EP1339910A1

EP1339910A1 - Highly branched polymers for the anti-crease dressing of cellulose containing textiles

Info

Publication number: EP1339910A1
Application number: EP01989443A
Authority: EP
Inventors: Jürgen Detering; Peter Neumann; Bernd Bruchmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2000-11-13
Filing date: 2001-11-08
Publication date: 2003-09-03
Anticipated expiration: 2021-11-08
Also published as: CN1545584A; MXPA03004012A; AU2002227908A1; US20040016060A1; ATE340284T1; BR0115300A; ES2272562T3; WO2002038851A1; CA2426969A1; DE10056183A1; DE50111057D1; EP1339910B1; JP2004513260A

Abstract

A process for wrinkleproofing cellulosic textiles by treating the textiles with a finish and drying the treated textiles, which comprises using a finish comprising one or more highly branched polymers in dissolved or dispersed form.

Description

Highly branched polymers for anti-crease finishing of cellulose-containing textiles

The invention relates to processes for the anti-crease treatment of cellulose-containing textiles, finishing agents for anti-crease treatment containing highly branched polymers, the use of the finish agents and the highly branched polymers, as well as textile treatment agents, solid and liquid detergent formulations and laundry detergents which contain highly branched polymers.

Textiles containing cellulose are easy to care for, for example, by treatment with condensation products made from urea, glyoxal and formaldehyde. The equipment takes place during the manufacture of the textile materials. Other additives such as plasticizing compounds are often used in the finishing. The textiles finished in this way have the advantage over the untreated cellulose textiles after the washing process that they have fewer creases and folds, are easier to iron and are softer and smoother.

WO 92/01773 discloses the use of microemulsified aminosiloxanes in fabric softeners to reduce the formation of creases and wrinkles during the washing process (anti-crease equipment). At the same time, ironing should be made easier by using the aminosiloxanes.

A method for pretreating textile materials is known from WO 98/4772, a mixture of a polycarboxylic acid and a cationic plasticizer being applied to the textile materials. You can achieve anti-jam protection.

From EP-A 0 300 525, fabric softeners based on crosslinkable amino-functionalized silicones are known which bring about a crease protection or an easy ironing effect for the textiles treated with them. Formulations are known from WO 99/55953 which cause an anti-creasing effect in the treated textiles. The formulations consist of lubricants, polymers that ensure the dimensional and dimensional stability of the textiles, lithium salts and optionally other ingredients such as plasticizers, ionic and nonionic surfactants, odor-binding substances and bactericides. The formulation is preferably applied to the textile material by spraying.

EP-A 0 978 556 describes a mixture of a plasticizer and a crosslinking component with cationic properties as an agent for providing textiles with anti-crease and wrinkle protection, and a method for anti-wrinkling finishing of textiles.

The object of the invention is to provide a further process for the anti-crease treatment of cellulose-containing textiles as well as further finishing agents for the anti-crease treatment of such textiles.

The object is achieved by a process for the anti-crease treatment of cellulose-containing textiles by treating the textiles with an finishing agent and drying the treated textiles, characterized in that the finishing agent contains one or more highly branched polymers in dissolved or dispersed form.

The task is also solved by a finishing agent for anti-wrinkle finishing of cellulose-containing textiles, which contains these highly branched polymers.

Highly branched polymers are known per se. Dendrimers, arborols, starburst polymers and hyperbranched polymers are names for polymer structures which are distinguished by a branched structure and high functionality.

Dendrimers are molecular and structurally uniform macromolecules with a highly symmetrical structure. They are built in multi-step syntheses and are therefore very expensive.

In contrast, hyperbranched polymers are both molecularly and structurally inconsistent. They have branches of different lengths and branches. The highly branched polymers used according to the invention are preferably such hyperbranched polymers in the narrower sense. But it can also be structural and molecularly uniform dendrimeric polymers are used. The term "highly branched polymers" in the sense of this invention therefore encompasses hyperbranched and dendrimeric polymers.

The highly branched polymers used according to the invention can in particular be prepared from so-called AB _x monomers. These have two different functional groups A and B, which can react with one another to form a link. The functional group A is only contained once per molecule and the functional group B twice or more. The reaction of the AB _x monomers with one another creates uncrosslinked polymers with regularly arranged branching points. The polymers have almost exclusively B groups at the chain ends. Further details are, for example, in JMS - Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997).

Highly branched polymers containing functional groups can be synthesized in a manner known in principle using AB _X , preferably AB ₂ monomers. The AB monomers can be fully incorporated in the form of branches, they can be incorporated as terminal groups, that is to say they still have two free B groups, or they can be incorporated as linear groups with one free B group. Depending on the degree of polymerization, the highly branched polymers obtained have a more or less large number of B groups, either terminally or as side groups. Further information on hyperbranched polymers and their synthesis can be found, for example, in JMS - Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997) and the literature cited therein.

