EP2992075A1 - Comb polymers as detergency boosters for washing and cleaning agents - Google Patents

Abstract

The invention relates to the use of comb polymers in washing and cleaning agents, in particular in textile finishing, and corresponding means. The comb polymers used according to the invention can be obtained by A) a radical polymerization of monoethylenic unsaturated monomers of a group A1) monoethylenic unsaturated acids and salts thereof and a group A2) monoethylenic unsaturated polyether and/or a group A3) monoethylenic unsaturated acids, which were previously esterified with unilaterally terminally hydrophobically blocked polyalkylene-oxides, or by B) a polymeric analogous conversion by esterification and/or amidation of a group B1) polycarboxylic acids and salts thereof with a group B2) monohydroxypolyethers and/or a group B3) monoamine compounds.

Description

 Comb polymers as detergency booster for washing and

 cleaning supplies

The present invention relates to the use of comb polymers in detergents and cleaners, in particular in textile finishing and corresponding agents. The comb polymers used according to the invention are obtainable by

 A) a radical polymerization of monoethylenically unsaturated monomers

a group AI) monoethylenically unsaturated acids and their salts and

a group A2) monoethylenically unsaturated polyethers and / or a group A3) of monoethylenically unsaturated acids which have been previously esterified with polyalkylene oxides which have been terminally hydrophobically blocked on one side, or

 B) a polymer-analogous reaction by esterification and / or amidation

a group Bl) polycarboxylic acids and their salts

With

a group B2) monohydroxypolyethers and / or a group B3) monoamine compounds. Detergents and cleaners contain surfactants as indispensable ingredients for the washing and cleaning process. The surfactants as the main component influence primarily the result of the washing process and also represent the largest cost block of the ingredients. To support the washing performance, today already a variety of washing aids, such as builders to mask the water hardness, graying and

Color transfer inhibitors, foam regulators, bleaching agents and bleach activators used in household detergents and cleaners. 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 WO 2006/131197 Al hydrophobic polymers consisting of styrene, methacrylic acid, hydroxyethyl methacrylate and

Methyl methacrylate known that show a very good dirt-removing effect especially on cotton-containing textiles. EP 2 065 403 A1 discloses the preparation of polymers via esterification of polyacrylic acids with end-capped polyols or amines. In general, one possible application is mentioned as a builder component for hardness masking in liquid household detergents.

The use of polyether-hydroxycarboxylate copolymers of maleic acid and itaconic acid is known from EP 1 020 485 B1. 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 DE 10 2011 112 777 AI. 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 Primärwaschkraft is also disclosed in DE 10 2011 112 778 AI. 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 AI. 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 WO 2003/054044 Al.

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

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. Also the treatment temperatures in the textile pretreatment differ significantly from the temperatures that are common in household linen. 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 the textile pretreatment, the natural accompanying 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 must be 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 mesh or woven fabric, it is necessary to effectively remove the contained natural fats and waxes of cotton, as well as the preparations used for the preparation (eg 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 tested after the bleaching process on a good and uniform hydrophilicity (absorbency) of cotton. The invention is therefore in particular the object of providing polymers with excellent under these conditions washing power enhancing effect.

A further object is to provide for the washing of elastane-containing materials (mesh or woven fabric) a polymer which effectively removes the silicone oil used for the preparation 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.

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 AI) monoethylenically unsaturated acids or their salts and

a group A2) monoethylenically unsaturated polyethers and / or the group A3) of monoethylenically unsaturated acids, which were previously esterified with one-sided terminal hydrophobic blocked polyalkylene oxides.

A second embodiment of the invention relates to the use of comb polymers

a group B) obtainable by a polymer-analogous reaction

Esterification and / or amidation of polymers

a group B1) polycarboxylic acids or salts thereof with a group B2) monohydroxypolyethers and / or a group B3) monoamine compounds in detergents and cleaners.

Thus, in the first embodiment, the comb polymers used according to the invention contain the components Al + A2 or Al + A3 or Al + A2 + A3 but not the combination A2 + A3 without Al. In the second embodiment, the components Bl + B2 or Bl + B3 or Bl + B2 + B3 are basically included, but not the combination B2 + B3 without Bl, wherein the combination Bl + B2 or Bl + B3 are preferred.

The preparation of the comb polymers of group A according to the invention via radical polymerization is known to the person skilled in the art and can be carried out on the basis of EP 0 537 870 A1. In that regard, full reference is made to this publication.

The preparation of the comb polymers of the group B used according to the invention via polymer-analogous reaction is likewise known to the person skilled in the art and can be performed on the basis of EP 2 065 403. In that regard, full reference is made to this publication.

