MX2008006843A - Migration-stable dyes in polymeric materials via complex formation of polyisobutene derivatives with dyes - Google Patents

Abstract

Dye concentrate comprising at least one polyisobutene derivative formed from at least one hydrophobic block (X) and at least one hydrophilic block (Y) as component A and at least one dye as component B, and also a dye concentrate which, as well as components A and B, comprises at least one polyolefin as component C1 and/or at least one solvent as component C2, processes for producing the dye concentrates, processes for coloring polymeric materials by contacting the polymeric materials with the inventive dye concentrates, colored polymer compositions formed from at least one inventive dye concentrate and at least one polymeric material, fibers, films, packagings, moldings composed of the inventive colored polymer composition, the use of the inventive dye concentrates for coloring polymeric materials, and the use of polyisobutene derivatives formed from at least one hydrophobic block (X) and at least one hydrophilic block (Y) as assistants for the migration-stable coloring of polymeric materials. The present invention further relates to the process according to the invention for coloring polymeric materials, the polymeric materials additionally being contacted with a block copolymer (component E), the inventive colored polymer composition which, as well as the at least one dye concentrate and the at least one polymeric material, comprises at least one block copolymer (component E), and the inventive use of the inventive dye concentrates for coloring polymeric materials, the polymeric materials being present in apolymer composition which, as well as the at least one polymeric material, has at least one block copolymer E, and the inventive use of polyisobutene derivatives formed from at least one hydrophobic block (X) and at least one hydrophilic block (Y) for the migration-stable coloring of polymeric materials by means of introduction of a dye concentrate, a block copolymer E additionally being introduced.

Description

COLORANTS STABLE TO MIGRATION IN MATERIALS POLYMERICOS BY COMPLEX FORMATION OF DERIVATIVES OF ISOBUTENOUS POLY WITH COLORANTS The present invention relates to concentrated dyes containing at least one polyisobutene derivative composed of at least one hydrophobic block (X) and at least one hydrophilic block (Y) as component A and at least one dye as component B and also a concentrated colorant which, like components A and B, contains at least one polyolefin as component Cl and / or at least one solvent as component C2, the production of the concentrated dyes, the coloring of polymeric materials by means of of the contact of polymeric materials with the concentrated dyes of the present invention, colored polymeric compositions composed of at least one concentrated dye of the present invention and at least one polymeric material, fibers, films, gaskets, composite molds of the colored polymeric composition of the present invention, the use of the concentrated dyes of the present invention for cabbage prayer of polymeric materials, and also the use of polyisobutene derivatives composed of at least one block hydrophobic (X) and at least one hydrophilic block (Y) as an auxiliary for the migration resistant coloration of polymeric materials. The present invention furthermore relates to the processes of the present invention for the coloration of polymeric materials wherein the polymeric materials are additionally in contact with a block copolymer (component E), the colored polymer composition of the present invention, which, as well as the at least one concentrated dye and the at least one polymeric material, contain at least one block copolymer (component E) and the use of the present invention of the concentrated dyes of the present invention in a polymeric composition. which, as well as the at least one polymeric material, contains at least one block copolymer E, and also the use of the present invention of the polusobutene derivatives composed of at least one hydrophobic block (X) and at least a hydrophilic block (Y) for the migration resistant coloration of polymeric materials by means of the incorporation of a colorant and concentrate in which an E. block copolymer is additionally incorporated.

Polymeric materials such as polyolefins, in particular polypropylene, have numerous properties Outstanding as it can be low specific density, high breaking strength, good resistance to chemicals, low wetting capacity by polar means, low water absorption, good recycling facility and also low cost. These can be processed in an outstanding manner in various forms such as fibers, films and molded parts.

Due to their low wetting capacity by means of polar substances and / or their low ability to absorb polar substances, polyolefins and other apolar polymeric materials and also fibers, films and molded parts produced from them are very difficult to color in a way that the dyes used do not migrate during the use of polyolefins and other apolar polymeric materials.

In order to achieve intense and migration resistant shades in apolar polymeric materials such as polyolefins, it has been customary to employ massive coloration with which a particulate colored pigment is added to the polymer while still in the extruder, in the first step of a thread manufacturing operation for example. Mass coloration actually provides colorations that are dark and fast to the rigors of real service, but pigment coloring if you clearly need more expensive colorants than coloration with dyes. Moreover, the natural particulate of the pigments may for example cause the fine dyes used to extrude yarns to become clogged, or the fiber breaking strength to decrease. Moreover, the coloring of polyolefins and other apolar polymeric materials with pigments is expensive.

In principle it is possible to color polyolefins with dyes of an aqueous liquor. However, coloring is disadvantageous when coloring thick articles, because dyes applied from an aqueous liquor penetrate the articles from the outside inwards and a homogeneous coloration of comparatively thick articles is difficult in this way.

There have been numerous attempts of the prior art to improve the ease of coloration, in particular the ease of migration resistant coloration, of apolar polymeric materials, in particular polyolefins.

The coloration of polyolefins from an aqueous liquor is described, for example, in DE-A 2 240 534 and EP-A 0 039 207.

DE-A 2 240 534 relates to polymeric polyolefin-based polymer compositions containing as additive for improving the coloration of the polymeric compositions a polyamine adduct containing at least one hydrocarbon chain of at least 25 carbon atoms which binds to a nitrogen atom. The additives are incorporated into the polymer composition by mixing them with the polyolefin. The polyolefins are colored with pre-metallized or dispersed dyes or preferably with acid dyes in an aqueous dye bath.

EP-A 0 039 207 discloses a modified polyolefin fiber incorporating nitrogen, basic copolymers in the melt spinning of a polyolefin material. The basic copolymers are therefore bound in the macromolecule. These modified polyolefins then have an affinity for anionic dyes. The modified polyolefin fiber is colored from an aqueous liquor.

As mentioned above, when comparatively coarse polyolefin articles are colored from an aqueous liquor, the achieved colorations are generally not homogeneous. To achieve colorations homogeneous, resistant to the migration of polyolefins, the mass coloration of the polyolefins is therefore preferable. As well as the pigments that are being used in bulk dyeing, there is prior art with which the modified dyes are used for mass dyeing of polyolefins.

EP-A 0 215 322 relates to colored thermoplastic compositions containing a thermoplastic and a colorant in the form of a polyalkyleneoxy-substituted chromophore group provided in the thermoplastic in a minor amount sufficient to provide coloration to the thermoplastic. According to EP-A 0 215 322, the chromophore group is linked to the polyalkyleneoxy radical by covalent bonding. The specific dye is incorporated into the thermoplastic, for example, by melt addition of the thermoplastic. Polyolefins are mentioned as an example of thermoplastics. EP-A 0 445 926, EP_A 0 398 620 and EP-A 0 435 105 in the same way refer to dyes modified by covalent attachment of polyoxyalkylene groups to the chromophore group used. However, this technology is very expensive, because each particular dye has to be adequately modified before being used.

It is an object of the present invention against the aforementioned prior art to provide concentrated dyes which are suitable for the mass coloration of polymeric materials such as polyolefins, in particular polypropylene, so that the dyes used can not migrate from the colored polyolefins . These concentrated dyes will be simple to obtain and can be used with a wide range of dyes. Preferably, the colorations to be achieved are strong, bright and transparent with the help of the concentrated dyes and also any combination of desired shades, and the concentrated dyes will have a high color strength in order to make an economical coloring possible. of polymeric materials such as polyolefins.

We find that this objective is achieved by a concentrated dye containing a) At least one polyisobutene derivative composed of at least one hydrophobic block (X) and at least one hydrophilic block (Y) as component A, and b) At least minus one dye as component B, The weight ratio of component A to component B in the concentrated dye being in the range of : 1 to 1:30, preferably in the range from 10: 1 to 1:10, more preferably in the range from 3: 1 to 1: 3 and more preferably in the range of 2: 1 to 1: 2.

The concentrated dyes of the present invention thus use an amphiphilic polyisobutene derivative XY as component A. The hydrophilic part of component A coordinates that the dye has no chemical connection between the dye (component B) and component A.

The hydrophobic part of the component A interacts with the polymeric material, for example polyolefin, to be colored. The amphiphilic component A thus constitutes a kind of "glue" between the polymeric material, for example polyolefin, to be colored and the hydrophobic part of component A on the other hand by subtracting Van der Waal interactions and, on the other hand, the interaction between the dye and the hydrophilic part of component A subtracting from the principle of coordination.

Component A provides migration resistant coloration of polymeric materials, for example polyolefins, with dyes. Moreover, the dyes Concentrates of the present invention can be used to achieve any desired combination of shades in high and bright color resistance. Unlike pigments, the dyes used are generally non-particulate, so the clogging of fine dyes used in the extrusion of yarns for example can be avoided. Moreover, the use of the component A provides excellent dispersion of the dye B in the polymeric materials, for example polyolefins, so that colorations of high and bright color resistance are achieved.

In a preferred embodiment of the present invention, the concentrated dye of the present invention contains at least one polyolefin as component Cl and / or at least one solvent as component C2 as well as components A and B.

In a preferred embodiment, the present invention thus provides a concentrated dye Fl containing a) from 0.8% to 25% by weight, preferably from 1.5% to 15% by weight, more preferably from 3% to 10% by weight, and more preferably from 5% to 10% by weight of component A, b) from 0.8% to 25% by weight, preferably from 1.5% to 15% by weight, more preferably from 3% to 10% by weight, and more preferably from 5% to 10% by weight of component B, c) from 50% to 98.4% by weight, preferably from 70% to 97% by weight, more preferably from 80% to 94% by weight, and more preferably from 80% to 90% by weight of the Cl component, The sum total of the components A, B and Cl is 100% by weight.

