DE1617113B2 - White detergent - Google Patents

Description

R ₁ -CXY

R ₂ -CXY

N-CXY-R ₃

- CH, - N

CXY-R,

CXY-R,

and R _{3 represents} a —PO ₃ H ₂ group.

2. Agent according to claim 1, characterized by an additional content of aminopolycarboxylic acids or their salts, the total amount of aminopolyphosphonic acids and aminopolycarboxylic acids or their salts are 0.2 to 5 percent by weight.

It is known that optical brighteners of the pyrazoline derivative type are suitable, such as those described, for example, in the German Auslegeschriften 1 080 963 and 1 104 483, the USA.-Patent 2 639 990, the Austrian Patent specification 211 262 and Swiss patent 288 169 are described, preferably for Lightening of textiles made from polyamide and polyacrylonitrile fibers. However, they become common, anionic or containing nonionic surfactants, condensed phosphates and oxidative bleaching agents When detergents are used, the number of washing treatments increases, irreversible yellowing of the fabric.

It has now been shown that the properties of the optical brightening agents mentioned are not fully to satisfy. Will they be in common, anionic or nonionic surfactants, condensed phosphates and Detergents containing oxidative bleaching agents are used, one shows up with the number of Washing treatments increase the yellowing of the fabric. This yellowing can neither be known with Use optical brighteners to reverse or compensate for bleaching agents.

It was now an optical brightener, oxidative bleaching agent and sequestering agent found containing white detergent which does not have these disadvantages and is characterized by this that it is 0.02 to 2 percent by weight of an optical brightening agent from the class of the aryl-substituted Pyrazoline compounds with 0.1 to 3 percent by weight of at least one in the form of free acid or its alkali or ammonium salts present aminopolyphosphonic acid as follows Structure includes:

R,

CXY

N —CXY-R,

R ₇ -CXY

where X and Y are a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, R ₁ and R _{2 are} a - PO ₃ H ₂ group or a group of the formula

where X and Y are a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, R ₁ and R _{2 are} a —PO ₃ H ₂ group or a group of the formula

- CH, -N

CXY-R ₃

CXY- R,

and R _{3 represents} a - PO ₃ H ₂ group.

Preferred compounds of this class are:

Amino (trimethylene phosphonic acid),

Ethylenediaminetetra- (methylenephosphonic acid),

Diethylenetriaminepenta- (methylenephosphonic

acid),

Aminotri- (ethylidenephosphonic acid),
Aminotri (propylidenephosphonic acid),
Aminotri- (isopropylidenephosphonic acid),
Ethylenediaminetetra- (ethylidenephosphonic acid)
and
Diethylenetriaminepenta- (methylenephosphonic

acid).

The phosphonic acids can be in the form of their neutral or acidic salts. Under ammonium salts are also the salts of organic ammonium bases to be understood, z. B. the salts of mono-, dioder Triethanolamine.

Even small amounts of the aminopolyphosphonic acids or their salts are sufficient to eliminate the undesired To largely prevent yellowing, i.e. 0.1 to 3 percent by weight, based on the amount of detergent, are sufficient for the stated purpose.

The following pyrazoline derivatives known per se are particularly suitable as optical brightening agents Formula in question:

Ar ₇ -C-

-CH ₂
CHR

Ar ₁ '

In this formula, R denotes a hydrogen atom, an alkyl radical or an aryl radical. which can optionally be substituted. Ar ₁ and Ar _{2 are} aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or haloene atoms.

1,3-Diarylpyrazolines are preferably used, in which R represents a hydrogen atom. The pyrazoline derivatives are used in an amount of 0.02 to 2, preferably 0.05 to 0.5 percent by weight, based on the amount of detergent mixture, used.

The detergents also contain anionic and / or nonionic washing active substances. As an anionic Substances come into question: alkali soaps of fatty acids, fatty acid protein condensation products, primary or secondary alkyl sulfates, fatty acid alkanolamide sulfates, sulfated alkyl or alkylphenol polyglycol ethers, Fatty acid isethionates, fatty acid taurides, alkanesulfonates, olefin sulfonates, alkylbenzenesulfonates, Salts of -sulfo fatty acid esters and other known surfactants of the sulfate or sulfonate type. Suitable nonionic washing active substances are, for example, alkyl and acyl polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid alkanolamides and their ethoxylation products, ethoxylated polypropylene glycol ethers, Amine oxides and fatty acid sugar esters.

