EP2408895B1 - Use of polymers comprising carboxyl groups in combination with bivalent cations for creating a protective layer - Google Patents

Description

The present invention relates to the use of polymers having carboxyl groups in combination with divalent cations for forming a protective layer on textile fabrics and textile treatment agents, in particular detergents and cleaners containing such polymers in a suitable dosage form to allow the formation of a protective layer on textile fabrics.

In addition to the desire to effectively remove soiling of textiles, another approach to providing clean laundry is to prevent the buildup of dirt on the fabrics. For this purpose, polymers are already described which have dirt-repellent properties, so-called "soil release" or "soil repellency" polymers.

This is especially true in US4007305 In this sense, the finishing of textiles with an alkaline aqueous solution comprising fluorinated chemicals, water-soluble polyvinylpyrrolidone and polymers having carboxyl groups is disclosed.
In US3993830 discloses the improved deposition of soil-release (meth) acrylate copolymers from dilute solution by the addition of salts of polyvalent cations.
In WO03 / 040279 the use of substituted polysaccharides to furnish textiles is disclosed.

According to the invention, it has now surprisingly been found that by using polymers with carboxyl groups in combination with divalent cations an extremely effective protective layer can be formed on textile fabrics.

1. a) Polymere mit Carboxylgruppen in einer Konzentration von 1 bis 10 Gew.-%, besonders bevorzugt 2 bis 4 Gew.-%,
2. b) zweiwertige Kationen in einer Konzentration von 0,001 bis 1,0 Gew.-%, besonders bevorzugt 0,005 bis 0,5 Gew.-%, vor allem 0,01 bis 0,1 Gew.-%.

wobei mindestens 20 % der Monomer-Einheiten des Polymers Carboxylgruppen tragen, es sich bei dem Polymer um ein Polysaccharid handelt und mindestens 20 % der Monomer-Einheiten des Polysaccharids Uronsäuren sind.A first subject of the present invention are therefore textile treatment agents, in particular detergents and cleaners, containing polymers with carboxyl groups and divalent cations. A textile treatment agent according to the invention preferably contains in this case

1. a) polymers with carboxyl groups in a concentration of 1 to 10 wt .-%, particularly preferably 2 to 4 wt .-%,
2. b) divalent cations in a concentration of 0.001 to 1.0 wt .-%, particularly preferably 0.005 to 0.5 wt .-%, especially 0.01 to 0.1 wt .-%.

wherein at least 20% of the monomer units of the polymer carry carboxyl groups, the polymer is a polysaccharide and at least 20% of the monomer units of the polysaccharide are uronic acids.

Another object of the present invention is therefore the use of said polymers with carboxyl groups in combination with divalent cations or the use of a textile treatment agent according to the invention for finishing textile fabrics.

Another object of the present invention is therefore in particular also the use of said polymers with carboxyl groups in combination with divalent cations or the use of a textile treatment agent according to the invention for forming a protective layer on textile fabrics. In this case, the protective layer is preferably suitable for at least partially keeping soiling away from the textile fabric, as these are deposited on the protective layer.

The present invention therefore also provides a process for finishing textile fabrics, characterized in that the textile fabrics are treated with a combination of said polymers with carboxyl groups and divalent cations or with a textile treatment agent according to the invention, this treatment being carried out both in one process step and in one can be carried out in successive steps. Thus, for example, first a treatment with said polymers and then a treatment with the divalent cations, or conversely first a treatment with the divalent cations and then a treatment with the said polymers. In a preferred embodiment, however, a treatment with the said polymers as well as with the divalent cations takes place at the same time.

In a particularly preferred embodiment according to the invention, at least one of the components selected from said polymers with carboxyl groups and divalent cations in the fabric softening cycle of the textile washing and the addition of the other component either likewise in the fabric conditioning cycle or in the preceding washing step of the textile washing. In this case, either the addition of the said polymers with carboxyl groups or the addition of the divalent cations in the fabric rinse cycle or else the addition of the divalent cations preferably takes place in the fabric rinse cycle and the addition of said polymers with carboxyl groups takes place in the preceding washing step.