In another preferred embodiment the present invention provides a concentrated dye F2 containing a) from 0.8% to 25% by weight, preferably from 1.5% to 15% by weight, more preferably from 3% to 10% by weight and more preferably from 5% to 10% by weight % to 10% by weight of component A, b) from 0.8% to 25% by weight, preferably from 1.5% to 15% by weight, more preferably from 3% to 10% by weight and more preferably from 5% to 10% by weight of component B, c) from 50% to 98.4% by weight, preferably from 70% to 97% by weight, more preferably from 80% to 94% by weight, and more preferably from 80% to 90% by weight of the component C2, The total sum of components A, B and C2 is 100% by weight.

It is also possible for the concentrated dye Fl to additionally contain the component C2, preferably in an amount of = 25% by weight, based on the total amount of components A, B and Cl, or for the concentrated dye F2 additionally containing the Cl component, preferably in an amount of = 10% by weight, based on the total amount of components A, B and C2.

The concentrated dye Fl generally consists of a concentrated solid dye at room temperature useful for the coloring of polymeric materials, in particular polyolefins, in the form of master batches. The solid concentrated dye Fl can be present in any desired form, for example as powder or pellets. The concentrated dye F2 generally consists of a liquid dye concentrated at room temperature useful in liquid form for the coloring of polymeric materials, in particular polyolefins.

Component A Component A contains at least one polyisobutene derivative composed of at least one hydrophobic block (X) and at least one hydrophilic block (Y). Compound A in this manner contains amphiphilic polyisobutene derivatives.

The hydrophobic blocks (X) and the hydrophilic blocks (Y) can each be linear, branched or star-shaped. The X and Y blocks are covalent bonds by means of suitable linking groups.

Those amphiphilic polyisobutene derivatives useful as component A are known in the prior art and can be prepared by starting from compounds and initial methods known to the person skilled in the art.

The hydrophobic blocks (X) are essentially composed of isobutene units. They are obtained by the polymerization of isobutene. However, the blocks may also contain a small amount of other comonomers as building components. These building components can be used to fine-tune the properties of the blocks. Suitable comonomers, as well as 1-butene and cis- or trans-2-butene included in particular isoolefins having from 5 to 10 carbon atoms such as 2-methyl-1-butene-1,2-methyl. l-pentene, 2-methyl-l-hexene, 2-ethyl-l-pentene, 2-ethyl-l-hexene and 2-propyl-1-heptene or vinylaromatics such as styrene and α-methylstyrene, alkylstyrenes of C? -C, such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene. However, the fraction of these comonomers should not be very long. In general, the comonomers should not count more than 20% by weight based on the amount of all the building components of the hydrophobic blocks (X). The blocks, as well as the isobutene and mononomer units, may also contain the initiator molecules to initiate the polymerization, or fragments thereof. Hydrophobic blocks (X) composed of isobutene units, and if appropriate, the aforementioned comonomers can be linear, branched or star-shaped.

The hydrophilic block (Y) of component A contains "polar groups", and these may contain not only protic group but also aprotic polar group. These polar groups contain, for example, acid radicals sulphonic, anhydrides, carboxylic groups, carboxamides, carboximides, OH groups, polyalkylene groups, amino groups, epoxies or suitable silanes, whichever is more suitable to replace.

Preferably, the hydrophilic blocks (Y) contain nitrogen groups bonded to one or more chain ends of the hydrophobic blocks (X). The nitrogen groups may contain one or more nitrogen atoms. The nitrogen atoms can be incorporated in the terminal group, for example, in the form of amino groups, for example primary, secondary, tertiary and / or aromatic ammo groups, or else as amide groups. Preferably, there are 1 to 10 amino groups per terminal group. It is also preferable that these amino groups, which are primary, secondary and / or tertiary. There can be, for example, straight or branched chain alkylene polyamines derivatives groups. The terminal, the nitrogen groups, as well as the nitrogen functionalities, may still contain other functionalities. Suitable functionalities include in particular oxygen functional groups, such as OH groups or ether groups.

The component A used according to the present invention may contain a hydrophobic block (X) which is preferably as defined above and has only one hydrophilic block (Y) at one of its chain ends (X-Y). However, it is also possible that a plurality of hydrophobic blocks (X) are attached to a terminal hydrophilic block (Y) ((X) X-Y, where x = 2, preferably 2 to 5 and more preferably 2 to 3). It is further possible for a linear or essentially linear hydrophobic block (X) to have a hydrophilic block (Y) as a terminal group at both ends. The hydrophobic block (X) may also contain a star or branched group having one or more terminal hydrophilic blocks (Y) (X- (Y) and, where y = 2 preferably from 2 to 5, more preferably from 2 to 3). The hydrophobic block (X) contains at least one, preferably from 1 to 5, more preferably from 1 to 3 and more preferably an isobutene group. As well as the above-mentioned branching patterns for the hydrophobic block (X), the object of the present invention also contains imaginable branching patterns. It will be apparent that component A in the concentrated dyes of the present invention may also contain mixtures of various polusobutene derivatives.

In addition, blocks X and Y may be connected to two or more of the other blocks respectively. The blocks X and Y can be linked for example lmeally in an alternative arrangement. In principle, any desired number of blocks can be used. In general, however, no more than 8 X blocks and no more than 8 Y blocks are present in any particular case. This results in the simplest case in a polnosobutene derivative of the general formula X-Y.

The structure of the polusobutene derivatives used according to the present invention as component A can be influenced through the selected identity and quantity of the starting materials for the X and Y blocks and also through the reaction conditions, in particular the order of addition.

The hydrophobic blocks (X) of the polusobutene derivatives used according to the present invention generally have an average number of molecular weight Mn in the range of 200 to 10,000 g / mol. Mn is preferably in the range of 300 to 8000 g / mol, more preferably in the range of 400 to 6000 g / mol and more preferably in the range of 500 to 5000 g / mol.

The polusobutene derivatives used according to the present invention are obtained by functionalization of reactive polyusobutenes used as starting materials, providing these reactive polyusobutenes used as starting materials with functional groups in single or multistage reactions known in principle by persons having experience in the technique. The reactive polyusobutenes for the purposes of the present invention are polybutenes having a very high fraction of terminal α-olefin end groups.

Preferably, the present invention thus contains concentrated dyes containing a component A which is obtained by functionalization of the reactive polusobutene.

Preference is given to the group of reactive polusobutenes whose terminal groups contain olefin groups of at least 85%.

The preparation of reactive polusobutenes is known and described, for example, in WO 2004/09654 and WO 2004/35635.

The reactive polyisobutenes are obtained commercially, for example under the name of Glissopal® (BASAF AG).

The hydrophilic blocks (Y) are incorporated by functionalizing the reactive polyisobutenes with suitable reagents to form the desired polyisobutene derivatives having at least one hydrophobic block (X) and at least one hydrophilic block (Y). Suitable functionalizations are described, for example, in WO 2004/09654 and WO 2004/35635 and the references cited therein. The polyisobutene derivatives which according to the present invention are used as component A and which contain nitrogen end groups as hydrophilic groups (Y) are advantageously synthesizable by reacting the olefinic end groups of the aforesaid reactive polyisobutenes with compounds which they are capable of reacting with the double bond and those which in turn are available for later functionalization. An example is the reaction of polyisobutene with maleic anhydride to form polyisobutenylsuccinic anhydride (PIBSA) or the reaction of polyisobutene with phenols to form polyisbutenylphenols. The polyisobutenes functionalized in this way can then react in a second step with nitrogen compounds and also, if adequate, other reaction counterparts to form nitrogen groups.

Component A more preferably contains polyisobutene derivatives which are obtained by reaction of PIBSA with suitable nitrogen compounds.

The examples are polyisobutenes having succinimide units. These polymers are also known as PIBSI. In a more preferred embodiment of the present invention, the concentrated dyes of the present invention thus contain an A component containing polyisobutenyl succinimides (PIBSI).

These polyisobutenyl succinimides (PIBSI). They are products of the general formula (I): where R1 and R2 are each as defined below: R1 is a hydrophobic block (X) as defined above; R2 is a hydrogen or preferably a hydrocarbyl radical containing primary, secondary or tertiary amino groups.

Preferred R2 hydrocarbyl radicals contain aliphatic hydrocarbyl radicals having from 1 to 60 carbon atoms and preferably have from 2 to 30 carbon atoms. They may contain, for example, groups derived from straight or branched chain alkylene polyamides, preferably groups containing methyl, ethylene, propylene, butylene, pentylene or hexylene groups. Examples of these groups contain? -aminoalkylene groups, for example -CH2-CH2-NH2, -CH2-CH2_CH2_NH2, -CH2-CH2-CH2-CH2-NH2, -CH2-CH-CH2-CH2CH2-NH2.

Other examples of R2 contain groups of the general formula (II) - (CH2) x-NH- [(CH2; -NH '; CH2) X-NR4R5 (II where x and y are independently a natural number from 1 to 5 and preferably from 2 to 4 and z is an integer from 0 to 8. R4 and R5 are independently H or an alkyl group having from 1 to 5 carbon atoms, preferably H or a methyl group, more preferably H. The radical II contains more preferably the following radical: -CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH R2 may also contain a radical derived from polyethyleneimines. The radicals R2 can optionally contain still further functional groups, in particular OH groups or ether groups. Preferably, however, they are carbon radicals containing only N-atoms as heteroatoms.

