CN1038944C - Color-stabilization system in liquid detergent compositions - Google Patents

Abstract

Presented herein are liquid detergent compositions containing common detergent ingredients and color stabilizing compounds that generate sulfite ions in the final product.

Description

Color stabilization system in liquid detergent compositions

This invention relates to liquid detergent compositions. Compositions according to the invention are stabilized by preventing color change.

Liquid detergent compositions are well known in the art. As the aesthetics of the composition becomes a key factor in consumer acceptance, there is a need for such a composition to have an attractive color. Detergent formulators can employ a wide palette of dyes to accommodate this need.

Alternatively, some compositions may be marketed without dyes when the color of the dye-free product is entirely attractive.

However, it has been seen that the color of new products formulated in certain liquid detergents does not remain the same for long periods of time. This is a problem for manufacturers of detergents, since detergents should not change appreciably in any respect including product aesthetics, and it should be able to withstand long-term storage. While the cause of the color change has not been definitively identified, we believe ingredients like alkanolamines are partly responsible for this phenomenon. Spices also seem to play a role, but because of the complex properties of spices, this is less clear. Thus, the color of the composition changes to varying degrees throughout the period.

We have observed that the color change phenomenon also occurs without dye in the detergent, that is, the "true color" without dye is changed. Unfortunately, the presence of dyes does not always completely cover up the color change phenomenon.

The above-mentioned problem is all the more acute in the prevailing liquid detergents since these detergents are intended to be formulated as so-called liquid concentrate detergents, in which the interaction of the different ingredients and thus the color change is promoted. These liquid concentrates also often include the use of alkanolamines which, as noted above, can cause some degree of color change phenomena.

It is then an object of the present invention to formulate liquid detergent compositions which are stable against color change over a long period of time.

In addition to this purpose, the present invention also recommends formulating liquid detergent compositions which contain small amounts of various sulfite ions which are produced in detergent compositions as color stabilizing compounds.

An advantage of the present invention is that it provides a color stabilizing system that is effective in all products that produce a color change with or without a dye. Another advantage of the present invention is that it provides the use of common chemicals, which are commercially available and relatively inexpensive.

The composition according to the present invention is a liquid detergent composition containing general detergent ingredients, characterized in that it also contains 0.001%-10% of a color-stabilizing compound that accounts for the total weight of the composition, and the compound is selected from the group consisting of sulfite, sulfite Bisulfate or pyrosulfite, sulfur dioxide, sulfurous acid, alpha-hydroxyalkylsulfonic acid, mercaptoethanol, sodium thioglycolate, 2-aminoethanethiol, cysteine, polycystine, glutathione and formamidine sulfite or mixtures thereof.

Liquid detergent compositions according to the present invention comprise conventional detergent ingredients and a color stabilizing system.

The detergent composition according to the present invention contains from 0.001% to 10% of the total weight of the composition as a color stabilizing system compound selected from the group consisting of sulfite (SO ₃ ²⁻ ), bisulfite (HSO ₃ ⁻ ) or Pyrosulfite (S ₂ O ₅ ^2- ), sulfur dioxide, sulfurous acid, 2-hydroxyalkylsulfonic acid, mercaptoethanol, sodium thioglycolate, 2-aminoethanethiol, cysteine, polycystine, Glutathione and formamidine sulfite or mixtures thereof. Suitable sulfites, bisulfites and pyrosulfites include metal, ammonium and alkanolammonium salts. The most preferred salts for use herein are sodium, potassium, calcium, alkanolammonium and ammonium salts. These compounds are generally used as food preservatives, so they are available in the market. Solutions of bisulfite, sulfur dioxide and sulfurous acid are also commercially available.

The most preferred color stabilizing compound according to the present invention is sodium metabisulfite.

Without being bound by theory, we believe that the hydrosulfite ion is primarily responsible for the observed color stabilizing effect. Thus, any of the compounds mentioned above can be added to detergent compositions since it is absolutely certain that said compound will generate bisulfite ions in the final product. Alpha-hydroxyalkylsulfonic acids are also suitable for use in compositions according to the invention due to their ability to generate bisulfite ions in the final product. [alpha]-Hydroxyalkylsulfonic acids can be prepared by reacting aldehydes or ketones with sodium sulfite, as described, for example, in Advanced Organic Chemistry, March 1977, P816 Mc Graw-Hill. The alkyl chain length and the configuration of the α-hydroxyalkylsulfonic acid are not critical here. The most preferred alkyl chains are C ₁ -C ₁₅ aliphatic chains.

