DE1156927B - Liquid heavy duty detergent - Google Patents

Description

It is known that liquid detergents are made from detergent substances, washing alkali and water-soluble ones To manufacture cellulose derivatives; however, it has been found that after prolonged standing, these separate and tend to form precipitation.

On the other hand, it is known to use liquid fatty alcohol sulfate detergents to add larger amounts of polyvinyl compounds as thickeners. If you set but polyvinyl compounds are a liquid heavy duty detergent that has a higher content of washing alkalis exhibits, alone, these are deposited as an upper layer when standing.

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 you consider them to be dirt-carrying capacity improving substances a mixture of a small amount of a water-soluble cellulose compound and added to a water-soluble vinyl polymer.

The invention therefore relates to a substantially homogeneous, liquid rough detergent which is characterized is through a content

a) about 5 to 30% of a water-soluble, non-cationic, organic detergent substance,

b) about 5 to 30% water-soluble washing alkali and

c) about 0.1 to 5% of a mixture of a water-soluble Cellulose compound and a water-soluble vinyl polymer in the ratio of about 20: 1 to 1:20.

The new coarse detergent preferably contains a water-soluble, anionic, organic sulfonate detergent. It is also useful if a mixture of carboxymethyl cellulose is used as component c) (Cellulose glycolic acid) and polyvinyl alcohol or polyvinylpyrrolidone is used. The detergent can preferably also 4 to 12% of a water-soluble, hydrotropic aryl sulfonate and potassium polyphosphate contain.

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 and the mixture of carboxymethyl cellulose and the Vinyl polymers.

In the new detergents, the dirt-bearing substances separate when they are stored, even when they are higher Temperatures and after cooling down and rewarming. They are extremely fluid Heavy duty detergent

Applicant:

Colgate-Palmolive Company,
New York, NY (V. St. A.)

Representative:

Dr. rer. nat. J.-D. Mr. v. Uexküll, patent attorney,
Hamburg-Hochkamp, Königgrätzstr. 8th

Claimed priority:
V. St. ν. America, December 22, 1959 (No. 861192)

Harold Eugene Wixon, Jersey, NJ (V. St. A.),
has been named as the inventor

constant and are superior to similar products that contain only one of the dirt-bearing substances. the Rough detergents according to the invention can be poured out easily and can be in any suitable container be kept. They show a high washing power and are particularly suitable for synthetic resin-treated cotton fabrics, for synthetic fabrics made of polyamides, polyesters, etc. and for cotton blends suitable. The combination of the two dirt-bearing substances, namely the water-soluble cellulose compound when mixed with the vinyl polymer, manifests itself in a superior degree of whiteness white items of laundry compared with products that contain only one of these two dirt-bearing agents contain.

As water-soluble or water-dispersible cellulose compounds that prevent the redeposition of dirt When washing prevent, alkali salts of a carboxyalkyl cellulose having 2 carbon atoms are preferred in the alkyl radical, e.g. B. the sodium or potassium salt of carboxymethyl cellulose is used. 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 (»Ullmanns Encyclopedia of Industrial Chemistry ", Vol. 5, 1954, p. 166, middle) of the carboxymethyl group per glucose anhydride unit in the cellulose molecule is 0.5

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to 2, suitably about 1.25. A carboxylated potassium tripolyphosphate, or acid salts, e.g. B. sour

Cellulose with a degree of substitution of 0.5 to 0.9, potassium tripolyphosphate, but preferably penta

expediently from 0.5 to 0.7, is for particularly effective, potassium tripolyphosphate and / or tetrapotassium pyro-

Suitable for dirt-bearing mixtures. Also use the alkyl phosphate. The alkali salts of the tetra-

and oxyalkyl ethers, such as methyl, ethyl and oxy-5 phosphoric acid and sodium tripolyphosphate and

Ethyl cellulose, as well as cellulose sulfate, can be used its hexahydrates and tetrasodium pyrophosphate

will. are suitable. Furthermore, soluble alkali salts can be used alone

When used in a mixture with the cellulose compound or together with polyphosphates

water-soluble vinyl used according to the invention.

polymer, the degree of polymerization is not essential, io silicates with a ratio of alkali oxide to

provided that the compound has the desired water-soluble SiO ₂ from 1: 1 to 1: 4 and preferably from 1: 2 to

speed, dispersibility and the required soil i _: 3, such as. B. Sodium Silicates with a Na ₂ O: SiO ₂ -

has carrying capacity. Generally these ratios are from 1: 3.2 to 1: 1 and include potash silicates

Polymers linear and have an average ratio of 1: 2 to 1: 2.5 are suitable.