It is otherwise possible to use mixtures of several PIBSI derivatives each having different radicals R2 and R1. PIBSI derivatives are commercially available, for example under the name of Kerocom® PIBSI (BASF AG).

The preparation of the aforementioned PIBSI derivatives is known. They are obtained according to existing processes by reaction of reactive polyisobutene (as defined above) with maleic anhydride to form polyisobutenyl-succinic anhydride (PIBSA). The polyisobutenyl succinimides (PIBSI) are obtained by reaction of PIBSA with ammonium and / or amines of the general formula H2N-R2, where R2 is as defined above. The details concerning the preparation of these PIBSI derivatives are described, for example, in DE-A 101 235 33 and also in the application not yet published EP 0 401 869 6.7. The polyisobutene derivatives in question may also contain by-products, for example, unconverted polyisobutene, PIBSA unconverted and also (in addition to the monosuccinimides mentioned above) amic acids (III) or succinamides (IV) And also disuccinimides (V).

R1 and R2 are each, as defined above. R3 contains a radical that is derived from R2 and in which one of the amino groups is incorporated into the second succinimide ring.

The compounds of the formulas (III), (IV) and (V) are also obtained as main products through the appropriate alteration of the reaction conditions. For example, the reaction of PIBSA with the amine in equimolar amounts produces the amic acid (III) which needs higher temperatures, in general, from 120 to 160 ° C, to react intermolecularly to form the desired PIBSI derivative of the formula (I ). The product ratio is thus easy to control through the chosen reaction temperature.

The possible synthesis for the terminal polyisobutene succinimide derivatives preferably used according to the present invention are indicated below by means of the example for the reaction of block X which forms hydrophobic units and are substituted by succinic anhydride groups S, with units Y which form Hydrophilic blocks and are replaced by NH groups: The following groups are preferred to be used as units from which polyisobutene derivatives are constructed, which according to the present invention are used as component A.

HN- [Y] -NH Units Y that form hydrophilic blocks and that are substituted by two terminal NH groups [Y] -NH Y units that form hydrophilic blocks and have only one NH group [Y] - (NH) X Y units that form hydrophilic blocks and having x NH groups where x is a natural number from 1 to 5, preferably from 1 to 3 and more preferably 1; [X] -S Polyisobutene units x that form hydrophilic blocks and have a terminal succinic anhydride group S. S- [X] -S Polyisobutene units that form hydrophobic blocks X and have two terminal succinic anhydride groups S. [X] - Sy Polyisobutene units forming hydrophobic blocks X and having and groups of succinic anhydride S, where y is a natural number generally from 1 to 5, preferably from 1 to 3 and more preferably 1.

The NH groups can be linked in a manner known in principle with the succinic anhydride groups S to form amide groups. The reaction can be carried out for example by heating it in the absence of a solvent. Suitable reaction temperatures vary from 80 to 200 ° C for example.

The polyisobutene derivatives XY used as component A are obtained, for example, by reacting one equivalent of HN- [Y] -NH with an equivalent [X] -S. This is depicted below by way of the example using the reaction of PIBSA with a diamine of the general formula H2N- (CH2-CH2-NH) z-CH2-CH2-NH2 where z is 0 to 8.

Glissopal®1000 Marshmallow anhydride (MA) polyisobutenyl succinic anhydride = PIBSA Imitation H2N- (CHjCH2-NH) £ -CH2-CH2 2-N '• "H' 2. in onde z = 0 to 8 Polyisobutylensuccinic acid succinimide = PIBSI n in the above scheme is a natural number in general from 15 to 20. In general, n is chosen to produce the molar masses specified above for the hydrophobic blocks.

The star-shaped or branched polyisobutene derivatives Y- (X) X are obtained by reaction of [Y] - (NH) X with x equivalents of [X] -S.

As mentioned above, a person skilled in the art will quickly understand that the polyisobutene derivatives obtained as useful A components may also contain residues of starting materials, depending on the conditions under which the polyisobutene derivatives are produced. They may also contain mixtures of various polyisobutene derivatives. The polyisobutene derivatives of the general formula X-Y-X can for example also contain polyisobutene derivatives of the general formula X-Y and also functionalized and non-functionalized polyisobutene. Preferably, the polyisobutene derivatives or mixtures obtained are used for another application and without further purification. Of course, it is otherwise possible for the polyisobutene derivatives obtained to be further purified. Suitable methods of purification are known to persons having skill in the art.

As well as the polyisobutene derivatives having at least one terminal nitrogen group, other derivatives of Functionalized polyisobutene, mentioned above, can be used as component A. The other functionalized polyisobutene derivatives are obtained for example by means of the process described in WO 2004/035635.

The polyisobutene derivatives preferably useful as component A are polyisobutene derivatives of the general formula X-Y, the hydrophilic block contains polyethylene-amine. Particular preference is given to the polyisobutenyl succinimides containing polyethylene imine radicals.

Component B Component B contains at least one dye. Component B may be a single dye or mixtures of various dyes. The combination of shading colors are obtained using mixtures of various dyes. For example, a particular predetermined tone is achieved as a result.

In principle, any colorant known to the person skilled in the art can be used, in particular any dye having good light fastness or thermal stability as well as high color strength and transparency.

Examples of suitable groups of dyes are infrared and / or UV absorbing dyes, photochromic, thermochromic and fluorescent dyes. The fluorescent dyes, it should be understood that in the present, refer not only to customary dyes referred to as fluorescent dyes but also optical brighteners. Preferred fluorescent dyes are perylene derivatives, for example Lumogen ® dyes F-range from BASF AG, rhodamines, for example rhodamine B and rhodamine 6G. Preferred suitable optical brighteners are bistyrylbenzene, stilbene and pyrene derivatives. Other suitable optical brighteners are specified in the Ullmann Encyclopedia of the Chemical Industry 5th edition, A18, pages 156 to 161.

The infrared and / or UV absorbing dyes include dyes that have little or no inherent color in the visible region of the electromagnetic spectrum. However, infrared and / or UV absorbing dyes for the purposes of the present invention also include dyes as they are absorbed in infrared and / or UV light, and at the same time have an inherent color in the visible region of the spectrum electromagnetic.

Suitable colorants are in particular those capable of interacting, for example complexing, with a component A. Preferred dyes are selected from metallized dyes, cationic dyes, ammonium dyes, caustic dyes, direct or substantial dyes, disperse dyes, dyes in branch, vat dyes, reactive dyes and sulfurized dyes. The use of the various dyes depends inter alia on the functionalization of the polusobutene derivatives used as component A so that in particular the good coordination of the dye with the hydrophilic group Y of the polusobutene derivative can be achieved.

Metallized dyes are particularly suitable. Metallized dyes have one or more metal atoms in the chromophore. They can contain various 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 28, SBk 29, SBk 45, RBk 31.

A preferred embodiment uses dyes that are transparent in the NIR region.

The amount of colorant in the concentrated colorant of the present invention is decided by a person having experience in the art according to the intended application. The weight ratio of the polyisobutene derivative used according to the present invention (component A) and the colorant (component B) is in the range of 30: 1 to 1:30, preferably in the range of 10: 1 to 1: 10, more preferably in the range of 3: 1 to 1: 3 and more preferably in the range of 2: 1 to 1: 2. Other details related to the amount of dye used (compound B) in the concentrated dyes of the present invention are given above.

In addition to the components A and B, the concentrated dyes of the present invention preferably contain at least one polyolefin as component Cl and / or at least one solvent C2.

Cl component In principle, any polyolefin known to a person skilled in the art is suitable.

It can be a homopolymer or copolymer selected from basic C2-C8 species such as ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene or styrene derivatives such as styrene alone or α-methylstyrene and mixtures thereof.

The Cl component preferably contains polyolefins containing C2- to C4-olefins as a major constituent, more preferably homo- or copolymers of polyethylene or polypropylene. The copolymers may be random copolymers or block copolymers. Suitable comonomers in the copolymers depend on the particular basic polyolefin species used. The proper comonomers are in this way - depending on the basic polyolefin species - ethylene or other α-olefins - dienes such as 1, hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 1,7-octadiene, 6-methyl-1,5-heptadiene or polyenes such as octatriene and dicyclopentadiene. The copolymer fraction which is attributable to the comonomers is generally not more than 40% by weight, preferably not more than 30% by weight, based on the total sum of all the monomers used. For example, the fraction attributable to the comonomers may be in the range of 20% to 30% by weight or 2% to 10% by weight, depending on the application. As mentioned above, homopolymers can also be used.

A polyolefin based on polyethylene used as component Cl is preferably a linear polyethylene (HDPE, LLDPE). This can be used in the form of a homopolymer or as a random or block copolymer, in which case the usual comonomers, mentioned above, can be used.

In a particularly preferred embodiment the polyolefin used as component Cl is polypropylene. The polypropylene can be a homo- or polypropylene copolymer. Suitable comonomers are mentioned above. Preferred comonomers are ethylene, the aforementioned α-olefins, dienes and / or polyenes. Choosing polypropylene is not restricted. Particular preference is given to polypropylenes having a high melt flow rate of for example 25 to 55 g / 10 min (measured in accordance with ISO 1133). For example, polypropylene can have a melt flow index MFI (230 ° C, 2.16 kg) or less than 40 g / 10 min. Clear polypropylene is particularly very preferred.

The polyolefins in question can be combinations of various polyolefins, for example of polypropylene and polyethylene.

