DK164115B - DETERGENT COMPOSITION, DETERGENT ADDITIVE AND PROCEDURES FOR WASHING TEXTILES - Google Patents

Description

in

DK 164115B

The present invention relates to a detergent composition, a detergent additive and a method for washing fabrics.

The use of all cooling and alkenyl succinates as interface active agents is disclosed in the patent literature, for example, in US Patent No. 2,283,214, as detergent enhancers in GB Patent No. 1,293,753, in various liquid detergents in GB Patent No. 1,528,171 and U.S. Patent No. 4,277,378, as builders and the like in U.S. Patent No. 2,462,758, see also U.S. Patent No. 3,784,486.

Various similar uses of a number of substituted succinates and "sulfosuccinates" are also disclosed, cf. US Patent Nos. 3,912,663, 4,152,515, and 3,725,286.

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The use of various succinates in combination with certain detergent ingredients is also known, see EP 79.191 and EP 70.190 as well as German Publication No. 3,205,791 and German Publication No. 3,317,337.

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The use of carboxylate substances of various kinds in solid and liquid cleansers is in fact also well known, see GB Patent No. 1,514,276 for use in amine soap mixtures, GB Patent No. 1,429,143 for zeolite / polycarboxylate mixtures, US 25 Patent No. 2,264. 103 for mixtures with citrate and other carboxyl plus soap, US Patent No. 3,634,392 for polysaccharide carboxylate detergent builders, US Patent No. 3,898,187 for various sulfosuccinates in dishwashing detergents, and GB Patent No. 1,400,898 use 3Q with clay softeners.

Various polymers have been proposed for use in detergent compositions.

Continued research is underway for improved detergent compositions of all types, and the present invention relates to such compositions having better effect, as will be more fully described hereinafter.

DK 164115 B

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All ingredient percentages, ratios or proportions set forth below are by weight unless otherwise specified.

With the detergent composition of the present invention 5, better product action is achieved due to the proper and novel combination of various known carboxylate compounds and effective dirt-releasing polymers.

This is accomplished by a detergent blister comprising the usual 10 interface active cleaners and any usual cleansing aids, and which according to the invention is characterized in that it also contains: i) from 1 to 35% by weight of an all cooler or alkenyl dicarboxylate detergent builder and ii) at least 0.01% by weight of a dirt-releasing polymer which is an alkoxylated phthalic acid ester of the formula: 0 0 0 0 π η ir η

X (OCH2CH2) n (O-C-R1-C-OR2) u (O-C-R1-C-O) (CH2CH2O-) n-X

wherein X represents hydrogen or an alkyl or acyl group having 1-4 carbon atoms; n is an integer of from 6 to 120; u is an integer of 25 at most 5, u being between 3 and 5 in at least 20% of the polymer, preferably at least 40%; R * represents 1,4-phenylene in at least 50% of the R * units and in the remainder of the Re units denotes another arylene, alkarylene, alkylene, alkenylene or mixture thereof; R is ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1, 2-30 propyl, or a mixture thereof.

The present detergent compositions are especially intended for washing fabrics. The compositions may be formulated in liquid, solid or granular form, the liquid being preferred and such liquid compositions hereinafter referred to as "heavy duty liquids" or "heavy duty liquids" (HDLs) since they are intended to remove even the most difficult dirt deposits from textiles when used in a conventional washing operation.

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The fully formulated detergent compositions herein encompass a conventional all coolant or alkenyl dicarboxylate detergent builder of from 1% to 35%, preferably from 5% to 20%, usual anionic, nonionic, cationic or zwitterionic, purifying, surfactants ( typically in from 1% to 35%, preferably from 5% to 20%), as well as any conventional cleaning aids and carrier materials, and at least 0.01%, preferably from 0.075% to 5%, most preferably from 0.1% to 1%. , 5%, of the above-mentioned dirt-releasing polymer, which is described more fully hereinafter.

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The invention also relates to a detergent additive, characterized in that it comprises a) a dirt-releasing polymer which is an alkoxylated ester of phthalic acid ester as defined in point (ii) of claim 1, and b) an all coolant or alkenyl dicarboxylate composition. , where the weight ratio of builder to dirt-releasing polymer ranges from 100: 1 to 1: 100.

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Preferably, the ratio of builders to dirt-releasing polymers is at least 5: 1. Such compositions are intended for. use in combination with conventional commercial detergent detergents.

The essential components of the present compositions are the di carboxylate moiety and the dirt-releasing polymer. The cleansing, interface active agents, any cleansing aid ingredients as well as carriers, fillers, etc., are all well known to those skilled in the art.

