EP2992075B1 - Comb polymers as detergency boosters in detergent compositions - Google Patents

Description

The present invention relates to the use of comb polymers in textile pretreatment, in particular in textile finishing and corresponding agents. The comb polymers used according to the invention are obtainable by A) a free-radical polymerization of monoethylenically unsaturated monomers
a group A1) monoethylenically unsaturated acids and their salts and
a group A2) monoethylenically unsaturated polyethers.

Detergents and cleaners contain surfactants as indispensable ingredients for the washing and cleaning process. The surfactants as a main component influence primarily the result of the To assist the washing performance, a variety of laundry aids, such as builders to mask the water hardness, graying and color transfer inhibitors, foam regulators, bleaching agents and bleach activators in household washing and cleaning agents are already used today. Such excipients also include substances which enhance the detergency of the surfactants. Such substances are often referred to as "soil-release" agents or detergency boosters. As a rule, such substances themselves have no pronounced surfactant properties.

At the 53rd SEPAWA Congress 2006 Marie-Elise Chateau presented the detergency enhancing effect of hydrophobic polymers of acrylic acid and styrene. Also the lecture of Prof. Dr. med. B. Lindman discussed the interactions of hydrophobically modified polymers with surfactants for improved grease removal (Conference Proceedings 53 ^rd SEPAWA Congress with European Detergents Conference).

From the WO 2006/131197 A1 Hydrophobic polymers consisting of styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate are known, which show a very good dirt-removing effect especially on cotton-containing textiles.

The EP 2 065 403 A1 discloses the preparation of polymers via esterification of polyacrylic acids with end-capped polyols or amines. In general, a potential application as Builder component for hardness masking in liquid household detergents called.

The use of polyether-hydroxycarboxylate copolymers of maleic acid and itaconic acid is known from EP 1 020 485 B1 known. The increase in cleaning efficiency is achieved by inactivating hardness ions.

The improvement of the primary washing power by polymers selected from N-vinylcaprolactam, N-vinylpyrrolidone and other nitrogen-containing monomers is known from the DE 10 2011 112 777 A1 known. It has been found that certain polymers that increase the surface tension of anionic surfactant solutions improve the primary washing effect.

An improvement of the primary washing power is also in the DE 10 2011 112 778 A1 disclosed. The publication describes polymers which are derived from N, N-dimethylacrylamide for increasing the primary washing power, especially against oily and / or greasy stains.

The use of comb polymers in detergents and cleaners based on polycarboxylic acid, as a polymer backbone with polyester side chains is known from WO 2010/127809 A1 known. The comb polymers described here are characterized by a good "soil release" effect.

The soil release action of block copolymers of ethylenically unsaturated monomers and alkylene oxide, alkylene glycols, and cyclic ethers is known from US 5,156,367 WO 2003/054044 A1 known.

In the review article " Polycarboxylates - Essential and Multifunctional "by Mr. R. Ettl, et al., In Tenside, Surfactants, Detergents 46 (2009 ) are hydrophilically modified comb polymers with polyethylene side chains for use in pigment systems referred to as "superplasticizers".

Out JPH03185184 such as JP 2005 187 742 Detergents for textile pretreatment such as desizing, scouring, bleaching and soaps are disclosed which contain methoxy-PEG-methacrylate / (meth) acrylic acid copolymers.

US 5,064,563 describes the preparation of salts of maleic acid copolymers by free radical polymerization using hydrogen peroxide as the catalyst. The resulting salt is biodegradable and can be used as a builder in laundry detergents.

US 2005/0113541 discloses polymers as a builder substance in detergents containing acrylic acid, methacrylic acid, acrylic acid PEG esters and polyamine polyethers.

Out DE 10 225 794 sulfonic acid-containing copolymers are known which consist of at least one monoethylenically unsaturated carboxylic acid, at least one monomer containing sulfonic acid groups and at least one nonionic monomer are formed and should be used as an additive to detergents and cleaners.

The majority of the polymers known from this extensive prior art have the disadvantage that they have little or no effectiveness when used in textile pretreatment for washing and bleaching textile raw materials made from natural or synthetic fibers or mixtures thereof. For a subsequent dyeing process of the washed or bleached product optimum washing and cleaning performance is essential. Only by optimally pre-treated goods it is possible to achieve a uniform "level" coloration.