The polyolefins used as component Cl are obtained by conventional manufacturing methods, for example using Ziegler-Natta or metallocene catalysts.

Other details will be known by the person who has experience in the art and are described for example in the encyclopedia "Ullmann (of Technical Chemistry), 6th edition, Electronic Version" in the chapter "polyolefins" and references cited therein.

Component C2 In general, any solvent compatible with the polymeric material to be colored is suitable. Here, the solvents in general are organic compounds of high boiling temperature whose boiling point is generally above the temperature which predominates in the coloration of the polymeric materials, ie, preferably above 80 ° C, more preferably above of 120 ° C, even more preferably above 140 ° C and more preferably above 160 ° C. The solvents of the present invention are in particular of low viscosity, ie liquids, polymers and / or oligomers or long-chain hydrocarbons. In general, the viscosity of polymers and / or oligomers or long chain hydrocarbons used as a solvent is < 5 Pas when measured in DIN 51562. Particular preference is given to the use as a solvent of polyisobutenes or polyisobutene derivatives having molecular weights Mn in general of 200 to 1000 measured by gel permeation chromatography (GPC) against normal polystyrene. Polyisobutenes having the specified molecular weights are very particularly preferred for use as a solvent. The specified low viscosity polymers or oligomers are commercially available, for example the products of the Glissopal® group from BASF AG.

Component C2 may be present in the concentrated dyes of the present invention (see Concentrated dyes F2). Otherwise it is possible to mix those concentrated dyes of the present invention containing no C2 component with small amounts of C2 component before using them to dye polymeric materials in order to facilitate the incorporation of polymeric materials.

The concentrated dyes of the present invention as well as the appropriate components A, B and Cl and / or C2 can also contain customary and auxiliary additives such as component D. Examples of suitable additives and auxiliaries plasticizers, antioxidants, antistatics, stabilizers, biocides, flame retardants, fillers, dispersants, complexing agents, flow improvers, nucleating agents, and also stabilizers against UV degradation (UV absorbers) and IR absorbents, for example from the class of teplen and quatepene derivatives, cyanines, metal diolates and ammonium salts.

The concentrated dyes of the present invention are obtained by mixing components A, B and -if present- Cl and / or C2 and D if appropriate.

Preferably, the polusobutene derivatives used as component A are mixed intensively with the dyes used as component B and also if appropriate with the polyolefms used as component Cl and / or the solvents used as component C2 and optionally also as components D by means of suitable appliances after being heated to melt. Kneaders, mixers, single-shaft extruders, twin-shaft extruders or other dispersing assemblies, for example, are suitable apparatuses. The composition of the molten concentrated dye can be Discharge of the dispersing assembly in a basically known manner by means of matrices. For example, the strands can be extruded and cut into pellets. When the concentrated dye of the present invention contains Cl component - which is preferred - the melt can also be molded directly to form molded articles, for example by injection molding or blow molding or it can be extruded through suitable dies to form fibers. It is preferable to produce the concentrated dyes of the present invention in one step by heating the components A, B and the appropriate Cl and / or C2 and if appropriate D to melt while at the same time mixing intensively in the above-mentioned apparatus. The process for producing The concentrated dyes of the present invention can use the polyisobutene derivatives (component A) in solution or without a solvent, use without a solvent is preferred. The solvents mentioned as component C2 are suitable solvents.

The temperature for the mixture / combination of components A, B and if appropriate Cl and / or C2 and if appropriate D depends in general - when a polyolefin is present as a Cl component - on the identity of the polyolefin used. Polyolefins on the one hand they will soften enough to make it possible to mix them. On the other hand, they should not become too soft because otherwise it is impossible to introduce enough cutting energy and, furthermore, thermal degradation becomes a possible risk. As a general rule, the mixing / combining temperatures to produce the concentrated dyes of the present invention vary from 120 to 300 ° C when the Cl component is present. It is particularly advantageous that the polyisobutene derivatives used according to the present invention as component A possess sufficient thermal stability.

The process of the present invention provides the concentrated dyes of the present invention which contain the components A and B in the aforementioned proportions. Preference is given to obtain concentrated dyes containing the components A, B and Cl and / or C2 in the aforementioned amounts.

In a further embodiment of the process of the present invention for producing preferred concentrated dyes containing components A, B and Cly if appropriate D, the polyisobutene derivatives used as component A are incorporated into the polyolefins used as Cl component in a two-stage process. For this purpose, the polyisobutene derivatives used as component A are mixed only with a part of the polyolefins used as component Cl by heating. The aforementioned assemblies can be used to mix them. The level of polyisobutene derivatives used as component A that are present in that polyolefin concentrate can be generally in the range of 3% to 70% by weight, preferably in the range of 5% to 40% by weight, and more preferably from 10% to 30% by weight. The concentrate is subsequently mixed in a second step with the rest of the polyolefins used as the Cl component and the dyes used as component B, heating and molding according to the proposed use. For example, pellets or other items can be produced for further processing.

It is also possible to process the component A directly with the components B and if it is suitable Cl and / or C2 and also if it is suitable D in the aforementioned dispersant assemblies.

The concentrated dyes of the present invention that are produced according to the process described previously they are useful for the coloring of polymeric materials. Transparent, bright and migration resistant dyes are obtained.

Suitable polymeric materials can be thermoplastic or thermoelastic materials, of which thermoplastic materials are preferred.

Examples of suitable thermoplastic materials are polyolefins, for example polyethylene, polypropylene and also copolymers containing polyethylene and / or polypropylene units, polytetrafluoroethylene, piloxymethylene (POM), polyvinyl chloride, polyvinylidene chloride, cellulose polymers such as acetate cellulose, cellulose acetate butyrate and cellulose acetate propionate, acrylic polymers, such as polymethyl methacrylate, styrene-acrylonitrile (SAN) polymers, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene (ABS) polymers, methacrylonitrile-butadiene polymers -styrene (MABS), acrylonitrile-styrene-acrylic ester ASA polymers, polyamides such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate and polybutylene terephthalate or mixtures of these.

The specified thermoplastic materials can also be combined with other fibers, for example polyester and / or with natural materials such as wool and cotton. Polyolefins are the preferred polymeric materials.

Polyolefins suitable for coloring with the concentrated dyes of the present invention are the aforementioned polyolefins. That is, preferred polyolefins are polypropylene and its copolymers and clear polypropylene is particularly preferred. The polyolefins to be dyed may contain the same polyolefins as the polyolefins used as the Cl component or other polyolefins other than the Cl component. Preferably, the polyolefins to be dyed are compatible with one or more polyolefins preferably identical to those used as component C.

Accordingly, the present invention further provides a process for coloring polymeric materials, preferably polyolefins, by contacting the polymeric materials, preferably polyolefins, with a concentrated dye of the present invention. The temperatures for the coloration of the polymeric materials, preferably polyolefins, with the Concentrated dyes of the present invention depend on the identity of the particular polymeric materials, preferably polyolefms, and the dye used in the concentrated dyes. The vitreous transition temperatures and also the melting temperatures of suitable polymeric materials, in particular polyolefins, are known to persons of ordinary skill in the art, or are easily determined in a known manner. In general, the temperature in the process of the present invention for coloring polymeric materials, preferably polyolefins, is at least 80 ° C, preferably 120 to 200 ° C and more preferably 140 to 190 ° C. Particularly temperatures of 150 to 180 ° C will be advantageous for polypropylene homopolymers and copolymers.

The coloration is thus effected by mixing the polymeric materials, preferably polyolems, to be dyed with the concentrated dye of the present invention at an elevated temperature by melting and intensively mixing the components. The same assemblies as specified above in relation to the production of the concentrated dyes of the present invention can be used to mix. He The resulting melt can be extruded from the mixer assemblies by means of dies, for example as strands that can be divided into pellets. These dyed pellets can be further processed in any desired manner according to the processes known to a person skilled in the art. However, the melt can also be molded directly to form dyed shaped articles, for example by injection molding or blow molding, or it can be extruded through suitable dies to form colored fibers.

We have found that, surprisingly, the color strength and also the transparency and brightness of the colorations of the polymeric materials dyed with the concentrated dyes of the present invention can also be further improved if the polymeric materials, preferably polyolefins, are present in a composition polymer, which, as well as the polymeric materials, contains at least one block copolymer as component E, containing at least one hydrophobic block (V), composed essentially of polyisobutene units, and also at least one hydrophilic block (W ), essentially composed of oxalkylene units and having an average molar mass Mn of at least 1000 g / mol.

Accordingly, the present invention further provides the process of the present invention for dyeing polymeric materials, preferably polyolefins, by contacting polymeric materials, preferably polyolefins, with at least one concentrated dye of the present invention, wherein the polymeric materials, preferably polyolefins, or the concentrated dye is further contacted with at least one block copolymer as component E, containing at least one hydrophobic block (V), composed essentially of polyisobutene units, and also at least one hydrophilic block (W), composed essentially of oxalkylene units and having an average molar mass Mn of at least 1000 g / mol.

The preferred E-block copolymers and also the preferred amounts of E-block copolymer in the polymer compositions are specified below.

Without wishing to stick to any theory, we believe that the addition of at least one block copolymer E optimizes the distribution of the concentrated colorant of the present invention in the polymeric material. The combination of the concentrated dye of the present invention and the block copolymer E in the process of the present invention for the coloring of polymeric materials thus makes it possible to achieve optimum results in relation to the color strength, transparency and brightness of the colorations of polymeric materials dyed with the concentrated dyes of the present invention.

