DE1152779B - Liquid heavy duty detergent - Google Patents

Description

The invention relates to a liquid heavy duty detergent which contains about 5 to 30% detergent sulfonates and nonionic detergent raw materials and 10 to 30% inorganic polyphosphates. Such coarse detergents also contain 0.1 to 2% carboxymethyl cellulose to increase the dirt-carrying capacity. Such detergents, however, tend to settle or to form layers, since the carboxyalkyl cellulose easily settles. This serious disadvantage cannot be eliminated satisfactorily either by adding alcohol or by combining different cellulose derivatives. So z. B. proposed according to the German Auslegeschrift 1 054 636, to mix the easily settling carboxymethyl cellulose with about ten times the amount of easily rising methyl cellulose; but the latter does not act as a dirt suspension agent, so that the dirt-bearing effect is only slight. Finally, attempts have been made to achieve oxidative stabilization of the detergent _{by adding H 2} O _{2 and subsequent storage;} However, this process leads to undesirable decomposition of the detergent components, discoloration and losses. In order to avoid this annoying deposition of the carboxymethyl cellulose in such coarse detergents, lengthy tests have been carried out and a large number of waxes, types of gums and colloidal substances have been investigated. Microcrystalline waxes, mixtures of higher molecular weight fatty acid esters and fatty alcohols and also oxazoline waxes (Lindner, "Textilhilfsmittel und Waschrohstoffe", Stuttgart, 1954, p. 262) have proven to be unusable. Rubber-like substances, such as hydroxyethyl cellulose, sulfoethyl cellulose and tragacanth, were also unusable, as were other substances such as zinc stearate, lauryl alcohol, bentonite and urea.

The surprising observation has now been made that homogeneous liquid detergents from excellent dirt-carrying capacity, which does not separate even when stored for a long time and therefore does not show the aforementioned drawbacks of phase separation when used to prevent them the sedimentation of the carboxyalkyl cellulose, which improves the dirt-carrying capacity, is still hydrogenated Castor oil, preferably in an amount of 0.1 to 1%, is added.

The invention accordingly relates to a liquid aqueous heavy duty detergent with a content of

a) 5 to 30% of a mixture of water-soluble, anionic organic sulfonate detergent raw material and non-ionic organic detergent raw material, liquid heavy duty detergent

Applicant:
Colgate-Palmolive Company,

New York, N.Y. (V. St. A.)

Representative: Dr. rer. nat. J.-D. Mr. v. Uexkull,
Patent attorney, Hamburg-Hochkamp, Königgrätzstr. 8th

Claimed priority:
V. St. v. America of December 22, 1959 (No. 861 191)

William Ralph Hearn, Scarboro, Ontario,

Allister Neil MacLean

and Frederick William Trusler, Toronto, Ontario
(Canada),

have been named as inventors

b) 10 to 30% alkaline, inorganic polyphosphate which is soluble in the amount of water present and

c) 0.1 to 2% carboxyalkyl cellulose,

which is characterized in that it is used to prevent phase separation as a further component

d) hydrogenated castor oil, preferably in quantities

from about 0.1 to 1%.

The new detergent preferably contains sodium carboxymethyl cellulose and 4 to 12% hydrotropic alkali aiarylsulfonate, preferably sodium or potassium toluene or xylene sulfonate.

Furthermore, the water content of the preferably alcohol-free detergent can be 40 to 80%.

For example, a preferred homogeneous detergent contains higher molecular weight alkylbenzenesulfonates, Potassium polyphosphate, such as pyrophosphate and tripolyphosphate, a water-soluble, sulfonated hydrotropic Salt and a higher fatty acid alkylolamide.

In the new detergents, the dirt-bearing component also separates during storage higher temperatures and after cooling and rewarming. She is extraordinary stable and superior to similar products that do not contain hydrogenated castor oil. The inven-

309 667/265

Rough detergents according to the invention can be easily poured out and can be in any suitable container be kept. They show a high washing power and can easily be used in small quantities Add detergent solutions of the same composition, for washing dishes or in laundries.