Molecular weight less than one million.15 These inorganic salts should preferably be used in

usually from 5,000 to 500,000 and preferably present in amounts such that they are present in the liquid

up to 100,000. Both homopolymers and cleaning agents can be soluble at room temperature,

also mixed or copolymers, i.e. all polymers, which is generally the case at 5 to 30% and 10 to 25%.

with the characteristic vinyl group CH ₂ = CHX As anionic, sulfonated detergent substances that

can be used, in which H contains hydroxyl, alkylol, nitrile, _ao a sulfonic acid or sulfuric acid residue,

Carboxyl, amide, pyrrolidone or the like. Can mean. _whoever , easily soluble or dispersible,

A water-soluble polyvinyl product known per se is preferably used in amounts of 5 to 30% alcohol with a 4% aqueous solution at 20 ° C and preferably from 10 to 25% of the total specific viscosity of 1.8 to 65 and preferably used as a mixture. Water-soluble ones are special up to 6 cP used. The product can contain small amounts of alkylarylsulfonates, preferably with 8 to 15 amounts of carbon, z. B. 10 to 30% polyvinyl acetate, material atoms in the alkyl radical, and higher molecular weight such as B. polyvinyl alcohol with a viscosity of alkylbenzenesulfonate suitable. You can also wash 4 up to 6cP and a content of 12% ester (88 to active substances with a mononuclear aryl radical, such as 89% alcohol) or from 21 to 25 cP or 35 to 45 cP toluene, xylene or phenol can be used. the with about 12% ester. A polyvinyl alcohol with a higher molecular weight alkyl group of the aromatic nucleus Viscosity from 1.8 to 3 cP and a polyvinyl can be branched or straight chain, e.g. B. nonyl, acetate content of about 10 to 30% results in storage Docecyl and Pentadecylreste, which of polymers of the at elevated temperature the greatest resistance and lower monoolefins descended and branched the best dirt-carrying capacity. These have viscosity chains, or straight-chain decyl and keryl ranges corresponds to an approximate polymerisation residue. It can also be sulfated higher molecular weight degrees from about 35 to 100. Alkylphenoläthylenoxydkondensationsprodukte are particularly suitable, for. B. Polyvinyl alcohols with a viscosity of 2.34 cP and with 12 to 18 ethylene oxide groups per phenol nucleus and 22.3% polyvinyl acetate; 1.88 cP and 19.6% ester; 6 to 18 carbon atoms in the alkyl radical are used 1.98 cps and 29.4% ester; 2.38 cP and 12.8% ester, products with 4 to 6 moles of ethylene oxide and similar mixtures. 40 and 8 to 10 carbon atoms in the alkyl radical, preferably

Water-soluble polyvinylamides such as poly are also used. Furthermore, normal and second

vinylpyrrolidone with a molecular weight of higher molecular weight alkyl sulfates, especially with

15,000 to 100,000, as well as copolymers of low 8 to 15 carbon atoms in the fatty alcohol radical, such as

molecular N-alkyl acrylamide and vinyl alcohol lauryl sulfate or fatty alcohol sulfates from coconut oil

(Molar ratio 66:34 or 80:20) or of acrylic 45 fatty acids, sulfuric acid esters of polyhydric alcohols,

nitrile with acrylamide or low molecular weight alkyl - those with higher molecular weight fatty acids are incomplete

acrylamide, such as copolymers of N-methyl methacrylic esterified, i.e. partial esters of polyhydric alcohols,

amide and acrylonitrile (molar ratio 90:10 to 70:30), e.g. B. Coconut oil monoglyceride monosulfate, higher mol-

are suitable. molecular fatty acid esters of low molecular weight alkylol

The dirt-bearing substances are in the coarse wash 5 ° sulfonic acids, z. B. oleyl ester of isethionic acid, higher

medium in small amounts, e.g. from 0.1 to 5% and molecular fatty acid ethanol amide sulfates, e.g. the

preferably from 0.1 to 2%. The amount of coconut oil fatty acids, higher molecular weight fatty acid amides

and the ratio of vinyl polymers and cellulose of the aminoalkyl sulfonic acids, e.g. B. Lauroylamide des

is replaced by other additives, e.g. B. of waxy taurine, higher molecular weight alkyl glyceryl ether sulfonates,

Ricinol compounds, which affect the dirt-55 z. B. Dodecylglyceryläthersolfonat and sulfated

Keep carrying agents in suspension and the homo-condensation products of fatty alcohols with 6 to

improve genicity. In general, the ratio is 18 carbon atoms with 2 to 18 moles of ethylene oxide

from cellulosic compound to vinyl polymer can be used.