Another object of the present invention is the use of said polymers having carboxyl groups in combination with divalent cations or the use of a textile treatment agent according to the invention for removing stains from fabrics and / or for preventing the formation of stains on flat textile fabrics. The stains are hereby preferably selected from oily and greasy stains, in particular engine oil, edible fat, lipstick or make-up.

The present invention therefore also provides a process for removing soils from textile fabrics and / or for preventing the formation of stains on textile fabrics, characterized in that the fabrics are treated with a combination of said polymers with carboxyl groups and divalent cations, this treatment can take place both in one process step and in successive process steps. Again, the stains are preferably selected from oil and greasy stains, especially motor oil, edible fat, lipstick or make-up.

It is accordingly the polymer is a polysaccharide, wherein at least 20%, in particular at least 30, 40 or 50%, more preferably at least 60, 70 or 80%, especially at least 90 or 95% of the monomer units of the polysaccharide Uronic acids, in particular hexuronic acids represent, wherein the uronic acids are preferably selected from glucuronic acid, galacturonic acid, guluronic acid, iduronic acid and mannuronic acid.

Furthermore, the polymer having carboxyl groups preferably has a molecular weight of 1,000 to 500,000 g / mol, more preferably 10,000 to 200,000 g / mol.

The carboxyl groups of polymers according to the invention may also be partially esterified with alcohols, in particular C _1-6 -alkanols.

In a particularly preferred embodiment, the polymer having carboxyl groups selected from the polysaccharides alginate, pectin, Glucosaminoglucanen, in particular hyaluronic acid or heparin, tragacanth, gum arabic, Teichuronsäuren and carboxymethyl cellulose, with alginate and pectin are particularly preferred.

The polymer to be used according to the invention is used in a preferred embodiment in the form of a water-soluble salt, in particular as sodium, potassium or ammonium salt.

The polymer having carboxyl groups is used in accordance with the invention in an amount of 1 to 10% by weight, more preferably 2 to 4% by weight

The divalent cations according to the invention are preferably selected from Ca (II), Mg (II), Fe (II) and Zn (II). Particular preference is given to using Ca (II).

The divalent cations can be used in any soluble salt form, especially in the form of an inorganic or organic salt. Preference is given to using halides, in particular fluorides, chlorides or bromides, nitrates or sulfates.

The divalent cations according to the invention preferably in an amount of 0.001 to 1.0 wt .-%, in particular in an amount of 0.005 to 0.5 wt .-%, particularly preferably in an amount of 0.01 to 0.1 wt. -% used.

The equipment of the textiles or the washing process is preferably carried out at a temperature of 20 to 60 ° C, more preferably at a temperature of 20 to 40 ° C.

The textile treatment or the washing process is preferably carried out at a pH of 6 to 11, more preferably at a pH of 7.5 to 9.5.

The textile treatment agent according to the invention can be present in any desired dosage form. It may be, for example, powdered, liquid or gel. In a preferred embodiment it is liquid or of gel-like consistency. The said polymers with Carboxyl groups and the divalent cations are preferably present in dissolved form in the liquid or gel textile treatment agent.

In a particularly preferred embodiment, the textile treatment agent according to the invention is a washing or cleaning agent.

Detergents and cleaners

A washing or cleaning agent according to the invention and in particular a laundry detergent according to the invention may contain further washing or cleaning active ingredients, for example surfactants, especially anionic, nonionic, cationic and / or amphoteric surfactants, geroststoffe, especially inorganic and organic Bulldersubstanzen, cleaning active polymers (for example those with Cobuildereigenschaften ), Foam inhibitors, dyes, fragrances (perfumes), bleaching agents (such as peroxy bleach or chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, enzyme stabilizers, grayness inhibitors, optical brighteners, UV absorbers, desired repellents or soil release agents. Polymers, binding and disintegrating agents, electrolytes, non-aqueous solvents, pH adjusters, perfume carriers, fluorescers, thickeners, hydrotropes, silicone oils, anti-shrinkage agents, anti-wrinkling agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, fabric softening components, in particular esterquats, heavy metal complexing agents, abrasives, fillers and / or blowing agents.