Examples of the monomers of the group AI, 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 acid. The monomers of group AI 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 group A2, the monoethylenically unsaturated polyethers include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether and polyethylene

Polypropylenmonoallylether; these are commercially available, for example from the company Clariant under the product number A and polyglycol ^® by the company BASF under the product number Pluriol ^® A ... R. Further examples include Polyethylenglycolmonovinylether (Clariant range: polyglycol ^® R) Isoprenylethoxilate (product series from BASF: Pluriol ^® A ... I) and Vinyloxybutylethoxilate (product range of the company 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 be used on the polymer. Polyalkyl glycol monoallyl ethers are preferred, polyethylene glycol monoallyl ether and polyethylene are particularly preferred

Polypropylenmonoallylether.

Examples of the monomers of group A3, the monoethylenically unsaturated acids, which have previously been esterified with one-sided terminally hydrophobic blocked polyalkylene oxides include methoxy polyethylene glycol methacrylate and methyacrylate Methoxypolyalkylenglycol-, these are, for example, by the company Clariant under the product number polyglycol ^® MA or Genagen ^® M 5000 MA from Evonik under the product number Visiomer ^® MPEG and Sartomer commercially available. Preference is given to methoxy polyethylene glycol methacrylate. The monomers of group A3 are used in an amount of from 0 to 25% by weight, based on the polymer, more preferably in an amount of from 0 to 10% by weight, based on the polymer.

Polymers of the group Bl, the polycarboxylic acids and their salts may include polyacrylic acids, polymethacrylic acids, copolymers of acrylic acid and methacrylic acid or copolymers of acrylic acid and maleic acid. In a preferred embodiment, polycarboxylic acids having a molecular weight M _{w of} from 1,000 to 100,000 g / mol, in particular from 1,500 to 80,000 g / mol, preferably from 2,000 to 70,000 g / mol are used. Suitable polycarboxylic acids are commercially available and are offered, for example, by BASF under the trade name "Sokalan ^®". Group B2 polymers, the monohydroxypolyethers, may include unilatered end-capped polyoxyalkylenes. Examples of such monohydroxypolyethers are monomethoxy-polyethylene glycol, monomethoxy-polypropylene glycol, monomethoxy-polyethylene-polypropylene glycol, monobutoxy-polyethylene glycol, monobutoxy-polypropylene glycol, monobutoxy-polyethylene-polypropylene glycol. Suitable monohydroxy polyethers are commercially available and are offered, for example, by the company BASF under the trade designation "Pluriol ^®" or by the company Clariant under the trade designation "polyglycol ^®". The amount of monohydroxypolyether used is adjusted to achieve the desired degree of esterification of the base polymer. Of all carboxy groups present in the base polymer, 0.1 to 25 mol%, more preferably 0.5 to 20 mol%, are preferably esterified.

Group B3 polymers, the monoamine compounds may include end-capped amino-polyoxyalkylenes. Examples of such monoamine compounds include α-methoxy-ω-amino-polyoxyalkylenes, which are offered for example by Huntsman under the trade name "Jeffamine ^® ". The amount of the monoamine compound (s) used is adjusted to achieve the desired degree of amidation of the base polymer. Of all carboxy groups present in the base polymer, 0.01 to 4 mol%, particularly preferably 0.02 to 2 mol%, are preferably amidated.

The use according to the invention can be carried out as part of a washing, decoction, enzyme, desizing, demineralizing or Bleaching process in a continuous or discontinuous production process carried out in such a way that one adds the comb polymer separately to a detergent-containing liquor, or introduces the comb polymer as part of the detergent in the liquor. Another object of the invention is therefore a detergent for textile finishing containing 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.

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 agent for heavy metals, for example

Polyphosphonic acids, aminophosphonic acids,

Phosphonopolycarboxylic acids, aminopolycarboxylic acids and / or

hydroxy 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, for example water glass, sheet silicates or zeolites

 Solvents and / or solubilizers, for example dipropylene glycol monomethyl ether, butyl diglycol, butyl triglycol and / or other lower glycols and derived ethers thereof. Optical brighteners, for example stilbene derivatives

 contain.

The following examples illustrate the advantages of the claimed comb polymers

EXEMPLARY EMBODIMENTS:

1. Preparation of comb polymers:

Synthetic Example 1 (Radical Polymerization):

In a 2-liter four-necked flask equipped with thermometer, reflux condenser and connections for inlets and inert gas purge, 328 g water, 61 g (0.06 mol) of polyalkylene glycol Looo 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 solutions listed above via separate feeds with a constant mass flow over 3 hours (monomer and solution 2) and over 3.5 h (solution 1) were 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 :

Synthetic Example 2 (Radical Polymerization):

In a 2-liter four-necked flask equipped with thermometer, reflux condenser and connections for feeds and inert gas flushing 328 g of water and 5 g of butyl diglycol (solubilizer) were submitted. Separately, the following mixtures were prepared: Monomer solution: 365 g (5.07 mol) of acrylic acid, 61 g (0.08 mol) of methoxy-polyethylene glycol-750 methacrylate (MPEG 750 MA Visiomer ^® W, Evonik) 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 solutions listed above via separate feeds with a constant mass flow over 3 hours (monomer and solution 2) and over 3.5 h (solution 1) were 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 2 were prepared.