20: 1 to 1:20 and mostly at 10: 1 to 1:10, whereby the sulfates and sulfonates are preferably used as

phase separation is sufficiently prevented; pre- 60 alkali salts are used, although others are water-soluble

preferably with a ratio of 5: 1 to 1: 5 salts, e.g. B. low molecular weight alkylolamine salts, such as

worked. z. B. the ammonium, isopropanolamine, mono-, di-

As washing alkalis, poly- and triethanolamine salts can preferably be used,

phosphate salts are used, which the deposition Finally, water-soluble non-ionic, wash-

active substances containing calcium and magnesium compounds can be added, provided that they

prevent and not impair the liquid purity according to the invention such. B. polyalkylene

agent have the properties of a coarse detergent oxyde, which has a hydrophobic, organic residue

to lend. You can use neutral salts, e.g. B. Penta- at least 8 and preferably up to 30 carbon

5 6

have atoms that are at least 5 and usually the hydrotropic compound that is washed up to 50 alkylene oxide groups is condensed; alkalis and the detergents are added one after the other as well as other low molecular weight alkylene oxides, such as powders, aqueous solutions or as a slurry. Propylene oxide and butylene oxide, alkylolamides and waxy substances can be used. Furthermore, such condensation 5 moderately melted and with vigorous stirring products of alkylphenol, z. B. Polyoxyethylene ether incorporated homogeneously. The mixing temperature of alkylphenols with at least 6 and mostly 8 to not essential and can be from room temperature to 18 carbon atoms in the alkyl radical, an ethylene- about 90 ° C. Finally, oxide ratios of about 7.5 to 20 and 5 to 18 ethylene perfume, dyes, corrosion-preventing, germ oxide groups can be used. The alkyl radicals on the io killing and bleaching agents, optical brighteners and aromatic nucleus are z. B. di-isobutylene, diamyl, substances to change the viscosity are added. Polypropylene, dimerized C ₆ -C ₇ oils and the like. B. of higher molecular weight fatty acids, resin numbers refer to the finished cleaning agent, acids, tall oil acids or acids from oxidation 15.
of paraffin or petroleum hydrocarbons, poly- Example 1
alkylene oxide condensation products with higher mol- It was a liquid coarse detergent made from fatty acid amides, z. B. primary higher molar components produced:
kular acylamides mono- and diethanolamides with sodium dodecylbenzenesulfonate .... 9.7%

Ethylene oxide condenses, as well as the corresponding so sodium xylene sulfonate 8.0 ° /

Sulphonamides, polyalkylene oxide ethers of fatty alcohol, potassium pyrophosphate 20.0%

ifr ^ tH ^ t, ^y J ^ ^er ? ^le y ^Mkoho i ^ ₁ * ¹¹¹ coconut oil fatty acid isopropanolamide .. 2.7%

6 to 30 mol of ethylene oxide condensed are high-sodium carboxymethyl cellulose .. 0.5%

molecular alkyl mercaptans or thio alcohols the polyvinylpyrrolidone 0.5%

are condensed with ethylene oxide, and water-soluble 25 water remainder
Polyoxyethylene condensation products with hydrophobic polyoxypropylene glycols can be used. The alkyl aryl sulfonate was a propylene tetramer

It is desirable that the invention with about 10% sodium sulfate and derived from the detergent a higher molecular weight fatty acid alkylol- Production and purification of sulfonated pure amide with 8 to 18 carbon atoms in the acyl radical and 30 agents. The carboxymethyl cellulose had up to 3 carbon atoms in the alkyl radical, preferred purity of about 66%, a degree of substitution of wise monoethanolamides, diethanolamides and isopro-0.7, with the remainder consisting of soluble inorganic salts of panolamides with about 10 to 14 carbon atoms. The polyvinylpyrrolidone had a through acyl radical, e.g. B. diethanolamides, monoethanolamides average molecular weight of about 20,000.
and isopropanolamides of coconut oil fatty acids or of the 35 The product retained equivalent lauric, capric and myristic acid in its homogeneous consistency even after prolonged storage. A similar amount of 1 to 15% and preferably from 3 to Schung, in which only polyvinylpyrrolidone was added without adding 12% in order to improve the washing and foaming power to carboxymethyl cellulose, resulted in improvement. There is an upper one, enriched with the polymer

Optionally can improve the homo-40 layer, while a similar mixture that only the

genicity solvent, solubilizer, complex cellulose compound, a lower, essentially

Formative and / or hydrotropic substances, in particular borrowed from the cellulose compound layer

Alkali sulfonates with up to 6 carbon atoms in the settled.