The process conditions in the textile pretreatment of natural or synthetic fibers or mixtures thereof are fundamentally different from the conditions of household laundry. Thus, textile finishing processes in the strongly acidic range, such as the "acid demineralization" at a pH of about 2, up to strongly alkaline processes, such as "alkaline boiling", "cold bleaching" and "pad-steam bleaching" at pH Values from 13 to 14 are performed. The treatment temperatures in the textile pretreatment also differ significantly from those which are usual in household washing. The majority of the finishing processes are carried out at approx. 95 to 100 ° C. In some countries, high-temperature bleaching at 110 ° C is favored.

In addition to the process conditions, the types of dirt are also fundamentally different from the types of household waste. In textile pretreatment, the natural must Adjacent substances such as fats, waxes and the preparations used for the production of the synthetic fibers or textile fabrics, such as knitting oils and sizes, are removed.

The object of the present invention is to overcome the disadvantages described above with regard to insufficient effectiveness for the textile pretreatment of natural or synthetic fibers or mixtures thereof. It is intended to provide polymers which effectively support surfactants and thereby enable a reduced amount of surfactants to be used for optimum washing and cleaning performance.

For the alkaline bleaching with hydrogen peroxide of raw cotton as a knitted or woven fabric, it is necessary to effectively remove the contained natural fats and waxes of the cotton, as well as the preparations used for the preparation (e.g., knitting oils, paraffins). In addition, the lime soaps formed during bleaching from the natural triglycerides are to be effectively prevented from being rebuilt. Depending on the process, the alkaline bleaching processes are carried out at pH values between 10 and 14 and temperatures between 80 and 130 ° C. The cleaning performance is checked after the bleaching process by a good and uniform hydrophilicity (absorbency) of the cotton. The invention is therefore based, in particular, on the problem of providing polymers having an excellent washing-power-enhancing effect under these conditions.

Another object is for the washing of elastane-containing materials (mesh or woven fabric) a polymer which effectively removes the silicone oil used for production and stably emulsifies in the washing solution.

Surprisingly, it has been found that the effect of surfactants for textile pretreatment can be significantly increased with hydrophilic comb polymers which were hitherto used as concrete plasticizers, so-called "superplasticizers". The polymers used according to the invention enhance the cleaning performance of the surfactants used in relation to increasing the soil release (primary washing action) and reducing the re-use of the detached soil (secondary washing effect) by stabilizing the soil in the wash liquor.

• A) eine radikalische Polymerisation von monoethylenisch ungesättigten Monomeren
  einer Gruppe A1) monoethylenisch ungesättigter Säuren oder deren Salzen und
  einer Gruppe A2) monoethylenisch ungesättigter Polyether in der textilen Vorbehandlung.

The invention in a first embodiment is therefore the use of comb polymers obtainable by

• A) a radical polymerization of monoethylenically unsaturated monomers
  a group A1) monoethylenically unsaturated acids or their salts and
  a group A2) monoethylenically unsaturated polyethers in the textile pretreatment.

The comb polymers used according to the invention thus contain the components A1 + A2 in the first embodiment.

The preparation of the comb polymers used according to the invention via free-radical polymerization is known to the person skilled in the art and can be based on EP 0 537 870 A1 be performed.

Examples of the monomers of group A1, the monoethylenically unsaturated acids and their salts include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Vinylphosphonic. The monomers of group A1 can be used individually or as a mixture of different monomers in an amount of 5 to 95 wt .-%, in particular with an amount of 10 to 90 wt .-% based on the polymer. Preference is given to acrylic acid, methacrylic acid and maleic acid and particular preference is given to acrylic acid or methacrylic acid.

Examples of the monomers of the group A2, the monoethylenically unsaturated polyethers include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether; these are commercially available, for example, from Clariant under the Polyglykol® A product line and from BASF under the Pluriol® A ... R product line. Further examples include polyethylene glycol monovinyl ether (product series from Clariant: Polyglycol® R), isoprenyl ethoxylates (product series from BASF: Pluriol® A ... I) and vinyloxybutyl ethoxylates (product series from BASF: Pluriol® A ... V).

The monomers of group A2 can be used individually or as a mixture of different monomers in an amount of from 2 to 25% by weight, based on the polymer, in particular in an amount of from 5 to 20% by weight, based on the polymer. Polyalkyl glycol monoallyl ethers are preferred, and polyethylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether are particularly preferred.