With regard to inventively preferably employable builders (builders), surfactants, fabric softening components, in particular esterquats, polymers, bleaches, bleach activators, bleach catalysts, solvents, thickeners, optical brighteners, grayness inhibitors, wrinkle inhibitors, antistatic agents, glass corrosion inhibitors, corrosion inhibitors, "soil repellents", dye transfer inhibitors, Foam inhibitors, abrasives, disintegrating agents, acidifying agents, dyes, fragrances, antimicrobial agents, UV absorbers and blowing agents and their preferred amounts are disclosed in the Offenlegurtgsschriften WO2008 / 107346 and WO2009 / 071451 directed.

A separate subject of the invention are processes for the purification of textiles, in which at least in one of the process steps a combination of said polymers with carboxyl groups and divalent cations is used.

This includes both manual and mechanical processes, with mechanical processes being preferred on account of their more precise controllability, for example with regard to the quantities and reaction times used.

Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent. All conceivable washing or cleaning processes can be enriched in at least one of the process steps by a combination of said polymers with carboxyl groups and divalent cations, and then constitute embodiments of the present invention.

A separate subject of the invention is the use of a combination of said polymers with carboxyl groups and divalent cations for cleaning textiles. Embodiments include, for example, hand washing, manual removal of stains from textiles or hard surfaces, or use in conjunction with a machine process.

A further subject of the present invention is also a product comprising a composition according to the invention or a textile treatment agent according to the invention, in particular washing or cleaning agents, and a spray dispenser. The product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container. The spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (pressurized gas containers, also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate. Spray dispensers are more detailed in the WO 96/04940 (Procter & Gamble) and the US patents cited therein to Sprühspendern, to which all reference is made in this regard and the contents of which are hereby incorporated into this application described. Trigger spray dispensers and pump sprayers have the advantage over compressed gas tanks that no propellant must be used. By means of suitable particles-passing attachments, nozzles, etc. (so-called "nozzle valves") on the spray dispenser, optionally contained enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.

• 1 bis 20 Gew.-%, vorzugsweise 3 bis 15 Gew.-% und insbesondere 5 bis 12 Gew.-% nichtionische Tenside, insbesondere Fettalkoholethoxylate;
• 1 bis 20 Gew.-%, vorzugsweise 3 bis 15 Gew.-% und insbesondere 5 bis 12 Gew.-% anionische Tenside, insbesondere aus der Gruppe der Sulfate oder Sulfonate, vor allem lineare Alkylbenzolsulfonate;
• 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 8 Gew.-% und insbesondere 2 bis 6 Gew.-% Fettsäuren;
• 0,1 bis 8 Gew.-%, vorzugsweise 0,5 bis 6 Gew.-% und insbesondere 1 bis 5 Gew.-% organischer Säuren, vorzugsweise Polycarbonsäuren und insbesondere Citronensäure;
• 0,1 bis 5 Gew.-%, vorzugsweise 0,2 bis 4 Gew.-% und insbesondere 0,5 bis 3 Gew.-% Enzym(e), vorzugsweise ausgewählt aus Amylasen und Proteasen;
• 1 bis 10 Gew.-% und insbesondere 2 bis 4 Gew.-% besagter Polymere mit Carboxylgruppen, vor allem Alginat oder Pektin; sowie
• 0,001 bis 1,0 Gew.-%, vorzugsweise 0,005 bis 0,5 Gew.-%, insbesondere 0,01 bis 0,1 Gew.-% zweiwertige Kationen, insbesondere Ca(II), vorzugsweise in Form eines organischen oder anorganischen Salzes.

Particularly preferred textile treatment agents according to the invention

• 1 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 12 wt .-% of nonionic surfactants, in particular fatty alcohol ethoxylates;
• 1 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 12 wt .-% of anionic surfactants, in particular from the group of sulfates or sulfonates, especially linear alkylbenzenesulfonates;
• 0.5 to 10 wt .-%, preferably 1 to 8 wt .-% and in particular 2 to 6 wt .-% fatty acids;
• 0.1 to 8 wt .-%, preferably 0.5 to 6 wt .-% and in particular 1 to 5 wt .-% of organic acids, preferably polycarboxylic acids and especially citric acid;
• From 0.1 to 5% by weight, preferably from 0.2 to 4% by weight and in particular from 0.5 to 3% by weight of enzyme (s), preferably selected from amylases and proteases;
• 1 to 10 wt .-% and in particular 2 to 4 wt .-% of said polymers having carboxyl groups, especially alginate or pectin; such as
• 0.001 to 1.0 wt .-%, preferably 0.005 to 0.5 wt .-%, in particular 0.01 to 0.1 wt .-% bivalent cations, in particular Ca (II), preferably in the form of an organic or inorganic salt ,