As anionic, sulfonated detergent substances that contain a sulfonic acid or sulfuric acid residue, Any readily soluble or dispersible, per se known products, preferably water-soluble Alkylarylsulfonates, in particular with 8 to 15 carbon atoms used in the alkyl radical, as well as higher molecular weight alkylbenzenesulfonates. Furthermore can Detergent substances with a mononuclear aryl radical, such as toluene, xylene or phenol, can be used. The higher molecular weight alkyl radicals of the aromatic nucleus can be branched or straight-chain, e.g. B. Nonyl, dodecyl and pentadecyl radicals which are derived from polymers of the lower monoolefins and are branched Have chains, or straight-chain decyl and keryl radicals. It can also be sulfated higher molecular weight Alkylphenolethylene oxide condensation products, e.g. B. with 4 to 6 moles of ethylene oxide and 8 up to 10 carbon atoms in the alkyl radical can be used. Furthermore, normal and secondary alkyl sulfates, in particular with 8 to 15 carbon atoms in the fatty alcohol radical, such as lauryl sulfate or fatty alcohol sulfates from coconut oil fatty acids, sulfuric acid esters of polyhydric alcohols, those with higher molecular weight fatty acids are incompletely esterified, so partial esters of polyhydric alcohols, z. B. coconut monoglyceride monosulfate, higher molecular weight fatty acid esters of low molecular weight alkylolsulfonic acids, e.g. B. Oleyl ester of Isäthionäure, higher molecular fatty acid ethanol ammsulfate, z. B. the coconut oil fatty acids, higher molecular weight Fatty acid amides of aminoalkylsulfonic acids, e.g. B. lauroylamide of taurine, higher molecular weight alkyl glyceryl ether sulfonates, z. B. Dodecylglyceryläthersulfonat, and sulfated condensation products of fatty alcohols with 6 to 18 carbon atoms with 2 to 18 mol Ethylene oxide can be used. The sulfates and sulfonates are preferably used as alkali salts, although other water soluble salts, e.g. B. low molecular weight alkylolamine salts, such as. B. the Ammonium, isopropanolamine, mono-, di- and triethanolamine salts can be used.

The water-soluble, nonionic, washing-active substances used are polyalkylene oxides which have a hydrophobic organic radical with at least 8 and preferably up to 30 carbon atoms, which is condensed with at least five and usually up to 50 alkylene oxide groups. Polyoxyethylene condensates of ethylene oxide are preferred, although other alkylene oxides such as propylene oxide and butylene oxide can be used. Furthermore, such condensation products of alkylphenol, e.g. B. Polyoxyethylene ethers of alkylphenols with at least 6 and usually 8 to 12 carbon atoms in the alkyl radical, an ethylene oxide ratio of about 7.5 to 20 and 8 to 18 ethylene oxide groups can be used. The alkyl radicals on the aromatic nucleus are z. B. diisobutylene, diamyl, polypropylene, dimerized C ₆ -C ₇ olefin and the like. B. of higher molecular weight fatty acids, resin acids, tall oil acids or acids from the oxidation of paraffin or petroleum hydrocarbons, polyalkylene oxide condensation products with higher molecular weight fatty acid amides, e.g. B. primary higher molecular acylamides, mono- and diethanolamides, condensed with ethylene oxide and the corresponding sulfonamides, polyalkylene oxide ethers of fatty alcohols such as lauryl, ceryl or oleyl alcohol, which are condensed with 6 to 30 moles of ethylene oxide, higher molecular weight alkyl mercaptans or thioalcohols with are condensed, and water-soluble polyoxyethylene condensation products with hydrophobic polyoxypropylene glycols are used.

The content of organic detergent substance is 5 to 30% and preferably 10 to 25%. The polyphosphate salts used prevent the separation of calcium and magnesium compounds and give the liquid cleaning agent according to the invention the properties of a rough detergent. You can use neutral salts, e.g. B. pentapotassium tripolyphosphate, or acidic salts, e.g. acidic Potassium tripolyphosphate, but preferably pentapotassium tripolyphosphate and / or tetrapotassium pyrophosphate use.