In addition to the surface-active compounds mentioned or their mixtures, the detergents can Contains the usual build-up substances and additives. These include the washing alkalis, in particular the pyrophosphates, Tripolyphosphates, tetrapolyphosphates, metaphosphates, silicates, carbonates, bicarbonates and Borates of alkalis, and also bleaches which donate oxygen, such as perborates, perpyrophosphates, percarbonates and carbamide peroxide. Neutral salts such as magnesium silicate and sodium sulfate can also be used present as components of the mixture. In addition, there are substances that influence the foaming power, such as fatty acid alkanolamides or trialkyl melamines, dirt-dispersing agents, in particular cellulose glycolate, as well as skin protectants and germicides in question. In addition to the mentioned brighteners of the pyrazoline type The agents can contain other optical whiteners suitable for lightening cellulose fibers contain, for example those of the diaminostilbene, triazine or benzimidazole type.

The detergents can be in liquid, pasty or solid form. The addition of the aminopolyphosphonic acids or their salts and the optical brighteners to the detergents can before Spray drying by incorporation into the slurry or by subsequent mixing with the dried powder.

In addition to the aminopolyphosphonic acids or their salts, sequestering acids can also be used Aminopolycarboxylic acids or their salts are used. Suitable aminopolycarboxylic acids are in particular the nitrilotriacetic acid and the ethylenediaminetetraacetic acid, further z. B. hydroxyethylethylenediamine triacetic acid, 1,2-diaminocyclohexanetetraacetic acid, diethylenetriaminepentaacetic acid and Triethylenetetraminehexaacetic acid. The total amount of the two substances, based on the amount of detergent, can be 0.1 to 10, preferably 0.2 to 5 percent by weight. The effect of the two substances is not restricted to a certain mixing ratio; however, it is best to reduce the proportion of Aminopolyphosphonic acids, based on aminopolycarboxylic acids, should not be smaller than 10%.

The detergents according to the invention are particularly suitable for washing colorless or light-toned Synthetic fiber fabrics, preferably woolen based on polyamide or polyacrylonitrile. You can also for washing mixed fabrics of the mentioned textile materials with those made of wool, silk, Cellulose, acetate silk, polyester fibers, etc. can be used with success.

Examples

A detergent with the following composition was used:

5% sodium coconut fatty alcohol sulfate,

5% sodium dodecylbenzenesulfonate,

5% sodium soap of fatty acids C ₁₂ to C ₂₂ ,

3% oleyl alcohol polyglycol ether (10 ethylene glycol

Kolgruppen),
40% pentasodium triphosphate,

5% sodium silicate (Na ₂ O 3.3SiO ₂ ),

3% magnesium silicate,

1% sodium cellulose glycolate,
18% sodium perborate tetrahydrate,

8% water,

0.2% pyrazoline-type whitening agent,
0.1% diaminostilbene type whitening agent,
Remainder sodium sulfate, fragrances.

The lightening agents had the following structure:

Cl - <\ ~ C- - CH ₂

Il I

N CH ₂

SO ₂ NH ₂
Pyrazoline type

SO ₃ Na

N (C ₂ H ₄ OH) ₂

Diaminostilbene type

With this detergent commercially available tissues were washed out of polyamide fiber in enameled vessels 20 minutes at 6O ⁰ C. The concentration of the detergent was 4.5 g / l, the liquor ratio (kg laundry per liter of washing liquor) 1:40. The tap water used had a degree of hardness of 16 ° dH.

After twenty washes, the whiteness of the dried samples was measured with a photometer (»Elrepho« Carl Zeiss) determined, three different color filters were used in accordance with DIN 5033 to ensure a spectral distribution similar to daylight. The calculation of the Whiteness W was based on that of A. Berger

in the magazine "Die Farbe", vol. 8 (1959), pp. 187 to 201, proposed formula

W =

3 (R ₂ -R ₁ ),

whereby

R _x the one with red filter FMX / C
R ₅ , the one with the green filter FMY / C
R _z with the blue filter FMZ / C

the measured reflection value. Magnesium oxide with a reflection value was used as the calibration substance of R = 100. The value W obtained in this way largely agrees with the physiological impression of brightness in particular, as there is also a slight yellow tinge that is clearly perceptible to the eye is recorded quantitatively. Such a yellow tinge results from the photometric measurement that was used in the past when using a conventional daylight filter, there is no measurable drop in brightness and thus also no reproducible measured value.

