DE1617113A1 - White detergent - Google Patents

Description

Henkel & Ci e GmbH

Henkelstrasse

Patent department
Dr Wa / IP. J / Düsseldorf-Holthausen, April 28, 1960

Patent application P 16 I7 113.4 D 3240

"White detergent"

Addition to patent application H ................, (D 3228 ν. Ι9. ^ -

It is known that optical brighteners of the Pyra ~ type are suitable. zoline derivatives, such as those in German Aus. Legeschriften 1 080 963 and 1 104 483, the USA patent ' 2,639,990, Austrian patent specification 211 202 and the Swiss patent 288 169 are preferred for lightening textiles made of polyamide and polyacrylonitrile fibers. However, they become common, anionic or nonionic surfactants, condensed phosphates and oxidative detergents containing active bleaching agents are used, the number of wash treatments increases, irreversible yellowing of the fabric.

documents

109836/1398

Registration H (D 5228 of April 19, 1966)

relates to a white detergent, characterized by a content of optical brighteners from the class of the aryl-substituted Pyrazoline compounds and at least one compound from the class of the aminopolycarboxylic acids or their Alkali or ammonium salts. The agents mentioned have the advantage that the textiles washed with them are not irreversible yellow.

It has now been found that the aminopoIycarboxylic acids mentioned in the main patent are wholly or partly by the in the form their free acids or their alkali or ammonium salts to be used aminopolyphosphonic acids of the following structure replaced can be:

- CXY

N - CXY - IU ⁷

where X and Y are a hydrogen atom or an alkyl radical having 1 to K carbon atoms, R-. and Rp is a -PCUH ₂ group or a group of the formula

CXY - R ^ - CH ₂ - N

^X CXY - R ^

and R-, a -ΡΟ-, Ηρ group.

- 3 -109836/1398

Preferred compounds of this class are amino (trimethylene phosphonic acid), ethylenediamine tetrachine (ethylene phosphonic acid), Diethylenetriaminepenta- (methylenephosphonic acid), Aminotri-ethylidenephosphonic acid), aminotri-propylidenephosphonic acid), aminotri- (isopropylidenephosphonic acid), Ä ° thylenediamine tetra (ethyl idenophosphonic acid) and diethylenetriamine penta- (methylenephosphonic acid). The phosphonic acids can be in the form of their neutral or acidic salts. Among ammonium salts are also to understand the salts of organic ammonium bases, e.g. the salts of mono-, di- or triethanolamine.

Even small amounts of aminopolyphosphonic acids or Their salts are sufficient to largely remove the unwanted yellow coloration to prevent. In general, less than 5, preferably 0.1 to 3 percent by weight, based on the amount of detergent for the stated purpose.

Particularly suitable optical brightening agents are pyrazoline derivatives of the following formula, known per se:

- C-CH ₅
Il I ²

A.D
\ /

109836/1398

In this formula mean

R is a hydrogen atom, an alkyl radical or aryl

radical, which can optionally be substituted, Ar ₁ and Ar ~ 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 halogen atoms.

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

The detergents also contain anionic and / or nonionic washing active substances. Come as anionic substances in question: alkali soaps of fatty acids, fatty acid protein condensation products, primary or secondary alkyl sulfates, Fatty acid alkanolainide sulfates, sulfated alkyl or alkylphenol polyglyeol ethers, Fatty acid isathionates, fatty acid taurides, Alkanesulfonates, olefin sulfonates, alkylbenzenesulfonates, salts of oi-sulfofatty acid esters and other known surfactants from Sulfate or sulfonate type, suitable non-ionic detergent

1Of 8 36/1398 ^3AD original

Substances are, for example, alkyl and acyl polyglycol ethers, alkylphenol polyglycol ethers, fatty acid alkanolamides and their Ά thoxylation products, ethoxylated polypropylene glycol ethers, field oxides and fatty acid sugar esters.