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The detergent compositions herein are preferably formulated as powerful liquids, but may also be formulated in solid forms such as flakes, shavings, powders, pieces or spray dried granules.

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The detergent additive compositions may be in any of the above forms.

Articles comprising the detergent compositions or detergent compositions

DK 164115B

The additive compositions attached in a detachable manner to a sheet-shaped substrate or releasably contained in a pre-measured bag or purse suitable for use in an aqueous wash bath are also considered to be included in the invention.

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Finally, the invention relates to a method for washing fabrics by movement in a wash bath having at least 500 ppm of a composition according to at least one of the preceding claims.

10 Dicarboxylate Builders

The preferred builders referred to herein have the general formula: R-CH (C00H) CH2 (C00H), i.e. derivatives of succinic acid, wherein R is C--CQ alkyl alkyl, or alkenyl, preferably C2₂-C hvor, or wherein R can be substituted by hydroxyl, sulfo, sulfoxy or sulfonic substituents, all as described in the above-mentioned patents.

The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and all the canal ammonium salts.

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

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Dirt-releasing polymers

The dirt-releasing polymer used herein is of a very special type and has the generic formula: 30 0 0 0 0

It II II II

X- (0CH2CH2) n (0-C-R 1 -C-0R2) u (0-C-R1-C-0) (CH2CH20-) n-X

wherein X may be any end-ending group, each X being selected from the group consisting of H and all alkyl or acyl groups containing from 1 to about 5 4 carbon atoms, n is selected for water solubility, and is generally from ca. 6 to approx.

120, preferably from ca. 10 to approx. 50, and u is critical for the formulation of a relatively high ionic liquid detergent. there

DK 164115B

5 should be very little matter in which u is greater than 5. Furthermore, there should be at least 20%, preferably at least 40%, substance in which u is in the range of 3 to 5.

The R * units are essentially 1,4-phenyl units. As used herein, the term "R 2 units is essentially 1,4-phenylene units" refers to compounds wherein the P-units consist solely of 1,4-phenylene units or are partially substituted with other arylene or alkarylene units, all cooling units, alkenylene units or mixtures thereof . The arylene and alkarylene units which 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. The alkyl one and alkenylene units, which may be partially substituted, include ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1.8 -octamethylene, 1,4-cyclohexylene and mixtures thereof.

For the Purity units, the degree of partial substitution with units other than 1,4-phenylene should be such that the dirt-releasing properties of the compound are not adversely affected to any great extent. In general, the degree of tolerable partial substitution will depend on the backbone length of the compound, i.e. longer backbone may have greater partial substitution with other than 1,4-phenylene units. Usually, compounds wherein R * 50 to 25 100% 1,4-phenyl units (from 0 to about 50% units different from 1,4-phenylene), sufficient dirt-releasing activity. Eg. For example, polyesters prepared in accordance with the present invention with a 40:60 target ratio of isophthalic acid (1,3-phenylene) to terephthalic acid (1,4-phenylene) have sufficient dirt-releasing activity.

Because most polyesters used for fiber positioning include ethylene terephthalate units, it is usually desirable to minimize the degree of partial substitution with units other than 1,4-phenylene to obtain the best dirt release. activity. Preferably, the R * units consist solely of 35 (i.e., constitute 100%) of 1,4-phenyl units, i. each Purity is 1,4-phenylene. (Regardless of the mechanism of action, it is surprising that the dirt-releasing polymers truly provide excellent benefits in relation to textiles other than polyester textiles, and the compositions herein are intended for purification of all kinds

DK 164115B

6 fabrics and textiles).

ISLAND

Suitable ethylene or substituted ethyl units such as R units include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene and mixtures thereof. Preferably, the R units are substantially ethyl units, 1,2-propylene units or mixtures thereof. Inclusion of a larger percentage of ethyl units tends to improve the soothing effect of the compounds. Surprisingly, the inclusion of a greater percentage of 1,2-propylene units tends to improve the water solubility of the compounds.

The use of 1,2-propylene units or equivalent branched equivalents is, in the context of the present invention, essential for incorporating a substantial portion of the dirt-releasing compound into highly effective liquid detergent compositions.

Preferably, from ca. 75% to approx. 100%, more preferably from ca.

2 90% to approx. 100%, of the R units 1,2-propylene units.

The value of each n is at least approx. 6, but preferably at least approx. 10th

The value of each n is usually in the range of about. 12 to approx.

