -1,3,5-triazin-4,2-yl] amino] bis-1,4-benzenedisulfonic acid tetrasodium salt was added (in particular, a 0.3% aqueous solution having an absorption coefficient of 120 was used). .

The increase in whiteness between the formulations with and without the optical brightener according to the invention is evident to the naked eye. Spectrophotometer for various surfaces (Zeiss
Evaluation by Elrepho 2000) gave the following results:

[0041]

[Table 3]

It can be seen that the increase in whiteness obtained in this cream is appropriate in view of the strongly reduced yellowness.

Example 8 Bleaching of Slurry for Powder Detergent A slurry for detergent having the following composition was prepared: Anionic surfactant (alkyl ethoxy sulfate: C14, E02, S04, 28% solution) 31%・ Anionic surfactant (sodium lauryl sulfate) 7.7% ・ Chelating agent (sodium tripolyphosphate) 19% ・ Sodium perborate 12% ・ Tetracetylethylenediamine 4% ・ Zeolite 8% ・ Until water reaches 100% ・pH 9-10

The base formulation has 0.06% of 2,2 ′
-[1,2-ethenediyl-bis [(3-sulfo-4,
1-phenylene) imino- [6- [bis (2-hydroxyethyl) amino-1,3,5-triazine-4,2-
Hexasodium salt of diyl [imino]] bis 1,4-benzenedisulfonic acid was added (in particular, a 0.5% aqueous solution having an extinction coefficient of 75 was used).

Example 9 The same slurry as in Example 8 was prepared. 0.06% of 2,2 ′-[1,2-ethenediyl-
Bis [(3-sulfo-4,1-phenylene) imino-
[6- (2-Diethylamino) -1,3,5-triazine-4,2-diyl] imino]] bis-1,4-benzenedisulfonate hexasodium salt was added (in particular, an extinction coefficient of 75 and an extinction coefficient of 0.5). % Aqueous solution).

Example 10 The same slurry as in Example 8 was prepared. 0.06% of 2,2 ′-[1,2-ethenediyl-
Bis [5-[[4- [bis (2-hydroxyethyl) amino] -6-[(4-sulfophenyl) amino] -1,
3,5-triazin-4,2-yl] amino] bis1,
A tetrasodium salt of 4-benzenedisulfonic acid was added (in particular, a 0.3% aqueous solution having an absorption coefficient of 120 was used). The results are still satisfactory before and after drying as shown in the following table.

[0047]

[Table 4]

Example 11 Lightening agent paste for soap A soap having the following composition was prepared: 70% of naturally occurring fatty acids (fatty acids of animal fat, coconut and palm oil) 10% of glycerin Stearic acid 3.0% ・ Sodium chloride 2.0% ・ EDTA 0.2% ・ BHT 0.01% ・ Water reaches 100% ・ pH 8

After evaporating the mixture by heating, the following three individual samples were made: Sample B: as-soap Sample R: 0.5% of titanium oxide as reference brightener was added Soap Sample O: 0.06% of 2,2 ′-[1,2-ethenediyl-bis [(3-sulfo-4,1-phenylene) imino- [6- [bis (2-hydroxyethyl) amino −
1,3,5-triazine-4,2-diyl] imino]]
Soap to which hexasodium salt of bis 1,4-benzenedisulfonic acid was added (in particular, a 0.5% aqueous solution having an extinction coefficient of 75 was used)

[0050]

[Table 5]

It can be seen that the addition of the optical brightener according to the invention contributes more to the whitening of the paste than conventional brighteners such as titanium oxide.