Contacting the polymeric materials with at least one block copolymer as component E can be carried out before, after or concurrently by contacting the polymeric materials with the concentrated dye of the present invention. Moreover, the component E - in the case of concentrated dye Fl - can also be added to the polyolefin used as component Cl (i) where the polymeric materials, preferably polyolefin, are contacted with the block copolymer E is carried out before being contacted with the concentrated dye of the present invention, the step initial is to produce a polymer composition containing at least one polymeric material, preferably polyolefin, and at least one block copolymer E. Processes for producing suitable polymer compositions are described for example in the application not yet published supporting the reference file PCT / EP2006 / 062 69. The polymer compositions obtained are subsequently contacted with the concentrated colorants of the present invention according to the aforementioned process for dyeing polymeric materials according to the present invention. (ii) As mentioned above, the Cl component of the concentrated dye Fl can contain at least one block copolymer E before the concentrated dye Fl is produced by mixing the suitable components. In this case, the block copolymer E is contacted with the polyolefin used as the Cl component. A process for producing polymer compositions containing at least one polyolefin and at least one 4 Block copolymer E is described, for example, in the previously unpublished prior application supported by the reference file PCT / EP2006 / 062469. The polymer mixture obtained is contacted with the components A and B to produce the concentrated dye Fl. This concentrated dye according to the present invention can be contacted subsequently with at least one polymeric material, preferably polyolefin to obtain the polymeric color compositions of the present invention. (m) wherein when contacting the polymeric materials with at least one block copolymer E takes place after contacting them with at least one concentrated dye, it is preferable for the polymeric material to be first dyed with the concentrated dye as described above.

This is followed by the addition of the block copolymer E and the subsequent process according to processes known to a person having skill in the art. iv) in a further embodiment, contacting the polymeric materials with the block copolymer E is concurrently done by contacting the polymeric materials with the concentrated dye of the present invention. In this embodiment, the polymeric materials, preferably polyolefins, to be colored, the at least one concentrated dye of the present invention and the at least one block copolymer E are mixed, mixed, preferably at elevated temperature, the components melted and mixed intensively. The coloration is preferably effected as described above in connection with the process for dyeing the polymeric materials with the concentrated colorant of the present invention, except that the block copolymer E is also added.

Contacting the polymeric materials with at least one block copolymer as component E is preferably carried out according to one of the embodiments (ii) or (iv).

The present invention further provides color polymer compositions composed of i) at least one concentrated dye of the present invention, 11) at least one polymeric material, preferably polyolefin.

The concentration of at least one dye (component B of the concentrated dye of the present invention) in the polymeric color compositions is generally in the range of 0.01% to 5% by weight, preferably in the range of 0.05% to 1.5% by weight and more preferably in the range of 0.01% to 1.0% by weight.

Preferred concentrated dyes and preferred polymer materials are mentioned above.

In a preferred embodiment, the colored polymer compositions of the present invention, as well as the at least one concentrated dye and the at least one polymeric material, preferably polyolefin, contain: m) at least one block copolymer as component E containing at least one hydrophobic block (V) composed essentially of polyisobutene units and also at least one hydrophilic block (W) composed essentially of oxalkylene units and having an average molar mass Mn of at least 1000 g / mol.

As mentioned above, the addition of the block copolymer E provides optimum results in relation to the color strength, transparency and brightness of the colorations of polymeric materials, preferably polyolefins, colored with the concentrated dyes of the present invention.

Component E The block copolymer used as component E contains at least one hydrophobic block (V) and at least one hydrophilic block (W). The blocks (V) and (W) are connected to each other by means of suitable link groups. They can be linear or also contain ramifications.

These block copolymers are known and their preparation can be carried out starting from the compounds and initial methods known in principle by a person having experience in the art. Suitable E-block copolymers and also the appropriate hydrophilic and hydrophobic blocks and their bonds to form the block copolymers E are described for example in the previously unpublished previous application supported in the reference file PCT / EP2006 / 062469.

The hydrophobic blocks (V) correspond essentially to the hydrophobic blocks (X) of component A, which are described above.

The hydrophobic blocks (V) and the hydrophobic blocks (X) independently have the meanings described in relation to the hydrophobic blocks (X). Suitable hydrophobic blocks are also described in the previous application not yet published supported in the reference file PCT / EP2006 / 062469. Particularly preferred hydrophobic blocks (V) are polyusobutenes functionalized with succinic anhydride groups (polyisobutenyl succinic anhydride, PIBSA).

The hydrophilic blocks (W) are composed essentially of oxalkylene units. Suitable hydrophilic blocks are described in the application previous not yet published supported in the reference file PCT / EP2006 / 062 69.

In general, the hydrophilic blocks contain units of ethylene oxide - (CH2) 2-0- and / or propylene oxide units - CH2-CH (CH3) -0-, as main components, while the oxide units of Higher alkylene, ie, those having more than three carbon atoms, are present only in small amounts to refine the properties. The blocks may be random copolymers, gradient copolymers, alternating copolymers or block copolymers composed of ethylene oxide units and propylene oxide units. The amount of higher alkylene oxide units should not exceed 10% by weight and preferably not exceed 5% by weight. The blocks are preferably blocks containing at least 50% by weight of ethylene oxide units, preferably 75% by weight and more preferably at least 90% by weight of ethylene oxide units. More preferably, the blocks are blocks of pure polyethylene.

The block copolymers E can be synthesized preferably by the hydrophilic blocks (W), being first separately synthesized and reactivated in an analogous polymer reaction with the functionalized polyusobutenes to form block E copolymers.

The building components for the hydrophilic and hydrophobic blocks have complementary functional groups, ie groups capable of reacting with each other to form linking groups.

The functional groups of the hydrophilic blocks (W) are of course preferably OH groups, but they can also be, for example, primary or secondary groups. The OH groups are particularly useful complementary groups for the reaction with PIBSA, the preferred hydrophobic block (V).

The synthesis of the blocks (W) can be effected by reacting the polusobutenes containing polar functional groups (i.e., blocks (V)) directly with alkylene oxide to form blocks (W).

The structure of the block copolymers E can be influenced through the identity and quantity of the initial materials for blocks (V) and (W) and also through the reaction conditions, in particular the order of addition.

Blocks (V) and (W) may be in the terminal position; that is, they can be linked to another block only or they can be linked to two or more blocks. Blocks (V) and (W) can be linked together, for example, linearly in an alternate arrangement. In principle, any number of desired blocks can be used. In general, however, no more than 8 of each of the blocks (V) and (W) will be present. This results in the simplest case a diblock copolymer of the general formula VW. They can also be triblock copolymers of the general formula VWV or WVW. It is clear that it is possible for a plurality of blocks to follow each other, for example VWVW, WVWV, VWVWV, WVWVW or VWVWVW.

They can also be star-block and / or branched block copolymers or also block-type block copolymers where, in each case, more than two blocks (V) are connected to a block (W) or more than two blocks (W) ) are attached to a block (V). For example, they can be block copolymers of the general formula VWm or WVm, where m is a natural number = 3, preferably from 3 to 6 and more preferably from 3 or 4. It will be appreciated that a plurality of blocks (V) and (W) may also follow each other in the arms or branches, for example V (WV) m or W (VW) m. The possible synthesis is shown below for the OH groups and succinic anhydride groups (referred to as S) by means of the example without this invention being therefore restricted to use those functional groups.

HO- [W] -OH Hydropc blocks having two OH groups [V] -OH Hydropc blocks having an OH group only [W] - (OH) x Hydropc blocks having x OH groups (x > 3) [V ] -S Polusobutene having a terminal group S S- [V] -S Polusobutene having two terminal groups S [V] -Sy Polusobutene having and S groups (and > 3) The OH groups can be linked together with the succinic anhydride groups S in a manner known in principle to form ester groups. The reaction can be carried out for example by heating them in the absence of a solvent. Suitable reaction temperatures vary, for example, from 80 to 150 ° C.

The triblock copolymers V-W-V are obtained, for example, in a simple form by reacting one equivalent of H0- [W] -0H with two equivalents of [V] -S. This is shown below with complete formulas using the PIBSA reaction and a polyethylene glycol as an example: Here, n and m are each independently a natural number. They are chosen by a person skilled in the art to result in the molar masses defined above for the hydrophobic and hydropc blocks respectively.

The star block or branched WVX block copolymers are obtained by the reaction of [W] - (OH) x with x equivalents of [V] -S.

A person having experience in the polyisobutene technique will readily understand that the block copolymers obtained may also contain residues of initial materials, depending on the manufacturing conditions. They can also contain mixtures of different products. The triblock copolymers of the formula VWV can, for example, also contain VW diblock copolymers and also functionalized and non-functionalized polusobutene.

Advantageously, these products can be used for the application without further purification. Of course, however, the products can additionally be purified. Purification methods are known to those skilled in the art.

Preferred block copolymers for carrying out this invention are triblock copolymers of the general formula VWV or their mixture with diblock copolymers VW, and also, if appropriate, by-products.

The block copolymer that is used as component E and which, in one embodiment of the present invention, may be present in the color polymer compositions of the present invention is generally present in the polymeric color compositions, if any, in an amount of 0.01% to 10% by weight, preferably of from 0.03% to 5% by weight and more preferably from 0.05% to 3% by weight, based on the total mass of the colored polymer composition.