The use according to the invention can be carried out as part of a washing, decoction, enzyme, desizing, demineralization or bleaching process in a continuous or discontinuous production process such that the comb polymer is added separately to a detergent-containing liquor, or the comb polymer as a constituent of the detergent in bring in the fleet. Another object of the invention is therefore a detergent for the textile pretreatment of natural or synthetic fibers or mixtures thereof, which contains 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-%, of a corresponding comb polymer.

Detergents containing the comb polymer used in the invention may contain all the usual ingredients of such agents which do not undesirably interact with it.

In a preferred embodiment, such a detergent contains surfactants, such as fatty alcohol alkoxylates, fatty acid alkoxylates, fatty alkyl polyglycosides, fatty amine alkoxylates and / or fatty acid amides from the field of nonionic surfactants. From the field of anionic surfactants, it is possible to use alkylcarboxylates, alkyl ether carboxylates, alkane sulfates, alkane ether sulfates, alkane sulfonates, alkyl phosphates, alkyl ether phosphates, taurides and / or sarcosides.

• ▪ Enzyme, beispielsweise Amylasen, Cellulasen, Lipasen, Pektinasen, Laccasen und Proteasen
• ▪ Bleichaktivatoren und/oder Bleichkatalysatoren
• ▪ Komplexbildner für Schwermetalle, beispielsweise Polyphosphonsäuren, Aminophosphonsäuren, Phosphonopolycarbonsäuren, Aminopolycarbonsäuren und/oder Hydroxycarbonsäuren
• ▪ Farbübertragungsinhibitoren, beispielsweise Polyvinylpyrrolidon, Copolymere aus Vinylpyrrolidon und Vinylimidazol oder Polyvinylpyridin-N-oxid
• ▪ Entlüftungs- und/oder Schaumdämpfungsmittel, beispielsweise Organopolysiloxane
• ▪ Anorganische Magnesium-Salze, beispielsweise Magnesiumsulfat, Magnesiumchlorid oder Magnesiumoxid
• ▪ Anorganische Builder-Substanzen, beispielsweise Wasserglas, Schichtsilikate oder Zeolithe
• ▪ Lösungsmittel und/oder Lösungsvermittler, beispielsweise Dipropylenglykolmonomethylether, Butyldiglycol, Butyltriglycol und/oder weitere niedere Glycole und abgeleitete Ether daraus.
• ▪ Optische Aufheller, beispielsweise Stilbenderivate enthalten.

In addition, the agents may contain other ingredients commonly used in detergents and cleaners, such as

• ▪ Enzymes, for example amylases, cellulases, lipases, pectinases, laccases and proteases
• ▪ bleach activators and / or bleach catalysts
• Complexing agents for heavy metals, for example polyphosphonic acids, aminophosphonic acids, phosphonopolycarboxylic acids, aminopolycarboxylic acids and / or hydroxycarboxylic acids
• ▪ Color transfer inhibitors, for example polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinylimidazole or polyvinylpyridine N-oxide
• ▪ deaerating and / or foam-damping agents, for example organopolysiloxanes
• Inorganic magnesium salts, for example magnesium sulfate, magnesium chloride or magnesium oxide
• ▪ Inorganic builder substances, such as water glass, phyllosilicates or zeolites
• Solvents and / or solubilizers, for example dipropylene glycol monomethyl ether, butyl diglycol, butyl triglycol and / or further lower glycols and derived ethers thereof.
• ▪ Optical brighteners, such as stilbene derivatives.

The following examples illustrate the advantages of the claimed comb polymers

EXAMPLES 1. Preparation of comb polymers: Synthetic Example 1 (Radical Polymerization):

In a 2-liter four-necked flask equipped with thermometer, reflux condenser and feed and inert gas purge ports were added 328 g of water, 61 g (0.06 mol) of polyalkylene glycol 1000 monoallyl ether (Polyglycol® A 31/1000, Clariant) and 5 g Butyl diglycol, as a solubilizer submitted. Separately, the following mixtures were prepared: Monomer solution: 365 g (5.07 mol) of acrylic acid in 65 g of water. Solution 1: 10 g of sodium persulfate in 80 g of water. Solution 2: 26 g of sodium hypophosphite x 1 H ₂ O in 60 g of water. The original was heated to 90 ° C. At this temperature, the above solutions were added via separate feeds with a constant mass flow over 3 hours (monomer and solution 2) and over 3.5 hours (solution 1). added. After the end of addition, the reaction was continued at 90 ° C. for 1 hour. A clear, colorless, aqueous polymer solution having a solids content of 46% by weight was obtained.