The selection of highly branched polymers for use in the anti-wrinkle finishing process according to the invention is in principle not restricted to a specific polymer class. Highly branched polyesters, highly branched polyethers, highly branched polyurethanes, highly branched polyurethane polyurethanes, highly branched polyamines, highly branched polyamides, highly branched polysiloxanes, highly branched carbosilanes, highly branched polyether amides and highly branched polyester amides. However, highly branched polyurethanes, highly branched polyesters, highly branched polyethers, highly branched polyester amides and highly branched polyamines have proven to be particularly suitable. Among the highly branched polyamines, the highly branched polyethyleneimines should be mentioned in particular. Highly branched polyurethanes are very particularly preferred. Highly branched polymers can be produced, for example, as follows:

- highly branched polyurethanes according to WO 97/02304 or according to DE 199 04444

- highly branched polyesters according to SE 468771 or according to SE 503342 - highly branched polyethers according to DE 199 47 631

- highly branched polyester amides according to WO 99/16810

- highly branched polyamines according to WO 93/14147

Highly branched and highly functional polymers obtained by polymerizing AB ₂ molecules can in principle be used as such in the finishing agents according to the invention, provided that the functional groups obtained in the course of the particular embodiment of the synthesis are suitable for the use of the polymers in dissolved or dispersed form ,

However, the B groups originally present can also be functionalized by polymer-analogous reaction with suitable compounds.

Examples of suitable functional groups which can be introduced by means of suitable reactants include, in particular, acidic or basic groups having H atoms and their derivatives such as -COOH, -COOR, -CONHR, -CONH _2; -OH, -SH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H, -SO ₃ R, -NHCOOR, -NHCONH ₂ , -NHCONHR or their salts. The radicals R are generally straight-chain or branched alkyl radicals which can also be further substituted, for example - C ₈ alkyl radicals. However, other functional groups such as -CN or -OR can also be introduced.

In a preferred embodiment, the highly branched polymers used according to the invention have one or more functional groups selected from the group consisting of. -COOH, -COOR, -CONHR, -CONH _2, -OH, -SH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H, -SO ₃ R, -NHCOOR, -NHCONH ₂ , -NHCONHR or their salts.

Compounds used for the functionalization can on the one hand include the desired functional group and a second group which is capable of reacting with the B groups of the highly branched polymer used as starting material to form a bond. An example is the reaction of an isocyanate group with a hydroxy carboxylic acid. However, monofunctional compounds can also be used, with which existing groups are merely modified. For example, alkyl halides can be used for the quaternization of existing amino groups.

The hyperfunctionalization of the hyperbranched polymers can advantageously take place immediately after the polymerization reaction or in a separate reaction.

Functional groups that have sufficiently acidic H atoms can be converted into the corresponding salts by treatment with suitable bases. Analogously, basic groups can be converted into the corresponding salts using suitable acids. As a result, water-soluble highly branched polymers can be obtained.

Highly branched polymers can also be produced which have different functionalities. This can be done, for example, by reacting with a mixture of different compounds for the re-functionalization, or else by reacting only a part of the functional groups originally present.

Degree of polymerization, molar mass and type and number of functional groups can be chosen by a person skilled in the art depending on the intended application.

Particularly preferred functional groups are -COOH, -CONH ₂ , -OH, - NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ and -SO ₃ H and their salts.

In a special embodiment, the highly branched polymers used according to the invention have one or more functional groups selected from the group consisting of -COOH, -OH, -SO H and their salts.

In a further special embodiment, the highly branched polymers used according to the invention have one or more functional groups selected from the group consisting of -NH ₂ , -NHR, -NR, -NR ₃ ⁺ and their salts.

The highly branched polymers used according to the invention have on average at least 4 functional groups per molecule. In principle, there is no upper limit on the number of functional groups. However, products with too many functional groups often have undesirable properties, such as poor solubility or very high viscosity. Therefore, the Highly branched polymers used according to the invention preferably have on average no more than 200 functional groups. The highly branched polymers preferably have an average of 4 to 150 and particularly preferably 4 to 100 functional groups.

The molar masses of the highly branched polymers used according to the invention depend on the respective polymer class and are selected accordingly by the person skilled in the art. However, products with a weight-average molecular weight M of 1000 to 20,000 g / mol, preferably 1000 to 100,000 g / mol, have proven successful.

Preferred highly branched polymers which are used in the finishing agents according to the invention are highly branched polyurethanes.

The term “polyurethanes” in the sense of this invention encompasses, beyond the common understanding, polymers which can be obtained by reacting di- or polyisocyanates with compounds having active hydrogen, and which are obtained by urethane, but also, for example, by urea, allophanate, biuret -, Carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone structures can be linked.

For the synthesis of the hyperbranched polyurethanes used according to the invention, preference is given to using AB _x monomers which have both isocyanate groups and groups which can react with isocyanate groups to form a link. x is a natural number between 2 and 8, preferably 2 or 3. Either A is an isocyanate group and B is a group reactive therewith, or the reverse is true.

The groups reactive with the isocyanate groups are preferably OH,

NH ₂ , NHR or SH groups.

The AB _x monomers can be prepared in a known manner. AB _x monomers can be synthesized, for example, by the method described in WO 97/02304 using protective group techniques. This technique is exemplified by the preparation of an AB ₂ monomer from 2,4-tolylene diisocyanate (TDI) and trimethylolpropane. First, one of the TDI isocyanate groups is blocked in a known manner, for example by reaction with an oxime. The remaining free NCO group is reacted with trimethylolpropane, only one of the three OH groups reacting with the isocyanate group, while two OH groups are reacting Acetalization are blocked. After the protective group has been removed, a molecule with an isocyanate group and 2 OH groups is obtained.

The AB _x molecules can be synthesized particularly advantageously by the method described in DE-A 199 04 444, in which no protective groups are required. In this method, di- or polyisocyanates are used and reacted with compounds which have at least two groups reactive with isocyanate groups. At least one of the reactants has groups with different reactivities than the other reactants. Both reactants preferably have groups with different reactivities than the other reactants. The reaction conditions are chosen so that only certain reactive groups can react with each other.

