KR950004931B1 - Stable liquid detergent composition containing hydrophobic brightener - Google Patents

Abstract

Stable isotropic liquid laundry detergents containing a surfactant and a hydrophobic brightener to reduce brightener staining of fabrics. Suitable species of preferred hydrophobic brighteners include disulfonated tetra-anilino naphthotriazolyl stilbene brighteners.

Description

Liquid Detergent Composition Containing Hydrophobic Brightener

The present invention relates to a stable, preferably single phase, isotropic liquid laundry detergent containing certain hydrophobic disulfonate whitening agents that reduce or eliminate soiling of the fabric while maintaining good whiteness. Particularly preferred are disulfonated tetra-anilino naphthotriazolyl stilbene whitening agents. In some embodiments, the hydrophobic bleach may be mixed with various levels of conventional liquid detergent bleach to further improve and optimize the overall fabric appearance. In the case of using such mixed bleach, the hydrophobic bleach should be used in an amount of about 40% or more of the total amount of the bleach to provide the desired advantages.

In addition, suitable brighteners known as fluorescent brighteners are commonly used in laundry detergents. When the brightener is deposited on the fabric, it absorbs ultraviolet energy and is emitted back in blue light. Brighteners reduce or remove the yellowish color from the fabric to provide a more glossy appearance. However, undesirable brighteners may leave stains when the liquid detergent comes into direct contact with the cotton containing fabric. The present invention reduces or eliminates stains while maintaining proper fabric whiteness.

A substantial effort to remove or reduce undesirable brightener stains is to use asymmetric monosulfonated naphthotriazolyl stilbene brightener (MSB). Representative in the art is a series of published patents.

Gray's British Patent No. 2,028,365, issued March 5, 1980, describes an enhanced liquid detergent containing an anionic surfactant and one or more whitening agents, including MSB.

Inamorato, US Patent No. 3,812,041, issued May 21, 1974, describes a non-liquid liquid detergent containing a nonionic surfactant and an anionic surfactant such that the ratio of nonionic to anionic is at least 1 by weight. Is described. Any bleach can include MSB type.

Inamorato, US Pat. No. 3,959,157, issued May 25, 1976, describes a liquid detergent containing a nonionic surfactant, quaternary ammonium softener, and any brightener, including equally MSB.

Franks, US Pat. No. 4,430,236, issued February 7, 1984, contains a nonionic surfactant, any anionic surfactant, hydrogen peroxide, brightener, and preferably quaternary ammonium flexible compounds. Liquid detergents are described. MSBs are specifically mentioned as useful.

Japanese Patent Application No. 74-017004, published April 26, 1974, describes a liquid detergent containing MSB, which is stable against light.

Federal Patent Application No. 24 43 998, published April 7, 1977, describes a clear liquid detergent containing certain diphenyl distyryl bleaches. Examples 1 and 2 relate to liquid detergents containing a combination of MSB and disulfonated brighteners.

European Patent Application 85200988.5, filed June 21, 1985, discloses the use of optionally mixing MSB with conventional di-anilino di-morpholinyl distilbene whitening agents to reduce undesirable brightener deposition. Listed.

The prior art has been able to achieve a significant improvement with conventional whitening agents in connection with the reduction of contamination, but its washability, eg maintaining whiteness, is worse than that obtained from conventional disulfonate brighteners.

The primary object of the present invention is to prepare a heavy bleach containing a heavy concentrated liquid detergent composition which does not show heavy bleach stains in use and maintains at least equal whiteness as compared to conventional detergent brighteners.

The above and other objects can be achieved by incorporating a disulfonated whitening agent which is more hydrophobic than conventional disulfonated brighteners in a high efficiency liquid detergent.

The present invention comprises about 3% to about 60% by weight of surfactants selected from (a) anionic and nonionic surfactants and combinations thereof and (b) at least about 0.01% of the total brightener in the composition. A stable isotropic heavy laundry detergent composition comprising from about 1% by weight to about 1% by weight of a hydrophobic disulfonized brightener of the general formula wherein the brightener contains one or less morpholino groups:

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently selected from anilino, cyclohexylamino, piperazino, phenylenediamino, toluenediamino, morpholino and aminophenol.

The composition of the present invention contains 3% to 50% by weight of surfactant and 0.01% to about 1% by weight of hydrophobic brightener. Essential ingredients of the invention and any ingredients that may be incorporated in the compositions of the invention are described below.

The percentages shown throughout the specification herein are by weight unless otherwise indicated.

The hydrophobic brighteners of the present invention have the following general formula, except that the brightener contains one or less morpholino groups.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently anilino, cyclohexylamino, perrazino, phenylenediamino,

Toluenediamino, morpholino and aminophenol.

Suitable _classifying agents include combinations of possible R _1-4 residues provided such that up to one morpholino group is present. Examples of preferred brightener types are tetra-anilino, tetra-perferazino, tetra-cyclohexylamino and combinations thereof (e.g. di-anilinodiperferazino and dianilino-tercyclohexylamino species). .

Most preferred for minimizing brightener stains is 4,4'-bis ((4-anilino-6-anilino-5-triazin-2yl) amino) -2,2'-stilbene disulfonic acid sodium salt It is a tetraanilino derivative of (A). Preferred brightener systems for the present invention are at least 40% (based on the total amount of detergent brightener) mixed with conventional detergent brighteners (e.g., di-sulfonated dianilino, dimorpholino stilbene brighteners). Specific hydrophobic brighteners as described above.

Conventional detergent brighteners used in admixture with the aforementioned hydrophobic species included in conventional detergent brighteners are as follows:

4- (2H-naphtho (1,2-d) triazol-2-yl) -2-styrenebensulfonic acid sodium salt; (i)

4,4'-bis ((4-anilino-6 (N-2-hydroxyethyl-N-methylamino) -5-triazin-2-yl) amino) -2,2'-stilbenedsulfonic acid sodium Salts, (ii)

4,4'-bis ((4-anilino-6-morpholino-5-triazin-2-yl) amino) -2,2'-stilbendisulfonic acid sodium salt (iii)

2,2- (4,4'-biphenylene divinylene)-dibenzenesulfonic acid disodium salt; (ivi)

4,4'-bis (4-phenyl-2H-1,2,3-triazol-2-yl) disodium salt; (vi)

4,4'-bis ((4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) -2-stilbene sulfonate sodium salt. (vii)

Hydrophobic brighteners will be present in at least 40% of the total brightener, but this level may depend on the characteristics of conventional brighteners. As in the examples, the tetra-anilino hydrophobic brightener is preferably present from 55% to 80% of the total bleach when the conventional bleach is (i) above.

Surfactants may be present in the form of anionic and nonionic surfactants and mixtures thereof. Surfactant paper is usually present at 3% to 60%, preferably 10% to 50%. Suitable anionic surfactants are described in US Pat. No. 4,285,841 to Barrat et al., August 25, 1981, and US Pat. No. 3,929,678 to Laughlin, et al., December 30, 1975. It is described.

Useful anionic surfactants are water-soluble salts of organic sulfuric acid reaction products having alkyl structures of about 10 to about 20 carbon atoms, and sulfonic acid or sulfuric acid ester groups, in particular alkali metals, ammonium and alkylolammoniums (e.g. monoethanolammonium). Or triethanolammonium) salts, wherein the term “alkyl” refers to an alkyl moiety of an aryl group. Examples of such groups of synthetic surfactants include alkyl sulfates obtained by sulfated higher alcohols (C ₈ to C 1 ₈ carbon atoms) produced by reducing the glycerides of resins or coconut oil: and alkyl groups of about 9 Alkylbenzene sulfonates containing about 15 carbon atoms and in a straight or branched chain arrangement (described in US Pat. Nos. 2,220,099 and 2,477,383). Particularly useful are straight chain alkylbenzene sulfonates having an average carbon number of from about 11 to 14 alkyl groups.

Other anionic surfactants include paraffin sulfonates having about 8 to about 24 carbon atoms (preferably about 12 to 18); Alkyl glyceryl ether glyceryl ether sulfonates of C _8-18 alcohols (eg derived from resins and coconut oil); About 10 to about 20 carbon atoms in about 1 to about 4 units of ethylene oxide and alkyl groups per molecule. It is a water-soluble salt of the containing alkyl phenol ethylhen oxide ether sulfonate.