The compositions according to the invention preferably contain from 0.005% to 1%, most preferably from 0.01 to 0.1%, by weight of the total composition, of said color stabilizing compounds or mixtures thereof.

Liquid detergent compositions according to the present invention consist in part of the general detergent ingredients, namely water, surfactants, builders and other ingredients.

Here the liquid detergent composition contains 5%-60%, preferably 20-40% of the organic surfactant of the total weight of the liquid detergent composition, and the organic surfactant is selected from nonionic, anionic, cationic and zwitterionic Surfactants and their mixtures.

Suitable anionic surface-active salts are selected from the group of sulfonates and sulfates. Homoanionic surfactants are well known in the detergent art and are widely used in commercial detergents. The most preferred water-soluble anionic sulfonates or sulfates have alkyl groups of about 8-22 carbon atoms in their molecular structure. Preferred examples of such anionic surface-active salts are reaction products obtained by sulfidation of C ₈ -C ₁₈ fatty alcohols derived from, for example, tallow oils, palm oil, palm kernel oil and coconut oil; radical groups containing about 9-15 carbon atoms; sodium alkyl glyceryl ether sulfonates; ether sulfates of fatty alcohols derived from tallow and coconut oils, monococoglyceride sulfates and sulfonates, and Water-soluble paraffin sulfonate with about 8-22 carbon atoms in the base chain. Sulfonated alkene surfactants such as those described more fully in US 3,332,880 may also be used. Typical cations widely used in detergent technology, such as sodium, potassium, or alkyl alkanolammonium ions, can be represented as neutralizing cations in the synthesis of anionic sulfonates and/or sulfates.

Here, water-soluble alkylbenzene sulfonate, preferably sodium alkylbenzene sulfonate, preferably sodium alkylbenzene sulfonate with about 10-13 carbon atoms on the alkyl group represents a suitable synthetic anionic surfactant ingredients. Another preferred anionic surfactant ingredient herein is sodium alkyl sulfate having about 10-15 carbon atoms in the alkyl group.

Nonionic surfactants suitable herein include those produced by the condensation reaction of ethylene oxide with a hydrocarbon bearing an active hydrogen, such as a hydroxyl, carboxyl, or amide, in the presence of an acidic or basic catalyst. The compound suitable here also includes the compound of the general formula RA(CH ₂ CH ₂ O) _n H, wherein R represents a hydrophobic moiety, A represents a group with active hydrogen, and n represents the average number of oxirane moieties. Typical contains about 8-22 carbon atoms. They may also be products formed by the condensation of 1,2-propylene oxide with low molecular weight compounds. n typically varies between about 2-24.

The products of the condensation of fatty alcohols having 12-15 carbon atoms and 4-10 moles of ethylene oxide per mole of fatty alcohol represent the best class of nonionic ethoxylates. Suitable ethoxylated materials of this type include C ₁₂ -C ₁₅ oxo alcohols and condensation products with 3-9 moles of ethylene oxide per mole of alcohol, narrow range C ₁₄ -C ₁₅ oxo alcohols and per mole of fat Synthetic alcohol molecules have condensation products with 3-9 moles of ethylene oxide, narrow region C ₁₂ -C ₁₃ aliphatic synthetic alcohols and condensation products of 6.5 moles of ethylene oxide per mole of fatty alcohol, and the degree of ethoxylation is at 4 Condensation product of (EO(mol)/fatty alcohol(mol)) C ₁₀ -C ₁₄ coconut oil fatty alcohol of -8. On the other hand, the main chain of aliphatic oxo alcohols can have branching, especially short chains, such as methyl branching, depending on the process conditions and the raw material alkenes. 15% to 50% (wt%) branching is often found in commercial oxo alcohols.

Suitable cationic surfactants include quaternary ammonium compounds of the formula R ₁ R ₂ R ₃ R ₄ - wherein R ₁ , R ₂ and R ₃ are methyl and R ₁ is C ₁₂ -C ₁₅ alkyl, or R ₁ is ethyl or hydroxyethyl, R ₂ and R ₃ are methyl, and R ₄ is C ₁₂ -C ₁₅ alkyl.

Zwitterionic surfactants include various derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic moiety may be straight or branched, wherein one of the aliphatic substituents contains about 8- 24 carbon atoms, and another substituent contains at least one water-soluble cationic group. Particularly good zwitterionic substances are ethoxylated ammonium sulfonate and ammonium sulfate. These substances are published in Langhlin et al. in 1975.12.9. Introduced in the patent of US3,929,678.