These inorganic salts should be present in such amounts that they are present in the amount of water present are completely soluble at room temperature, which is generally 10 to 30% and preferably at 15 to 20% is the case. The detergent raw materials and the polyphosphates should, if necessary, under Addition of a solubilizer or complexing agent, dissolved in water or liquid to form a homogeneous one Mixture be workable. Dispersants or hydrotropes can also be added, such as alkylarylsulfonates and preferably sodium and potassium toluene and xylene sulfonates. The hydrotropic Substances are usually used in amounts of 4 to 12% and preferably 10% of the total mixture used. Even higher molecular weight fatty acid alkylolamides with 10 to 14 carbon atoms are expedient in the acyl radical, preferably diethanolamides, monoethanolamides and isopropanolamides of coconut oil fatty acids or the corresponding lauric, capric and myristic acids in amounts of 1 to 15% and preferably from 5 to 12Vo added to improve the washing and foaming power.

The carboxyalkyl cellulose with up to 3 carbon atoms in the alkyl radical is preferably used as an alkali salt, e.g. B. used as the sodium or potassium salt of carboxymethyl cellulose. Commercially available sodium carboxymethyl cellulose with a purity of 60 to 100% (dry matter) of low, medium or higher viscosity can be used. The degree of substitution (»Ullmann's Encyclopedia of Technical Chemie ", Vol. 5, 1954, p. 166, middle) of the carboxymethyl group per glucose anhydride unit in the Cellulose molecule is usually 0.5 to 0.9, suitably 0.5 to 0.7. These substances are reduced in size Amount, e.g. From 0.1 to 2% and preferably from 0.25 to 1.5% of the total mixture.

The hydrogenated castor oil, also called castor wax or castor wax, is used in smaller quantities of about 0.1 to 1% used. It has a melting point of around 84 to 87 ° C and is finely divided Form with an iodine number of a maximum of about 6 available. The acid number is a maximum of 0.2%, the saponification number about 17.5 to 18.5% KOH, and the specific gravity at 20 ° C is 0.98 to 1.00.

The solids content of the liquid detergent according to the invention is 20 to 60%, preferably between about 35 and 50%. The water content

from 40 to 80% is enough to dissolve the polyphosphates and form a homogeneous product in which the cellulose compound and the castor wax are retained in a homogeneous dispersion. That aqueous medium is alcohol-free, since it is not necessary to achieve a homogeneous aqueous product, add low molecular weight aliphatic alcohols.

The detergent can be produced in any way. It is generally recommended initially an aqueous solution or a slurry of the detergent substance and the hydrotropic component to prepare, which can be added as a powder or as an aqueous mixture. The cellulose compound can also be stirred in as an aqueous solution or as a powder. The mixture temperature is not essential and can range from room temperature to higher temperatures. The polyphosphate is added as a powder or previously dissolved in water. Then the Alkylolamide and the hydrogenated castor oil (Gastorwax) added, which may be used together with the solid alkylolamides is preferably melted.

Finally, perfume, dyes, anti-corrosive, germicidal and bleaching agents, Optical brighteners and substances to change the viscosity are added.

In the following examples, unless otherwise noted, all parts are parts by weight and percentages refer to the finished cleaning agent.

example 1

A liquid heavy duty detergent was made from the following ingredients:

Examples 2 and 3

Similar heavy duty detergent mixtures are made from the following ingredients:

example 2 3 10.0 10.0 % Sodium Dodecylbenzenesulfonate 20.0 20.0 % Tetrapotassium pyrophosphate 8.0 - % Sodium xylene sulfonate 8.0 % Sodium toluenesulfonate 0.5 0.3 ° / o sodium carboxymethyl cellulose 2.9 % Sodium silicate 5.0 5.0 % Lauroyl isopropanolamide 03 05 % Castor wax rest rest water

35

Sodium Dodecylbenzenesulfonate .. 10.0%

Tetrapotassium pyrophosphate 20.0%

Lauroyl isopropanolamide 5.0%

Sodium Toluenesulfonate 6.5%

Sodium carboxymethyl cellulose .. 0.5%

Castor wax 0.3%

Sodium silicate 3.0%

Water rest

These substances are processed according to the method described in Example 1, taking into account following changes:

The carboxymethyl cellulose solution is added to the SuKonate mixture with stirring at about 50 ° C. and the mixture is then heated to about 70 ° C. and stirred until a homogeneous solution is obtained. The phosphate and the mixture of amide and castor wax are then added. The mixture is then cooled to about 32 ° C. and, in Example 3, the sodium silicate (Na ₂ O: SiO, ratio of 1: 2.58) is added as a 44% strength aqueous solution, so that the end product has about 2.1% SiO ., contains. Then, fragrance, colors, etc. can be added in a manner similar to that in Example 1.

The product of Example 2 has a _pH value of 10.3 and of Example 3 such of 11.6. Both products show good resistance to aging at ordinary temperatures and at higher and lower temperatures. When small amounts are added to detergent solutions, they exert excellent washing power when cleaning dirty objects.

Examples 4 to 6

Other liquid cleaning agents are made from the following ingredients:

45

To produce the coarse detergent according to the invention, an aqueous solution of dodecylbenzenesulfonate (the dodecyl radical of which is derived from a propylene tetramer) with a purity of about 88% (remainder sodium sulfate) is added and aqueous solutions of toluenesulfonate and sodium silicate (Na ₂ O: SiO. ₂ - Ratio like 1: 2.34) stirred to a homogeneous mixture. The carboxymethyl cellulose of a purity of about 65% with about 0.7 carboxy groups per glucose anhydride unit is dissolved in water to form a 2.5% solution which is added at room temperature with stirring. The mixture is then heated to about 70 ° C. with stirring and stirring is continued until a uniform mixture is achieved. Finally, the product is cooled to room temperature and colorants and fragrances are added if necessary.

The product is also stored for long periods at room temperatures and at elevated temperatures or persistent on cooling and does not separate.

% Sodium alkylbenzenesulfonate

% Sodium nonylphenol ethylene oxide sulfate

% Sodium xylene sulfonate ..

% Potassium Toluenesulfonate ..

% Tetrapotassium pyrophosphate

% Fatty acid diethanolamide

% Fatty acid isopropanolamide

% Sodium carboxymethyl cellulose

% Castor wax

water

10.0

8.5

20.0 2.5

2.5

0.5

0.3

rest

example

5 i

13.0

6.75 2.25

15.0 2.5

2.5

0.5

0.3

rest

9.0

6.0 6.75

2.25

15.0 3.0

3.0

0.5

0.3

rest

The alkyl radical of the alkylbenzenesulfonate is derived from the propylene polymer, which consists of a

a mixture of propylene tetramers and propylene pentamers and on average one tridecyl radical is equivalent to. The nonylphenolethylene oxide sulfate has an average of 5 ethylene oxide groups per nonylphenol. The fatty acid diethanolamide and isopropanolamide contain mixtures of approximately equal parts Lauroyl and myristoyl residues. The carboxymethyl cellulose has about 0.7 carboxy groups. These too Mixtures can contain compatible additions of fragrances, dyes, fluorescent dyes and the like included.

Claims (3)

PATENT CLAIMS: 1. Liquid aqueous heavy duty detergent with a content of a) 5 to 30% of a mixture of water-soluble, anionic organic sulfonate detergent raw material and non-ionic organic washing raw material, b) 10 to 30% alkaline, inorganic polyphosphate which is soluble in the amount of water present and c) 0.1 to 2% carboxyalkyl cellulose, characterized in that it is used as a further component to prevent phase separation d) hydrogenated castor oil, preferably in amounts of about 0.1 to contains. 2. Detergent according to claim 1, characterized in that it is sodium carboxymethyl cellulose and 4 to 12% hydrotropic alkali aryl sulfonate, preferably sodium or potassium toluene or xylosulfonate. 3. Detergent according to claim 1 and 2, characterized in that the water content of the preferably alcohol-free detergent is 40 to 80%. Considered publications:
German publication no.1051440,
638; French Patent No. 1229408;
Austrian patent specification No. 206 086. © 309 667/265 8.63