Suitable di- and polyisocyanates are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Preferred di- or polyisocyanates are 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymer MDI), tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-

Methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine alkyl ester diisocyanate, where alkyl is ci- to cio-alkyl, 2,2,4- or 2,4,4-trimethyl-l, 6-hexamethylene diisocyanate, 1, 4 -Diisocyanatocyclohexane or 4-isocyanatomethyl-1, 8-octamethylene diisocyanate.

Di- or polyisocyanates with NCO groups of different reactivity, such as 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate, are particularly preferred

(2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDΪ), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) -

Isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane,

2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane 1,3-diisocyanate (H-TDI). Furthermore, isocyanates (b) are particularly preferred, the NCO groups of which are initially equally reactive, but in which the first addition of an alcohol or

Amine to an NCO group can induce a drop in reactivity in the second NCO group. Examples of this are isocyanates, the NCO groups of which are coupled via a delocalized electron system, e.g. B. 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate or

2,6-diisocyanate. It is also possible, for example, to use oligo- or polyisocyanates which are obtained from the di- or polyisocyanates mentioned or their mixtures by linking using urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures can be produced.

As compounds having at least two groups reactive with isocyanates, preference is given to using di-trifunctional or tetrafunctional compounds whose functional groups have a different reactivity towards NCO groups. Compounds with at least one primary and at least one secondary hydroxyl group, at least one hydroxyl group and at least one mercapto group are preferred, particularly preferably with at least one hydroxyl group and at least one amino group in the molecule, in particular amino alcohols, aminodiols and aminotriols, since the reactivity of the amino group with the hydroxyl group contributes to the reaction with isocyanate is significantly higher.

Examples of the compounds mentioned with at least two groups reactive with isocyanates are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1, 3-propanediol, 2-amino-2 -methyl-l, 3-propanediol or tris (hydroxymethyl) - aminomethane. Mixtures of the compounds mentioned can also be used.

The preparation of an AB ₂ molecule is exemplified for the case of a diisocyanate with an aminodiol. First, one mole of a diisocyanate is reacted with one mole of an aminodiol at low temperatures, preferably in the range between -10 to 30 ° C. In this temperature range, the urethane formation reaction is virtually completely suppressed and the more reactive NCO groups of the isocyanate react exclusively with the amino group of the aminodiol. The AB _x molecule formed has one free NCO group and two free OH groups and can be used to synthesize a highly branched polyurethane.

By heating and / or adding catalyst, this AB ₂ molecule can react intermolecularly to form a highly branched polyurethane. The highly branched polyurethane can advantageously be synthesized in a further reaction step at elevated temperature, preferably in the range between 30 and 80 ° C., without prior isolation of the AB _x molecule. When using the described AB ₂ molecule with two OH groups and one NCO group, a highly branched polymer is formed, which per Molecule has a free NCO group and - depending on the degree of polymerization - a more or less large number of OH groups. The reaction can be carried out up to high conversions, whereby very high molecular structures are obtained. However, it can also be terminated, for example, by adding suitable monofunctional compounds or by adding one of the starting compounds for the preparation of the AB ₂ molecule when the desired molecular weight has been reached. Depending on the starting compound used for the termination, either completely NCO-terminated or completely OH-terminated molecules are formed.

Alternatively, for example, an AB ₂ molecule can also be produced from one mole of glycerol and 2 moles of 2,4-TDI. At low temperature, the primary alcohol groups and the isocyanate group preferably react in the 4-position and an adduct is formed which has one OH group and two isocyanate groups, which, as described, can be converted to a highly branched polyurethane at higher temperatures. First, a highly distorted polymer is formed which has a free OH group and, depending on the degree of polymerization, a more or less large number of NCO groups.

In principle, the highly branched polyurethanes can be prepared without solvents, but preferably in solution. In principle, suitable solvents are all compounds which are liquid at the reaction temperature and are inert toward the monomers and polymers.

Other products are accessible through further synthesis variants. AB ₃ molecules can be obtained, for example, by reacting diisocyanates with compounds having at least 4 groups that are reactive toward isocyanates. The reaction of 2,4-tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned as an example.

Polyfunctional compounds which can react with the respective A groups can also be used to terminate the polymerization. In this way, several small, highly branched molecules can be linked to form one large, highly branched molecule.

Highly branched polymers with chain-extended branches can be obtained, for example, by adding a diisocyanate and a compound, the two with, in addition to the AB _x molecules in addition to the AB _x molecules in a molar ratio

Has isocyanate groups reactive groups can be used. These additional AA- or BB compounds can also have further functional groups, which, however, must not be reactive towards the A or B groups under the chosen reaction conditions. In this way, further functionalities can be introduced into the hyperbranched polymer.

Further synthesis variants for highly branched polyurethanes can be found in the applications with the file numbers DE 100 13 187.5 and DE 100 30 869.4.

The highly branched and highly functional polyurethanes obtained can already be used as such in the finishing agents according to the invention, provided that the functional groups obtained in the course of the synthesis are suitable for the use of the polyurethanes in dissolved or dispersed form.

However, as described above, the functional groups can also be hydrophobicized, hydrophilized or functionalized. In this way, particularly suitable highly branched polyurethanes are accessible for use as a solution or aqueous dispersion. Because of their reactivity, those highly branched polyurethanes which have isocyanate groups are particularly suitable for the functionalization. OH- or NH-terminated polyurethanes can also be functionalized using suitable reactants.