In addition to the surface-active compounds mentioned or their mixtures, the detergents can have customary structural and Contain additives. These include the washing alkalis, in particular the pyrophosphates, tr! polyphosphates, tetrapolyphosphates, Metaphosphates, silicates, carbonates, bicarbonates and borates of alkalis, furthermore oxygen-releasing bleaches, such as perborates, perpyrophosphates, percarbonates and Carbamide peroxide. Also neutral salts such as magnesium silicate and sodium sulfate, can be present as components of the mixture. There are also substances that influence the foam force, such as Fatty acid alkanolamides or trialkyl melamines, dirt-dispersing Agents, in particular cellulose glycolate, and skin protection agents and germicides in question. In addition to the mentioned brighteners of the pyrazoline type, the agents can also contain other optical whiteners suitable for lightening cellulose fibers, for example those from 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

109838/1398

can be used as a medium before spray drying by incorporating it into the slurry or by subsequently mixing it with it the dried powder.

If the aminopolyphosphonic acids or their salts are used together with the aminopolycarboxylic acids described in the main application or their salts, 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 gen. The effect of the two substances is not limited to a certain mixing ratio; however, it is recommended the proportion of aminopolyphosphonic acids, based on aminopolycarboxylic acids, should not be less than 10 #.

The detergents according to the invention are particularly suitable for Washing of colorless or light-tinted synthetic fiber fabrics, preferably those based on polyamide or polyacrylonitrile. You can also wash mixed fabrics of the textile materials mentioned with those made of wool, silk, cellulose,

Acetate silk, polyester fibers, etc. can be used with success.

109836/1398

Examples

A detergent with the following composition was used:

<? o

^c / o

fo

, ο

ζ « % 0.2 Jo 0.1 fo remainder

Sodium Coconut Fatty Alcohol Sulphate Sodium Dodecylbenzenesulphonate Sodium soap of fatty acids C,

Oleyl alcohol polyglygol ether (.10 ethylene glycol groups)

Pentasodium triphosphate sodium silicate (Na 0.3.3 SiO ₉ ) magnesium silicate sodium cellulose glycolate

Sodium perborate tetrahydrate -

Pyrazoline-type water whitening agent

Lightening agent from diaminostilbentyρ -

Sodium sulfate, fragrances

The lightening agents had the following structure:

Clrr

SO ₃ Na

Pyrazoline type

DiaTninos t i 1 b on typ

" ⁸ ^ 16Ί7113

Commercially available fabrics made of polyamide fibers ( PERLON ^ H NVLQN V? And NYLTEST®) were washed with this detergent in enamelled vessels at 60 ° C. for 20 minutes. The concentration of the detergent was A, 3 g / liter, the liquor ratio (kg laundry per liter of wash liquor) 1; 40 »The tap water used had a hardness of 16 dH.

After twenty washes, the whiteness of the dried samples was determined with a photometer ("Elrepho" from CARL ZEISS) using three different color filters in order to ensure a spectral distribution similar to daylight in accordance with DIN 5053. took place after A. BERGER in the magazine "Die Farbe" Jahrg, 8 (1959), pages 18? to 20I ₃ proposed formula

the mifc red filter

¹ row with green filter

R ₁₇ den with blue filter FMZ / G

Measured reflexion value indicates “Ilagnium oxide with a reflectance value of R = IQO was used as the calibration substance. The value W obtained in this way largely agrees with the physiological sensation of lipidness, since in particular a slight yellow tinge that is clearly perceptible with the eyes is quantitatively recorded. MiM such. Geliasfeich results in the previously used ph, o $ p ^ etris.ßhen measurement using a

normal daylight filter no measurable decrease in brightness and thus no reproducible measured value.

The table below shows the results for the samples numbered 1 to 6 and the mean values compiled from the individual results. In two series of tests, 0.5 percent by weight, based on detergent, was used of the hexasodium salt of amino (trimethylene phosphonic acid) (abbreviation ATP) is used. The deviations between the individual samples result from the different Fiber material or its differing initial Whiteness. In two test series B and D, the wash liquor was still 0.15 mg / liter of Cu ions in the form of copper. sulfate added.