The table below shows the results for samples numbered 1 to 6 and the mean values are compiled from the individual results. In two test series, on Detergent based, 0.5 percent by weight of the hexasodium salt of amino (trimethylene phosphonic acid) (Abbreviation ATP) used. The deviations between the individual samples result from the different fiber material or its differing initial degree of whiteness. In two Test series B and D were added to the wash liquor 0.15 mg / 1 Cu ions in the form of copper sulfate.

While the use of AT P (test series C) led to samples appearing pure white and also the presence of copper ions (test series D) only caused a barely noticeable decrease in brightness, Comparative Samples A and, to an even greater extent, Samples B, exhibited severe discoloration to yellow or yellowish brown. In the absence of the diamino stile type brightener, the get the same results. The same detergent was used without the pyrazoline-type brightener (Test series E), the washing result was unsatisfactory.

mg Cu / l 1 2 3 Whiteness W
4th 5 6th 0 A) Without ATP
B) Without ATP
C) 0.5% ATP
D) 0.5% ATP
E) Free of brighteners 0.15
0.15 174
145
192
190
170 177
136
194
188
172 168
138
185
182
168 164
143
183
180
165 165
140
184
181
167 165
140
183
181
71 169
140
187
184
152

The experiment was repeated, but instead of the salt of amino (trimethylene phosphonic acid) the Tetrasodium salt of ethylenediaminetetra (methylenephosphonic acid) and the hexasodium salt of Aminotri- (ethylidenephosphonic acid) was used. The results were correct within the error limits with the results of test series C and D.

If the amount of "ATP" was increased to 1 or 3 percent by weight, the test result was unchanged. The results also show that the aminopolyphosphonic acids to be used according to the main patent Outperform aminopolycarboxylic acids in their effect.

Instead of the aforementioned detergent, mixtures of the following composition can be used with the same success use:

3 to 20% surfactants of the sulfate and / or sulfonate type, such as fatty alcohol sulfates, sulfated alkyl or alkylphenol polyglycol ethers, Fatty acid alkanolamide sulfates, alkanesulfonates, olefin sulfonates, alkylbenzenesulfonates and salts of α-sulfo fatty acid esters,

1 to 10% nonionic surfactants, such as ethoxylation products of fatty alcohols, fatty acids, fatty acid amides and alkylphenols,

0 to 20% alkali soaps of fatty acids,

0.5 to 3% cellulose glycolate,

20 to 60% alkali polymer phosphates, such as pyro-, tripoly-, tetrapoly- and metaphosphates,

0 to 30% sodium perborate,

0 to 5% magnesium silicate,

0 to 5% sodium silicate,

0 to 5% skin protection substances, disinfectants, foam-improving or foam-suppressing substances, Fragrances,

0.05 to 1% optical brighteners of the pyrazoline type and diaminostilbene type,

0.1 to 3% neutral or acidic sodium or potassium salts of diethylenetriaminepenta- (methylenephosphonic acid), Aminotri - (propylidenephosphonic acid), aminotri - (isopropylidenephosphonic acid), ethylenediaminetetra (ethylidenephosphonic acid) and Diethylenetriaminepenta - (methylenephosphonic acid),

0 to 2% nitrilotriacetic acid or ethylenediaminetetraacetic acid or their alkali or ammonium salts

also water, diluents and neutral salts.

Claims (1)

Patent claims: 1. Containing optical brightening agents, oxidative bleaching agents and sequestering agents White detergent, characterized in that it is 0.02 to 2 percent by weight an optical brightening agent from the class of the aryl-substituted pyrazoline compounds with 0.1 to 3 percent by weight of at least one in the form of the free acid or its alkali or Ammonium salts present aminopolyphosphonic acid contains the following structure: