Cleaning compositions

laundry detergent

This invention relates to laundry detergent compositions containing alkyl 5 or alkenyl carboxylate compounds, especially alkyl or alkenyl succinates, as enhancing ingredients, together with polyesters which act as soil release agents.

The patent literature deals with the use of alkyl and alkenyl succinates as surfactants (U.S. Pat. No. 2,283,214), detergents (GB Patent No. 1,293,753), various liquid detergents (GB Patent No. 1,527,178) and U.S. Patent No. 1,528,171; , as builders (= surfactant enhancers) (U.S. Pat. No. 2,462,758) and the like. Also referred to

U.S. Patent 3,784,486.

A wide variety of substituted succinates and sulfur succinates have been described for many similar uses (U.S. Patent Nos. 3,912,663, 20,415,515, and 3,725,286).

The use of various succinates in combination with certain detergent ingredients is also known; see. EP publications 79 191 and 70 190 and DE patents 3 205 791 and 3 317 337.

The use of different types of carboxylate compounds in solid and liquid detergents is indeed well known; see. GB Patent 1,514,276 for amine soap mixtures, GB Patent 1,429,143 for zeolite polycarboxylate mixtures, U.S. Patent No. 30,226,103 for citrate-soap mixtures and other carboxylates and soap mixtures, U.S. Patent No. 394 U.S. Patent No. 3,898,187 for various sulfur succinates for use in dishwasher detergents and GB Patent No. 1,400,898 for use in connection with clay plasticizers.

A wide variety of polymers have been proposed for use in detergent compositions.

Better detergent compositions of all types are constantly being sought, and the present invention enhances the performance of such compositions, as described in more detail below.

The main advantage of the present invention is that by combining various known carboxylate ingredients in a suitable and hitherto unknown manner with effective soil release polymers, a better product performance is achieved.

All percentages, proportions and proportions of ingredients are given as percentages, proportions or proportions by weight, unless otherwise specified.

This invention relates to detergent compositions specifically for washing fabrics. Said compositions may be formulated in liquid, solid or granular form; the preferred form is the liquid form, and such liquid compositions are hereinafter referred to as high performance liquids (HDL) because they are intended to remove even the heaviest loads of dirt from fabrics when used in conventional washing.

The fully formulated detergent compositions contain a conventional alkyl or alkenyl dicarboxylate builder (typically 1-35%, preferably 5-20%), conventional anionic, nonionic, cationic or zwitterionic detersive surfactants (typically 1-35%, preferably 5-20%) and optionally conventional detergents and carriers, characterized in that they contain at least 0.01%, preferably 0.0755% and most preferably 0.1-1.5%, a soil release polymer which is an alkoxylated ester of phthalic acid, as described in more detail below.

This invention also relates to a method of washing fabrics by agitating said fabrics in an aqueous washing solution, said solution containing at least 0.05% by weight of a composition of the type described above.

Products of the laundry additive type consisting of a mixture of the above-mentioned Builder and a soil release polymer (generally in a ratio of 100: 1 to 1: 100, preferably with a Builder ratio of at least 5: 1 to the soil release polymer) are also within the scope of this invention. Such compositions are intended for use in conjunction with conventional commercial laundry detergents.

The essential ingredients of the compositions of this invention are a dicarboxylate builder and a soil release polymer. Detergent surfactants, possible detergent components as well as carriers, fillers, etc. are all familiar to those skilled in the art.

Detergent compositions are preferably formulated as high performance liquids, but may also be formulated in a solid form such as flakes, chips, powders, rods or spray dried granules.

Detergent additive compositions may be in any of the above forms.

Also within the scope of this invention are products containing detergent compositions or detergent compositions in a pre-measured form bound to a release substrate so as to be releasable therefrom, or packaged in a bag so as to be releasable therefrom, which are suitable for use in an aqueous laundry solution.

Dicarboxylate Builder - Preferably the builders in this context are builders corresponding to the general formula R-CH (COOH) CH₂(COOH), where R is C₁₀.₂₀-alkyl or -alkenyl group, preferably C₁₂.₁₆-alkyl or alkenyl group, or R may contain hydroxyl, sulfo, sulfoxy or sulfone substituents, all of which are as disclosed in the aforementioned patents, i.e., succinic acid derivatives.

Succinate builders are preferably used as water-soluble salts, including sodium, potassium, ammonium and alkanol ammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.