Other useful anionic surfactants are water-soluble salts of esters of α-sulfonated fatty acids containing about 6 to about 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group: Water-soluble salts of 2-acyloxyalkanes-1-sulfonic acids containing about 2 to 9 carbon atoms and containing about 9 to about 23 carbon atoms in the alkane residue: Water soluble of olewan sulfonate containing about 12 to 24 carbon atoms Salts; and β-alkyloxy alkanesulfonates containing about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane residue.

Preferred anionic surfactants are C ₁₀ to C ₁₈ alkyl sulfates, C ₁₁ to C _l3 linear alkylbenzene sulfonates and combinations thereof containing on average 0 to about 4 ethylene oxide units per mole of alkyl sulfate.

Nonionic surfactants may be species well known in the art and many are commercially available. Suitable ethoxylated nonionic surfactants for use in the present invention are those of the general formula R ₁ (OC ₂ H ₄ ) nOH, wherein R ₁ is a C ₁₀ to C ₈ alkyl group or a C ₈ to C ₁₂ alkyl phenyl group, n Is about 3 to about 9), and has an HLB (hydrophilic-lipophilic balance) of about 10 to about 13. Such surfactants are described in more detail in US Pat. No. 4,285,841 to Barat et al., Issued August 25, 1981 and US Pat. No. 4,284,532 to Leikhim et al., Issued August 18, 1981. have. Condensation products of C ₁₂ to C ₁₅ alcohols having about 3 to 8 moles of ethylene oxide per mole of alcohol, for example, C ₁₂ to C ₁₃ alcohols condensed with about 6.5 moles of ethylene oxide per mole of alcohol, are preferred. .

Well-known nonionic surfactants for use in the present invention may be amine oxide surfactants such as Cl 2 to C 16 alkyl dimethyl amine oxides.

Amine oxide surfactants are often used at levels of 0.5% to 4% in combination with conventional ethoxylated nonionic surfactants.

In the above nonionic system, the weight ratio of amine oxide to nonionic ethoxylate is in the range of 1: 8 to 1:50.

The compositions of the present invention may be based on all-anionic or all-nonionic surfactant combinations, but anionic and nonionic surfactants may be used in a weight ratio of 1: 1 to 3: 1. At the weight ratios expressed above, the nonionic surfactant may be a mixture of nonionic ethoxylates and amine oxide surfactants.

The composition of the present invention may contain other synthetic surfactants known in the art (such as cationic surfactants, zwitterionic surfactants and amphoteric surfactants) as optional ingredients in addition to the essential surfactants described above. These optional surfactants can be used at additional levels and usually should be less than 40% of the total surfactant.

Suitable examples of these optional surfactants are described in US Pat. Nos. 4,285,841 and 3,929,678.

The composition of the present invention is an aqueous composition, containing up to 100% balanced water, depending on the relative level of essential ingredients and the possible levels of any ingredient. In preferred heavy liquid compositions, the level of water may be in the range of, for example, 60% to 20%.

The composition of the present invention is determined to have a neutral to weakly alkaline range, i.e., a pH of 6.5 to 9 when a 1% aqueous solution is measured at 20 ° C.

In addition to the essential ingredients described above, the compositions of the present invention contain a convenient amount of a series of optional ingredients used for known functionality. These optional ingredients generally greatly enhance and enhance the detergent performance of the claimed composition. Examples of similar optional ingredients include fragrances, dyes, milk whites. disinfectant. Antioxidants, soap foam modifiers including silanic and hydrogenated fatty acids, tartrate monosuccinic acid, enhancers including sodium tripolyphosphate and sodium perophosphate, citric acid, fully hydrated zeolites with particle diameters ranging from 1 to 10 microns And alkenyl succinates having from 10 to 16 carbon atoms in the alkenyl moiety. Other optional ingredients include antifouling agents such as polyethylene glycol terephthalate, performance promoters (e.g. tetraethylenepentamine with EO 15-19), preservatives (e.g. aminosilane), enzymes, cationic surfactants, fabric softeners. (E.g. quaternary ammonium salts and bentonite clay), ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, fatty acids, alkylene polyaminopolyalkylenephosphonic acids, enzyme stabilization systems and liquid matrices containing water and a suitable solvent Contains ingredients.

