Patent Description:
In the polymer industry it is frequently necessary for an article manufactured from polymers to have a range of properties. Amongst others, a specific color of the article may be desired.

The optical properties of products are increasingly coming to the fore. The coloring of plastics is of central importance for the appearance of plastic products and their change in the course of their life.

The coloring of plastics to colored polymer components is usually achieved by using color master batches, colored micro granules, so-called dry liquid colors or liquid colors. Colored polymer components can for example be produced from color master batch concentrates blended into a polymer prior to molding or extruding or pre-colored polymers via melt blending/ compounding. The selection of one coloring method over the other may vary based on economics, secondary operations and specific requirements of the end application.

When coloring with a master batch, in an upstream step, the pigment or dye is first dispersed or dissolved in a polymeric carrier with the addition of dispersants and if necessary or required further additives. In order to achieve a fine and homogeneous distribution of the pigments or dyes, twin-screw extruders are often used to produce the master batches. Separate master batches are required for each different color and - depending on the carrier selected and the final application - for the different plastics that are to be colored with the master batch. This leads to an inefficient process, especially with small batch sizes and frequent color changes.

The most common method used by plastics processors is the use of concentrated pigments dispersed into a polymer carrier resin by molding process. During molding the master batch is let down into natural resin as it is feed into the extruder at a predefined ratio to achieve the desired color.

The processing of the master batches also has major disadvantages for the plastics processor. On the one hand this is connected with a complex storage of different color master batches, on the other hand frequent color changes on the extrusion or injection molding machine lead to an inefficient process due to material losses, cleaning processes and downtimes.

The selection of the color pigment depends, among other things, on the desired color, the polymer carrier to be used, the application and the associated requirements, but also on the further processing conditions at the plastics processor- e.g. conventional injection molding or hot runner technology. Hot runner technology is characterized by the fact that the gate system is heated separately from the rest of the mold in order to maintain the flowability of the plastic melt at a constant level. The melt and thus also the colorants are exposed to a higher thermal load which further restricts the choice of pigments.

Due to the different temperature loads, the available selection of color pigments is reduced as the temperature rises. In the case of polyolefins (polyethylene PE/ polypropylene PP) this number amounts to approx. <NUM> different colorants, in the case of polyamide (PA) only up to <NUM> colorants can be used and in the case of polyphenylene sulfide (PPS) only less than <NUM> colorants are available which meet the processing conditions.

There are various method of coloring co-polyester, co-polycarbonates, acrylonitrile-butadiene-styrene, polyamide, polyurethane, polyalkyl(meth)acrylate and copolymers thereof.

All these methods do not work efficient for the colorization of polar polymer materials comprising a substantial content of non-polar polymers, such as polyalkylenes, polyethylene (PE), polypropylene (PP), polybutylene (PB), polystyrene or mixtures thereof.

Further, there is a need to speed up the colorization time for coloring polar polymer materials comprising co-polyester, co-polycarbonates, acrylonitrile-butadiene-styrene, polyamide, polyurethane, polyalkyl(meth)acrylate, allyldiglycol carbonate, styrene copolymers or mixtures thereof, or in addition non-polar polymers, such as polyalkylenes, polyethylene (PE), polypropylene (PP), polybutylene (PB) or mixtures thereof.

The plastic parts, foils, etc. produced in this way can only be recycled at great expense after application (end-of-life). Especially for colored polymer articles recycling may be connected to separating the articles according to their color, in order to achieve high quality recycled material. These decolorization processes may be oxidation or reduction process, wherein the used dyes are decolorized by chemical modifying the dye such as destroying the conjugated double-bond system. This has the drawback that the destroyed dye compounds remain in the polymer material and the used oxidation or reduction agents are very aggressive and used in high amounts, which is not environmentally friendly.

Since the current processes are expensive and complex and so far lead to unsatisfactory results, many plastics cannot be reused in the same way and "down cycling" takes place. The unsorted plastics are melted together and processed to dark, mostly brown or black colored regranulates. New plastic products can only be produced to a very limited extent from this type of dyed recycling material. The regranulates are therefore often only processed into inferior products such as garbage bags, pallets, et cetera.