Nonionic surfactants of medium polarity include water-soluble amine oxides containing an alkyl or hydroxyalkyl moiety of about 8-28 carbon atoms, and a group of The two parts of the structure are the alkyl and hydroxyalkyl.

Molecular formula such as The polyhydroxy fatty acid amide surfactant is also applicable, wherein R ¹ is H, C _1-4 is hydrocarbon group, α-hydroxyethyl group, α-hydroxypropyl group or their mixture, R ₂ is C _5-31 hydrocarbon group , and E is a polyhydroxyl hydrocarbon group with at least 3 hydroxyl groups directly attached to a linear hydrocarbon chain, or an alkoxylated derivative thereof. Preferably R _is methyl, R _is C ₁₁ -C ₁₅ linear alkyl or alkenyl or a mixture thereof, and E is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction came. The compositions according to the invention additionally comprise a detergency building system. Any conventional builder system is suitable here, such materials are polycarboxylates and fatty acids, such as ethylenediaminetetraacetate, aminopolyphosphates, especially ethylenediaminetetramethylenephosphoric acid and diethylenediaminetetramethylenephosphoric acid Metal ion sequestrants such as ethyl triamine pentamethylene phosphoric acid. Phosphate builders, although rarely chosen because of environmental concerns, are suitable here as well.

Polycarboxylate builders suitable for use herein include citric acid, preferably in the form of a water-soluble salt, succinic acid derivatives of the formula RCH(COOH) _CH2 (COOH), wherein R is a C _10-20 alkane Group or alkenyl, preferably C _12-16 or where R can be substituted by hydroxyl, sulfo, sulfoxylate or sulfone. Specific examples include dodecylsuccinate, myristylsuccinate, hexadecylsuccinate, 2-dodecenylsuccinate, 2-tetradecenylsuccinate. Succinate builders including sodium, potassium, ammonium and alkanolammonium water soluble salt forms are preferred.

Other suitable polycarboxylates are oxydisuccinates and mixtures of tartrate succinate and tartrate disuccinate as described, for example, in US 4,663,071.

Fatty acid builders suitable for use herein are saturated or unsaturated _C10-18 fatty acids, and the corresponding soaps. The saturated moiety is preferably selected to have 12-16 carbon atoms in the alkyl chain. The most preferred unsaturated acid is oleic acid.

A preferred builder system for use herein is a combination of citric acid, fatty acids and succinic acid derivatives as described above. The builder system according to the invention preferably comprises from 5% to 35% by weight of the total composition.

Compositions according to the invention preferably also contain enzymes. Suitable enzymes for use herein are proteases, lipases, cellulases and amylases, and mixtures thereof. Compositions according to the invention also include enzyme stabilization systems. Any of the usual enzyme stabilization systems are suitable here, and the preferred enzyme stabilization systems consist of boronic acid or its derivatives, 1,2-propanediol, carboxylic acids and mixtures thereof.

The composition here may also contain a series of other optional ingredients, examples of similar additives are solvents, alkanolamines, pH regulators, soap solutions, opacifiers, agents for improving the mechanical compatibility of the coated glazing porcelain surface, Fragrances, dyes, fungicides, brighteners, stain removers, softeners, and the like. Some of these ingredients are believed to contribute to the color change problem that constitutes the present invention, particularly perfume and alkanolamines.

The composition according to the present invention can be formulated as a conventional liquid detergent composition, or as a so-called concentrated solution liquid detergent composition, i.e. a liquid detergent composition containing less than 30% water

Example

The following compositions illustrating the invention were prepared. Compositions I-IV and VIII are concentrated liquid detergent compositions.

I II II III III IV

% %% % Alkylbenzene Sulfonic Acid 15 13 18 16 Sodium Coconut Alkyl Sulfate 4 5 2 -7 Ethoxylated C _13-15 Yeast 13.4 15 13.5 133 Ethoxylated Coconut Alkyl Sulfate - - - 3 Coconut Oil N-Methyl Glucamide - - - - Coconut Oil Fatty Acid 11 4 8.5 7.5 Dodecenyl Succinate 6 8 7 6 Citric Acid 5.5 5.9 6 5 Tartrate Monosuccinate - - - Diethylene Triamine 0.9 0.9 1.1 -1,5-pentylidene phosphonic acid ethanol 1.5 1.5 3 -propylene glycol 9.5 8.8 9 6 monoethanolamine 8 12.5 14 1 triethanolamine - - - 15 sodium metaborate 2 2 2 - sodium metabisulfite 0.05 - - 0.01 sodium sulfite - 0.075 - - potassium bisulfite - - 0.1 - sulfur dioxide - - - enzyme 0.8 0.8 1.2 0.8 spices 0.5 0.5 0.6 0.5 dyes 25ppm - 25ppm 25ppm sodium hydroxide (potassium) to pH 7.5 7.5 7.5 7.5 water and other ingredients...  100………