Suitable fatty acids, saturated or unsaturated, have 10 to 18 carbon atoms in the alkyl chain. Unsaturated fatty acids containing 12 to 18 carbon atoms in the alkyl group are preferred, with oleic acid being most preferred. Corresponding soaps can equally be used. Any fatty acid / soap is used at levels of up to 20% by weight, often from 5% to 15% by weight.

Detergent enzymes help or remove certain stains. Suitable enzymes can be proteases, amylases, lipases, glucose-oxidases, cellulases or mixtures thereof. Proteases and amylases are preferred for the liquid concentrated compositions of the present invention. The enzyme is used at a level of about 0.01% by weight to about 2% by weight.

In general, all known enzyme stabilization systems can be used in the compositions of the present invention at levels approved in the art. Examples of suitable stabilization systems are short chain C mixed with calcium, boric acid and their water soluble salts, possibly with polyols. _1-4 carboxylic acids, especially formic acid.

Alkylene-polyaminopolyalkylenephosphonic acids suitable for the present invention are ethylene diamine tetramethylene.phosphonic acid, diethylenetriamine tenmethylenephosphonic acid or salts thereof. These polyphosphonates are preferably used in an amount of 0.1% to 3%, preferably 0.4% to 1.2%, and preferred tetra- and pentamethylene phosphonate species have a weight ratio of tetra: penta from 3: 1 to 3%. It can also be used in combination of 1: 3.

Acceptable detergent soap foam modifiers are hydrogenated fatty acids and alkylated polysiloxanes such as dimethinepolysiloxanes having from 16 to 22 carbon atoms in the alkyl chain. Fatty acid soap foam modifiers are used at levels of 0.5 to 5% and silicones are effective at levels ranging from 0.05 to 0.5%. Soap bubble modifiers may also be present as a combination of hydrogenated fatty acids and silicones.

Where oxidizable materials are present, the compositions of the present invention may contain known antioxidants at levels known in the art, for example, 0.001 to 0.25% (based on the total composition). These antioxidants are often mixed with unsaturated organic acids. Many direct antioxidants are known for this purpose and are acceptable for this purpose, but particularly preferred for use in the compositions of the invention are 2,6-di-tert-butyl-p-clesol, more particularly butyl Hydroxy toluene, BHT, and 2-3 butyl-4-hydroxyanisole. Other direct antioxidants are 4,4'-thiobis (6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonylphenol.

Sodium triliposphite, sodium perophosphite, tartrate monosuccinic acid, citric acid, (C ₁₂ -C ₁₆ ) alkenylsuccinates, exchangeable hydrated zeolites with particle sizes of 1 to 10 microns or combinations thereof Enhancers such as are often used at levels of 2% to 25%.

Chelating agents such as alkylenepliamino-polyalkylenepolycarboxylic acids and / or polyphosphonic acids are often used at levels of 0.1 to 3%.

Known fabric softeners including bentonite clay (known in DE-PS 23 34 899) as well as dietadimethylammonium salts and imidazolinium salts may be used depending on the intended functionality of the composition. Softeners may typically be present at 2% to 8%.

The liquid matrix component is an additional optional component in the composition of the present invention. Together with water the components may constitute a solvent matrix for the concentrated liquid. Suitable components are lower aliphatic alcohols having 2 to 6 carbon atoms and 1 to 3 hydroxyl groups, ethers of diethylene glycol and lower aliphatic monoalloes having 1 to 4 carbon atoms. Specific examples of phase control agents include n-propanol, isopropane, butane and 1,2-propanedi; 1,3-propanedi: monomethyl-, ethyl-, propyl-, and monobutyl ether of diethylene glycol. The liquid matrix component may be used at various levels depending on the total level of the component in the composition. In the concentrated HDL of the present invention, the liquid solvent may be present from 5% to 30%. The concentrated heavy liquid composition of the present invention forms a preferred composition of the claimed technology. These compositions may have the following components.

