WO2007077101A1 - Method of colouring polymer compositions and simultaneously introducing uv absorbers - Google Patents

Abstract

The present invention relates to a method of colouring polymer compositions and simultaneously introducing UV absorbers into the polymer compositions, the polymer compositions comprising at least one polyolefin and at least one polyisobutene which has been modified with polar groups and has a number-average molecular weight, M<SUB>n</SUB>, of 150 to 50 000 g/mol, by treating this polymer composition with an aqueous dyeing liquor comprising at least one dye and an aqueous dispersion, the aqueous dispersion A) comprising at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof and B) at least one surfactant; to the use of aqueous dispersions of at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof as auxiliaries for the colouring of such polymer compositions; and to an aqueous dyeing liquor comprising at least one dye, a polymer composition comprising at least one polyolefin and at least one polyisobutene which has been modified with polar groups and has a number-average molecular weight Mn of 150 to 50 000 g/mol, and the said aqueous dispersion.

Description

PROCESS FOR PURPOSING POLYMER COMPOSITIONS AND SIMULTANEOUS INTRODUCTION OF UV ABSORBERS

description

The present invention relates to a process for coloring polymer compositions and simultaneously introducing UV absorbers into the polymer compositions, wherein the polymer compositions comprise at least one polyolefin and at least one polar group-modified polyisobutene, and optionally polyester or polyamides, by treating this polymer composition with an aqueous dyeing liquor containing at least one dye and an aqueous dispersion which contains at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof and at least one surfactant. The present invention furthermore relates to the use of aqueous dispersions of at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof and as auxiliary agents in coloring the polymer compositions.

Polyolefins, especially polypropylene, are characterized by numerous excellent properties such as low specific gravity, high tear strength, good resistance to chemicals, low wettability by polar media, low water absorption capacity, good recyclability and a low price. They can be excellently processed into a variety of forms such as fibers, films and moldings.

Due to the low wettability by polar substances or the low absorption capacity of polar substances, it is only poorly possible to provide the polyolefins and fibers, films and moldings produced therefrom from aqueous baths with a UV absorber and to dye.

Methods for protection against UV radiation and for coloring polymers are known from the prior art.

DE-OS-24 53 146 relates to compositions which contain UV-ray absorbing compounds selected from benzophenones, pyrazoles and benzotriazines, for improving the light fastness of colored basic-modified polypropylenes, as well as fibers or fiber mixtures containing these compounds. Furthermore, this document discloses a process for improving the light fastness of basic modified polypropylene. in which the UV-absorbing substances are mechanically applied to the fibers and thermally fixed before, during or after the dyeing process.

EP 0 354 174 A1 discloses stable, aqueous compositions for improving the lightfastness. These compositions contain a 2- (2 ^{'hydroxyphenyl)} - benzotriazole, a condensation product of a non-ether-bridged aromatic sulfonic acid and formaldehyde, and a nonionic dispersant. These agents are used in a process for dyeing synthetic fiber materials, such as polyester or acid modified polyester fiber materials.

No. 6,723,256 B1 discloses an aqueous composition of UV-active reagents and a dispersant system of non-ionic, polymeric, hydrophilic dispersants or a mixture of such dispersants and non-ionic or anionic, vinyl-polymeric, hydrophilic thickeners or a mixture thereof Thickener for the UV-protective surface treatment of polyester, polyamide, polyurethane or cellulose acetate textile fibers or fibers of blends of these polymers.

The writing "D. A. Gordon and EC Rothstein, Polymer Engineering and Science, 1966, pages 231-239, disclose the stabilization of polypropylene from degradation by heat and UV radiation This stabilization is achieved by using antioxidants, UV absorbers, or mixtures thereof are present in the polypropylene, and protect it from degradation during processing and use. How the UV absorbers are incorporated into the polypropylene is not mentioned in this document.

The own, still unpublished application DE 102005025018.1 relates to polymer compositions which comprise polyolefins and amphiphilic block copolymers of polyisobutene blocks and polyoxyalkylene blocks, a process for dyeing such compositions and the use of amphiphilic block copolymers as auxiliaries for coloring polyolefins.

The prior art discloses methods in which UV absorbers on polymers such as polyesters, polyamides and the like are disclosed. be applied to protect them from UV radiation or it is disclosed that UV absorbers are incorporated into the polypropylene by, for example, coextrusion. It is also known that polymer compositions containing certain amphiphilic block copolymers in combination with polyolefins can be advantageously used in a process for coloring polyolefins.

The disclosed processes have the disadvantage that the application of UV absorbers to the optionally colored polymer is a further process step means. Furthermore, the UV absorber in large doses (with safety reserve) must already be present in the first step. This has the consequence that it has to be heated again and can not be flexibly adapted to the dye, for example. The application of UV absorbers during the dyeing process would avoid the disadvantage of a further process step. Furthermore, it is possible to flexibly adapt the amount of UV absorber applied from the aqueous bath to the amount required for the pulp. Furthermore, the UV absorber no longer needs to be heated, as required by the prior art processes.

The object of the present invention is to provide a process for protecting against UV radiation and for coloring polyolefins, in which the polymers can be dyed in one process step and at the same time a UV absorber can be applied.

This object is achieved by a process for coloring polymer compositions and simultaneously introducing UV absorbers into the polymer compositions, the polymer compositions comprising at least one polyolefin and at least one polar group-modified polyisobutene having a number average molecular weight M _n of 150 to 50,000 g / mol by treating the polymer compositions with an aqueous dyeing liquor comprising at least one dye and an aqueous dispersion, wherein the aqueous dispersion

A) at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof and

B) at least one surfactant

contains.

The simultaneous dyeing of polymer compositions and incorporation of UV absorbers has the effect that dye and UV absorbers penetrate into the polymers more uniformly and more intensely and thus coexist.

The polymer compositions obtained by the process according to the invention are distinguished from the materials of the prior art by more intensive and more uniform dyeings. They also have better rub fastness and very good wash fastness. In addition to these advantages, the UV absorber is particularly evenly distributed in the polymer compositions treated according to the invention. The UV absorber penetrates deeply and evenly into the fiber by the method according to the invention. In the process according to the invention, polymer compositions are used which comprise at least one polyolefin and at least one polar group-modified polyisobutene having a number-average molecular weight M _{n of} from 150 to 50 000 g / mol.

It is possible according to the invention for the polar groups in the modified polyisobutenes to be present in the polymer main chains, for example an ether function, and / or for the polar groups to be present terminally at the chain ends of the polymer chains.

The modified polyisobutene may be a polyisobutene modified with terminal polar groups, which may be obtained by functionalization of polyisobutene having a number average molecular weight M _n of 150 to 50,000 and a content of terminal double bonds (α- and / or β-olefins) or its precursor of at least 60 mol%.

The modified polyisobutenes may be linear or substantially linear polyisobutene derivatives which have a polar group only at one chain end. Such structures are also referred to as head-tail structures. It may also be linear or substantially linear polyisobutene derivatives having polar groups at both ends of the chain. Furthermore, it is also possible to use branched polyisobutene derivatives which have at least three chain ends with polar groups. The invention is not limited to a particular branching pattern. Of course, it is also possible to use mixtures of different polyisobutene derivatives for the novel polymer compositions. Furthermore, it is also possible to use dendrimers which may also be present in a mixture with polyisobutene derivatives.

The modified polyisobutene derivatives are obtainable by functionalization of reactive polyisobutene as starting material. For the purposes of the present application, reactive polyisobutene is polyisobutene which has reactive groups at one or two or, when branched reactive polyisobutenes are used, at least three chain ends, preference is given to using reactive polyisobutene as disclosed in WO 2004/035635.

For the purposes of this application, reactive polyisobutene is preferably understood as meaning a polyisobutene which comprises at least 60% of vinyl isomer (β-olefin, R-CH =C (CH ₃ ) ₂ ) and / or vinylidene isomer (α-olefin , RC (CH ₃ ) = CH ₂ ) or corresponding precursors such as RC (CH ₃ ) ₂ CI is constructed. The terminally modified polyisobutenes used according to the invention have a number average molecular weight of M _n of 150 to 50,000, preferably 200 to 35,000, particularly preferably 300 to 6,000, for example about 550, about 1,000 or about 2,300. The molecular weight distribution of the terminally modified polyisobutenes used according to the invention is generally narrow. Preferably, the molecular weight distribution (MJM _n ) is between 1, 05 and 4, more preferably between 2 and 3. However, if desired, it is also possible to use polyisobutenes having a broader molecular weight distribution of, for example, 2 to 3. B.> 5 or even> 12 to use.

The degree of functionalization of the modified polyisobutylene derivatives having terminal, polar groups is at least 65%, preferably at least 75% and very particularly preferably at least 85%. In the case of the polymers having polar groups only at one end of the chain, this information refers only to this one end of the chain. In the polymers having polar groups at both ends of the chain and the branched products, this statement refers to the total number of all chain ends. The non-functionalized chain ends are both those which have no reactive group at all and also those which, although having a reactive group, were not reacted during the functionalization reaction.

The term "polar group" is known to the person skilled in the art. The polar groups can be both protic and aprotic polar groups. The modified polyisobutenes thus have a hydrophobic moiety of a polyisobutene moiety and a moiety of at least some hydrophilic character from terminal polar moieties. They are preferably strongly hydrophilic groups. The terms "hydrophilic" and "hydrophobic" are known in the art.

Polar groups include, for example, sulfonic acid radicals, anhydrides, carboxyl groups, carboxamides, OH groups, polyoxyalkylene groups, amino groups, epoxides or suitable silanes, which may also be suitably substituted.

Suitable reactions for the introduction of polar groups (functionalization) are known in principle to the person skilled in the art.

In principle, the functionalization of the polyisobutenes used according to the invention can be carried out in one or more stages.

In a preferred embodiment, the functionalization of the polyisobutene used according to the invention takes place in one or more stages and is selected from: i) reaction with aromatic hydroxy compounds in the presence of an alkylation catalyst to give polyisobutenes-alkylated aromatic hydroxy compounds,

ii) reaction of the polyisobutene with a peroxy compound to give an epoxidized polyisobutene,

iii) Reaction of the polyisobutene with an alkene which substituted an electrophile

Having double bond (enophile), in an ene reaction,

iv) reaction of the polyisobutene with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to obtain a hydroformylated polyisobutene,

v) reaction of the polyisobutene with hydrogen sulfide or a thiol to give a thio-functionalized polyisobutene,

vi) reaction of the polyisobutene with a silane in the presence of a silylation catalyst to give a silyl-functionalized polyisobutene,

vii) reaction of the polyisobutene with a halogen or a hydrogen halide to give a polyisobutene functionalized with halogen groups,

viii) reaction of the polyisobutene with a borane and subsequent oxidative cleavage to obtain a hydroxylated polyisobutene,

ix) reaction of the polyisobutene with a SO ₃ source, preferably acetyl sulfate, to give a polyisobutene having terminal sulfonic acid groups,

x) reaction of the polyisobutene with nitrogen oxides and subsequent hydrogenation to give a polyisobutene having terminal amino groups.

In the embodiment iii), for example, maleic anhydride is used for the reaction. This results in succinic anhydride groups (succinic anhydride groups) functionalized polyisobutenes (poly-isobutenyl succinic anhydride, PIBSA).

With regard to the polyisobutenes modified with terminal, polar groups, reference is made to WO 2004/035635. For example, polyisobutene derivatives which are obtainable by reacting PIBSA with suitable nitrogen-containing compounds are suitable.

It may be here z. B. be polyisobutenes with succinimide units. Such polymers are also known as PIBSI. In a further preferred embodiment of the present invention, the polymer compositions comprise polyisobutenes modified as polar groups, polyisobutenyl succinimde (PIBSI). PIBSI and methods for producing PIBSI are disclosed in WO 2004/035635, DE-A 101 235 33 and in the as yet unpublished application EP 0 401 869 6.7. Furthermore, PIBSI derivatives are commercial, e.g. available under the name Kerocom® PIBSI (BASF AG).

As polyisobutenes modified with polar groups, in a preferred embodiment block copolymers comprising

at least one hydrophobic block (A) consisting essentially of isobutene

Units is constructed, and at least one hydrophilic block (B), which is composed essentially of oxalkyl units, and whose weight-average molar mass Mn is at least 1000 g / mol,

used.

In these polyisobutenes modified with polar groups, the polar groups, for example ether groups, are also present in the polymer chain.

Block copolymers of this type are known and their preparation can be carried out starting from starting compounds and methods which are known in principle from the person skilled in the art.

The hydrophobic blocks (A) are composed essentially of isobutene units. They are obtainable by polymerization of isobutene. However, the blocks may still have minor comonomers other than building blocks. Such devices can be used for fine control of the properties of the block. Notable as comonomers are, in addition to 1-butene and cis- or trans-2-butene, especially isoolefins having 5 to 10 carbon atoms, such as 2-methyl-1-butene-1, 2-methyl-1-pentene, 2-Me ethyl-1-hexene, 2-ethyl-1-pentene, 2-ethyl-1-hexene and 2-propyl-1-heptene or vinylaromatics such as styrene and α-methylstyrene, C 1 -C ₄ -alkylstyrenes such as 2, 3 and 4-methylstyrene and 4-tert-butylstyrene. The proportion of such comonomers should not be too large. As a rule, their amount should not exceed 20% by weight, based on the amount of all building blocks in the block. In addition to the isobutene units or comonomers, the blocks may also contain the initiators or initiators used to start the polymerization. Starter molecules or fragments thereof. The polyiso- butenes can be linear, branched or star-shaped. They can have functional groups only at one chain end or at two or more chain ends.

Starting material for the hydrophobic blocks A are functionalized polyisobutenes. Functionalized polyisobutenes can be prepared starting from reactive polyisobutenes by providing them with functional groups in single-stage or multistage reactions which are known in principle to those skilled in the art. The term "reactive polyisobutene" is understood by the person skilled in the art to mean polyisobutene which has a very high proportion of terminal α-olefin end groups. The preparation of reactive polyisobutenes is likewise known and described, for example, in detail in WO 04/9654, pages 4 to 8, or in WO 04/35635, pages 6 to 10.

Preferred embodiments of the functionalization of reactive polyisobutene have already been mentioned above under i) to x).

With regard to all details for carrying out the above reactions, we refer to the comments in WO 04/35635, pages 1 1 to 27.

The molar mass of the hydrophobic blocks A is determined by the skilled person depending on the desired application. The hydrophobic blocks (A) preferably each have an average molar mass M _{n of} from 200 to 10,000 g / mol. M _n is particularly preferably from 300 to 8000 g / mol, very particularly preferably from 400 to 6000 g / mol and particularly preferably from 500 to 5000 g / mol.

The hydrophilic blocks (B) are composed essentially of oxalkyl units. Oxalkyl units are in a manner known in principle to units of the general formula -R ¹ -O-. Here, R ^{1 is} a divalent aliphatic hydrocarbon radical, which may also optionally have further substituents. Additional substituents on the radical R ¹ may in particular be O-containing groups, for example> C = O groups or OH groups. Of course, a hydrophilic block may also comprise several different oxalkylene units.

The oxalkyl units may in particular be - (CH ₂ ) ₂ -O-, - (CH ₂ ) 3-O-, - (CH ₂ J ₄ -O-, -CH ₂ -CH (R ² ) - O-, -CH ₂ -CHOR ³ -CH ₂ -O-, where R ² is an alkyl group, in particular C 1 -C ₂₄ -alkyl or an aryl group, in particular phenyl, and R ³ is selected from a group from the group of hydrogen, C ¹ -C ₂₄ -alkyl, R ¹ -C (= O) -, R ¹ -NH-C (= O) -. The hydrophilic blocks may also comprise further structural units, such as, for example, ester groups, carbonate groups or amino groups. Furthermore, they may also comprise the initiator or starter molecules used to start the polymerization or fragments thereof. Examples include terminal groups R ² - O-, where R ^{2 has} the meaning defined above.

As a rule, the hydrophilic blocks comprise as main components ethylene oxide units - (CH ₂ ^ -O- and / or propylene oxide units -CH ₂ -CH (CH ₃ ) -O, while higher alkylene oxide units, ie those having more than 3 C atoms The blocks may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide units The amount of higher alkylene oxide units should be 10% by weight, preferably 5% Preferably, these are blocks which comprise at least 50% by weight of ethylene oxide units, preferably 75% by weight and particularly preferably at least 90% by weight of ethylene oxide units ,

The hydrophilic blocks B are obtainable in a manner known in principle, for example by polymerization of alkylene oxides and / or cyclic ethers having at least 3 C atoms and optionally further components. They can also be prepared by polycondensation of di- and / or polyalcohols, suitable initiators and optionally further monomeric components.

Examples of suitable alkylene oxides as monomers for the hydrophilic blocks B include ethylene oxide and propylene oxide and furthermore 1-butoxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide , 2-methyl-1, 2-butene oxide, 3-methyl-1, 2-butene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1, 2-pentenoxide, 2-ethyl-1 , 2-butene oxide, 3-methyl-1, 2-pentenoxide, decene oxide, 4-methyl-1, 2-pentenoxide, styrene oxide or be formed from a mixture of oxides of technically available raffinate streams. Examples of cyclic ethers include tetrahydrofuran. Of course, mixtures of different alkylene oxides can be used. Depending on the desired properties of the block, the person skilled in the art makes a suitable choice among the monomers or further components.

The hydrophilic blocks B may also be branched or star-shaped. Such blocks are available by using starter molecules with at least 3 arms. Examples of suitable initiators include glycerol, trimethylolpropane, pentaerythritol or ethylenediamine. The synthesis of alkylene oxide units is known to the person skilled in the art. Details are detailed in, for example, "Polyoxyalkylenes" in Ullmann's Encyclopedia of Industrial Chemistry, 6 ^th Edition, Electronic Release.

The molar mass of the hydrophilic blocks B is at least 1000 g / mol and is determined by the skilled person depending on the desired application. At less than 1000 g / mol, the results are often unsatisfactory.

The hydrophilic blocks (B) preferably each have an average molar mass M _{n of} from 1000 to 20 000 g / mol. With particular preference M _{n is} 1250 to 18000 g / mol, very particularly preferably 1500 to 15000 g / mol and particularly preferably 2500 to 8000 g / mol.

The synthesis of the block copolymers used according to the invention can preferably be carried out by first preparing the hydrophilic blocks B separately and reacting them in a polymer-analogous reaction with the functionalized polyisobutenes to form block copolymers.

The building blocks for the hydrophilic and hydrophobic blocks in this case have complementary functional groups, i. Groups that can react with each other to form linking groups.

The functional groups of the hydrophilic blocks are of course preferably OH groups, but they may also be, for example, primary or secondary amino groups. OH groups are particularly suitable as complementary groups for reaction with PIBSA.

The synthesis of blocks B can also be carried out by reacting polar functional group-containing polyisobutenes (i.e., blocks A) directly with alkylene oxides to form blocks B.

The structure of the block copolymers used in the present invention can be influenced by selecting the kind and amount of the starting materials for the blocks A and B and the reaction conditions, particularly the order of addition.

The blocks A and / or B may be terminal, ie they are only connected to another block, or they may be connected to two or more other blocks. For example, the blocks A and B may be linearly linked together in an alternating arrangement. In principle, any number of blocks can be used. As a rule, however, there are no more than 8 blocks A or B in each case. This results in the simplest case a two-block copolymer of the general formula AB. Furthermore, it may be triblock copolymers of general formula ABA or BAB. Of course, several blocks can follow each other, for example ABAB, BABA, ABABA, BABAB or ABABAB.

Furthermore, it may be star-shaped and / or branched block copolymers or comb-like block copolymers, in which more than two blocks A are each bound to a block B or more than two blocks B to a block A. For example, they may be block copolymers of the general formula AB _m or BA _m , where m is a natural number> 3, preferably 3 to 6 and particularly preferably 3 or 4. Of course, in the arms or branches also several blocks A and B follow each other, for example A (BA) _m or B (AB) _m .

The synthesis possibilities are shown below by way of example for OH groups and succinic anhydride groups (denoted as S), without the invention being restricted to the use of such functional groups. It is also possible to use NH-- groups instead of the OH groups.

HO- [B] -OH Hydrophilic blocks containing two OH groups

[B] -OH Hydrophilic blocks containing only one OH group.

[B] - (OH) _x Hydrophilic blocks with x OH groups (x> 3)

[A] -S polyisobutene with a terminal group S

S- [A] -S polyisobutene with two terminal groups S

[A] -Sy polyisobutene with y groups S (y> 3)

The OH groups can be linked together in a manner known in principle with the succinic anhydride groups S to form ester groups. The reaction can be carried out, for example, while heating in bulk. Suitable, for example, reaction temperatures of 80 to 150 ° C. If NH groups are used instead of the OH groups, then a-mid groups are formed during the reaction.

For example, triblock copolymers ABA are readily prepared by reacting one equivalent of HO- [B] -OH with two equivalents of [A] -S. This is illustrated below by way of example with complete formulas. An example is the reaction of PIBSA and a polyethylene glycol:

Here, n and m independently represent natural numbers. They are selected by the person skilled in the art so that the initially defined molar masses result for the hydrophobic or hydrophilic blocks.

Star-shaped or branched block copolymers BA _x can be obtained by reacting [B] - (OH) _x with x equivalents [A] -S.

It is clear to the person skilled in the art of polyisobutenes that the resulting block copolymers may also have residues of starting materials, depending on the preparation conditions. In addition, they can be mixtures of different products. For example, triblock copolymers of the formula ABA may also contain two-block copolymers AB as well as functionalized and unfunctionalized polyisobutene. Advantageously, these products can be used without further purification for the application. Of course, the products can also be cleaned. The person skilled in cleaning methods are known.

Preferred block copolymers for carrying out this invention are triblock copolymers of the general formula ABA, or their mixture with two-block copolymers AB and optionally by-products.

In a preferred embodiment, a block copolymer is used in the process according to the invention, wherein

the average molar mass M _{n of} the hydrophobic blocks (A) of the block copolymer 200 to 10,000 g / mol, and

- The average molar mass M _{n of} the hydrophilic blocks (B) of the block copolymer is 1000 to 20,000 g / mol. The blocks (A) and (B) are interconnected by means of suitable linking groups. They can each be linear or also have branches.

The described polar group-modified polyisobutenes, preferably the abovementioned block copolymers, are used in conjunction with polyolefins in the process according to the invention, since such an application of UV absorbers selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, Hydroxyphenyltriazinen and mixtures thereof and in simultaneous coloring of the polymer compositions is possible.

The polar group-modified polyisobutene, preferably the block copolymer, serves as an aid for improving the ability of the polyolefin to take up the UV absorber from the aqueous liquor. Moreover, if mixtures of different polyolefins or one polyolefin with another polymer are used, it acts as an efficient compatibilizer.

As polyolefins, basically all known polyolefins are suitable. For example, they may be homopolymers or copolymers which are ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene or α-methylstyrene as monomers include. Preference is given to polyolefins which comprise C ₂ - to C ₄ -olefins as the main constituent, more preferably to polypropylene or polyethylene homo- or copolymers. Copolymers may be random copolymers or block copolymers. Suitable comonomers in copolymers are preferably - depending on the polyolefin basic bodies - ethylene or other α-olefins, dienes such as hexadiene-1, 4, hexadiene 1, 5, heptadiene-1, 6, 2-methylpentadiene 1, 4, octadiene-1, 7 , 6-methylheptadiene-1, 5, or polyenes such as octatriene and dicyclopentadiene. The proportion of comonomers in the copolymer is generally not more than 40% by weight, preferably not more than 30% by weight, relative to the sum of all constituents of a monomer, for example from 20 to 30% by weight or from 2 to 10% by weight Dependence on the application.

In a preferred embodiment, the polyolefin is a polypropylene or polyethylene homo- or copolymer.

In a particularly preferred embodiment of the invention, the polyolefin is polyethylene, for example LDPE, HDPE or LLDPE.

In a further particularly preferred embodiment, the polyolefin is polypropylene. These may be polypropylene homopolymers or copolymers. Suitable comonomers may in particular be ethylene and the above-mentioned α-olefins, dienes and / or polyenes act. The choice of polypropylene is not limited. With particular advantage, viscous polypropylenes having a high melt flow index can be processed. For example, it may be polypropylene having a melt flow index MFR (230 ° C, 2.16 kg) of less than 40 g / 10 min.

Furthermore, it may also be mixtures (blends) of different polyolefins, for example polypropylene and polyethylene or copolymers of ethylene and propylene.

In addition to the polyolefins and the block copolymers, the compositions according to the invention may also comprise chemically different polymers. For example, other polymers may be polyamides and / or polyesters, for example PET.

In a preferred embodiment, the polymer composition further contains polyesters or polyamides.

The amphiphilic block copolymers used according to the invention advantageously not only facilitate the ability to absorb UV absorbers selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof and, but also act as efficient compatibilizers for blending various polymers. Particularly noteworthy here are blends of various polyolefins, such as, for example, polypropylene and polyethylene or polypropylene with polyesters or polyamides.

The polymer compositions may optionally also include other typical additives and adjuvants. Examples include antistatic agents, absorbers or fillers. Such additives are known in the art. Details of this are shown, for example, in "Polyolefins" in Ullmanns Encyclopedia of Technical Chemistry, 6 ^th Edition, 2000, Electronic Release.

The polymer compositions may be in any form, for example as any shaped bodies or films. The polymer composition is preferably also in the form of shaped articles, films, fibers, yarns, woven fabrics, nonwovens, knitted fabrics, knitted fabrics and / or other textile materials. Processes for producing fibers or yarns, fabrics, nonwovens and / or other textile materials from polymers or polymeric compositions produced therefrom are known to the person skilled in the art. The preparation of the polymer compositions can be carried out by various techniques. For example, the polyolefins can be prepared in the presence of the polar group-modified polyisobutenes used in the present invention. Furthermore, it is possible first to produce polyolefin shaped bodies, in particular fibers, yarns, woven fabrics and / or nonwovens, and subsequently to treat them superficially with the polyisobutenes used according to the invention, optionally followed by a heat treatment step.

The polyisobutenes can be thoroughly mixed with the polyolefins and optional other components by heating to the molten liquid by means of suitable equipment. For example, kneaders, single-screw extruders, twin-screw extruders or other dispersing aggregates can be used. The discharge of the molten polymer composition from the mixing units can take place in a manner known in principle via nozzles. For example, strands can be formed and cut into granules. The molten mass can also be formed directly, for example by injection molding or blow molding into moldings or it can be formed by means of suitable nozzles to form fibers.

The modified polyisobutene or the mixture of different modified polyisobutenes can preferably be added in substance to the polyolefins, but they can also be added in solution.

The temperature for mixing is selected by the person skilled in the art and depends on the type of polyolefins used or, if appropriate, other polymers. The polyolefins should on the one hand sufficiently soften, so that mixing is possible. On the other hand, they should not become too thin, because otherwise sufficient shear energy input can no longer take place and, under certain circumstances, thermal degradation is also to be feared. As a rule, temperatures of 120 to 300 ° C can be applied without the invention being restricted thereto. It proves to be particularly advantageous that the modified polyisobutenes used have a high thermal stability.

The polymer compositions according to the invention generally contain from 75 to 99.95% by weight of the polyolefins, preferably from 85 to 99.9% by weight, particularly preferably from 90 to 99.85% by weight and very particularly preferably from 95 to 99.8% by weight, in each case based on the sum of all components of the composition.

The amount of modified polyisobutene will be determined by those skilled in the art according to the desired properties of the composition. It is usually From 0.05 to 10% by weight, based on the sum of all components of the composition, preferably from 0.1 to 6% by weight, particularly preferably from 0.3 to 5% by weight and very particularly preferably from 0.5 to 3.5% by weight ,

In a preferred embodiment of the process for preparing the polymer compositions, the modified polyisobutene can also be incorporated in a two-stage process. For this purpose, at least one modified polyisobutene is mixed with only a portion of the polyolefins with heating. In this case, the already described techniques can be used for mixing. Such a concentrate may contain from 5 to 50% by weight, preferably from 20 to 40% by weight, of the modified polyisobutene. The concentrate is then mixed with the remainder of the polyolefins with heating in a second step and shaped according to the intended use. For example, threads can be made that can be further processed into yarns, fabrics, nonwovens or other textile materials.

The still undyed polymer compositions prepared as described, in particular in the form of fibers, yarn fabrics, nonwovens and / or other textile materials or in the form of moldings or films can be selected in a simple manner by means of the process according to the invention with a UV absorber from Group consisting of benzotriazoles, benzophenones, cyanoacrylates, Hydroxyphenyltriazinen and mixtures thereof are treated and colored. The presence of the modified polyisobutenes markedly increases the affinity of the polyolefins for the UV absorbers and dyes, in particular for disperse dyes or metal complex dyes.

In the process according to the invention, the polymer compositions are generally obtained by treatment with an aqueous dyeing liquor comprising at least one dye and an aqueous dispersion and heating the polymer composition during and / or after the treatment to a temperature greater than its glass transition temperature T _G but less than its melting temperature protected against UV radiation and colored.

In principle, all known dyes, such as, for example, cationic dyes, anionic dyes, mordant dyes, direct dyes, disperse dyes, development dyes, vat dyes, metal complex dyes, reactive dyes, sulfur dyes, acid dyes or substantive dyes, can be used as dyes in the process.

For carrying out the invention, preference is given to a dye selected from the group consisting of disperse dye, metal complex dye, acid dye and used. Particular preference is given to using a disperse dye or an acid dye.

The term "disperse dye" is known to the person skilled in the art Disperse dyes are dyes with a low water solubility, which are used in disperse, colloidal form for dyeing, in particular for dyeing fibers and textile materials.

In principle, any disperse dyes can be used to carry out the invention. These can have different chromophores or mixtures of the chromophores. In particular, these may be azo dyes or anthraquinone dyes. Furthermore, they may be quinophthalone, naphthalimide, naphthoquinone or nitro dyes. Examples of disperse dyes include Cl. Disperse Yellow 3, Cl. Disperse Yellow 5, Cl. Disperse Yellow 64, Cl. Disperse Yellow 160, Cl. Disperse Yellow 21 1, Cl. Disperse Yellow 241, Cl. Disperse Orange 29, Cl. Disperse Orange 44, Cl. Disperse Orange 56, Cl. Disperse Red 60, Cl. Disperse Red 72, Cl. Disperse Red 82, Cl. Disperse Red 388, Cl. Disperse Blue 79, Cl. Disperse Blue 165, Cl. Disperse Blue 366, Cl. Disperse Blue 148, Cl. Disperse Violet 28 or Cl. Disperse Green 9. The nomenclature of dyes is known to those skilled in the art. The complete chemical formulas can be found in relevant textbooks and / or databases (eg "Color Index") Further details on disperse dyes and other examples are also given for example in "Industrial Dyes", Edt. Klaus Hunger, Wiley-VCH, Weinheim 2003, pages 134 to 158 in detail.

It is also possible to use mixtures of different disperse dyes. In this way, mixed colors can be obtained. Preference is given to those disperse dyes which have good fastness properties and in which trichromaticity is possible.

The term "acid dye" is known to the person skilled in the art and has one or more acid groups, for example a sulfonic acid group, or a salt thereof, which may contain various chromophores or mixtures of the chromophores include monoazo dyes such as Cl Acid Yellow 17, Cl Acid Blue 92, Cl Acid Red 88, Cl Acid Red 14 or Cl Acid Orange 67, disazo dyes such as Cl Acid Yellow 42, Cl Acid Blue 1 13 or Cl. Acid Black 1, trisazo dyes such as Cl. Acid Black 210, Cl. Acid Black 234, metal complex dyes such as Cl. Acid Yellow 99, Cl. Acid Yellow 151 or Cl. Acid Blue 193 Pickling dyes such as Cl. Mordant Blue 13 or Cl. Mordant Red 19 or acid dyes with various other structures such as Acid Orange 3 Cl, Cl Acid Blue 25 or Cl Acid Brown 349. Further details units for acid dyes and other examples are also described in detail, for example, in "Industrial Dyes", Edt., Klaus Hunger, Wiley-VCH, Weinheim 2003, pages 276 to 295. It is of course also possible to use mixtures of different acid dyes.

The metal complex dyes have one or more metal atoms in the chromophore. They may have different chromophores or mixtures of chromophores. Examples of suitable metal complex dyes are those having formulas with the following color indices: SY 79, SY 81, SY 82, SO 56, SO 54, SO 99, Sbr. 42, SR 122, SR 118, SR 127, SB 70, SBk 27, SBk 29.

The aqueous dispersion used in the process according to the invention contains

A) at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and

Mixtures thereof and

B) at least one surfactant.

The individual components of the dispersion are explained below.

Component A):

The aqueous dispersion used in the process according to the invention comprises as component A) at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof.

Particularly suitable according to the invention are benzotriazoles of the general formula (I):

mit den folgenden Bedeutungen:

with the following meanings:

R ^{1 is} hydrogen, saturated or unsaturated, branched or linear hydrocarbon radical having 1 to 12 carbon atoms, one or more of which is optionally substituted by heteroatoms selected from N, O, P or S may be substituted, aromatic or heteroaromatic radical having 6 to 20 carbon atoms, which may be replaced directly or via alkyl chains having 1 to 12 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S. the basic skeleton of the formula (I) may be bonded, halogens such as chlorine, bromine or iodine, particularly preferably linear or branched alkyl radicals having 1 to 6 carbon atoms or chlorine, bromine, iodine, particularly preferably methyl, ethyl or propyl, chlorine, bromine , R ² , R ^{3 are} independently hydrogen, saturated or unsaturated, branched or linear hydrocarbon radical having 1 to 20 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S, aromatic or heteroaromatic radicals having 6 to 20 carbon atoms, which may be replaced directly or via alkyl chains having 1 to 12 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S, or the keto, carboxyl, amido or imido groups in the chain, may be bonded to the skeleton of the formula (I), particularly preferably methyl, ethyl, propyl, isopropyl, sec-butyl, benzyl, CMe ₂ Ph, tert-butyl, tert-amyl, tert-butyl, tert-octyl, CMe ₂ CH ₂ CMe ₂ CH ₃ , CMe ₂ CH ₂ CH ₃ , dodecyl and / or

CH ₂ CH ₂ O (C =O) C (CH ₂ ) CH ₃ .

Preferably, the substituent R ^{1 is} in the 5-position. The substituents R ² and R ³ are preferably arranged in the 4- and 6-position.

As the UV absorber is also a mixture containing 52% of the compound of the general formulas (II) (CAS number 104810-48-2), 35% of the compound of general formula (IM) (CAS number 104810-47-1) and 13% of the compound of general formula (IV) (CAS number 25322-68-3):

In einer besonders bevorzugten Ausführungsform sind die als Komponente A) in der wässrigen Dispersion eingesetzten Benzotriazole ausgewählt aus der Gruppe bestehend aus - 6-tert.-Butyl-2-(5-chlor-2H-benzotriazol-2-yl)-4-methylphenol (CAS-Nummer 3896- 1 1-5),

In a particularly preferred embodiment, the benzotriazoles used as component A) in the aqueous dispersion are selected from the group consisting of - 6-tert-butyl-2- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol (CAS number 3896-1 1-5),

2,4-di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -phenol, (CAS number 3864-99-

1 ),

2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, (CAS number 25973-55-1), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutylphenol), (CAS number 3147-75-9)

2- (2H-benzotriazol-2-yl) -4-methylphenol, (CAS number 2440-22-4),

2- (2H-Benzotriazol-2-yl-4,6-bis (1-methyl-1-phenylethyl) phenol, (CAS number 70321-86-7), 2-benzotriazol-2-yl-4, 6-di-tert-butylphenol, (CAS number 3864-71-7),

2- (2H-Benzotriazol-2-yl) -4- (tert-butyl) -6- (sec -butyl) phenol, (CAS number 36437-37-

3)

- 2,2 ^{'methylenebis} (6- (2H-benzotriazol-2-yl) -4-1, 1, 3,3-tetramethylbutyl) phenol) (CAS number 103597-45-1) - 2- ( 2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, branched and linear, (CAS number 23328-53-2 / 125304-04-3 / 104487-30-1),

2- (2 ^" -hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, (CAS number 96478-09-0),

2- (2H-Benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, (CAS number 73936-91-1) .

Isomeric mixture of the alkylation of 2- (2H-benzotriazol-2-yl) -p-cresol with dodecane (CAS number 125304-04-3),

Mixture containing 52% of the compound of general formula (II) (CAS number 104810-48-2), 35% of the compound of general formula (IM) (CAS number 104810-47-1) and 13% of the compound of general formula (IV)

Number 25322-68-3) and mixtures thereof.

The compounds of the formulas (I), (II), (III) and (IV) can be prepared by processes known to the person skilled in the art. Some of the compounds of formula (I), (M), (IM) and (IV) are commercially available.

Benzophenones which can be used according to the invention as UV absorbers correspond to the general formula (V) or (Va): with

(V) (Va)

R ⁴ , R ^{5 are} independently hydrogen, saturated or unsaturated, branched or linear carbon radicals having 1 to 20 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S, aromatic or heteroaromatic radicals 6 to 20 carbon atoms, which may be replaced directly or via alkyl chains having 1 to 12 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S, or the keto, carboxyl, amido or imido Groups in the chain can carry.

In a further preferred embodiment, R ⁵ = O-alkyl, more preferably OMe, ON-octyl or OH and R ⁴ is hydrogen. In a further preferred embodiment, R ⁴ and R ^{5 are} hydrogen. In a further preferred embodiment, R ⁴ and R ^{5 are located} in the para position for better interaction with the C = O functionality. In the compound of general formula (Va), R ⁴ and R ^{5 are} preferably OH or OMe.

Cyanoacrylates which can be used according to the invention as UV absorbers correspond to the general formula (VI):

(VI) with

R ^{6 of} saturated or unsaturated, branched or linear carbon radicals having 1 to 20 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S, aromatic or heteroaromatic radicals having 6 to 20 carbon atoms directly or via alkyl chains having 1 to 12 carbon atoms, one or more of which is optionally substituted by heteroatoms, can be replaced by N, O, P or S, or can carry the keto, carboxyl, amido or imido groups in the chain,

R ⁷ , R ⁸ independently of one another are aromatic radicals having 6 to 20 carbon atoms or heteroaromatic radicals having 6 to 20 carbon atoms and heteroatoms selected from N, O, P or S, the radicals having at least one substituent selected from alkyl radicals having 1 to 12 carbon atoms , functional groups selected from amido, imido, carbonyl, carboxyl groups and halogens may be substituted.

Preferably, R ⁷ and R ⁸ in the compound of general formula (VI) are phenyl. R ⁶ in the compound of the general formula (VI) is preferably an alkyl radical having 1 to 10 carbon atoms, more preferably ethyl or 2-ethylcyclohexyl.

Particularly preferred cyanoacrylates are selected from the group consisting of 1, 3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis - {[(2'-cyano-3' , 3'-diphenylacryloyl) oxy] methyl} -propane (CAS number 178671-58-4), ethyl 2-cyano-3,3-diphenylacrylate (CAS number 5232-99-5), (2-ethylhexyl) 2-cyano-3,3-diphenylacrylate (CAS number 6197-30-4) and mixtures thereof.

Hydroxyphenyltriazines which can be used according to the invention as UV absorbers correspond to the general formula (VII):

(VII) with

10a R ⁹ , R

R 11a o10b _R 11b are independently hydrogen or saturated or unsaturated, branched or linear carbon radicals having 1 to 20 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S, aromatic or heteroaromatic radicals 6 to 20 carbon atoms, directly or via Alkyl chains having 1 to 12 carbon atoms, one or more of which may optionally be replaced by heteroatoms selected from N, O, P or S, or may carry the keto, carboxyl, amido or imido groups in the chain.

Preferably, R ^{9 is} = 0-C ₈ H ₁₇ or 0-C ₆ H ₁₃ . R ^10a , R ^10b , R ^11a and R ^11b are independently of one another preferably hydrogen or C ₁ -C ₆ -alkyl, particularly preferably hydrogen or methyl.

In a preferred embodiment, the substituent R ^{9 is} in the 4-position. The substituents R ^10a , R ^10b R ^11a and R ^11b , if present, are preferably in the 2- and 4-positions.

R ⁹ is preferably a linear or branched alkyl radical having 1 to 8 carbon atoms attached via a heteroatom selected from O, S or N to the phenyl ring, more preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl , Heptyl and octyl. The radicals R ¹⁰ and R ¹¹ are preferably hydrogen. Most preferably, R ^{9 is} a C ₆ H ₁₃ radical attached via an oxygen atom.

Of the group of hydroxyphenyltriazines, very particular preference is given to using 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol (CAS No. 147315-50-2).

The UV absorbers used in the process according to the invention are essentially water-insoluble. This means that 0 to 0.2 g / l, preferably 0 to 0.1 g / l, particularly preferably 0 to 0.02 g / l of the UV absorber dissolve in water.

Component A) is generally present in the aqueous dispersion used in the process according to the invention in an amount of from 5 to 50% by weight, preferably from 10 to 40% by weight, more preferably from 15 to 30% by weight, based on the total weight of the suspension or dispersion.

Component B):

The aqueous dispersion used in the process according to the invention contains as component B) at least one surfactant.

In general, all surfactants known to the person skilled in the art can be used in the aqueous dispersion used in the process according to the invention. These Surfactants may be nonionic, anionic, cationic or zwitterionic or amphoteric surfactants.

Nonionic surfactants:

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is linear or preferably methyl-branched in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. ₁₄ - - The preferred ethoxylated alcohols include, for example, ₁₂ C, alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C _3- I ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ -is-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci _2- i ₄ -alcohol with 3 EO and Ci ₂ -i8-alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants, it is also possible to use alkyl glycosides of the general formula R ⁴ O (G) _x in which R ^{4 is} a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms. Atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of ongonomation x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.

Other suitable surfactants are polyhydroxy fatty acid amides. The polyhydroxy fatty acid amides are known substances, usually by reductive amination of a reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose, with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid , a fatty acid alkyl ester or a fatty acid chloride can be obtained. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Preferred nonionic surfactants are furthermore ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.

Suitable alkylene oxide units which may be present in addition to ethylene oxide units in the nonionic surfactants usable according to the invention are units derived from propylene oxide, butylene oxide, propylene oxide, hexylene oxide. However, further alkylene oxides are also suitable.

Particularly preferred nonionic surfactants are

C12 / C14 fatty alcohol ethoxylates, i. Ethoxylates of straight chain oleochemical alcohols (Lutensol® A..N brands of BASF Aktiengesellschaft), - C13 / C15 oxo alcohol ethoxylates, i. Ethoxylates of largely linear alcohols (Lutensol® AO brands of BASF Aktiengesellschaft),

Alkylphenylethoxylates (Lutensol® AP brands of BASF Aktiengesellschaft), C16 / C18 fatty alcohol ethoxylates (Lutensol® AT brands of BASF Aktiengesellschaft), fatty amine and amide ethoxylates (Lutensol® F brands of BASF Aktiengesellschaft), alkyl polyglucosides (Lutensol® GD grades from BASF Aktiengesellschaft), C10 oxo alcohol ethoxylates (Lutensol® ON brands of BASF Aktiengesellschaft), C13 oxo alcohol ethoxylates (Lutensol® TO brands of BASF Aktiengesellschaft), surfactants based on C10 Guerbet alcohol (Lutensol® XL brands or Lutensol® XP brands of BASF Aktiengesellschaft )

Fatty alcohol ethoxylates (Plurafac® brands of BASF Aktiengesellschaft), PO / EO block polymers (Pluronic® PE grades, Pluronic® RPE grades or Tetronic® grades from BASF Aktiengesellschaft),

Methyl polyethylene oxides (Pluriol® A .. E brands of BASF Aktiengesellschaft), surfactant based on butylpropylene oxide (Pluriol® A .. P brands of BASF Aktienge- Seilschaft),

Alkyl-modified polypropyleneglycol-polyethyleneglycol copolymers (Pluriol® A .. PE brands of BASF Aktiengesellschaft),

- Pluriol® A .. R brands of BASF Aktiengesellschaft,

Polyalkylene oxides based on a trifunctional alcohol (Pluriol® A .. TE brands of BASF Aktiengesellschaft), alkoxylated bisphenol A derivatives (Pluriol® BP brands of BASF Aktiengesellschaft),

Polyethylene glycols (Pluriol® E brands of BASF Aktiengesellschaft), polypropylene glycols (Pluriol® P brands of BASF Aktiengesellschaft), - Emulan® brands of BASF Aktiengesellschaft, water-soluble homopolymers and copolymers based on vinylpyrrolidone, vinylimidazole and monomers with nonionic character (Sokalan® HP brands BASF Aktiengesellschaft), water-soluble copolymers based on acrylic and maleic acid (Sokalan® C brands of BASF Aktiengesellschaft),

- water-soluble homopolymers based on acrylic acid (Sokalan® PA brands of BASF Aktiengesellschaft)

Mixtures thereof.

Anionic surfactants:

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type are preferably Cg. ₁ 3- alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C ₂ i ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation gets into consideration. Also suitable are alkanesulfonates, which are for example obtained from C ₂ i ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Likewise suitable are the esters of [alpha] sulfo fatty acids (ester sulfonates), for example the [alpha] sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Also suitable are salts of aromatic sulfonic acid condensates.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester Ci ₂ - ₁ 8 fatty alcohols, for example coconut fatty alcohol, fatty alcohol TaIg-, lauryl, myristyl, cetyl or stearyl alcohol, or CIO ₂ 0- Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. The Ci ₂ - ₁ 6-alkyl sulfates and Ci ₂ -is-alkyl sulfates and Ci ₄ - ₁ 5-alkyl sulfates preferred. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C _7-2 i alcohols, such as 2-methyl-branched C ₉ n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci ₂ -i8 Fatty alcohols containing 1 to 4 EO are suitable.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-i8 fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Particularly preferred anionic surfactants are

high molecular weight ether sulphates (Emulphor® brands of BASF Aktiengesellschaft),

- alkylnaphthalenesulfonates (Nekal® brands of BASF Aktiengesellschaft),

- Sodium salts of naphthalenesulfonic acid condensates (Tamol® N brands of BASF Aktiengesellschaft,

- Lutensit® trademarks of BASF Aktiengesellschaft or

- mixtures thereof.

The anionic surfactants which can be used in the surfactant mixture according to the invention can be prepared by processes known to the person skilled in the art.

Cationic surfactants:

Cationic surfactants are surface-active substances in which the surface-activity-dependent high molecular weight hydrophobic group is in the cation during dissociation in aqueous solution. The most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula (R ⁵ ₄ N ⁺⁾ X \ where the radicals R ⁵ can be identical or different, and are selected from Ci- ₂ o-Kolhenst.offrest.en, preferably methyl In a particularly preferred two R ⁵ radicals are short chain, such as methyl, and the two remaining radicals are long chain, such as stearyl or palmityl. X- may be any anion, preferably a halide, for example chloride or bromide.

In addition, all cationic surfactants known to the person skilled in the art can be used in the process according to the invention.

Particularly preferred cationic surfactants are

- Multifunctional, non-toxic, cationic polymers based on ethyleneimine with molecular weights between 800 and 2,000,000 Da (Lupasol® brands of BASF Aktiengesellschaft).

Zwitterionic or amphoteric surfactants:

The terms amphoteric surfactants and zwitterionic surfactants are used synonymously in this document. In the surfactant mixture according to the invention, all surfactants having at least two functional groups which can ionize in aqueous solution and, depending on the conditions of the medium, impart anionic or cationic character to the surface-active compounds can be used as amphoteric surfactants.

The amphoteric surfactants which can be used in the mixture according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acetylated amino acids or surfactants of natural origin, such as lecithins or saponins.

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines and the phosphobetaines.

The amine oxides which can be used according to the invention as amphoteric surfactants include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids, which carry ³ COOH at the amino nitrogen is the acyl radical R ³ CO a saturated or unsaturated fatty acid R, where R ³ is a saturated or unsaturated C6 ₂₂ - alkyl radical, preferably ₂₂ Cβ- alkyl group, in particular a saturated CIO ₁₆ alkyl radical, for example a saturated C ₂ i ₄ is alkyl. The acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt. Exemplary acylated amino acids are the acyl derivatives, for example sodium cocoyl glutamate, lauroyl glutamic acid, caproyloyl glycine or myristoyl methylanine.

In the dispersion used according to the invention, 0.01 to 10% by weight, preferably 1 to 10, particularly preferably 4 to 8, of at least one surfactant, based on the total weight of the suspension (dispersion), are present.

In the method according to the invention, the polymer composition is treated with a formulation (dyeing liquor) comprising at least one dye and an aqueous dispersion comprising a UV absorber and a surfactant. An aqueous formulation for coloring textile materials is called "liquor".

The formulation preferably comprises only water as the solvent. However, even small amounts of water-miscible organic solvents may be present. Examples of such organic solvents include monovalent or polyhydric alcohols, such as methanol, ethanol, n-propanol, i-propanol, ethylene glycol, propylene glycol or glycerol. Furthermore, it may also be ether alcohols. Examples include monoalkyl ethers of (poly) ethylene or (poly) propylene glycols such as ethylene glycol monobutyl ether. The amount of such solvents other than water should, however, generally not exceed 20% by weight, preferably 10% by weight and more preferably 5% by weight, relative to the sum of all solvents of the formulation or liquor.

The formulation may comprise, in addition to solvents and dyes, other auxiliaries. Examples include typical textile auxiliaries, such as dispersants and leveling agents, acids, bases, buffer systems, complexing agents, rheology aids, surfactants or defoamers.

A neutral or acidic formulation is preferably used in the process according to the invention, for example with a pH of from 3 to 7, preferably from 4 to 6.

The treatment with the polymer composition, in particular the fibers, yarn fabrics, nonwovens and / or other textile materials with the dye and the aqueous dispersion can be carried out by customary processes, for example by immersion in the formulation containing the dye and the aqueous dispersion contains, the spraying of this formulation or the application of this formulation by means of suitable equipment. It may be continuous or discontinuous. Suitable apparatuses are known to the person skilled in the art. The treatment can be carried out, for example, discontinuously with winch runners, yarn dyeing apparatuses, unit beam dyeing apparatuses or jets or continuously by padding, padding, spraying or foam application methods with suitable drying and / or fixing devices.

In a preferred embodiment, the aqueous dispersion and the dye are added to the formulation at the beginning of the treatment.

The ratio of polymer composition, in particular of the fibers, yarns fabrics, nonwovens and / or other textile materials to the treatment bath (also referred to as "liquor ratio") and in particular the UV absorber and the color itself is determined by the person skilled in the art according to the desired application As a rule, a ratio of polymer composition / formulation of from 1: 2 to 1:50, preferably 1:10 to 1:50, and an amount of dye in the formulation of about 0.5 to 10% by weight, have proven suitable. preferably 1 to 5 wt .-%, based on the polymer composition, without the invention being set to this area. In a preferred embodiment, the polymer composition is in a solvent, preferably water and / or monohydric or polyhydric alcohols, such as methanol, ethanol, n-propanol, i-propanol, ethylene glycol, propylene glycol, glycerol, ether alcohols such as monoalkyl ethers of (poly) ethylene glycol or (poly) propylene glycols, such as ethylene glycol monobutyl ether, in an amount of such solvents other than water of <20% by weight, preferably <10% by weight and more preferably <5% by weight, based on the sum of all solvents Formulation or liquor, which optionally contains other auxiliaries, submitted. To this mixture are then added the dye and the aqueous dispersion.

Buffer solutions, leveling agents or other auxiliaries are optionally contained in the treatment bath when the process is carried out batchwise.

The polymer composition is generally heated during and / or after the treatment to a temperature greater than its glass transition temperature T ₉ but less than its melting temperature. This may preferably be carried out by heating the entire formulation to the relevant temperature and immersing the polymer composition in the formulation.

However, it is also possible to treat the polymer composition with the dispersion at a temperature below T ₉ , to dry it if necessary, and then to heat the treated polymer composition to a temperature above T ₉ . Of course, combinations of both approaches are possible.

The temperature in the treatment depends naturally on the nature of the respective polyolefin, the UV absorber used and the dye used. The glass transition temperatures and melting temperatures of polyolefins and other polymers are known in the art or can be easily determined in a known manner. As a rule, the treatment temperature is at least 60 ° C., in particular 60 to 140 ° C., preferably 80 to 140 ° C. For polypropylene homopolymers and copolymers, especially temperatures of 95 to 140 ° C have been proven.

The UV absorber and the dye are incorporated into the polymer composition during the course of the thermal treatment to form a UV-protected and colored polymer composition. In the thus-treated polymer composition, the ultraviolet absorber and the dye are preferably uniformly distributed, but the composition may also have concentration gradients.

In a preferred embodiment of the method according to the invention, the dispersion is added to the treatment bath at the beginning of the treatment, which already has the

Dye contains, added and applied by exhaustion. A typical addition Composition of the treatment bath is 2 - 5 g of dye and 0.1 - 3 g UV absorber, each based on 100 g to be treated polymer composition.

The duration of the treatment is determined by the skilled person depending on the type of polymer composition, the formulation and the treatment conditions.

It is also possible to change the temperature as a function of the duration of treatment. For example, it may be initially started at a lower temperature, e.g. at 70 to 100 ° C and then the temperature is slowly increased to 120 to 140 ° C. A heating phase of 10 to 90 minutes, preferably 20 to 60 minutes, and a high-temperature phase of 10 to 90 minutes, preferably 20 to 60 minutes, have proven useful. Alternatively, a short-term treatment, for example of about 0.5 to 5 minutes with steam or superheated steam is possible.

In a further preferred embodiment, the aqueous dispersion is added and the mixture is rapidly heated to 60 to 100.degree. C., preferably 70 to 90.degree. C., particularly preferably 80.degree. Thereafter, within 20 to 60 minutes, preferably 30 to 50 minutes, more preferably 40 minutes and a heating rate of 0.2 to 1, 0 ° C per minute, preferably 0.4 to 0.6 ° C per minute, particularly preferred 0.5 ° C per minute to a temperature of 80 to 120 ° C, preferably 90 to 1 10 ° C, particularly preferably 100 ° C heated. Thereafter, the heating rate is increased to 1 to 3 ° C per minute, preferably 1, 5 to 2.5 ° C, more preferably 2 ° C, so that within 10 to 20 minutes, preferably 15 minutes, a temperature of 120 to 140 ° C, preferably 130 ° C receives. This temperature is maintained for 40 to 80 minutes, preferably 50 to 70 minutes, more preferably 60 minutes. Subsequently, the liquor is cooled to 80 to 100 ° C, preferably 90 ° C.

The process according to the invention can also be carried out in continuous form, as is customary in the textile industry. Furthermore, the introduction of the aqueous dispersion in a printing paste is possible, which is then fixed in the usual manner by the action of temperature.

The treatment may be followed by a customary aftertreatment, for example with detergents or oxidative or reductive clearing agents or fastness improvers. Such post-treatments are known in principle to the person skilled in the art.

By means of the process according to the invention, UV-protected and colored polymer compositions are obtainable which, in addition to the already described components, also select dyes, in particular disperse dyes or acid dyes, more preferably disperse dyes, and UV absorbers from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof. The sum of the amount of the dyes and the UV absorber is preferably from 2 to 8% by weight, based on the amount of all components of the composition.

The present invention also relates to colored polymer compositions prepared by the process of the invention.

The polymer compositions according to the invention are distinguished from prior art materials by more intensive and more uniform dyeings. They also have better rub fastness and very good wash fastness. In addition to these advantages, the UV absorber is particularly evenly distributed in the polymer compositions according to the invention. The UV absorber penetrates deep into the fiber by the method according to the invention.

Furthermore, the present invention also relates to the use of aqueous dispersions of at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof as auxiliaries for coloring polymer compositions comprising at least one polyolefin and at least one Polyisobutene having a number-average molecular weight M _{n of} from 150 to 50 000 g / mol modified with polar groups, the dyeing is preferably carried out in the process according to the invention.

Preferred UV absorbers which are used in aqueous dispersions as auxiliaries for coloring polymer compositions and preferred polymer compositions are mentioned above. The dye used for dyeing is preferably a disperse dye or a metal complex dye.

In a preferred embodiment of this use, the polar group-modified polyisobutene is a block copolymer comprising

- At least one hydrophobic block (A), which is composed essentially of isobutene units, as well as

- At least one hydrophilic block (B), which is composed essentially of oxalkyl units, and its average molar mass M _n at least

1000 g / mol.

Preferred block polymers are mentioned above.

In a further preferred embodiment of this use, there are additionally polyesters or polyamides in the polymer composition. In a further preferred embodiment, the aqueous dispersion used as auxiliary contains at least one surfactant in addition to the UV absorber. For this surfactant, what has already been said regarding the method according to the invention applies.

In a further preferred embodiment, the aqueous dispersion is used as auxiliary in the process according to the invention.

With respect to the use of the aqueous dispersion, what has been said with regard to the process according to the invention applies.

The present invention also relates to an aqueous dyeing liquor comprising at least one dye, a polymer composition comprising at least one polyolefin and at least one polar group-modified polyisobutene having a number average molecular weight M _n of 150 to 50,000 g / mol and an aqueous dispersion, wherein the aqueous dispersion

A) at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof and

B) at least one surfactant

contains. With regard to the individual ingredients of the aqueous dyeing liquor, what has already been said applies. Preferred dyes, polymer compositions, preferred UV absorbers and preferred surfactants are mentioned above.

In a particularly preferred embodiment of the aqueous dyeing liquor, the polyisobutene modified with polar groups is a block copolymer comprising at least one hydrophobic block (A), which is composed essentially of isobutene units, and at least one hydrophilic block (B), which consists essentially of Oxalkyl units is constructed, and whose average molar mass M _{n is} at least 1000 g / mol.

With regard to the aqueous dyeing liquor, what has been said with regard to the process according to the invention applies.

Examples:

Figure 1 shows P P-substance samples 1 to 4 (vertical), which are colored with different dyes. The following dyes are used: 1 Dianix black S2B

2 Dianix blue ER

3 Dianix Blue ACE 4 Dianixrubin SEB

The fabric samples are each treated without UV absorber (Sample A) or with the composition according to the invention (Sample B). The lightfastness was carried out according to ISO 105-B02, 7 days exposure to a blue scale.

It can be seen that the fabric sample treated with the composition according to the invention is more intensely colored than the comparative samples. Thus, Figure 1 shows that the light fastness of the dyes on PP fabrics is significantly increased by the presence of UV absorbers in the composition of the invention.

Claims

claims A process for coloring polymer compositions and simultaneously incorporating UV absorbers into the polymer compositions, the polymer compositions comprising at least one polyolefin and at least one polar group-modified polyisobutene having a number average molecular weight M _{n of} from 150 to 50,000 g / mol, by treating them Polymer composition with an aqueous dyeing liquor containing at least one dye and an aqueous dispersion, wherein the aqueous dispersion A) at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazinen and mixtures thereof and B) at least one surfactant contains. 2. The method according to claim 1, characterized in that it is the polyolefin is a polypropylene or polyethylene homo- or copolymer. 3. The method according to claim 1 or 2, characterized in that the at least one polar group modified polyisobutene is a block copolymer comprising - At least one hydrophobic block (A), which is composed essentially of isobutene units, as well as - At least one hydrophilic block (B), which is composed essentially of oxalic kyl units, and whose average molar mass M _{n is} at least 1000 g / mol. 4. The method according to any one of claims 1 to 3, characterized in that the composition further contains polyester or polyamides. 5. The method according to claim 3, characterized in that a block copolymer is used, wherein the average molar mass M _{n of} the hydrophobic blocks (A) of the block copolymer 200 to 10,000 g / mol, and - The average molar mass M _{n of} the hydrophilic blocks (B) of the block copolymer is 1,000 to 20,000 g / mol. 6. The method according to any one of claims 1 to 5, characterized in that a benzotriazole is used as the UV absorber, selected from the group consisting of 6-tert-butyl-2- (5-chloro-2H-benzotriazole-2 yl) -4-methylphenol, 2,4-di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -phenol, 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl-phenol), 2- (2H-benzotriazol-2-yl) -4 -methylphenol, 2- (2H-Benzotriazol-2-yl-4,6-bis (1-methyl-1-phenylethyl) phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2- (2H-Benzotriazol-2-yl) -4- (tert-butyl) -6- (sec -butyl) -phenol, 2,2 ^" -methylenebis (6- (2H-benzotriazol-2-yl) -4-1, 1,3,3-tetramethylbutyl) phenol), 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, branched and linear, 2- (2 ^" -hydroxy-5'-methacryloxyethylphenyl) -2H- benzotriazole, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) -phenol, isomeric mixture of the alkylation of 2- (2H- benzotriazol-2-yl) -p-Cres ol with dodecane and mixtures thereof. 7. The method according to any one of claims 1 to 6, characterized in that it is the dye is a disperse dye or an acid dye. 8. The method according to any one of claims 1 to 7, characterized in that one uses the polymer compositions in the form of moldings, films, fibers, yarns, fabrics, fleece, knitted fabrics, knitted fabrics and / or other textile materials. 9. A colored polymer composition prepared by the process according to any one of claims 1 to 8. 10. Use of aqueous dispersions of at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazines and mixtures thereof as auxiliaries for coloring polymer compositions comprising at least one polyolefin and at least one polar group-modified polyisobutene having a number average molecular weight M _n of 150 to 50,000 g / mol. 1 1. Use according to claim 10, characterized in that the at least one polar group modified polyisobutene is a block copolymer comprising at least one hydrophobic block (A), which is composed essentially of isobutene units, and at least one hydrophilic block (B), which is composed essentially of oxalkyl units, and whose average molar mass M _{n is} at least 1000 g / mol , 12. Use according to claim 10 or 1 1, characterized in that additionally present in the polymer composition are polyesters or polyamides. 13. Use according to one of claims 10 to 12, characterized in that the aqueous dispersion contains at least one surfactant in addition to the UV absorber. 14. Use according to one of claims 10 to 13, characterized in that one uses for dyeing a disperse dye or a metal complex dye. 15. Use according to one of claims 10 to 14, characterized in that a benzotriazole is used as the UV absorber, selected from the A group consisting of 6-tert-butyl-2- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol, 2,4-di-tert-butyl-6- (5-chloro-2H- benzotriazol-2-yl) -phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1, 1 , 3,3-tetramethylbutyl-phenol), 2- (2H-benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl-4,6-bis (1-methyl-1-phenylethyl ) phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6- (sec-butyl) phenol, 2,2 ^" -Methylenebis (6- (2H-benzotriazol-2-yl) -4-1, 1, 3,3-tetramethylbutyl) phenol), 2- (2H-Benzotriazol-2-yl) -6-dodecyl- 4-methylphenol, branched and linear, 2- (2 ^" -hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4 - (1, 1, 3,3-tetramethylbutyl) phenol, isomeric mixture of the alkylation of 2- (2H-benzotriazol-2-yl) -p-cresol with dodecane and mixtures thereof. 16. Use according to one of claims 10 to 15, characterized in that the dyeing takes place in a method according to one of claims 1 to 8. 17. Aqueous dyeing liquor, comprising at least one dye, a polymer compositions comprising at least one polyolefin and at least one polar group-modified polyisobutene having a number average molecular weight M _n of 150 to 50,000 g / mol and an aqueous dispersion, wherein the aqueous dispersion A) at least one organic UV absorber selected from the group consisting of benzotriazoles, benzophenones, cyanoacrylates, hydroxyphenyltriazinen and mixtures thereof and B) at least one surfactant contains. 18. Aqueous dyeing liquor according to claim 17, characterized in that the at least one polar group-modified polyisobutene is a block copolymer comprising at least one hydrophobic block (A), which is composed essentially of isobutene units, and at least one hydrophilic block (B), which is composed essentially of oxalkyl units, and whose average molar mass M _{n is} at least 1000 g / mol ,