V VI VII VIII IX

% %% % Alkylbenzene Sulfonic Acid 10.4 10.2 12 - - Sodium Coconut Oil Alkyl Sulfate 2.5 2.8 2 - -7 Ethoxylated _C13-15 Alcohol 9.2 11.6 8.5 5 33 Ethoxylated Coconut Oil Alkanes - - - 20 13 Base Sulfate 3 Coconut Oil N-Methyl Glucose - - - 11 6 Sugar Amide Coconut Fatty Acid - 12 - 8 5 Dodecenyl Succinate 6 - 10.5 3 - Citric Acid 8 - 3.5 5 2 Tartrate Monosuccinate Salt - - - - 3 diethylenetriamine 0.7 0.7 0.5 0.5 0.51, 5-pentylidene phosphonic acid

I VI VII VIII IX Ethanol 4 4 4 4 4 4 4 4 Polycol 4.5 1.5 2 6 3 Monathanine--5 2 Totoethalamine-6.5-2 Sodium Borne 1-2 2 2 (Sodium Sodium Sodium-0.02-0.05-Sodium Sodium-0.01 ----0.03 sulfur dioxide 0.01---enzyme 0.8 0.5 0.7 1 0.7 spice 0.5 0.3 0.5 0.3 dye 25ppm 10ppm 15ppm-25 ppm sodium hydroxide (potassium) up to pH 7.5 7.5 7.5 7.5 water and water and water and water Other ingredients ... ... to 100 ... ...

  Test part               Prepare the following composition %

Alkylbenzenesulfonic acid 15.2

MEA Coconut Alkyl Sulfate 4

7 Ethoxylated C _13-15 Alcohol 13.4

3 Ethoxylated Coconut Oil Alkyl Sulfates -

Coconut Oil N-Methyl Glucamide -

Coconut Oil Fatty Acid 8.5

Dodecenyl succinic acid 6.9

Citric acid 5.9

Tartrate Monosuccinic Acid -

Diethylenetriaminepentylphosphonic acid 0.9

Ethanol 1.5

Propylene Glycol 8.8

Sodium Hydroxide -

Potassium Hydroxide 0.25

Monoethanolamine 12.5

Triethanolamine -

MEA Metaborate 2

Enzyme 0.8

Spices 0.5

Opacifier 1.2

Acid Blue 80 25ppm

Acid Blue 7 14ppm

water and other ingredients up to 100

Immediately after the composition was prepared, its Hunter parameters (La and b values) were measured to determine its color. So one of the samples of this composition (sample 1) was supplemented with 1000 ppm sodium metabisulfite and left at room temperature for 2 weeks. Another sample of the above composition (sample 2 is comparative) was also placed under the same conditions without adding any color stabilizer. After two weeks, the Hunter parameters of the two samples were determined. The result is as follows:

                                    

Sample 1 Sample 2 (for comparison)

L 37 37 36

a -9 -9 -12

b -22 -23 -12

Color rendering blue blue green

in conclusion:

After two weeks of storage at room temperature, the color of the sample without adding any color stabilizing system according to the present invention is significantly different from the color of the new product, while the color of the sample containing the color stabilizing system according to the present invention is practically unchanged, even if there is a change The difference is also invisible to the naked eye.

Claims (3)

1. A stable liquid detergent composition that prevents color change in long-term storage, characterized in that the composition contains: A) 5%-60% (weight) organic surfactant; B) 5%-35% (weight) builder system; C) 4%-16% (weight) alkanolamine component selected from monoethanolamine, triethanolamine and mixtures thereof; D) 0.3%-0.6% (weight) of perfume ingredients that are prone to color changes; and E) 0.01%-0.1% (by weight) selected from ammonium sulfite, alkanolammonium sulfite, metal sulfite, ammonium bisulfite, alkanolammonium bisulfite, metal bisulfite, pyrosulfurous acid Color stabilizing compounds of ammonium, alkanolammonium metabisulfite, and metal metabisulfite, or mixtures thereof. 2. The composition of claim 1, wherein said color stabilizing compound is sodium metabisulfite. 3. The composition of claim 1, comprising less than 30% water by weight of the total composition.