Preferred groups which are introduced into the highly branched polyurethanes are -COOH, -CONH ₂ , -OH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H and their salts. Particularly preferred are -NH ₂ , -NHR, -NR ₂ , and -NR ₃ ⁺ according to an embodiment of the invention and -COOH, -OH and -SO ₃ H according to a further embodiment of the invention.

Groups with sufficient acidic H atoms can be converted into the corresponding salts by treatment with suitable bases. Analogously, basic groups can be converted into the corresponding salts using suitable acids. As a result, water-soluble highly branched polyurethanes can be obtained.

Hydrophobicized products can be obtained by reacting NCO-terminated products with alkanols and alkylamines, in particular alkanols and alkylamines with C ₈ -C ₄ o-alkyl radicals. Hydrophilized but non-ionic products can be obtained by reacting NCO-terminated polymers with polyether alcohols, such as di-, tri- or tetra- or polyethylene glycol.

Acid groups can be introduced, for example, by reaction with hydroxycarboxylic acids, hydroxysulfonic acids or amino acids. Examples of suitable reactants are 2-hydroxyacetic acid, 4-hydroxybenzoic acid,

Called 12-hydroxydodecanoic acid, 2-hydroxyethanesulfonic acid, glycine or alanine.

By reaction with compounds comprising acrylate groups, such as alcohols comprising acrylate groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, it is possible to obtain highly branched polyurethanes which have polymerizable olefinic groups.

Oxidatively drying, highly branched polyurethanes can be obtained by first reacting mono- or polyunsaturated fatty acids, in particular C ₈ -C ₄ o-fatty acids, with an aliphatic alcohol with at least two OH groups, at least one OH group not being esterified. For example, linoleic acid, linolenic acid or elaeostearic acid can be reacted. The fatty acid ester obtained, which still has OH groups, is then reacted with the NCO groups.

It is also possible to produce highly branched polyurethanes which have different functionalities. This can be done, for example, by reaction with a mixture of different compounds, or by reacting only part of the functional groups originally present, for example only part of the OH and / or NCO groups.

Furthermore, one or more functional groups of the highly branched molecule can also be reacted with fiber-affine reagents, for example with polyamines, such as polyethyleneimine or polyvinylamine. This gives a highly branched polymer which has a fiber-affine molecular part as an anchor group for the fiber.

The functionalization of the highly branched polyurethane can advantageously be carried out immediately after the polymerization reaction without the NCO-terminated polyurethane being isolated beforehand. However, the functionalization can also take place in a separate reaction. The highly branched polyurethanes used according to the invention generally have on average at least 4 and not more than 200 functional groups. The highly branched polyurethanes preferably have 4 to 150 and particularly preferably 4 to 100 functional groups. Highly branched polyurethanes preferably used have a weight-average molecular weight Mψ of 1000 to 200,000 g / mol, preferably 1000 to 100,000 g / mol.

The invention also relates to the use of highly branched polymers, in particular highly branched polyurethanes, in finishing agents for the anti-crease treatment of textiles containing cellulose. Finishing agents are any liquid formulations which contain the highly branched polymer, in particular the highly branched polyurethane, for application to the textile material in dissolved or dispersed form. The finishing agents according to the invention can be present, for example, as finishing agents in the narrower sense in the manufacture of the textiles or in the form of an aqueous washing liquor or as a liquid textile treatment agent. Suitable solvents are e.g. Water, alcohols such as methanol, ethanol and propanol, THF or their mixtures. For example, it is possible to treat the textiles with the finishing agent in connection with textile production. Textiles that have not yet been treated or have been insufficiently treated with finishing agents can be treated, for example, in the home area before or after washing, for example when ironing, with a textile treatment agent which contains the highly branched polymers. However, it is also possible to treat the textiles with highly branched polymers in the main wash cycle or after the main wash cycle in the care or fabric softener cycle of the washing machine.

The present invention also relates to the use of the highly branched polymers, in particular the highly branched polyurethanes, in the manufacture of the textiles, in the treatment of the textiles before and after washing, in the main wash cycle, in the wash cycle, and in the ironing process. Different formulations are required for this.

In the treatment before or after the textile washing, a textile treatment agent can be used as the finishing agent which, in addition to a highly branched polymer, contains a surface-active agent in dissolved or dispersed form. In this treatment, the cellulose-containing textiles are sprayed, for example, with the highly branched polymers, the application amount generally being from 0.01 to 10% by weight, preferably 0.1 to 7, particularly preferably 0.3 to 4% by weight, based on the weight of the dry textile goods. The finishing agent can, however, also be applied to the textile material by immersing the textiles in a bath which is generally 0.1 to 10% by weight, preferably 0.3 to 5% by weight, based on the weight of the contains dry textile goods, a highly branched polymer dissolved or dispersed. The textile is either only briefly immersed in the bath or can also remain there for a period of, for example, 1 to 30 minutes.

The cellulose-containing textiles, which have been treated with the finishing agent either by spraying or by immersion, are optionally pressed off and dried. The drying can be done in air or in a dryer or by hot ironing the treated textile. The finishing agent is fixed on the textile by drying. The cheapest for this

Conditions can easily be determined with the help of experiments. The temperature during drying, including ironing, is generally 40 to 150 ° C, preferably 60 to 110 ° C. This is particularly suitable for ironing

Cotton program of the iron. The textiles made after the above

Processes with which the highly branched polymers have been treated in dissolved or dispersed form have excellent crease and wrinkle protection which persists over several washes. Ironing the textiles is often no longer necessary. The textiles treated in this way also have fiber and color protection.