In an analogous manner, the comb polymers listed in Table 1 were prepared. Table 1: comb polymer Monoethylenically unsaturated polyethers Quantity [g] Monoethylenically unsaturated acid Quantity [g] KP-1 Polyglycol® A 31/1000 61 acrylic acid 365 KP-2 Polyglycol® A 11/1800 61 acrylic acid 365 KP-3 Pluriol® A 10 R 61 acrylic acid 365 KP-4 Polyglycol® A 1100 61 acrylic acid 365

In all the examples according to the invention, the content of residual monomer for the side chains was determined semiquantitatively by thin-layer chromatography. The residual monomer results were always below 0.5% by weight in the polymer solution.

2. Application comb polymers Use Example 1: (Discontinuous bleaching at 98 ° C)

A raw cotton jersey knit fabric with a base white of 17 Berger units was bleached in a Labomat from Mathis for 30 minutes at 98 ° C. The liquor ratio was 1:10 and the water used had a set water hardness of 5 ° dH, adjusted with CaCl ₂ × 2 H ₂ O. The heating or cooling gradient was 3 ° C / min. Subsequently, the product was rinsed for 10 min at 80 ° C, then neutralized with 0.5 g / L acetic acid 60% for 10 min at 30 ° C and rinsed once more for 10 min at 30 ° C. At the end, the product was spun for 30 seconds and dried for 30 seconds at a surface temperature of 120 ° C in the tenter. The bleaching formulations are shown in Table 4.1 and the associated whiteness and absorbency results for the product in Table 4.2.

The absorbency, also referred to as hydrophilicity, the product is dependent on the cleaning performance of the detergent used. It is tested using the TEGEWA Drip Test, which measures the amount of time a stained drop of water needs to sink into the fabric. The exact description is in the Journal Melliand Textilberichte 68 (1987), pages 581-583 released. A better differentiating method is the determination of absorbency according to the riser method according to DIN 53924.

The surfactants used were Lutensol® AO 5 and Lutensol® AO 7 from BASF, C _13/15 fatty alcohol ethoxylates with 5 or 7 mol of ethylene oxide. The comb polymers were used as polymer solutions with a solids content of 46% by weight. As comparison polymer V-1 was Sokalan® PA 25 CL PN from BASF, an acrylic acid homopolymer having an average molecular weight of 4,000 g / mol and a solids content of 49% by weight and Comparative Polymer V-2 was Alcosperse® 747 from Akzo Nobel, a hydrophobically modified copolymer having an average molecular weight of 3,000 g / mol and a solids content of 40 wt .-% used. Table 4.1: Bleichrepturen number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 Lutensol® AO 5 g / L 0.6 0.7 0.8 KP-1 g / L 0.06 KP-2 g / L 0.06 KP-3 g / L 0.06 KP-4 g / L 0.06 V-1 g / L 0.06 V-2 g / L 0.06 NaOH 50% g / L 2.0 H ₂ O ₂ 35% g / L 2.3 Blefchrezepturen No. 10 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 Lutensol® AO 7 g / L 0.6 0.7 0.8 KP-1 g / L 0.06 KP-2 g / L 0.06 KP-3 g / L 0.06 KP-4 g / L 0.06 V-1 g / L 0.06 V-2 g / L 0.06 NaOH 50% g / L 2.0 H ₂ O ₂ 35% g / L 2.3 bleaching results number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 basic White [Berger] 64 66 66 67 65 64 63 65 65 drop test [Sec] 35 2 3 2 1 25 40 20 2 Climbing height after 30 sec [Mm] 0 6 3 4 9 1 0 2 11 60 sec [Mm] 0 11 5 8th 19 3 0 4 20 90 sec [Mm] 3 21 10 15 28 5 2 8th 29 300 sec [Mm] 8th 41 25 30 47 14 5 18 48 bleaching results No. 10 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 basic White [Berger] 65 67 67 66 66 65 63 66 67 drop test [Sec] 55 6 5 6 4 35 72 30 6 rising height to 30 sec [Mm] 0 2 3 4 5 0 0 0 5 60 sec [Mm] 0 8th 8th 9 10 0 0 2 12 90 sec [Mm] 1 13 14 16 17 3 0 5 18 300 sec [Mm] 5 25 25 26 28 7 3 10 30

Application example 2: (discontinuous bleaching at 110 ° C.)