embodiments Example 1: Washing tests with alginate and calcium ions

A detergent composition comprising: Fettalkoholpolyethylenoxid 7.0% READ 9.0% Coconut Fatty Acid 4.0% boric acid 1.0% citric acid 2.0% propylene glycol 6.0% PTPMP 0.2% NaOH 3.1% protease 0.8% amylase 0.1% water rest was mixed on the one hand with 2 wt .-% of alginate (Texamid 558 P from Cognis), on the other hand with 2 wt .-% of alginate and 0.15 wt .-% of CaCl ₂ . Subsequently, textiles of pure cotton were washed with these detergent compositions and for comparison with a detergent composition without addition of alginate and CaCl ₂ .

For the washing tests, a washing machine Miele W 918 Novotronic was used. Washed according to the standard program with a simple wash at 40 ° C 3.5 kg of clean laundry using water with a water hardness of 16 ° German hardness. The liquid volume was 18 liters. In order to obtain a statistical mean, 5 parallel washing tests were carried out in each case.

The clean textiles were each washed three times under the conditions mentioned above with 100 g each of the abovementioned detergent compositions. After the third wash, the textiles were stained with engine oil. The intensity of the soiling was recorded with a Minolta CR 200 camera and then allowed to stand for 7 days at room temperature. Thereafter, the aged stains were again washed under the conditions mentioned above, then allowed to dry and again determined the intensity values of stains with the camera Minolta CR 200.

In the following, the differences of the intensity values obtained by respectively forming the difference between the obtained intensity values before and after the washing of the soiled fabrics are plotted. The greater the difference, the stronger the lightening achieved. soiling reference alginate Alginate + 0.15% CaCl ₂ Engine oil 30.8 38.0 42.0

The results show that even by adding the alginate to the detergent composition, an increase in the fat-dissolving power with respect to the engine oil could be achieved, but that by adding the CaCl _2, a further significant increase in the fat-dissolving power could be achieved.

Example 2: Washing experiments with pectin and calcium ions

A detergent composition comprising: Fettalkoholpolyethylenoxid 7.0% READ 9.0% Coconut Fatty Acid 4.0% boric acid 1.0% citric acid 2.0% propylene glycol 6.0% PTPMP 0.2% NaOH 3.1% protease 0.8% amylase 0.1% water rest was mixed on the one hand with 2% by weight of pectin (Pectin AMID AF 025 from Herbstreith & Fox), on the other with 2% by weight of pectin and 0.15% by weight of CaCl ₂ . Subsequently, pure cotton textiles were washed with these detergent compositions as well as for comparison with a detergent composition without added pectin and CaCl ₂ .

For the washing tests, a washing machine Miele W 918 Novotronic was used. Washed according to the standard program with a simple wash at 40 ° C 3.5 kg of clean laundry using water with a water hardness of 16 ° German hardness. The liquid volume was 18 liters. In order to obtain a statistical mean, 5 parallel washing tests were carried out in each case.

The clean textiles were each washed three times under the conditions mentioned above with 100 g each of the abovementioned detergent compositions. After the third wash, the textiles were stained with engine oil. The intensity of the soiling was recorded with a Minolta CR 200 camera and then allowed to stand for 7 days at room temperature. Thereafter, the aged stains were again washed under the conditions mentioned above, then allowed to dry and again determined the intensity values of stains with the camera Minolta CR 200.

In the following, the differences of the intensity values obtained by respectively forming the difference between the obtained intensity values before and after the washing of the soiled fabrics are plotted. The greater the difference, the stronger the lightening achieved. soiling reference pectin Pectin + 0.15% CaCl ₂ Engine oil 30.8 40.7 45.7

The results show that even by adding the pectin to the detergent composition, it was possible to achieve an increase in the fat-dissolving power with respect to the engine oil, but that a further significant increase in the fat-dissolving power could be achieved by adding the CaCl ₂ .