Recyclers may counter this with the addition of other colorants such as titanium dioxide. However, this impairs the physical properties and processability of the plastics, which further restricts their range of application. In particular, further recycling is made much more difficult because additional colorants are added with each cycle, further impairing the physical properties of the polymer.

<CIT> discloses a method for repeatedly tinting and changing colors.

Accordingly, there is a need for a method for reversible and selective coloring synthetic polar-polymer material, especially polar-polymer material containing a substantially content of non-polar polymers, that can be decolored by removing the dyes from the colored polymer material.

It is an object of the invention to provide a method for reversible and selective coloring synthetic polar-polymer material, a colored synthetic polar-polymer material and an article comprising at least one colored synthetic polar-polymer material.

The object is solved by the features of the independent claim. Preferred embodiments are described by the features of the dependent claims.

Thus, the object is solved by a method for reversible and selective coloring a synthetic polar-polymer material comprising the steps:.

The basic idea of method for reversible and selective coloring synthetic polar-polymer material is to use at least one organic aromatic coloring agent having a molecular weight Mw in the range of ≥ <NUM>/mol to ≤ <NUM>/mol.

Without being bond to a specific theory the inventors assume that the organic aromatic coloring agent may have the ability to migrate into the synthetic polar-polymer material and therefore coloring the synthetic polar-polymer material. A migration of the organic aromatic coloring agent into the synthetic polar-polymer material may also allow a migration of the organic aromatic coloring agent out of the colored synthetic polar-polymer material. Therefore a decoloring of the colored material may be possible. In order to enable a migration as unhindered as possible, the organic aromatic coloring agent preferably has a rather planar structure and preferably comprises at least one free rotation center outside the planar structure. Further in case of ligands and/or remnants which may be spatially or sterically demanding, the ligands and/or remnants may be as freely movable as possible around a center of rotation. This may give the organic aromatic coloring agent the ability to adapt its shape to the environment given by the matrix of the synthetic polar-polymer material. Preferably the organic aromatic coloring agent may not comprise a spiro-center and/or the organic aromatic coloring agent may not comprise a large moiety that is rotation-impaired. In this context a large moiety that is rotation impaired may mean that the molecular weight of this rotation impaired moiety is about <NUM>/mol +/- <NUM>%.

Furthermore, the aqueous dispersed coloring solution comprises at least one dispersing agent for dispersing the organic aromatic coloring agent in the aqueous solution. The organic aromatic coloring agent may only be partially soluble in the aqueous solution. The dispersing agent may enhance the stability of the aqueous dispersed coloring solution by distributing the organic aromatic coloring agent in the phase of the aqueous solution.

In addition, the aqueous dispersed coloring solution optionally may comprise at least one solubilizer. The solubilizer may enhance the solubility of the organic aromatic coloring agent in the aqueous solution. The amount of molecularly solved organic aromatic coloring agent may be enhanced by the solubilizer. Therefore, the solubilizer may improve the result of the coloring process.

During the coloring process the outer surface of the synthetic polar-polymer material is exposed to the aqueous dispersed coloring solution, wherein the aqueous dispersed coloring solution has a temperature in the range of about ≥ <NUM> to about ≤ <NUM>. As a result of this process the synthetic polar-polymer material is colored.

At temperatures below <NUM> of the aqueous dispersed coloring solution the colorization process may be carried out in an open reactor without pressure. At temperatures about ≥ <NUM>, preferably about ≥ <NUM>, of the aqueous dispersed coloring solution the colorization process may be carried out in a closed reactor under pressure.

According to a further preferred embodiment the method for reversible and selective coloring a synthetic polar-polymer material comprises the steps:.

The polar additive may be solid at <NUM>. The polar additive may be not a dye. The polar additive may be solid at <NUM> and is not a dye. The polar additive may be solid at <NUM> and is not a dye, is selected different from the dispersing agent and is selected different from the solubilizer.

