EP0302340B1 - Liquid detergent - Google Patents

Description

The present invention relates to liquid detergents containing white toner with improved behavior with regard to the formation of white toner spots ("spotting").

In the detergent sector, this phenomenon is understood to mean the undesired soiling of an unbleached white or pastel-colored textile material when it comes into direct contact with a liquid detergent containing whitening agent, as is the case, for example, when treating a dirt stain with such an agent. This "spot" caused by the high concentration of the white toner in the undiluted detergent is not or only partially removed or compensated for in a subsequent wash with the same liquid detergent.

It has therefore already been proposed (cf. US 4,559,169 = EP 167,205) instead of the otherwise usual one two or more sulfonated whiteners, which are characterized by a high substantivity, to incorporate the less fiber-affine whitener monosulfonic acids into the liquid detergent.

In this way, a reduced tendency to "spotting" is actually achieved, but on the other hand, this advantage is bought by a lower overall white effect of the material to be lightened.

EP-A-0 021 752 discloses liquid detergent preparations which contain bis-triazinylamino-stilbenesulfonic acid compounds having 3 to 5 sulfonic acid groups as optical brighteners.

US Pat. No. 3,632,491 describes bis-triazinylamino-stilbenedisulfonic acid compounds which are substituted by a 2,6-dimethylmorpholine residue in both triazinyl parts and are used as optical brighteners in powder detergents.

oder deren Salzen entsprechen, worin unabhängig voneinander

B =

O, NH, NY oder NH(CH₂)_n

R =

H, C₁-C₄-Alkyl, C₁-C₄-O-Alkyl, F, Cl, CF₃ oder OCF₃

X₁ =

C₄-C₁₂-Alkyl oder C₅-C₇-Cycloalkyl

X₂ =

H oder C₁-C₁₂-Alkyl

O =

-O-, -CH₂-, -CH₂CH₂- oder direkte Bindung,

Y =

C₁-C₄-Alkyl

Z =

R

n =

1, 2 oder 3

bedeuten, mit der Maßgabe, daß R ≠ H,
wenn Z = H und B = NH,
oder Verbindungen der Formel (I) oder deren Salzen entsprechen, worin

R

für H, n für 1 und A für

steht, oder

R

für m-CF₃ oder p-OCF₃, n für 1 und A für

steht.

It has now surprisingly been found that white detergent-containing liquid detergents with improved "spotting" behavior and, at the same time, good brightening effect are obtained if, as whitening agents, compounds are used which are in the form of the free acid of the formula

or their salts, in which independently

B =

O, NH, NY or NH (CH₂) _n

R =

H, C₁-C₄-alkyl, C₁-C₄-O-alkyl, F, Cl, CF₃ or OCF₃

X₁ =

C₄-C₁₂-alkyl or C₅-C₇-cycloalkyl

X₂ =

H or C₁-C₁₂ alkyl

O =

-O-, -CH₂-, -CH₂CH₂- or direct bond,

Y =

C₁-C₄ alkyl

Z =

R

n =

1, 2 or 3

mean with the proviso that R ≠ H,
if Z = H and B = NH,
or compounds of the formula (I) or their salts, in which

R

for H, n for 1 and A for

stands, or

R

for m-CF₃ or p-OCF₃, n for 1 and A for

stands.

Preferably said C₁-C₄-alkyl radicals are C₂H₅ and in particular CH₃, while the higher alkyl radicals X₁ are especially n-butyl to n-hexyl.

Cyclohexyl is particularly suitable as the cycloalkyl.

Preferred white toners are those of the formula (I) in which B is not NH or NY.

R =

H und

bedeuten.Those of this formula, in which

R =

Dog

mean.

These whiteners not only show good application properties, but are also very easily accessible.

The compounds of the formula I can of course also be present in the form of their salts, in particular alkali metal, amine and ammonium salts. Suitable alkali salts are the Na, Li or K salts.

mit Verbindungen der Formel A-H umsetzt - vorzugsweise in Gegenwart eines Säureakzeptors.The whiteners of the formula (I) are known (cf. DE-A 1 545 920 CA 65 (1966) 12317c) or can be obtained by methods known per se, for example by using compounds of the formula

with compounds of the formula AH - preferably in the presence of an acid acceptor.

• a) Kombination anionisch/nichtionisch
• b) Kombination anionisch/nichtionisch/kationisch
• c) Kombination nichtionisch/kationisch
• d) Kombination anionisch/nichtionisch + "Builder"
• e) Rein nichtionisch.

The liquid detergents can be divided into the following classes with regard to the surfactant systems used:

• a) Combination anionic / nonionic
• b) Combination anionic / nonionic / cationic
• c) Combination non-ionic / cationic
• d) Combination anionic / nonionic + "builder"
• e) Purely non-ionic.

Systems a), b), d) and e) are preferred in the context of this invention.

Suitable surfactants are described in U.S. Patent 4,559,169, columns 2-4.

Commercial preferred products are preferred non-ionic surfactants, e.g. the addition products of ethylene oxide with higher aliphatic alcohols and alkylphenols, acids such as higher fatty acids, resin acids, tall oil acids and acids of the oxidation products of the petroleum, and alkylene oxide adducts of higher fatty acid amides, the fatty acid part generally having 8 to 22 carbon atoms and 10 to 50 mol Ethylene oxide is condensed.