Table 2:

 methoxy

Polyalkylene glycol ester amount monoethylenic amount

comb polymer

 of monoethylenically [g] unsaturated acid [g] unsaturated acids

Visiomer ^® MPEG

 KP-5 61 acrylic acid 365

 750 MA W

Polyglycol ^® MA 1000/70

 KP-6 87 acrylic acid 365

 (70% in water)

Visiomer ^® MPEG

 KP-7 2005 MA W 122 acrylic acid 365

(50% in water) Synthesis Example 3 (Polymer Analog Reaction):

In a 1-liter three-necked flask with stirrer, thermometer, and vacuum distillation unit 500 g of aqueous 49% strength by weight polyacrylic acid (Sokalan ^® PA 25 XS, BASF) having an average molecular weight of 5,000 (about 3.5 mol of carboxylic acid groups) were charged. To this was added 100 g (0.1 mol) of methoxy polyethylene glycol-1000 (polyglycol ^® M 1000, Clariant) and 9.2 g sulfuric acid 37% was added. Subsequently, the reaction mixture was heated to 175 ° C and stirred for 30 minutes at this temperature. Subsequently, the reaction was continued at a vacuum of 100 mbar to the desired degree of conversion and the resulting water of reaction was distilled off. After the desired degree of conversion was achieved, the resulting comb polymer was cooled and diluted with water to a solids content of 40% by weight. A clear, yellowish, aqueous polymer solution was obtained.

In an analogous manner, the comb polymers listed in Table 3 were prepared.

Table 3:

 Quantity quantity

Comb polymer monohydroxypolyether polycarboxylic acid

 [g] [g]

KP-8 polyglycol ^® M 1000 100 Sokalan ^® PA 25 XS 500

KP-9 M 2000 FL polyglycol ^® 100 Sokalan ^® PA 25 XS 500

KP-10 Pluriol® ^® A 3010 E 100 Sokalan ^® PA 25 XS 500 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 published in the journal Melliand Textilberichte 68 (1987), pages 581-583. A better one The differentiating method is the determination of the absorbency according to the rise height method according to DIN 53924.

Suitable surfactants Lutensol ^® AO 5 and Lutensol ^® AO 7 BASF, Ci3 / i5-fatty alcohol ethoxylates with 5 or 7 moles of ethylene oxide was used. The comb polymers were used as polymer solutions having a solids content of 46% by weight and 40% by weight, respectively, for KP-8. As a comparative polymer Vl 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 wt .-%, and as a comparison polymer V-2 Alcosperse ^® 747 from Akzo Nobel , a hydrophobically modified copolymer having an average molecular weight of 3,000 g / mol and a solid content of 40 wt .-% used.

Table 4.1:

KP-2 g / L 0.06

 KP-3 g / L 0.06

 ΚΡ-4 g / L 0.06

 ΚΡ-5 g / L 0.06

 ΚΡ-8 g / L 0.06

 V-1 g / L 0.06

 V-2 g / L 0.06

 NaOH 50% g / L 2.0

Η ₂ 0 ₂ 35% g / L 2,3

Table 4.2:

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 bleaching formulations are in Table 5.1 and the associated results in terms of whiteness and absorbency of the product, see Table 5.2.

Table 5.1:

Table 5.2:

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 at 30 ° C for 20 hours. 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 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:

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

claims 1. Use of comb polymers obtainable by  A) a radical polymerization of monoethylenically unsaturated monomers a group AI) monoethylenically unsaturated acids and their salts and a group A2) monoethylenically unsaturated polyethers and / or a group A3) of monoethylenically unsaturated acids which have been previously esterified with polyalkylene oxides which have been terminally hydrophobically blocked on one side, or  B) a polymer-analogous reaction by esterification and / or amidation a group Bl) polycarboxylic acids and their salts with a group B2) monohydroxypolyethers and / or a group B3) Monoamine compounds in detergents and cleaners. 2. Use according to claim 1 for enhancing the cleaning performance of detergents in the washing of textiles. 3. Use according to claim 1 or 2 for enhancing the cleaning performance in textile finishing, in particular in washing, Abkoch-, enzyme, desizing, demineralization or bleaching processes in a continuous or discontinuous procedure. 4. Use according to claim 2 or 3, characterized in that one uses textiles of natural or synthetic fibers or mixtures thereof. 5. Detergent for textile finishing, containing a comb polymer according to claim 1. 6. Detergent according to claim 5, characterized in that it contains 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-% of the laundry-boosting comb polymer. 7. Detergent according to claim 5 or 6, characterized in that the surfactant component is selected from nonionic and anionic surfactants. 8. Detergent according to one of claims 5 to 7, characterized in that it as a complexing agent component of phosphonic acids, in particular HEDP, ATMP and / or DTPMP, phosphonopolycarboxylic acids, in particular PBTC, aminopolycarboxylic acids, in particular MGDA, GLDA, IDS and / or EDDS and / or hydroxycarboxylic acids, in particular gluconic acid and / or citric acid.