The aqueous dispersed coloring solution may not comprise a glycol ether, glycol and/or butanediol.

According to a further preferred embodiment the method for reversible and selective coloring a synthetic polar-polymer material, wherein the synthetic polar-polymer material contains ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of a synthetic non-polar-polymer, based on the total weight of the synthetic polar-polymer material, the method may comprise the steps:.

According to a further preferred embodiment the method for reversible and selective coloring a synthetic polar-polymer material, wherein the synthetic polar-polymer material contains about ≥ <NUM> wt. -% to <NUM> wt. -% of a synthetic non-polar-polymer, based on the total weight of the synthetic polar-polymer material, comprises the steps:.

According to another further preferred embodiment the method for reversible and selective coloring a synthetic polar-polymer material, wherein the synthetic polar-polymer material contains ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of a synthetic non-polar-polymer, preferably ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of a synthetic non-polar-polymer, more preferably ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of a synthetic non-polar-polymer, further preferably about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of a synthetic non-polar-polymer based on the total weight of the synthetic polar-polymer material, the method may comprise the steps:.

According to a further preferred embodiment the synthetic polar-polymer material that is colored comprises at least one synthetic polar-component, wherein the synthetic polar-component comprises:.

According to a further preferred embodiment the synthetic polar-polymer material that is colored comprises:.

the polar-additive is selected different to the organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ <NUM>/mol to about ≤ <NUM>/mol.

According to a further preferred embodiment the method for reversible and selective coloring a synthetic polar-polymer material, wherein the synthetic polar-polymer material contains about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of a synthetic non-polar-polymer, based on the total weight of the synthetic polar-polymer material, comprises the steps:.

The synthetic polar-polymer material may comprise a mixture of different components. The synthetic polar-polymer material may comprise at least one synthetic polar-component. Polar in this context may mean that the component shows an enhanced polarity compared to a component that exclusively consist of C-atoms and H-atoms.

According to another preferred embodiment the synthetic polar-polymer having a Mw about ≥ <NUM>/mol, the synthetic polar-oligomer having a Mw about ≥ <NUM>/mol and < <NUM>/mol, and the polar-additive having a Mw about ≥ <NUM> and < <NUM>/mol may each comprise at least about ≥ <NUM> wt. -% of heteroatoms, wherein the weight % is calculated based on the individual weights of the synthetic polar-polymer, the synthetic polar-oligomer, and the polar-additive, respectively. In this context a heteroatom may be any atom excluding C-atoms and H-atoms. Preferably, the heteroatom may be selected from the group comprising: N, O, F, Cl, Br, I, S, and P. Furthermore, preferably the synthetic polar-polymer having a Mw about ≥ <NUM>/mol, the synthetic polar-oligomer having a Mw about ≥ <NUM>/mol and < <NUM>/mol, and the polar-additive having a Mw about ≥ <NUM> and < <NUM>/mol may each comprise at least about ≥ <NUM> wt. -% and preferably < <NUM> wt. -% of O-atoms.

The polarity of the synthetic polar-polymer material may enhance the ability of the organic aromatic coloring agent to migrate into the synthetic polar-polymer material. According to this in an another embodiment the synthetic polar-polymer material that is colored may comprise at least about ≥ <NUM> wt. -% of the synthetic polar-component, preferably about ≥ <NUM> wt. -% of the synthetic polar-component, and further preferred about ≥ <NUM> wt. -% of the synthetic polar-component, in addition preferred about ≥ <NUM> wt. -% of the synthetic polar-component, also preferred about ≥ <NUM> wt. -% of the synthetic polar-component, or about ≥ <NUM> wt. -% and about ≤ <NUM> wt. -% of the synthetic polar-component, wherein the weight % is calculated based on the total weight of the synthetic polar-polymer material.