Claims (13)

[Claims] 1. A method for increasing the whiteness of a cleaning composition.
And 0.0001% to 1% by weight based on the composition.
% Of one or more compounds of formula (I)
Said method comprising adding. Embedded image(Where R and R₁May be the same or different.
-H, -CH_Three, -CH _TwoCH_Three, -CH_Two-CH_TwoOH
And X is a sodium, potassium or ammonium cation.
Ion, amine or alkanolamine. ) 2. The method of claim 1, wherein said composition is selected from the group consisting of abrasive creams, cleaning pastes, powdered soaps, soaps and slurries. 3. The method according to claim 1, wherein the compound of formula (I) is 2,2′-
[1,2-ethenediyl-bis [(3-sulfo-4,1
-Phenylene) imino- [6- [bis (2-hydroxyethyl) amino-1,3,5-triazine-4,2-diyl] imino]] bis 1,4-benzenedisulfonate hexasodium salt. Item 1. The method of Item 1. 4. The compound of the formula (I) is 2,2′-
[1,2-ethenediyl-bis [(3-sulfo-4,1
-Phenylene) imino- [6- (2-diethylamino)
-1,3,5-Triazine-4,2-diyl] imino]] bis-1,4-benzenedisulphonic acid hexasodium salt. 5. The compound of the formula (I) is 2,2′-
[1,2-ethenediyl-bis [5-[[4- [bis (2-hydroxyethyl) amino] -6-[(4-sulfophenyl) amino] -1,3,5-triazine-4,
2. The method of claim 1 which is the tetrasodium salt of 2-yl] amino]] bis-1,4-benzenedisulfonic acid. 6. A method for increasing the whiteness of a laundry detergent.
And 0.0001% to 1% by weight based on the composition.
% Of two or more of the compounds of formula (I)
Such a method, comprising adding the mixture. Embedded image(Where R and R₁May be the same or different.
-H, -CH_Three, -CH _TwoCH_Three, -CH_Two-CH_TwoOH
And X is a sodium, potassium or ammonium cation.
An ion, an amine or an alkanolamine, of the formula
The mixture of the compounds of (I) is based on hydrophobic and hydrophilic compounds.
Is formed. ) 7. A cleaning composition having improved whiteness.
And 0.0001% to 1% by weight based on the composition.
% Of one or more compounds of formula (I)
The composition comprising: Embedded image(Where R and R₁May be the same or different.
-H, -CH_Three, -CH _TwoCH_Three, -CH_Two-CH_TwoOH
And X is a sodium, potassium or ammonium cation.
Ion, amine or alkanolamine. ) 8. The composition of claim 7, wherein said composition is selected from the group consisting of abrasive creams, cleaning pastes, powdered soaps, soaps and slurries. 9. The compound of the formula (I) is 2,2′-
[1,2-ethenediyl-bis [(3-sulfo-4,1
-Phenylene) imino- [6- [bis (2-hydroxyethyl) amino-1,3,5-triazine-4,2-diyl] imino]] bis 1,4-benzenedisulfonate hexasodium salt. Item 7. The composition according to Item 7. 10. The compound of the formula (I) is 2,2′-
[1,2-ethenediyl-bis [(3-sulfo-4,1
-Phenylene) imino- [6- (2-diethylamino)
The composition of claim 7, which is a hexasodium salt of -1,3,5-triazine-4,2-diyl] imino]] bis 1,4-benzenedisulfonic acid. 11. The compound of the formula (I) is 2,2′-
[1,2-ethenediyl-bis [5-[[4- [bis (2-hydroxyethyl) amino] -6-[(4-sulfophenyl) amino] -1,3,5-triazine-4,
8. The composition of claim 7, which is a tetrasodium salt of 2-yl] amino]] bis-1,4-benzenedisulfonic acid. 12. The liquid cleaning composition of claim 7, wherein the composition is selected from the group consisting of up to 70% by weight of ionic surfactants, nonionic surfactants, alkali metal salts of fatty acids and mixtures thereof. Surfactant, and 0.0001 to 1% by weight, preferably 0.001 to 0.
5% by weight of one or more optical brighteners of the formula (I) and known organic auxiliaries such as optical brighteners often used for whitening washed textiles. A composition comprising: 13. Laundry detergent having improved whiteness
0.0001% by weight to 1% by weight of the composition
It does not include mixtures of compounds of formula (I) in amounts in the range of% by weight.
Said detergent. Embedded image(Where R and R₁May be the same or different.
-H, -CH_Three, -CH _TwoCH_Three, -CH_Two-CH_TwoOH
And X is a sodium, potassium or ammonium cation.
An ion, an amine or an alkanolamine, of the formula
The mixture of the compounds of (I) is based on hydrophobic and hydrophilic compounds.
Is formed. )