113. Typically, the value of each n in the range is from ca. 12 to approx.

43rd

A preferred process for preparing the preferred dirt-releasing component comprises extracting a polymer having a normal distribution, a substantial portion of which is a material in which u is greater than 6, with substantially anhydrous ethanol at low temperatures, e.g. .g. from approx. 10 ° C to approx. 15 ° C. The ethanol soluble fraction is substantially free of the longer polymers and is much easier to formulate in sootropic, powerful liquids, especially those having higher ionic strengths, e.g. with more than approx. 10% succinate builder.

Although the polymers in which u is less than ca. 3, substantially 35 being of no value in providing dirt-releasing effects, it appears that they significantly affect the overall product effect.

In particular, the anti-fat effect of compositions containing succinate builders may be suboptimal, but this effect is restored to more acceptable levels when degrading

DK 164115B

7 polymers are present.

Purifying Surfactants 5 The detergent compositions of the present invention will contain organic, surfactants ("surfactants") to provide the usual purification benefits associated with the use of these materials.

Purifying interface active agents useful in the present invention include well-known synthetic anionic agents, nonionic agents, amphoteric and zwitterionic interface active agents. Typical examples of these are all alkyl benzene sulphonates, all alkyl and alkyl ether sulphates, paraffin sulphonates, olefin sulphonates, amine oxides, α-sulphonates of fatty acids and fatty acid esters, ethoxylated alcohols and ethoxylated all alkyl phenols and the like, which are well known in the field of detergent. In general, such purifying interface actives contain an alkyl group in the Cg-Cjg range; the purifying interface active anionic agents can be used in its sodium, potassium or triethanol ammonium salt form. Standard reference works, such as McCutcheon's Index, contain detailed indications of such typical purifying surfactants. alkyl benzene sulphonates, C 1-6 paraffin sulphonates and C 1-6 alkyl sulphates are particularly preferred in compositions of the present kind.

Water-soluble soaps, e.g. the common sodium and potassium, coconut or tallow soaps well known in the art are also useful in the compositions herein.

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The purifying interface active component may comprise as little as 1% of the detergent compositions herein, but generally the compositions will contain from 5% to 40%, preferably from 6% to 30%, interface active agent. Mixtures of the anionic agents, such as all cool benzenesulfonates, all cool sulfates and paraffin sulfonates, with Cg-Cjg-ethoxylated alcohols surfactants are preferred to provide textile purification for a wide range of dirt and stains throughout the wash operation.

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Cleansing and pesticides

The compositions herein may contain other ingredients which promote the purification effect. For example, it is highly preferred that the detergent compositions of the present invention further contain enzymes for enhancing the cleaning effect against a variety of dirt types and stains throughout the washing operation. Amylase and proteinase enzymes suitable for use in detergents are well known in the art and from commercially obtainable liquid and granular detergents. Commercial purifying enzymes (preferably a mixture of methylase and protease) are typically used in the present compositions in the range of 0.001% to 2% and more.

Furthermore, the compositions of this invention, in addition to the ingredients already mentioned, may contain various other optional ingredients which are typically used in commercial products for imparting aesthetic or other additional product effect. Typical ingredients include pH regulators, perfumes, dyes, bleaches, optical whites, dirt suspending agents, hydrotropes, 20 gel control agents, freeze / thaw stabilizers, bactericides, preservatives, foam regulators, bleach activators and the like.

During the wash operation, the compositions are typically used at a concentration of at least 500 ppm, preferably from 0.10% to 2.5%, in an aqueous wash bath at pH 7-11 for washing fabrics. The wash can be performed with excellent results by moving the fabrics in the presence of the compositions at temperatures ranging from 5 ° C to the boiling point.

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Industrial Use The following examples are typical of the preferred compositions of the present invention.

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Example I

A preferred HDL has the following composition:

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Ingredient% (wt. 2-Dodecenylsuccinate 15.00

Dirt-releasing polymer * 0.50 5 Di ethylenetriamine penta (methylene phosphonate) 0.85

CaClg 0.01

Formate (Na) 0.9

Trethanolamine 5.00

NaOH ** 5.6 Ethanol 9.0

C1-6 cool benzene sulfonate 10.2

Coconut Alkyl Sulfate 3.88

Ethoxylated C13₂j5 alcohol (EOy) 11.6

Oleic Acid 3.88 15 Enzymes 0.15

Water and minor constituents to 100

Product pH_7.6 - 7.7 * 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 provide a cold ethanol solution in fraction having a U-value predominantly between 3 and 5. The average ethoxylation value (s) is between 12 and 43.