The preferred colored polymer compositions containing component E are composed of: i) from 0.1% to 15% by weight, preferably from 0.3% to 10% by weight and more preferably from 0.5% to 8% by weight of at least one concentrated dye of the present invention, n) from 75% to 99.89% by weight, preferably from 85% to 99.67% by weight and more preferably from 89% to 99.45% by weight of at least one polymeric material, preferably polyolefin, m) from 0.01% to 10% by weight, preferably from 0.03% to 5% by weight and more preferably from 0.05% to 3% by weight of at least one block copolymer as component E, containing at least one hydrophobic block (V) composed essentially of polusobutene units and also of at least one hydropc block (W) composed essentially of oxalkylene units and having an average molar mass Mn of at least 1000 g / mol.

Preferred concentrated dyes, polymeric materials and block copolymers (component E) are mentioned above. The polymer compositions may also contain suitable additives and auxiliaries, component D. The substances useful as component D are specified above.

The colored polymeric compositions of the present invention may be present in any desired form, for example in the form of molded parts, packaging materials, films or as fibers, yarns, fabrics, nonwovens, knitting or other textile materials. Suitable processes for using polymers or polymer compositions to produce molded parts, films, packaging materials, fibers or descending yarns, woven, non-woven, and / or other textile materials are known to one skilled in the art.

The present invention therefore further provides molded parts, packaging materials, films or fibers composed of the colored polymer composition of the present invention.

As well as by the aforementioned processes for producing colored polymer compositions and also pellets, molded parts and fibers thereof, the colored polymeric compositions of the present invention can be produced by other processes using the concentrated dyes of the present invention.

The present invention therefore further provides for the use of the concentrated colorants of the present invention for the coloration of polymeric materials or polymetallic compositions containing, as well as the polymeric materials, at least one block copolymer as component E as described previously. The preferred polymeric materials and concentrated dyes and also the preferred block copolymers are specified above.

The polymeric materials, in particular the polyolefins, colored with the concentrated dyes of the present invention have more intense, brighter and more transparent colorations than the pigmented colored polymeric materials, in particular polyolefins, according to prior art processes. The intensity of the desired nuances it is clearly achieved with less colorant than when pigments are used. Moreover, compared to other colored polymeric dye materials, in particular polyolefins, they have better resistance to migration. Moreover, the coloration of the polymeric materials is possible in any desired shade (combination of shades). The tone remains bright, in contrast to the coloration with pigment.

In another embodiment, the present invention provides for the use of concentrated dyes of the present invention for the coloration of polymeric materials used for laser welding transmission.

Suitable polymeric materials are known to those skilled in the art and mentioned above. The preferred polymeric materials are polyolefins such as polyethylene and polypropylene and also copolymers containing polyethylene and / or polypropylene units, polycarbonates, polymethyl, methacrylate, polyesters such as polyethylene, terephthalate, polyamides, polystyrene, ABS, MABS, SAN, chloride of polyvinyl, polytetrafluoroethylene, polyoxymethylene or mixtures thereof. The concentrated dyes of the present invention in this embodiment contain at least one dye B which is transparent in the NIR region, particular preference is given to coloring the polymeric materials in black, ie, the at least one dye B more preferably contains at least one black dye or a combination of black trichromatic dye that is transparent in the NIR region. These black polymeric materials are of particular interest, because the carbon black typically used to color polymeric materials absorbs black in the NIR region and the prior art black dyes or dye combinations are highly prone to igra, which is undesirable .

The present invention further provides colored polymeric materials used for laser welding transmission, which contain at least one inventive concentrated dye containing at least one dye B that is transparent in the NIR region, preferably at least one black B dye. Suitable polymeric materials are specified above.

The present invention further provides for the use of the concentrated dyes of the present invention that they contain at least one black dye B which is transparent in the NIR region for coloring black polymeric materials. Suitable polymeric materials are specified above.

The polymeric materials colored in black with the concentrated dyes of the present invention contain at least one dye B which is transparent in the NIR region have the advantage over the polymeric materials colored in black with carbon black is that they do not heat up like the colored materials with black smoke, because the carbon black absorbs in the visible region and in the IR region. The combinations of trichromatic black dye typically used in the prior art tend to migrate in the colored materials. By comparison, the concentrated dyes of the present invention are advantageous in that they resist migration.

The present invention further provides colored polymeric materials in blacks and contain at least one inventive concentrated dye containing at least one black dye B which is transparent in the NIR region. Suitable materials are specified above.

Examples of suitable black dyes B with SBk 27, SBk 28, SBk 29, SBk 45 and RBk 31.

The concentrated dyes of the present invention can be used in a further embodiment of the present invention to build multi-layer systems.

Multilayer systems contain at least two layers I and II. The first layer I is generally a substrate that reflects NIR, for example metals, in particular aluminum, iron or steel, or white layers, in particular any substrate coated with Ti02. Suitable substrates are for example polymeric materials, suitable polymeric materials are specified above, for example POM, composite materials and wood.

The second layer II is composed of a material that contains at least one concentrated dye of the present invention. Suitable materials are for example the polymeric materials specified above, the second layer II contains at least one inventive concentrated dye containing at least one dye B which is transparent in the NIR region. It is particularly preferable for the at least one dye B which is transparent in the NIR region and black. The suitable transparent black-NIR dyes are specified above.

Accordingly, the present invention further provides a multi-layer system composed of i) a first layer I in the form of a reflective-NIR substrate; ii) a second layer II composed of a material containing at least one concentrated dye of the present invention.

Suitable and preferred layers I and II, suitable and preferred materials for layer II and also suitable and preferred concentrated dyes according to the present invention are specified above.

The multilayer system, as well as layers I and II, may contain one or more layers, for example clear coatings and any kind and / or other polymeric layers, suitable polymeric materials include for example the polymeric materials specified above.

The concentrated dyes of the present invention can also be used in value applications.

Accordingly, the present invention further provides for the use of the concentrated dyes of the present invention the anti-counterfeit article trademark, wherein concentrated dyes are generally used as an IR-transparent component.

Suitable concentrated dyes are particularly those which contain at least one dye B which is transparent in the NIR region.

Suitable items for marking with the concentrated dyes of the present invention include for example anti-counterfeit marks such as banknote marks, stocks and other securities, checks and credit cards, identification papers and packaging marks such as packaging for semi-luxury foods and tobacco products, brands on admission tickets, entrance tickets, coupons and luxury items. The anti-counterfeit trademarks in general serve to prevent counterfeiting and / or avoid brand piracy.

The articles produced with the concentrated dyes of the present invention which contain at least one dye B in the NIR region becomes transparent in the NIR light, that is, it becomes invisible. This way is possible for example for a motif applied with a usual carbon black pigment to be completely covered with a transparent black-NIR concentrate colorant of the present invention. When seen under the NIR light, the original motif becomes visible again.

The present invention further provides for the use of polyisobutene derivatives A compounds of at least one hydrophobic block (X) and at least one hydrophilic block (Y) for the migration resistant coloration of polymeric materials, preferably polyolefins, by incorporating an inventive concentrated dye containing at least one dye B and at least one polyisobutene derivative A in a non-aqueous form. One embodiment of the present invention relates to the aforementioned use wherein additionally a block copolymer is incorporated as component E as defined above in the polymeric materials, preferably polyolefins.

Suitable concentrated colorants and also processes suitable for coloring polymeric materials in a non-aqueous form, ie, not in an aqueous coloring liquor, and also suitable polymeric materials and suitable block copolymers (component E) are specified above.

The following examples will further clarify the present invention.

Examples The PIBSAiooo used in the examples that follow is commercially available from BASF AG under the trademark of GlissopalT. The viscosity DIN 51562 at 80 ° c is 1400 MM2 / s.

A) Preparation of polusobutene derivatives used as coloring auxiliaries Derived from polusobutene: The preparation of polyusobutene derivatives of structure X-Y of PIBSA 100 and tetraethylenepentamine or triethylenetetram Derived from polusobuteno 1: The reaction of PIBSAiooo (saponification index SN = 86 mg / g KOH with tetraethylene-pentamine A 2-L four-neck flask was charged with 582 g of PIBSA (85% α-olefin fractions, Mn = 1000, DP = 1.70, based on polusobutene) and 63.8 g of ethylhexanol under an inert gas atmosphere (N2 protection). ). After heating to 140 ° C, 99.4 g of tetraethylpentam a were added dropwise. At the end of the addition, the temperature was raised to 160 ° C and maintained at 160 ° C for 3 h. During the reaction, some volatile constituents were distilled. Finally, the pressure was reduced to 500 mbar for 30 min towards the end of the reaction. After this it was cooled to room temperature.

IR spectrum: NH vibration at 3295, 1652 cm "1, C = 0 vibration by tension of succinimide scaffold at 1769, 1698 cm" 1. Subsequent vibrations of the PIB scaffolding: 2953, 1465, 1396, 1365 and 1238 CM "1.

Derivatives of polusobutene 2 to 6: Reaction of PIBSAiooo (saponification index SN = 95 mg / g KOH) with tetraethylenepentamine (derivatives of polysbutene 2,3 and 4) or triethylenetramma (derivatives of polusobutene 5 and 6).

The polusobutene derivatives 2 to 6 were prepared according to Examples 3 to 7 in DE 101 23 553 Al. Examples 2, 3, 4, 5 and 6 of the present invention correspond to examples 3, 4, 5, 6 and 7 respectively of DE 101 23 553 Al.

Derived from polusobutene 7: Reaction of PIBSAiooo (saponification index SN = 170 mg / g KOH) with tetraethylenepentamma The polusobutene derivative 7 was prepared according to Example 2 (Product number 7) of EP 0 271 937 A2.