Dirt Remover Polymer - The dirt remover polymer used in this context is of a very special type and has the general formula:

0 0 0

X- (OCH₂CH₂ )_of(OC-R'-C-OR² ) and (0-CR¹-C-O) (CH 2 CH₂O-)_of-X wherein X may be any suitable end group, each X being H or an alkyl or acyl group containing from one to about four carbon atoms, n is selected so as to account for water solubility, and is generally about 6 to 120, preferably about 10 -50. u is crucial for formulation in a liquid detergent with a relatively high ionic strength. It should contain very little substance where u is greater than 5. In addition, it should contain at least 20%, preferably at least 40% of a substance where u is 3-5.

R^xgroups are mainly 1,4-phenylene groups. As used herein, the term R¹groups are mainly 1,4-phenylene groups referring to compounds in which R^xgroups consist entirely of 1,4-phenylene groups or are partially substituted by other arylene or alkarylene groups, alkylene groups, alkenylene groups or mixtures thereof. Arylene and alkarylene groups that can partially replace 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4.4 -biphenylene and mixtures thereof. Alkylene and alkenylene groups that can partially replace 1,4-phenylene include ethylene-1,1-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1, 8-Octamethylene, 1,4-cyclohexylene and mixtures thereof.

What R¹groups, the degree of partial substitution of 1,4-phenylene with other groups should be such that it does not significantly impair the soil release properties of the compound. The degree of partial substitution allowed generally depends on the length of the body of the compound, i. in longer bodies, the substitution of 1,4-phenylene groups may be greater. Generally, compounds containing about 50-100% of 1,4-phenylene groups (about 0-50% of groups other than 1,4-phenylene groups) have a sufficient soil release effect. For example, polyesters prepared in accordance with this invention using isophthalic acid (1,3-phenylene) and terephthalic acid (1,4-phenylene) in a molar ratio of 40:60 have a sufficient soil release effect. However, since most polyesters used in the preparation of cultures contain ethylene terephthalate units, it is usually desirable to minimize the degree of partial substitution of 1,4-phenylene with other groups to achieve the best soil release effect. Preferably R¹groups consist entirely (i.e. 100%) of 1,4-phenylene groups, i.e. each R¹the group is 1,4-phenylene. (Without interfering with the mechanism of action, it is surprising that soil release polymers have excellent advantages over non-polyester fabrics, and the compositions presented herein are intended for cleaning all types of fabrics and textiles).

What R²suitable ethylene or substituted ethylene groups include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene, and mixtures thereof. Preferably R²groups are mainly ethylene or 1,2-propylene groups or mixtures thereof. A higher percentage of ethylene groups tends to enhance the soil release effect of the compounds. Surprisingly, a higher percentage of 1,2-propylene groups tends to improve the water solubility of the compounds.

In the case of the present invention, the use of 1,2-propylene groups or their branched counterparts is essential to incorporate a significant portion of the soil release component into the high performance washing liquid compositions. Preferably about 75-100% and even more preferably about 90-100% R²groups are 1,2-propylene groups.

Each n is at least about 6, preferably at least about 10. Usually each n is about 12-113. A typical value for each n is about 12-43.

A preferred method of making the preferred soil release component comprises the step of extracting a polymer having a normal distribution and consisting substantially in part of a material having a u greater than 6 with substantially anhydrous ethanol at low temperature, for example at about 10-15 ° C. The ethanol-soluble fraction is substantially free of elongated polymers and is much easier to incorporate into isotropic high power liquids, especially those with high ionic strength (e.g., containing more than 10% succinate builder).

Although polymers with u less than about 3 are somewhat worthless in terms of providing a soil release effect, they appear to have a significant effect on the overall performance of the product. In particular, compositions containing succinate builders may have less than ideal degreasing ability; instead, with the presence of soil release polymers, this ability is maintained at a more satisfactory level.

Detergent Surfactants - The detergent compositions of this invention contain organic surfactants to achieve the conventional cleaning benefits associated with the use of such detergents.

Detergent surfactants useful in this context include known synthetic anionic, nonionic amphoteric and zwitterionic surfactants. Typical of these are alkylbenzene sulfonates, alkyl and alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, amine oxides, alpha-sulfonates of fatty acids and fatty acid esters, ethoxylated alcohols and ethoxylated alkylphenols, and the like, which are Generally, such detergent surfactants contain C₉-₁₈alkyl group; anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts. Basic works such as the McCutcheon’s Index contain detailed lists of such typical detergent surfactants. C₁₁_₁₄-alkylbenzenesulfonates, C_xi_₁₈paraffin sulfonates and C₁₁.₁₈sulfates are particularly preferred in compositions of the type of this invention.