** The viscosity can be modified by replacing some of the NaOH with KOH at the composer's request. A stable, homogeneous, isotropic product is ensured.

It was discovered that the viscosity of the composition of Example I was rapidly reduced by dilution with water. This is in direct contrast to many HDLs whose viscosity increases when added to water. The rapid reduction of viscosity after the addition of water helps the HDL compositions of the present invention to avoid the problem of dispenser clogging in automatic washing machines or other detergent dispensers.

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Example II

A detergent additive product is prepared by adding up to 15 grams of lauryl succinate to 1 gram of the dirt-releasing polymer of Example 1. The mixture is filled into an elastic polyethylene bag which is sealed along one edge with a water-soluble polyvinyl alcohol adhesive. In use, the bag is simply deposited into the aqueous wash liquid with some conventional detergent to provide an additional builder and dirt-releasing action, including clay removal and particulate dirt from cotton and poly yarn textiles.

Example III

A granular detergent composition contains the following ingredients:

Ingredient% phenyl C12-alkyl benzenesulfonate 8.0 C12-C13 alcohol ethoxylate (EO 6.5) 5.0

Talgal kohol sul fat 3.0

Sodium perborate (41 °) 19.0

Mixed C ^-Cj alkenyl succinate 20.0 Sodium sulfate 40.0

NaOH / COH to a crutcher pH of 10.2

Enzyme mixture1 0.25

Dirty polymer2 0.75 TAED3 1.0 30 Water and minor constituents_Balance

Alcalase / maxatase 1: 1 (dry mix) 2

As in Example I (dry mix) 3

Jetraacetylethyl endi amine (dry mixture) 35

An aqueous crutcher-bl breath is prepared and spray dried. The enzyme mixture, the dirt-releasing polymer and the TAED bleach activator are dry blended with the resulting granules.

Claims (10)

A detergent composition comprising usual interface active cleaners and any usual cleansing aids, characterized in that it also contains: i) from 1 to 35% by weight of an all cooler or alkenyl dicarboxylate detergent builder, and ii) at least 0, 0% by weight of a dirt-releasing polymer which is an alkoxylated phthalic acid ester of the formula: 0 0 0 0 II II It II X- (OCH2CH2) n (0-C-R1-C-OR2) u (0-C-R1-C -X) where X represents hydrogen or an alkyl or acyl group of 1-4 carbon atoms; n is an integer of from 6 to 120; u is an integer of no more than 5, u being between 3 and 5 in at least 20% of the polymer, preferably at least 40%; R * represents 1,4-phenylene in at least 50% of the 20 units, and in the remainder of the units, represents a second aryl, alkarylene, alkylene, alkenylene or mixture thereof; R is ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene or a mixture thereof. Composition according to claim 1, characterized in that the dicarboxyl substituent is a C 12 C 16 alkyl or alkenyl succinate. Composition according to claim 2, characterized in that it comprises from 5 to 20% by weight of the succinate substance as a builder. 30 Composition according to claim 1, characterized in that in the formula for the dirt-releasing polymer: 0 0 0 0 II II II II X (OCH2CH2) n (O-C-R1-C-OR2) u (O-C-R1-C-O) (CH2CH2O-) nX12 represents R 1,4-phenylene, R represents 1.2 -propylene, X represents hydrogen, n is an integer of 6 to 120, u is generally an integer of 5 or less, u being between 3 and 5 in at least 20%, preferably in at least 40% of polymer. Composition according to claim 4, characterized in that it is liquid. Liquid composition according to claim 5, characterized in that it comprises from 5 to 20% by weight of a C 1-6 C 1-6 alkyl or alkenyl succinate builder. Detergent additive, characterized in that it comprises: a) a dirt-releasing polymer which is an alkoxylated phthalic acid ester as defined in point (ii) of claim 1, and b) an alkyl or alkenyl dicarboxylate builder. , where the weight ratio of builder to dirt-releasing polymer ranges from 100: 1 to 1: 100. 20 Additive according to claim 7, characterized in that it contains the dirt-releasing polymer according to claim 4 and the builder according to claim 2 in a builder-polymer weight ratio of at least 5: 1. 25 Composition according to claim 1 or additive according to claim 7, characterized in that it is releasably contained in a bag or purse or attached in a detachable manner to a sheet-shaped substrate. 30 A method for washing fabrics by movement in a wash bath having at least 500 ppm of a composition according to at least one of the preceding claims. 35