Derived from polusobuteno 8: Reaction of PIBSAOoo with tetraethylenepentamma The polusobutene derivative 8 was prepared according to Example 1 of WO 98/12282, except that PIBSAiooo (Glisopal®) was used in place of Indopol® H-100 from Amoco Chemical Company.

THE preparation of polusobutene derivatives of the structure Y-X-Y of PIBSAiooo and tetraethylenepentamine or triethylenetramma Polyisobutene derivatives 9 to 12: The reaction of PIBSAiooo (saponification index SN = 95) with tetraethylenepentamine (polyisobutene derivatives 9 and 10) or triethylene tetramine (polyisobutene derivatives 11 and 12).

The polyisobutene derivatives 9 to 12 were prepared according to Examples 8 to 11 of DE 101 23 553 Al. Examples 9, 10, 11 and 12 of the present invention correspond to examples 8, 9, 10 and 11 respectively of DE 101 23 553 Al.

A) Color tests Production of inventive color concentrates, The following polymers were used for the tests: Polypropylene: Moplen HP 561S (from Basell), Moplen HP 561S is a homopolypropylene (metallocene catalysis) which has a very narrow molecular weight distribution. It is specifically suitable for spinning continuous and non-continuous filaments. The data of homopolypropylene products without other additions: In each of the two different tests 5% by weight of the aforementioned polusobutene derivatives 1 to 12 were added to 85% of polypropylene pellets. At the same time, 10% copper phthalocyanine metal complex dye (SB 70 (color index: Blue solvent 70)) was extruded in an extruder with the mixture at 180 ° C. The extruded colored polymers obtained were cut into pellets. For comparison, an example of the same dye with the comparative polymer without polusobutene derivative 1 was also produced. In addition, a comparable pigment was incorporated into the polymer matrix in a third formulation.

The tests were carried out in an extruder with two propeller shafts at a cylindrical body temperature of 180 ° C and 200 rpm. The products of the matrix are 1 x 4 mm.

The dye is mixed together with the polypropylene pellets and introduced by feeding screw into the front end of the extruder. The yield is 5 kg / h. The particular polyisobutene derivative is liquefied at 80 ° C and added at 250 g / h in the aforementioned extruder. The measuring pump can be adjusted to a product between 100-300 g / n in order that the concentration of a particular polyisobutene derivative in the formula can be established.

Incorporation of the concentrated dye into the polyolefin without coloring: The concentrated dye is incorporated by the extruders in the desired concentration in the uncolored polymers and mixed together at about 180 ° C. A dye concentration of 0.01% to 5% is chosen in the final formula. The composition of a polymer composition suitable for injection molding processing is set forth below as an example form: Bl: injection molding 0. 05% by weight of copper phthalocyanine metal complex dye used 0.025% by weight of PIBSI 1000 (derived from polusobutene 1) 0.425% by weight of highly transparent polypropylene containing nucleating agents, such as polymer without color C) Preparation of block copolymers used as coloring auxiliaries Copolymer block 1: Preparation of a block copolymer of VWV structure of PIBSA 550 and polyethylene glycol 1500 Reaction of PIBSA55o (molar mass Mn, saponification index SN = 162 mg / g KOH) with Plur? Ol®-E1500 (polyethylene oxide, Mn = 1500) A 4-L three-necked flask equipped with an internal thermometer, reflux condenser and nitrogen intake was charged with 693 g of PIBSA (mn = 684); DP = 1.7) and 750 g of Pluriol® E1500 (Mn = 1500, DP = 1.1). In the course of heating to 80 ° C, the flask was evacuated and covered with N 2 3x. The reaction mixture was heated to 130 ° C and maintained at 130 ° C for 3 h. Thereafter, the product was cooled to room temperature. The following spectra were recorded: IR spectrum (KBr) in cm "1: Vibration to voltage OH to 3308, vibration to voltage C-H to 2953, 2893, 2746, vibration to voltage C = 0 a 1735; vibration at tension C = C to 1639; other vibrations of the scaffold PIB: 1471, 1390, 1366, 1233; Pluriol ether vibration at 1111. Spectrum 1-H NMR (CDCl 3, 500 MHz, TMS, room temperature) in ppm: 4.9-4.7 (C = C of PIBSA); 4.3 - 4.1 (c (o) -o-CH2-CH2-); 3.8 - 3.5 (o-CH2-ch2-0, PEO chain); 3.4 (0-CH3); 3.1 - 2.9; 2. 8-2.4; 2.3 - 2-1; 2.1 - 0.8 (methylene and methine chain GDP) Block copolymer 2 Preparation of a block copolymer of VWV structure of PIBSA 1000 and polyethylene glycol 6000 Reaction of PIBSAiooo (SAPONIFICATION INDEX sn = 86 mg / g KOH) with Plupol® E6000 (polyethylene oxide, Mn * 6000) A 4-L three-neck flask equipped with an internal thermometer, reflux condenser and nitrogen intake was charged with 783 g of PIBSA (Mn = 1305, DP = 1.5) and 1800 g of Pluriol® E6000 (Mn * 6000, DP = 1.1). In the course of heating to 80 ° C, the flask was evacuated and covered with N 2 3x. The mixture was subsequently heated to 130 ° C and maintained at 130 ° C for 3 h. Thereafter, the product was allowed to cool to room temperature and was analyzed spectroscopically.

IR spectrum (KBr) in cm_ ?: Vibration at voltage OH at 3310; vibration at voltage C-H at 2956, 2890, 2745, vibration at voltage C = 0 to 1732; vibration at tension C = C to 1640; Other vibrations of the scaffold PIB: 1471, 1388, 1365, 1232; Ether vibration from Pluriol to 1109. 1-H NMR spectrum (CDCI3, 500 MHz, TMS, room temperature) in ppm: Comparable with Example 1, different intensities: 4.9-4.7 (C = C of PIBSA); 4.3 - 4.1 (C (O) -0-CH2-CH2.); 3.8 - 3. 5 (0-CH2-CH2-0, PEO chain); 3.4 (0-CH3); 3.1 - 2.9; 2.8 - 2.4; 2.3 - 2-1; 2.1 - 0.8 (methylene and methine chain GDP) D) Color tests Production of an inventive concentrated dye The inventive concentrated dyes are produced as described in subparagraph B), the polypropylene pellets contain the block polymer 2 in the amounts specified below.

The concentrated dye contains 10% by weight of a copper phthalocyanine metal complex dye with solvent blue color index 70 (SB 70) and 5% by weight of PIBSI1000 (derived from polusobutene 1), 5% by weight of copolymer in block 2 and also 80% by weight of polypropylene pellets (Moplen HP 5615).

Incorporation of the concentrated dye in polyoleph without coloring Incorporate (extend) the concentrated dye into high transparency transparent polypropylene containing Nucleation agents by coextrusion of the concentrated dye and polypropylene of high transparency at 180 ° C. Compositions were produced to produce polymeric fibers and injection molds containing various amounts of the concentrated colorant in relation to the high transparency polypropylene: DI: Polymeric fibers The colored copolymer contains: 0. 4% by weight of the copper metal phthalocyanine complex dye used 0. 2% by weight of PIBSI 1000 (derived from polyisobutene 1) 0. 2% by weight of block copolymer used (block copolymer 2) 3. 2% by weight of propylene (Moplen HP5615), and 96. 0% by weight of high transparency polypropylene containing nucleating agents.

D2: Injection molding 0. 05% by weight of the copper metal phthalocyanine complex dye used 0. 025% by weight of PIBSI 1000 (derived from polyisobutene 1) 0. 025% by weight of block copolymer used (block copolymer 2) 0. 40% by weight of polypropylene (Moplen HP5615), and 99. 50% by weight of high transparency polypropylene containing nucleating agents.

Evaluation of injection molds obtained: The evaluation is made with reference to the following parameters: • Intensity of shade (or color strength) achieved: compared to a color concentrate with pigment color, approximately 5-10 times less than Dyeing is needed to obtain the desired shade intensity.

• Migration strength: To determine the migration strength, the particular inventive and comparative injection mold is contacted with a PVC film without color or white and loaded with a weight. The two polymers in mutual contact are stored in a dry cabinet at 60 ° C for 10 days. The dyeing of the PVC film without color or white is evaluated by means of the mold by injection. The particular color is concentrated with the polyisobutene derivative and has a solids 4-5, the comparative batch without the polyisobutene derivative having a strength of 2.

The robustness of migration was determined by the following method in accordance with NF EN ISO 183: 2000: The exudation / diffusion of a dye was determined qualitatively after its final application.

Basic principle: Close physical contact of a colored experimental section rich in depths of the neck on a leaf or plate of the experimental material with two acceptor substances and the subsequent heating of the complete system under precisely defined conditions.

Apparatus: A drying oven with air circulation and adjustable temperature set at +/- 2 ° C between 50 and 100 ° C.

Two glass plates that have a surface area that is larger than the test section. Two acceptor substances in a sheet have a surface area that equals exactly that of glass plates and a thickness of about 1 mm: A flat white filter made of calendered Plastisol paper Process: A test section to be evaluated was applied to a square of the calendered plastisol and covered with a dry white filter made of paper and a physical contact between the various parts is established by Pressure. This assembly slides between the two glass plates.

- The ends of the complete assembly are adhesively bonded together to ensure permanent contact.

Prepare a comparative sample (test section without color made of the same material) by the same method.

Place the complete assembly in a cabin to dry at 70 ° C +/- 2 ° C for 72 hours.

Subsequently, several traces that have formed in the plastisol or in the paper filter are examined.

Results presentation: The result of each absorbent chart was assessed according to the following criteria: 1: impeccable support 2: confusing points (points without clear outline) 3: small points 4: large points : complete and uniform coloring • Transparency: Colored injection molding with the concentrated dyes of the present invention exhibits excellent transparency in visual inspection, colored injection molds with pigments exhibit substantial spots in the transmitted light.

• Brilliance: The colored injection mold with the concentrated dyes of the present invention exhibits excellent brilliance in the visual inspection, the injection molds colored with pigments have fewer bright shades.

• Miscibility: Used dyes can be mixed to form any desired shade (TRICHROMISM), while pigments can only be used close to their original shade.

E) Comparative examples The polymer compositions Bl and D2 are injection molded to produce plates whose color strength is compared colorimetrically in transmission (using a Datacolor colorimeter) with the corresponding injection molded plates produced from a comparative polymer composition.

The comparative polymer composition contains 0.05% by weight of a Milliken blue dye wherein the chromophoric group is covalently attached to a polyalkylenoxy radical, as described in EP-A 0215 322, EP-A 0445 926, EP-A 0 398 620 and EP-A 0 437 107. The dye is commercially available (Cleartint® PP Blue 9805). The other components (polypropylene and polypropylene of high transparency contain nucleating agents) corresponding to the examples used in the inventive examples Bl and D2. The amounts of the individual components of the comparative polymer composition are indicated below: VI: Comparative polymer composition 0. 05% by weight of Milliken blue dye used 0. 45% by weight of polypropylene (Moplen HP 5615), and 99. 50% by weight of high transparency polypropylene containing nucleating agents.

The polymer compositions Bl, D2 and the comparative polymer composition each contain 0.05% by weight of the dye used.

The table below lists the results of the comparison of the color strength of the injection molded plates produced from the three blue polymeric compositions (the color strength is measured colorimetrically in transmission (using a Datacolor colorimeter); they are relative values): Relative values The values determined colorimetrically reported in the aforementioned table agree very well with the visual assessment of color strength.

The results clearly show an improvement in color strength for the inventive compositions over the prior art composition.

Claims (23)

1. A concentrated dye Fl, containing: a) from 0.8% to 25% by weight, of at least one polyisobutene derivative composed of at least one hydrophobic block X and at least one hydrophilic block Y as component A, b) from 6% to 25% by weight, from at least one dye as compound B, c) from 50% to 93.2% by weight, from at least one polyolefin as component Cl the total sum of components A, B and Cl is from 100% by weight, or a concentrated dye F2 containing a) from 0.8% to 25% by weight of component A, b) from 6% to 25% by weight of component B, c) from 50% to 93.2% by weight of a solvent as component C2, the total sum of components A, B and C2 is 100% by weight, the proportion by weight of component A to component B in the concentrated dye is in the range of 30: 1 to 1: 30, preferably in the range of 10: 1 to 1:10, particularly in the range of 3: 1 to 1: 3 and more preferably in the range of 2: 1: 2.
2. A concentrated dye Fl or F2 according to claim 1, contains in the case of the concentrated dye Fl-a) from 1.5% to 15% by weight, preferably from 3% to 10% by weight, and more preferably from 5% by weight. 10% by weight of component A, b) from 6% to 15% by weight, preferably from 6% to 10% by weight of component B, c) from 70% to 92.5% by weight, preferably from 80% to 91% by weight, and more preferably 80% by weight 89% by weight of component Cl, the total sum of components A, B and Cl is 100% by weight, or - in the case of concentrated dye F2 -a) of 1.5% to 15% by weight, preferably 3 % to 10% by weight and more preferably from 5% to 10% by weight of component A, b) from 6% to 15% by weight, preferably from 6% to 10% by weight of component B, c) from 70% to 92.5% by weight, preferably from 80% to 91% by weight, and more preferably from 80% by weight 89% by weight of component C2, the total sum of components A, B and C2 is 100% by weight.
3. The concentrated dye according to claim 1 or 2 wherein the component A is obtained by the functionalization of reactive polusobutene.
4. The concentrated dye according to any of claims 1 to 3 wherein component A is a polusobutenylsuccinimide.
5. The concentrated dye according to any of claims 1 to 4 wherein component B is a metallized dye.
6. The concentrated dye according to any of claims 1 to 5 wherein the polyolefins used as component Cl are selected from the group consisting of homo- or copolymers composed of C2 to Cg units and / or styrene or styrene derivatives respectively.
7. The concentrated dye according to any of claims 1 to 5 wherein the solvent used as component C2 is a polusobutene having a molecular weight Mn in the range of 200 to 1000.
8. A process for producing a concentrated dye according to any of claims 1 to 7, which contain a mixture of the components A, B and Cl or C2 with each or each other.
9. A process for coloring a polymeric material, preferably a polyolefin, by contacting said polymeric material, preferably polyolefin, with a concentrated dye according to any of claims 1 to 7.
10. The process according to claim 9 wherein the polymeric material, preferably the polyolefin, or the concentrated dye is further contacted with at least one block copolymer as component E, containing at least one hydrophobic block (V) compound essentially of polyisobutene units and also at least one hydrophilic block (W) composed essentially of oxalkylene units and having an average molar mass Mn of at least 1000 g / mol.
11. A colored polymeca composition composed of i) at least one concentrated dye according to any of claims 1 to 7, n) at least one polymeric material, preferably the polyolefin.
12. The colored polymer composition according to claim 11 contains in addition to at least one concentrated dye and the at least one polimecop material, preferably the polyolefin: i) at least one block copolymer as component E containing at least one hydrophobic block (V) composed essentially of polusobutene units and also at least hydrophilic block (W) composed essentially of oxalkylene units and having an average molar mass Mn of at least 1000 g / mol.
13. The colored polymeric composition according to claim 12 wherein the average molar mass Mn of the hydrophobic blocks (V) of the block copolymer E is in the range of 200 to 10 000 g / mol and the average molar mass Mn of the blocks hydrophilic (W) of the block copolymer E is the range of from 1000 to 20,000 g / mol.
14. The colored polymeric composition according to claim 12 or 13 wherein the hydrophilic block (W) has at least 50% by weight of ethylene oxide units.
15. The colored polymer composition according to any of claims 12 to 14 wherein the block copolymer E contains at least one triblock copolymer of the general formula V-W-V.
16. The colored polymeric composition according to any of claims 12 to 15 comprised of: i) from 0.1% to 1.5% by weight, preferably from 0.3% to 10% by weight and more preferably 0.5% by weight 8% by weight of at least one concentrated dye according to claims 1 to 7, ii) from 75% to 99.89% by weight, preferably from 85% to 99.67% by weight and more preferably from 89% to 99. 45% by weight of at least one polymeric material, preferably the polyolefin, iii) from 0.1% to 10% by weight, preferably from 0.03% to 5% by weight and more preferably from 0.05% by weight 3% by weight of at least one block copolymer according to any of claims 12 to 15.
17. A molded part, a film, a package or fiber composed of a colored polymer composition according to any of claims 11 to 16.
18. A use of a concentrated dye according to any of claims 1 to 7 for coloring a polymeric material, preferably a polyolefin.
19. The use according to claim 18 wherein the polymeric material, preferably the polyolefin, is present in a polymeric composition containing, in addition to at least one polymeric material, preferably the polyolefin, at least one block copolymer E as defined in any of claims 1 to 15.
20. 20. The use of a concentrated dye according to any of claims 1 to 7 for coloring a polymeric material used for laser welding transmission.
21. 21. The use of a concentrated colorant according to any of claims 1 to 7 for the counterfeit test mark of an article.
22. 22. A use of a polyisobutene derivative composed of at least one hydrophobic block X and at least one hydrophilic block Y for the migration resistant coloration of a polymeric material, preferably a polyolefin, incorporating a concentrated colorant according to any of claims 1 to 7 in a non-aqueous form.
23. 23. The use according to claim 22 wherein a block copolymer E is further incorporated as defined in any of claims 10 to 15 in the polymeric material, preferably the polyolefin. SUMMARY OF THE INVENTION A concentrated dye containing at least one isobutene derivative formed from at least one hydrophobic block (X) and at least one hydrophilic block (Y) as component A, and at least one dye as component B is disclosed. , and also a concentrated colorant which, like components A and B, contains at least one polyolefin as component Cl and / or at least one solvent as component C2, the processes for producing the concentrated dyes, the processes for coloring polymeric materials by contacting the polymeric materials with the inventive concentrated dyes, the colored polymeric compositions that are formed from at least one inventive concentrated dye and at least one polymeric material, fibers, films, packaging materials, molded parts, compounds of the colored polymer composition, inventiveness, the use of the inventive concentrated dyes to color polymeric materials, and the use of polyisobutene derivatives that are formed from a block hydrophobic (X) and at least one hydrophilic block (Y) as auxiliaries for the staining, stable to the migration, of the polymeric materials. The present invention also refers to process, according to the invention, for coloring polymeric materials, the polymeric materials being, furthermore, contacted with a block copolymer (component E), the colored, inventive polymer composition, which, as well as at least one colorant concentrate and at least one polymeric material, contains at least one block copolymer (component E), and the inventive use of the inventive concentrated dyes to color polymeric materials, the polymeric materials being present in a polymeric composition which, as minus one polymeric material, has at least one block copolymer E, and the inventive use of the polyisobutene derivatives that are formed from at least one hydrophobic block (X) and at least one hydrophilic block (Y) for the coloration, stable to the migration, of polymeric materials by means of the introduction of a concentrated dye, being also introduced a snowflake block limer E.