Example 3: Recipes

E1 E2 E3 C12-18 fatty acid 7.5 6 3 C12-18 fatty alcohol with 7 EO 12 12 10 Sodium lauryl ether sulfate with 2 EO 5 2 5 C12-C14 APG - - 2.5 Linear C10-C13 alkyl benzene sulfonic acid 9.6 16 - citric acid 3 3.5 1 phosphonic 1 0.8 0.2 boric acid 1 1 1 polyacrylate 0.35 0.75 0.1 NaOH (50%) 4.70 5.4 1.48 Optical brightener 0.08 0.1 0.04 1,2-propanediol 7 8.5 - glycerin - - 4.5 Silicone antifoam 0.1 0.1 0.01 Enzymes (cellulase, protease & amylase) 1.4 1.4 0.6 Perfume 1.5 1.5 0.75 alginate 2.5 - 1 pectin - 3 2.5 CaCl ₂ 0.05 0.1 0.1 dye + + + water Ad 100 Ad 100 Ad 100

Claims (11)

1. A textile treatment agent containing

   a) polymers with carboxyl groups in a concentration of 1 to 10% by weight, preferably 2 to 4% by weight,

   b) bivalent cations in a concentration of 0.001 to 1.0% by weight,

   wherein at least 20% of the monomer units of the polymer carry carboxyl groups, the polymer is a polysaccharide, and at least 20% of the monomer units of the polysaccharide are uronic acids.
2. The textile treatment agent according to claim 1, characterized in that the polysaccharide is selected from the group comprising alginate, pectin, glucosaminoglucans, in particular hyaluronic acid or heparin, tragacanth, gum arabic, and teichuronic acids.
3. The textile treatment agent according to one of the preceding claims, characterized in that the bivalent cations are selected from Ca(II), Mg(II), Fe(II), and Zn(II) and the bivalent cations are used preferably in the form of an inorganic or organic salt.
4. The textile treatment agent according to one of claims 1 to 3, characterized in that it is a fabric softener.
5. Use of polymers with carboxyl groups in combination with bivalent cations or of a textile treatment agent according to one of claims 1 to 4 for finishing textile fabrics, wherein the treatment of the textile fabric with the polymers and the bivalent cations can occur both in one process step and in sequential process steps, wherein at least 20% of the monomer units of the polymer carry carboxyl groups, the polymer with carboxyl groups is a polysaccharide, and at least 20% of the monomer units of the polysaccharide are uronic acids.
6. Use of polymers with carboxyl groups in combination with bivalent cations or of a textile treatment agent according to any one of claims 1 to 4 for removing stains from textile fabrics and/or for preventing the formation of stains on textile fabrics, wherein at least 20% of the monomer units of the polymer carry carboxyl groups, the polymer with carboxyl groups is a polysaccharide, and at least 20% of the monomer units of the polysaccharide are uronic acids.
7. The use according to claim 6, characterized in that the stains are selected from oil- and fat-containing stains, in particular from motor oil, cooking fat, lipstick, or makeup.
8. The use according to one of claims 5 to 7, characterized in that the bivalent cations are selected from Ca(II), Mg(II), Fe(II), and Zn(II), whereby the bivalent cations are used preferably in the form of an inorganic or organic salt.
9. A method for finishing textile fabrics, characterized in that the textile fabrics are treated with a combination of polymers with carboxyl groups and bivalent cations or with a textile treatment agent according to one of claims 1 to 4, wherein the treatment of the textile fabric with the polymers and the bivalent cations can occur both in one process step and in sequential process steps, wherein at least 20% of the monomer units of the polymer carry carboxyl groups, the polymer with carboxyl groups is a polysaccharide, and at least 20% of the monomer units of the polysaccharide are uronic acids.
10. A method for removing stains from textile fabrics and/or for preventing the formation of stains on textile fabrics, characterized in that the textile fabrics are treated with a combination of polymers with carboxyl groups and bivalent cations, wherein the treatment of the textile fabric with the polymers and the bivalent cations can occur both in one process step and in sequential process steps, wherein at least 20% of the monomer units of the polymer carry carboxyl groups, the polymer with carboxyl groups is a polysaccharide, and at least 20% of the monomer units of the polysaccharide are uronic acids.
11. The method according to claim 9 or 10, characterized in that at least one of the components selected from polymers with carboxyl groups and bivalent cations is used in the softening rinse step of the textile washing.