Alkyl radical, preferably aryl sulfonates, such as sodium example 2
and potassium toluene and xylene sulfonates, used 45

will. The hydrotropes are usually several according to the table below

Prepared in amounts of 4 to 12% and preferably up to 10% detergent, all of which when stored in the

of the total mix used. remained essentially homogeneous. In these attempts

The solids content of the inventive liquid derived from the alkyl radical of the alkylbenzene cleaning agent used is usually 15 to 75 and 50 sulfonates of propylene polymers, which are preferably 30 to 60% of mixtures, while the remainder mostly consisted of propylene tetramers and pentamers, so water is. If the solids content is high, there may be a tridecyl radical on average. The viscosity due to the addition of solvents, ζ. B. of Aiko-Nonylphenoläthylenoxydsulfat had about 5 ethylene sources, such as ethanol or isopropanol, or of uric oxide groups per nonylphenol. The lauryl ether sulfate, diethylene glycol monobutyl ether and alkylol had an average of about 3 ethylene oxide amine, such as triethanolamine, condensed in small amounts with lauryl alcohol. The sodium silicate, for example less than 15 and preferably 5%, had a Na ₂ O: SiO ₂ ratio of about 1: 2.35; will. the amount refers to the solid content.

The Liquid Cleaning Agent According to the Invention The carboxymethyl cellulose had 0.7 carboxy groups and can be produced in any desired manner. The 60 per glucose hydride unit, and the pyrrolidone had cellulose compound and the vinyl polymer can have a molecular weight of about 40,000. The polyalous aqueous solutions at any time during the mixing vinyl alcohol had a viscosity of about 4 to 6 cP and the remaining ingredients in any order and about 88% Alcohol or 12% ester. The weights are added. In general, the proportions should relate first to the effective pure main amount of water, then to the cellulose compound 65 constituents. The polyvinyl alcohol can also have a viscosity of about 1.8 to 3 cP and the vinyl polymer in the form of an aqueous jelly and 10 to or of a powder containing 30% ester added with sufficient stirring, e.g. B. 2.34 cP and 22.3%
until a uniform product is obtained. vinyl acetate.

A. B. C. D. E. F. G H I. 10.0 10.0 9.0 9.0 9.0 9.0 9.0 10.0 9.0 - - 6.0 6.0 - 6.0 - - 6.0 - - - - 6.0 - - - - - - - - - - 6.0 - - 2.5 2.5 3.0 3.0 3.0 3.0 3.0 3.0 3.0 2.5 2.5 3.0 3.0 3.0 3.0 3.0 2.5 3.0 8.0 6.0 6.0 7.0 6.8 6.5 6.0 6.0 6.5 - 2.0 2.0 2.0 2.3 2.0 2.0 2.0 2.0 20.0 20.0 15.0 15.0 15.0 15.0 15.0 20.0 - - - - - • - ■ - - - 15.0 0.5 0.5 0.5 0.25 0.25 - - - - - - - - - 0.25 0.25 0.25 0.25 0.2 0.2 0.1 0.25 0.25 0.25 0.25 0.25 0.25 - _ - 0.3 0.3 0.3 0.3 - 0.3 rest rest rest rest rest rest rest rest rest

Sodium alkylbenzenesulfonate ..

Sodium monylphenol ethylene oxide sulfate

Sodium lauryl alcohol sulfate. Sodium lauryl ether sulfate

Lauroyl myristoyl (70:30) isopropanolamide

Lauroyl myristoyl (70:30) diethanolamide

Sodium xylene sulfonate

Potassium Toluenesulfonate

Potassium pyrophosphate

Sodium silicate

Polyvinyl pyrrolidone

Polyvinyl alcohol

Sodium carboxymethyl cellulose

Waxy ricinol product .. water

In addition to the homogeneous nature, the liquid cleaning agent mixtures according to the invention show a high degree of detergency, especially a high dirt-carrying capacity when washing Fabrics, e.g. B. of resin-treated cotton fabrics and synthetic fibers such as polyamides and polyesters. In general, those containing cellulose compounds and polyvinyl alcohol Mixtures to be preferred because they have a noticeably better dirt-bearing effect even during longer periods Bear in relation to similar comparable mixtures.

Claims (5)

Patent claims: 1. Liquid heavy duty detergent, characterized by a content of a) about 5 to 30% of a water-soluble, non-cationic, organic detergent substance, b) about 5 to 30% water-soluble washing alkali and c) about 0.1 to 5% of a mixture of a water-soluble cellulose compound and one 20.0 0.25 0.2 remainder water soluble vinyl polymers in the ratio of about 20: 1 to 1:20. 2. Cleaning agent according to claim 1, characterized in that it is a water-soluble anionic contains organic sulfonate detergent. 3. Cleaning agent according to claim 1 or 2, characterized in that the component c) consists of a mixture of carboxymethyl cellulose (cellulose glycolic acid) and polyvinyl alcohol or polyvinyl pyrrolidone consists. 4. Cleaning agent according to claim 1 to 3, characterized in that it is about 4 to 12% of a water-soluble, hydrotropic aryl sulfonate. 5. Cleaning agent according to claim 1 to 4, characterized by a content of potassium polyphosphate. Documents considered: German Auslegeschrift No. 1 049 037; British Patent No. 800,705; U.S. Patent No. 2,645,615. © 309 747/366 10.63