While the use of ATP (test series C) too pure white appearing samples and the presence of copper ions (test series D) only led to a barely noticeable decrease in brightness caused the comparative samples A and in To an even greater extent, samples B show a strong discoloration of yellow or yellowish brown. In the absence of the brightener diaminostilbene type gave the same results obtain. Using the same detergent without the pyrazoline type brightener (test series E) gave the washing result unsatisfactory.

- 10 1098 36/1398 i;. ^

without ATP mg - Cu / 1 1 2 Whiteness W 3 4th 5 6th 0 without ATP 0, 174 177 168 164 165 I65 I69 A) 0.5? S ATP - 15th 145 136 138 143 14O 140 l40 B) 0.5? i ATP 0, 192 194 I85 183 184 I83 187 C) brightener-free - 15th 190 188 182 180 181 181 184 D) 170 172 168 165 167 71 152- E)

The experiment was repeated, the tetrasodium salt of ethylenediaminetetra (methylenephosphonic acid) and the hexasodium \ salt of aminotri (ethylidenephosphonic acid) being used instead of the salt of amino (tr ime thylenephosphonic acid). The results agreed with the results of test series C and D within the error limits.

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

- 11 -

109836/1398

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

3 - 20 % surfactants of the sulfate and / or sulfate type,

such as fatty alcohol sulfates, sulfated alkyl or alkylphenol polyglycol ethers, fatty ^{acid alkane sulfate ... ^ =} sulfates, alkane sulfate, olefin sulfate, alkyl benzel sulfate and salts of the sulfate acid esters

1 - 10 % non-dipnic surfactants, such as ethoxylation products, of fatty alcohols, fatty acids, fatty acid amides and alkylphenyls,

0 - 20 fa alkaline soaps of fatty acids, 0.5 - 5 $> CellulpseglycQlatj

- 60 % alkali polymer phosphates, such as Pyrp ^ jf Tripplyrf Tetra · -

F ·! · And Metaphpsphatej

0 - 3Ö i> sodium perbprate j,

0 τ * S % magnesium silicate,

Q · »■ $ ■% sodium silicate ₉

0 - 3 f <> skin protection agents, disinfectants, substances that improve or suppress the eyesight, air conditioning agents

0.05 * 1 % optical brighteners VQm pyrazoline type and I) iaminp-

® * t ~ 3 % neutral or acidic sodium? or "i ^ llum salts of diethylene defiami" ipenta

- 12 -

(isopropylidenephosphonic acid), ethylenediaminetetra- (ethylidenephosphonic acid) and diethylenetriarainpenta- (methylenephosphonic acid)

- 2 % nitrilotriacetic acid or ethylenediaminetetraacetic acid or their alkali or ammonium salts

also water, extenders and neutral salts,

ι
/ "

109 ^ 36 / I3SS

Claims (2)

.Patent claims l) Optical brightening agents from the class of the aryl-substituted Pyrazoline compounds and compounds from the class of aminopolycarboxylic acids or White detergent containing their alkali or ammonium salts according to patent (patent application H ... · ') j characterized in that the amino polycarboxylic acids in whole or in part by in the form of their free acids or their alkali metal or ammonium salts Aminopolyphosphonic acids of the following structure are replaced: R ₁ - CXY N - CXY - IU R ₂ - CXY. where X and Y are a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, R, and Rp a -PO-J-Ip group or a group of the formula CXY - R ₅ - CH ₂ - ü '" CXY - R, and R- represent a -PO ^ H ₂ group. 109836/1398 2) Composition according to claim 1, characterized in that the content of the detergent equipment is aryl-substituted Pyrazole compounds 0.05 to 0.5 and of aminopolyphosphonic acids and their salts 0.1 to 3 Weight percent is. / ->. 109836/1398