TABLE 1

Example 1

Fabric staining tendencies of various brighteners are evaluated in the following compositions.

The non-diluent detergent containing the above detergent whitening agent is applied directly to the non-whitened 100% cotton cloth and left to stand for 10 minutes. The cloth is then washed with the same detergent solution (1% product concentration, 30 ° C., lightly shaken), inverted and dried.

This cloth is evaluated by UV light for bleach stains on the following scales.

O No stains appear.

T stains appear very little.

1.0 stain is very weak

1.5 stain is weak

2.0 The stain is a bit weak.

2.5 stains are common.

3.0 The stain is dark.

The result is as follows.

TABLE 2

As a result of this, reduced brightener stains on various fabrics of the tetra-anilino brightener (A) according to the invention are identified.

The brightener deposition excellence at the time of washing is assessed with the aid of brightener build-up measurements in an adjuvant manner.

Brightener build-up means the rate at which the brightener is deposited in brightening and non-whitening cloths. Build-up measurements are performed as follows:

Test condition: Miele W 765, 60 ℃ short cycle, 180m1

Product usage (1% product concentration)

Safe load = 2 kg 100% bleached (washed with perborate / STPP at 90 ° C), non-whitening cotton.

Tracers unbleached terry cloth = unbleached

Non-bleached terry fabric is bleached by washing once at 90'c with perborate / STPP.

Bleached terry fabric = bleached, white terry fabric is washed five times with HDD at 90 '.

Measurements: Non-whitening terry fabric 440nm Re-emitter Start: 83.88

Medium White Terry Fabric 440nm Re-release Departure: 149.13

Result: Re-release 440nm

TABLE 3

Example 2

Further liquid compositions according to the invention contain the following ingredients.

TABLE 4

* expressed in pH units

(1) European Patent Application No. 85202053.6 (12 December 1985).

Claims (10)

(a) from about 3% to about 60% by weight of surfactants selected from anionic and nonionic surfactants and mixtures thereof, and (b) hydrophobic disulfonates of the general formula: A heavy liquid aqueous detergent composition comprising 0.01% to 1% by weight of a heavy bleach, wherein the brightener contains up to one morpholino group.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently selected from anilino, cyclohisylamino, piperazino, phenylenediamino, toluenediamino, morpholino and aminophenol. 2. The hydrophobic bleach of claim 1 wherein the R _1-4 residues are tetra-anilino, tetra-perferazino, tetra-cycloxylamino, dianilino-diperrazino and dianilino-dicyclohexylamino A composition selected from the group consisting of: The composition of claim 1, wherein 10% to 50% by weight of the surfactant is present. 4. The composition of claim 3 wherein the hydrophobic brightener is a tetra-anilino derivative present from 0.07% to 0.3% by weight. The composition of claim 1 wherein the surfactant is a mixture of anionic and nonionic surfactants having a weight ratio of anion to nonionic of 1: 1 to 3: 1. 6. The composition of claim 1 or 5, wherein the nonionic surfactant is a mixture of nonionic ethoxylates and amine oxides having a weight ratio of ethoxylate to amine oxide of 50: 1 to 8: 1. The method of claim 1, wherein the brightener is a hydrophobic brightener having a hydrophobic brightener present in at least 40% by weight of the total brightener (i.e., the sum of the hydrophobic bleach and the conventional bleach). A composition that is a mixture. The method of claim 1 or 7, wherein the conventional brightener is 4,4'-bis ((4-anilino-6-morpholino-1,3,5triazin-2-yl) amino) -2 -A composition which is a stilbene sulfonate natzo salt. A heavy liquid concentrated detergent composition having the following composition. 10 to 50 wt% surfactant Enhancer 2-25% by weight 0.1 to 3% by weight of chelating agent 0.1-1.5 wt% of enzyme-protease Amylase 0.05-0.8 wt% 0.01 to 1% by weight of hydrophobic brightener of claim 1 70 to 20% by weight of water 3 to 30 wt% solvent 10. The composition of claim 9 wherein the hydrophobic bleach is a tetra-anilino derivative present in an amount of 0.07% to 0.3% by weight.