The invention also relates to a textile treatment composition containing

a) 0.1 to 40% by weight, preferably 0.5 to 25% by weight, of at least one highly branched polymer, in particular at least one highly branched polyurethane,

b) 0 to 30% by weight of one or more silicones,

c) 0 to 30% by weight of one or more cationic and / or nonionic surfactants,

d) 0 to 60% by weight of further ingredients such as further wetting agents, plasticizers, lubricants, water-soluble, film-forming and adhesive polymers, fragrances and colorants, stabilizers, fiber and color protection additives, viscosity modifiers,

Soil release additives, anti-corrosion additives, bactericides, preservatives and spraying aids, and e) 0 to 99.9% by weight of water,

the sum of components a) to e) being 100% by weight.

Preferred silicones are amino group-containing silicones, which are preferably in microemulsified form, alkoxylated, in particular ethoxylated silicones, polyalkylene oxide polysiloxanes, polyalkylene oxide aminopolydi ethylsiloxanes, silicones with quaternary ammonium groups (silicone quats) and silicone surfactants. Suitable plasticizers or lubricants are, for example, oxidized polyethylenes or waxes and oils containing paraffin. Suitable water-soluble, film-forming and adhesive polymers are, for example, (co) polymers based on acrylamide, N-vinylpyrrolidone, vinylformamide, N-vinylimidazole, vinylamine, N, N'-dialkylaminoalkyl (meth) acrylates, N, N'-dialkylaminoalkyl (meth) acrylamides, (meth) acrylic acid, (meth) acrylic acid alkyl esters and / or vinyl sulfonate. The basic monomers mentioned above can also be used in quaternized form.

If the textile pretreatment formulation is sprayed onto the textile material, the formulation can additionally contain a spraying aid. In some cases it can also be advantageous to add alcohols such as ethanol, isopropanol, ethyl diglycol or propylene glycol to the formulation. Other common additives are fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives in the amounts customary for this.

The textile treatment agent can also generally be applied by spraying when the textile is ironed after washing. This not only makes ironing considerably easier, the textiles are also equipped with long-lasting crease and wrinkle protection.

The highly branched polymers can also be used when washing the textiles in the main washing cycle of the washing machine.

The invention relates to a solid detergent formulation containing

a) 0.05 to 20% by weight of at least one highly branched polymer, in particular at least one highly branched polyurethane, b) 0 to 20% by weight of silicones,

c) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

d) 0 to 50% by weight of one or more inorganic builders,

e) 0 to 10% by weight of one or more organic cobuilders,

f) 0 to 60% by weight of other conventional ingredients such as bulking agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, cationic surfactants, color transfer inhibitors, graying inhibitors, soil-release polyesters, dyes, bactericides, dissolution improvers and / or disintegrants,

the sum of components a) to f) being 100% by weight.

Suitable anionic surfactants are in particular:

(Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ to Cn alcohol sulfates, ₂ to ₄ alcohol sulfates,

C ₂ -C ₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate,

Stearyl sulfate and tallow fatty alcohol sulfate; sulfated alkoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates). Connections this

Type are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a Cio to C 1 alcohol, for example a fatty alcohol, and that

Alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation; linear C ₈ - to C o-alkylbenzosulfonates (LAS), preferably linear C ₉ - to Cι ₃ -

Alkylbenzenesulfonates and alkyltoluenesulfonates; - Alkanesulfonates such as C ₈ - to C ₂₄ -, preferably C _JO - to -C ₈ alkanesulfonates;

Soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

The specific anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium ions such as hydroxyethylammomum, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium. Suitable nonionic surfactants are in particular:

alkoxylated C ₈ to C ₂₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These can be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of one of the above-mentioned alkylene oxides added can be used as surfactants. Here, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. The nonionic surfactants generally contain 2 to 50, preferably 3 to, per mole of alcohol

20 moles of at least one alkylene oxide. These preferably contain ethylene oxide as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, the alkoxylates have a broad or narrow alkylene oxide homolog distribution; - Alkylphenolalkoxylate such as alkylphenol ethoxylates with C ₆ - to -C ₄ alkyl chains and 5 to 30 alkylene oxide units;

Alkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5, glucoside units; - N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

Suitable inorganic builders are in particular:

crystalline or amorphous aluminosilicates with ion-exchanging properties such as, in particular, zeolites. Suitable zeolites are in particular zeolites A, X, B, P,

MAP and HS in their Na form or in forms in which Na is partially against others

Cations such as Li, K, Ca, Mg or ammonium are exchanged; crystalline silicates such as, in particular, disilicates or layered silicates, for example δ-Na ₂ Si ₂ O ₅ or ß-Na ₂ Si ₂ O. The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li or Mg silicates; amorphous silicates such as sodium metasilicate or amorphous disilicate;

Carbonates and hydrogen carbonates. These can be in the form of their alkali metal,

Alkaline earth metal or ammonium salts are used. Na, Li and Mg carbonates or bicarbonates are preferred, in particular sodium carbonate and / or sodium bicarbonate;

Polyphosphates such as pentasodium triphosphate. Suitable organic cobuilders are in particular low molecular weight, oligomeric or polymeric carboxylic acids.