Following Example of Use 1, the bleaching temperature was increased to 110 ° C and the bleaching time was shortened to 10 minutes. Rinsing, neutralization and drying processes were maintained. The bleach formulas are listed in Table 5.1 and the associated whiteness and absorbency results are shown in Table 5.2. Table 5.1: bleach recipes number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 Lutensol AO® 5 g / L 0.5 0.6 0.7 KP-1 g / L 0.05 KP-2 g / L 0.05 CP-3 g / L 0.05 KP-4 g / L 0.05 V-1 g / L 0.05 V-2 g / L 0.05 NaOH 50% g / L 3.0 H ₂ O ₂ 35% g / L 2.0 Bleic results number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 basic White [Mountain he] 69 70 71 70 72 69 68 71 72 drop test [Sec] 5 2 1 2 1 4 10 2 1 Climbing height after 30 sec [Mm] 16 31 32 30 33 25 12 28 34 60 sec [Mm] 18 38 38 35 39 30 15 34 40 90 sec [Mm] 20 42 40 38 42 34 18 38 43 300 sec [Mm] 27 59 59 55 61 45 24 50 61

Use Example 3: (Cold bleaching at 30 ° C.)

A raw cotton terry cloth with a base white of 21 Berger units was padded with a liquor pick-up of 100% and then dwelt for 20 hours at 30 ° C. Subsequently, the product was rinsed twice for 10 min at 95 ° C, then once for 10 min at 80 ° C and finally neutralized with 2 mL / kg of acetic acid 60% for 10 min at 30 ° C. After the rinsing processes, the product was spun for 30 seconds and dried for 30 seconds at a surface temperature of 120 ° C. in the tenter. The bleaching formulations and the associated whiteness and absorbency results of the product are shown in Table 6. Table 6: bleach recipes number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 Lutensol® AO 7 g / L 1.2 1.8 2.4 1.2 1.8 2.4 1.2 1.8 2.4 KP-4 g / L 0.048 0.072 0.096 V-1 g / L 0.048 0.072 0.096 NaOH 50% g / L 60 H ₂ O ₂ 35% g / L 100 bleaching results number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 basic White [Berger] 61 63 66 63 65 67 62 63 66 drop test [Sec] > 300 12 1 12 3 1 130 10 1

From the results of Examples 1 to 3, the significant washing power enhancing effect of the comb polymers can be clearly seen. By using the comb polymers, a savings of> 20% can be realized compared to a use of pure surfactant. Due to the small amount of comb polymers used, the costs can be significantly reduced.

Claims (7)

1. Use of comb polymers obtainable by free-radical polymerization of monoethylenically unsaturated monomers of a group A1) of monoethylenically unsaturated acids and salts thereof; and
   a group A2) of monoethylenically unsaturated polyethers
   in textile pretreatment.
2. The use according to claim 1 for enhancing the cleaning performance of detergents in textile pretreatment.
3. The use according to claim 1 or 2 for enhancing the cleaning performance in textile finishing, especially in washing, kier boiling, enzyme, desizing, demineralizing or bleaching process in a continuous or discontinuous process.
4. The use according to claim 2 or 3, characterized in that textiles made from natural or synthetic fibers or mixtures thereof are employed.
5. A detergent for textile pretreatment of natural or synthetic fibers or mixtures thereof, characterized by containing from 0.1 to 20% by weight, especially from 0.5 to 15% by weight, of the detergency-boosting comb polymer as defined in claim 1.
6. The detergent according to claim 5, characterized in that it further contains a surfactant ingredient, and said surfactant ingredient is selected from non-ionogenic and anionic surfactants.
7. The detergent according to either of claims 5 or 6, characterized by containing a complexing agent ingredient selected from phosphonic acids, especially HEDP, ATMP and/or DTPMP, phosphonopolycarboxylic acids, especially PBTC, aminopolycarboxylic acids, especially MGDA, GLDA, IDS and/or EDDS, and/or hydroxycarboxylic acids, especially gluconic acid and/or citric acid.