Preferred anionic surfactants are fatty alcohol sulfates and alkylbenzenesulfonates and fatty acids, as described in US Pat. No. 4,559,169, column 6.

Suitable “builder” -containing detergents are described in GB 2 028 365. Preferred builders are phosphates, NTA, citrates and polycarboxylates.

The liquid medium for the detergents according to the invention is aqueous and can consist of water alone or of water and additional solvents as solubilizers. The additional solvents can make up up to 20, preferably up to 15% of the total solvent content. The following are suitable: low alkanols or a low diol or polyol.

The liquid detergent according to the invention can also contain conventional additives, such as soil suspending agents or graying inhibitors, foam inhibitors, preservatives and perfumes. These are of course chosen so that they are compatible with the main components of the detergent.

The whiteners to be used according to the invention are added in quantities of 0.005 to 1% or more, based on the weight of the detergent, regardless of the surfactant system. The detergents according to the invention can be used in soft or hard water at temperatures of 10 to 60 ° C. and above.

The washing treatment is carried out, for example, as follows: the textiles are treated in a washing bath at 20 to 100 ° C. for 1 to 30 minutes, that contains 0.1 to 10 g / kg of detergent. The liquor ratio can be 1: 3 to 1:50.

In the examples below, "percentages" mean percentages by weight.

Examples

12,5 %

Kokos-Seife

8,5 %

Lineares Alkylbenzolsulfonat

5,5 %

C₁₂₋₁₅-Fettalkoholethoxylat (7 EO)

7,5 %

Kaliumcitrat

5,0 %

Propylenglykol

8,5 %

Ethanol

1,0 %

Na-Formiat

13,5 %

C₁₂₋₁₄-Fettalkoholethersulfat

ad 100,0 %

vollentsalztes Wasser

wurden die in der folgenden Tabelle aufgeführten Weißtöner gelöst:

In a liquid detergent of type d) consisting of

12.5%

Coconut soap

8.5%

Linear alkyl benzene sulfonate

5.5%

C₁₂₋₁₅ fatty alcohol ethoxylate (7 EO)

7.5%

Potassium citrate

5.0%

Propylene glycol

8.5%

Ethanol

1.0%

Na formate

13.5%

C₁₂₋₁₄ fatty alcohol ether sulfate

ad 100.0%

completely desalinated water

the white toners listed in the following table were solved:

Material:

gebleichter Baumwoll-Nessel

Dosierung:

5 g/l

Flottenverhältnis:

1:20

Temperatur:

50°C

Wasserhärte:

6° DH

Washing tests were carried out with the detergents thus obtained:

Material:

bleached cotton nettle

Dosage:

5 g / l

Fleet ratio:

1:20

Temperature:

50 ° C

Water hardness:

6 ° DH

After 9 washes, the degree of whiteness of the cotton rags was determined using a colorimeter (RFC 3, Zeiss) and calculated using the CIE formula.

The "spotting" of the liquid detergents on the unwashed textile was checked as follows:

(O =

kein Fleck

+ =

geringer Fleck

++ =

starker Fleck).

1 ml of the liquid detergent was applied to 20 g of the test specimen (bleached cotton nettle, basic white CIE = 78). After an exposure time of 20 minutes, the test specimen was washed once in a washing liquor of 5 g / l of the same detergent at 50 ° C. The white toner stain was evaluated under a UV lamp.

(O =

no stain

+ =

minor stain

++ =

strong stain).

Claims (4)

1. Whitener-containing liquid detergents which contain as whitener a bis-triazinylamino-stilbenedisulphonic acid compound, characterised in that the bis-triazinylamino-stilbenedisulphonic acid compound corresponds to the free acid of the formula (I)

   

   or salts thereof, in which independently of each other

   A   denotes

   

   B   denotes O, NH, NY or NH(CH₂)_n

   R   denotes H, C₁-C₄-alkyl, C₁-C₄-O-alkyl, F, Cl, CF₃ or OCF₃

   X₁   denotes C₄-C₁₂-alkyl or C₅-C₇-cycloalkyl

   X₂   denotes H or C₁-C₁₂-alkyl

   Q   denotes -O-, -CH₂-, -CH₂CH₂- or a direct bond,

   Y   denotes C₁-C₄-alkyl

   Z   denotes R and

   n   denotes 1, 2 or 3

   with the proviso that, if Z is H and B is NH, R is not H,
   or corresponds to a compound of the formula (I) or salts thereof, in which

   R   represents H, n represents 1 and A represents

   

   R   represents m-CF₃ or p-OCF₃, n represents 1 and A represents

   
2. Liquid detergents according to Claim 1, characterised in that the whitener contained therein corresponds to the formula mentioned in which

   R   denotes H and

   A   denotes

   
3. Liquid detergents according to Claim 1, characterised in that the whitener contained therein corresponds to the formula mentioned in which

   R   denotes H and

   A   denotes

   
4. Liquid detergents according to Claim 1, characterised in that the whitener contained therein corresponds to the formula mentioned in which

   R   denotes H and

   A   denotes