- Suitable low molecular weight carboxylic acids are, for example, citric acid, hydrophobically modified citric acid such as. B. agaricinic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid,

Cyclopentanetetracarboxylic acid, alkyl and alkenyl succinic acids and amino polycarboxylic acids such as e.g. Nitrilotriacetic acid, ß-alaninediacetic acid,

Ethylenediaminetetraacetic acid, serine diacetic acid, isoserine diacetic acid,

N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic acid; Suitable oligomeric or polymeric carboxylic acids are, for example, homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid,

Methacrylic acid, C ₂ -C ₂₂ olefins such as isobutene or long-chain α-olefins, vinyl alkyl ether with Cr alkyl groups, vinyl acetate, vinyl propionate, (meth) acrylic esters of C ₁ -C ₈ alcohols and styrene. The homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid are preferably used. Polyaspartic acids are also suitable as organic cobuilders. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.

Suitable bleaches are, for example, adducts of hydrogen peroxide with inorganic salts such as. As sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate and percarboxylic acids such as. B.

Phthalimidopercaproic.

Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylene diamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methyl sulfate.

Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.

- Suitable color transfer inhibitors are, for example, homopolymers and copolymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-Nynylpyridine-N-oxide and homo- and copolymers of 4-nynylpyridine reacted with chloroacetic acid.

A solid detergent formulation according to the invention is usually in powder or granule form or in extrudate or tablet form.

The invention further relates to a liquid detergent formulation

a) 0.05 to 20% by weight of at least one highly branched polymer, in particular at least one highly branched polyurethane,

b) 0 to 20% by weight of one or more silicones,

c) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

d) 0 to 20% by weight of one or more inorganic builders,

e) 0 to 10% by weight of one or more organic cobuilders,

f) 0 to 60% by weight of other customary ingredients, such as soda, enzymes, perfume,

Complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, cationic surfactants, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, bactericides, non-aqueous solvents, solubilizers, hydrotropes, thickeners and / or alkanolamines,

g) 0 to 99.85% by weight of water,

the sum of components a) to g) being 100% by weight.

The above-mentioned silicones, nonionic and anionic surfactants, builders and cobuilders can be used.

A detailed description of the detergent ingredients mentioned can be found, for example, in WO 99/06524 or WO 99/04313 and in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, pp. 272-304. The concentration of the highly branched polymers in the wash liquor is, for example, 10 to 5000 ppm and is preferably in the range from 50 to 1000 ppm. The textiles treated with the highly branched polymers in the main washing cycle of the washing machine not only wrinkle significantly less than untreated textiles. They are also easier to iron, softer and smoother, more dimensionally and dimensionally stable and, after being washed several times, look less "used" due to their fiber and color protection, ie they have less lint and knots and less color damage or fading.

The highly branched polymers can be used in the so-called soft or conditioner rinse after the main wash cycle. The concentration of the highly branched polymers in the wash liquor is, for example, 10 to 5000 ppm and is preferably in the range from 50 to 1000 ppm. Ingredients typical for a fabric softener or conditioner may possibly be present in the wash liquor. The textiles treated in this way also have very good protection against the cold after drying on a line or preferably in a tumble dryer, which is associated with the positive effects on ironing already described above. The anti-crease can be significantly increased by briefly ironing the textiles after drying. Treatment in a soft or conditioner cycle also has a positive effect on the shape stability of the textiles. Furthermore, the formation of knots and lint is inhibited and color damage is suppressed.

The invention also relates to a laundry detergent containing

a) 0.05 to 40% by weight of at least one highly branched polymer, in particular at least one highly branched polyurethane,

b) 0 to 20% by weight of one or more silicones,

c) 0.1 to 40% by weight of at least one cationic surfactant,

d) 0 to 30% by weight of one or more nonionic surfactants and

e) 0 to 30% by weight of other customary ingredients, such as silicones, other lubricants, wetting agents, film-forming polymers, fragrances and colorants, stabilizers,

Fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives, and f) 0 to 99.85% by weight of water,

the sum of components a) to f) being 100% by weight.

Preferred cationic surfactants are selected from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoamine esters and imidazolium salts. These are preferably contained in the laundry detergent in an amount of 3 to 30% by weight. Examples are quaternary diester ammonium salts which have two Cπ to C ₂₂ alk (en) ylcarbonyloxy (mono- to pentamethylene) residues and two Ci to C ₃ alkyl or hydroxyalkyl residues on the quaternary N atom and, for example, chloride as a counter ion , Bromide, methyl sulfate or sulfate.

Quaternary diesterammonium salts are furthermore, in particular, those which have a Cπ to C ₂ alk (en) ylcarbonyloxytrimethylene radical which has a Cπ to C ₂₂ alk (en) ylcarbonyloxy radical on the middle C atom of the trimethylene group, and three C _\ - to C ₃ alkyl or hydroxyalkyl radicals on the quaternary nitrogen atom and having as a counterion carry, for example, chloride, bromide, methylsulfate, or sulfate.

Quaternary tetraalkylammonium salts are in particular those which have two Ci to C ₆ -alkyl radicals and two C ₈ - to C ₄ alk (en) yl radicals on the quaternary nitrogen atom and having, as counterion, chloride, bromide, methylsulfate, or sulfate wear.

Quaternary diamidoammonium salts are in particular those which have two C ₈ -C ₂₄ -alk (en) ylcarbonylaminoethylene radicals, a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene with up to 5 oxyethylene units and as the fourth radical a methyl group on the quaternary N. -Atom and have as counterion, for example, chloride, bromide, methyl sulfate or sulfate.

Amidoamino esters are, in particular, tertiary amines which, as substituents on the N atom, have a Cπ to C ₂₂ alk (en) ylcarbonylamino (mono- to trimethylene) radical, a Cπ to C ₂₂ alk (en) ylcarbonyloxy (mono- to trimethylene) residue and a methyl group.

Imidazolinium salts are in particular those in which the 2-position of the heterocycle a Cι ₄ - to Cι ₈ -alk (en) yl radical, the neutral N-atom form a Cι ₄ - to Cι ₈ -alk (en) ylcarbonyl (oxy or amino) ethylene residue and on the N atom carrying hydrogen, hydrogen, Carry methyl or ethyl, counterions are, for example, chloride, bromide, methyl sulfate or sulfate.

The invention is illustrated in more detail by the examples below.

Examples

The percentages in the examples mean% by weight, unless the context indicates otherwise.

The following equipment was used:

Equipment A

1% by weight alkaline solution of the highly branched polyurethane A, which was prepared as follows:

168 g of hexamethylene diisocyanate (HDI), dissolved in 386 g of dimethylacetamide (DMAc), were placed under a blanket of nitrogen at room temperature. 134 g of dimethylolpropionic acid, dissolved in 313 g of DMAc, were then added with vigorous stirring over the course of 1 min. After 0.2 g of dibutyltin dilaurate had been metered in, the reaction mixture was heated to 70 ° C. and the decrease in the NCO content was monitored titrimetrically. When the NCO content reached 1.5% by weight, the reaction product had an average functionality with respect to NCO of 1, with respect to COOH with 3 and with respect to OH with 1.

22 g of trimethylolpropane (TMP), dissolved in 50 g of DMAc, were then added to this polyaddition product and the mixture was stirred at 70 ° C. for 3 h. During this time the NCO content of the mixture dropped to 0%. The product was then freed from solvent on a rotary evaporator at 80 ° C. in vacuo.

The solid end product had the following parameters:

Average functionality with respect to OH approx. 5 and with respect to COOH approx. 9. Average molar mass: 6018 g / mol Equipment B

1% by weight alkaline solution of the highly branched polyurethane B, which was prepared as follows:

336 g of hexamethylene diisocyanate (HDI), dissolved in 336 g of dimethylacetamide (DMAc), were placed under a blanket of nitrogen and cooled to 0.degree. 105 g of diethanolamine were then added with vigorous stirring over the course of 20 minutes, and the mixture was subsequently stirred at 0 ° C. for 30 minutes. 134 g of dimethylolpropionic acid, dissolved in 239 g of DMAc, were then added. After 0.5 g of dibutyltin dilaurate had been metered in, the reaction mixture was heated to 60 ° C. and the decrease in the NCO content was monitored titrimetrically. When an NCO content of 1.2% by weight was reached, an excess of methanol was added to react any NCO groups still present. The product was then freed from solvent on a rotary evaporator at 80 ° C. in vacuo.

The reaction product had the following parameters:

Average functionality with respect to COOH approx. 3 and with respect to OH approx. 4 Average molar mass: 175J g / mol

Equipment C

1% by weight alkaline solution of the highly branched polyurethane C, which was prepared as follows:

222 g of isophorone diisocyanate (IPDI) were placed under a blanket of nitrogen. A mixture of 67 g of TMP and 67 g of dimethylolpropionic acid, dissolved in 356 g of DMAc, was then added with vigorous stirring within 1 minute. After 0.4 g of dibutyltin dilaurate had been metered in, the reaction mixture was heated to 60 ° C., stirred at this temperature and the decrease in the NCO content was monitored by titration. When the NCO content reached 1.0% by weight, the reaction product had an average functionality with respect to NCO of 1, with regard to COOH with 3 and with respect to OH with 4. 32 g of polytetrahydrofuran with an average molecular weight of 250 g / mol were then added to this polyaddition product and stirring was continued at 60 ° C. for 3 h. While during this time the NCO content of the mixture dropped to 0%. The product was then freed from solvent on a rotary evaporator at 80 ° C. in vacuo.

The solid end product had the following parameters:

Average functionality with respect to OH approx. 20 and with respect to COOH approx. 15. Average molecular weight: 22610 g / mol

Equipment D

1% by weight alkaline solution of the highly branched polyurethane D, which was prepared as follows:

168 g of hexamethylene diisocyanate (HDI), dissolved in 168 g of dimethylacetamide (DMAc), were placed under a blanket of nitrogen and cooled to 0.degree. Then, with intensive stirring, 52.5 g of diethanolamine, dissolved in 52.5 g of DMAc, were added over the course of 20 minutes and the mixture was subsequently stirred at 0 ° C. for 30 minutes. Then 59.9 g of N-methyldiethanolamine, dissolved in 59.5 g of DMAc, were added. After 0.2 g of dibutyltin dilaurate had been metered in, the reaction mixture was heated to 40 ° C. and the decrease in the NCO content was monitored by titration. When an NCO content of 1.2% by weight was reached, an excess of methanol was added to react any NCO groups still present. The product was then freed from solvent on a rotary evaporator at 80 ° C. in vacuo.

The reaction product had the following parameters:

Average functionality with regard to NR ₂ approx. 3 and with respect to OH approx. 4 Average molar mass: 1782 g / mol.

Equipment of tissue samples

Fabrics made of cotton (BW) of the size given in Table 1 with a weight per unit area of 160 g / m ² were sprayed with the finishing agents A, B, C and D on both sides, so that the application amount was 2%, based on the respective weight of the dry Textile goods, and then hot ironed in a slightly damp state. The tissue samples treated in this way were washed for comparison with untreated tissue samples of the same size and in the presence of ballast tissue with a liquid detergent at 40 ° C. in an automatic household washing machine (load between 1.5 and 3.0 kg) and then dried in a drum dryer. A standard washing or drying program was used (40 ° C colored wash program or cupboard dry program). After drying, the flat tissue samples were visually graded in accordance with the AATCC test method 124, where grade 1 means that the fabric is very creased and has many folds, while grade 5 is given for crease-free and wrinkle-free fabric. The tissue samples pretreated with equipment A, B and C received grades between 2.5 and 3.5. In contrast, the untreated tissue samples were given grade 1.

Table 1:

Claims

claims

1. A method for anti-creasing of cellulose-containing textiles by treating the textiles with a finishing agent and drying the treated textiles, characterized in that the finishing agent contains one or more highly branched polymers in dissolved or dispersed form.

2. The method according to claim 1, characterized in that the highly branched polymers are highly branched polyurethanes.

3. The method according to any one of claims 1 or 2, characterized in that the highly branched polymers one or more functional groups selected from the group consisting of -COOH, -COOR, -CONHR, -CONH _2, -OH, -SH, - NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H, - SO ₃ R, -NHCOOR, -NHCONH ₂ , -NHCONHR and their salts.

4. The method according to claim 3, characterized in that the functional groups are selected from the group consisting of -COOH, CONH, -OH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H and their salts.

5. The method according to claim 4, characterized in that the functional groups are selected from the group consisting of -COOH, -OH, -SO ₃ H and their salts.

6. The method according to claim 4, characterized in that the functional groups are selected from the group consisting of -NH ₂ , -NHR, -NR ₂ ,

-NR ₃ ⁺ and their salts.

7. The method according to any one of claims 1 to 6, characterized in that the highly branched polymers have on average at least 4 functional groups.

8. The method according spoke 7, characterized in that the highly branched polymers have an average of 4 to 100 functional groups.

9. Use of highly branched polymers, as defined in one of claims 1 to 8, in textile treatment agents, in solid and liquid

Detergent formulations and laundry detergents.

10. Use of finishing agents containing highly branched polymers, as defined in one of claims 1 to 8, in the manufacture of the textiles, in the textile treatment, in the main wash of textile laundry, in textile washing.

Fabric softener, and when ironing.

11. Finishing agent for anti-creasing of cellulose-containing textiles, containing highly branched polymers as defined in one of claims 1 to 8.

12. Textile treatment agent containing

a) 0.1-40% by weight of at least one highly branched polymer, as defined in one of claims 1 to 8,

b) 0 to 30% by weight of one or more silicones,

c) 0 to 30% by weight of one or more cationic and / or nonionic surfactants,

d) 0 to 60% by weight of further ingredients such as further wetting agents, plasticizers, lubricants, water-soluble, film-forming and adhesive polymers, fragrances and colorants, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives,

Corrosion protection additives, bactericides, preservatives and spray aids, and

e) 0 to 99.9% by weight of water,

the sum of components a) to e) being 100% by weight.

13. Containing solid detergent formulation

a) 0.05 to 20% by weight of at least one highly branched polymer as defined in one of claims 1 to 8,

b) 0 to 20% by weight of one or more silicones,

c) 0.1 to 40% by weight of at least one nonionic and / or anionic surfactant,

d) 0 to 50% by weight of one or more inorganic builders,

e) 0 to 10% by weight of one or more organic cobuilders,

f) 0 to 60% by weight of other customary ingredients, such as setting agents, enzymes,

Perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, cationic surfactants, bleaching catalysts, color transfer inhibitors, graying inhibitors, soil release polyesters, dyes, bactericides, dissolution improvers and / or disintegrants,

the sum of components a) to f) being 100% by weight.

14. Containing liquid detergent formulation

b) 0 to 20% by weight of one or more silicones,

c) 0.1 to 40% by weight of at least one nonionic and / or anionic

surfactant,

d) 0 to 20% by weight of one or more inorganic builders,

e) 0 to 10% by weight of one or more organic cobuilders, f) 0 to 60% by weight of other conventional ingredients such as soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleaching catalysts, cationic surfactants, color transfer inhibitors, graying inhibitors, soil-release polyesters, dyes, bactericides, non-aqueous solvents, Solubilizers, hydrotropes, thickeners and / or alkanolamines,

g) 0 to 99.85% by weight of water,

the sum of components a) to g) being 100% by weight.

15. Laundry detergent containing

b) 0 to 20% by weight of one or more silicones,

c) 0.1 to 40% by weight of at least one cationic surfactant,

d) 0 to 30% by weight of one or more nonionic surfactants,

e) 0 to 30 wt .-% other common ingredients such as silicones, others

Lubricants, wetting agents, film-forming polymers, fragrances and dyes, stabilizers, fiber and color protection additives,

Viscosity modifiers, soil release additives, corrosion protection additives,

Bactericides and preservatives, and

f) 0 to 99.85% by weight of water,

the sum of components a) to f) being 100% by weight.