Also useful in this connection are water-soluble soaps, for example the usual sodium and potassium coconut or coconut soaps known in the art. The surfactant component may be present in only 1% of the laundry detergent compositions of this invention, but generally the compositions contain 5-40%, preferably 6-30%, of surfactant. Mixtures of anionic surfactants such as alkylbenzenesulfonates, alkyl sulfates and paraffin sulfonates, and ethoxylated alcohols having 9 to 16 carbon atoms are preferred for use in cleaning a fabric from a variety of soils and stains by washing.

Detergent Aids - The compositions of this invention may contain other ingredients that enhance their cleaning performance. For example, it is highly desirable that the laundry detergent compositions described herein also contain enzymes to improve their cleaning performance against various soils and stains in a wash-through manner. Amylase and protease enzymes suitable for use in detergents are known in the art and in commercial liquid and granular detergents. Commercial cleaning enzymes (preferably a mixture of amylase and protease) are usually used in the compositions of this invention in concentrations of 0.001-2% and higher.

In addition, the compositions of the invention may contain, in addition to the ingredients already mentioned, a wide variety of other optional ingredients commonly used in commercial products to achieve aesthetic benefits or additional functional benefits of the product. Typical ingredients include pH adjusters, perfumes, dyes, bleaches, optical brighteners, dirt suspending agents, hydrotropes and anti-gelling agents, antifreeze stabilizers, bactericides, preservatives, defoamers, bleach activators.

In the wash-by-wash method, the compositions are used to wash fabrics in an aqueous wash solution having a pH of 7-11 at a concentration of at least 500 ppm, preferably 0.10-2.5%. Washing can be performed with excellent results by agitating the fabrics in the presence of the compositions of this invention at a temperature between 5 ° C and the boiling point.

The following examples are typical examples of the compositions of this invention.

Example I

One preferred HDL is as follows:

<td>Constituent</td><td>weight Percent</td>

<td>2-dodekyylisukkinaattia Dirt-removing polymer * Diethylene triamine penta (methylene phosphonate)</td><td> 15,00 0, 50 0,85</td>

<td>CaCl₂Formate (Na)</td><td> 0,01 0,9</td>

<td>triethanolamine</td><td> 5,00</td>

<td>NaOHzta **</td><td> 5,6</td>

<td>ethanol</td><td> 9,0</td>

<td>C 1-4 alkylbenzenesulfonate Kookosalkyylisulfaattia Ethoxylated C 1-4 alcohol (EO 7) oleic acid enzymes Water and secondary substances Product pH 7.6 to 7.7</td><td>10.2 3.88 11.6 3.88 0.15 to 100</td>

* Prepared by esterification of 1,4-phthalic acid (chloride) with 1,2-propanediol and ethoxylation of the polymer with ethylene oxide. The resulting polymer mixture is fractionated in cold (15 ° C) ethanol to give a fraction soluble in cold ethanol, where u is mainly 3-5. The average ethoxyl number (n) is 12-43.

** Viscosity can be changed by replacing part of NaOH

With KOH according to the formulator's wishes. A stable homogeneous isotropic product is secured.

It has been found that diluting the composition of Example I with water rapidly reduces the viscosity of the composition. This is in stark contrast to many HDLs, whose viscosity increases with the addition of water. The rapid decrease in viscosity helps the HDLs of this invention to avoid the problem of clogging of dispensers of automatic washing machines.

Example II

The detergent additive product is prepared by mixing 15 g of lauryl succinate and 1 g of the soil release polymer of Example I. The composition is placed in a flexible polyethylene bag sealed at one edge with a water-soluble polyvinyl alcohol adhesive. In use, the bag is simply dropped into the wash water along with a conventional laundry detergent to achieve additional washing performance and soil removal benefits, including the release of clay and particulate dirt from the cotton and polyester fabrics.

Example III

The granular detergent composition contains the following ingredients:

Constituent

weight Percent

C ^ 2^_aAlkylbenzenesulfonate 8.0 C 1-4 alcohol ethoxylate (EO 6.5) 5.0 Tallow alcohol sulfate 3.0

Sodium perborate (4 ^ 0) C 1-4 alkenyl succinate mixture Ingredient

Sodium sulfate

NaOH / K0H: ta

The enzyme mixture *

Dirt-removing polymer **

TAED ***

Water and secondary substances

19,0

20,0

weight Percent

40.0 to agitator pH 10.2 0.25 0.75 1.0 remainder * Alkalase-liverase mixture 1: 1 (dry mixture) ** According to Example I (dry mixture) *** Tetraacetylethylenediamine (dry mixture)

A stirrer containing water is prepared and spray dried. The resulting granules are dry blended with an enzyme mixture, a soil release polymer, and a TAED bleach activator.