According to another embodiment the synthetic polar-polymer material that is colored may comprise at least about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of a synthetic non-polar polymer, preferably about ≥ <NUM> wt. -% of the synthetic non-polar polymer, and further preferred about ≥ <NUM> wt. -% of the synthetic non-polar polymer, in addition preferred about ≥ <NUM> wt. -% of the synthetic non-polar polymer, also preferred about ≥ <NUM> wt. -% of the synthetic non-polar polymer, or about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -%, or about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -%, or about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -%, or about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -%, or about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -%, or about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -%, or about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -%, wherein the weight % is calculated based on the total weight of the synthetic polar-polymer material.

The migration capability of the organic aromatic coloring agent into the synthetic polar-polymer material may also be influenced by the morphology of the synthetic polar-polymer and/or the synthetic polar-oligomer. It may be possible that the synthetic polar-polymer and/or the synthetic polar-oligomer may show a mixed morphology having a mixture of crystalline phases, semi-crystalline phases and amorphous phases.

The volume % of the amorphous phase of the synthetic polar-polymer and/or the synthetic polar-oligomer may be determined by light microscopy, light scattering, X-ray diffraction, electron microscopy, electron diffraction, and/or neutron scattering, wherein light microscopy is preferred.

The migration capability of the organic aromatic coloring agent into the synthetic polar-polymer material may also be influenced by a free volume of the synthetic polar-polymer and/or the synthetic polar-oligomer. It may be advantage to the result of the coloring process when the synthetic polar-polymer and/or the synthetic polar-oligomer trap a large amount of interconnected free volume in the glassy state.

The free volume may be determined by positron annihilation spectroscopy and more preferably by positron annihilation lifetime spectroscopy. These are non-destructive spectroscopy techniques for studying voids and defects in solids. The measurement data may be interpreted according to the concept of free volume given by Simha and Boyer.

In this context according to a further preferred embodiment the glass-transition temperature Tg of the synthetic polar-polymer may be in the range of about ≥ -<NUM> to about ≤ <NUM>, preferably about ≥ -<NUM> to about ≤ <NUM>, further preferred about ≥ <NUM> to about ≤ <NUM>.

The glass transition may be the gradual and reversible transition in amorphous regions of the synthetic polar-polymer from a hard and relatively brittle state into a viscous or rubbery state as the temperature is increased. The glass transition temperature Tg of the synthetic polar-polymer may be determined by differential scanning calorimetry (DSC), which is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature.

The glass transition temperature Tg of the synthetic polar-polymer may be determined according to the following standards: DIN <NUM> (Thermal Analysis - Differential Thermal Analysis and Differential Scanning Calorimetry - General Principles), ASTM E <NUM>, ASTM D <NUM>, DIN EN ISO <NUM>-<NUM> (Plastics - Differential Scanning Thermal Analysis Part <NUM>: General principles. (<NUM>)), ISO <NUM>-<NUM> (Plastics - Differential Scanning Calorimetry Part <NUM>: Determination of the glass transition temperature. (<NUM>)), ISO / DIS <NUM>-<NUM> (Plastics - Differential Scanning Calorimetry Part <NUM>: Determination of the melting and crystallization temperature and the melting and crystallization enthalpy. (<NUM>)), ISO <NUM>-<NUM>(Plastics - Differential Scanning Thermal Analysis (DSC) Part <NUM>: Determination of specific heat capacity.

The glass transition temperature Tg of the synthetic polar-polymer may be determined using a Mettler Toledo DSC <NUM>+ differential calorimeter, a sample amount of <NUM> +/- <NUM>, nitrogen as purge gas, and the following settings: <NUM>. Heating: -<NUM> to <NUM> with <NUM>/min, Hold: <NUM> minutes at <NUM>, Cooling: <NUM> to -<NUM> at <NUM>/min, Hold: <NUM> minutes at -<NUM>, <NUM>. Heating: -<NUM> to <NUM> at <NUM>/min.

With regard to the synthetic polar-polymer and the synthetic polar-oligomer:.

A homopolymer or a homo oligomer may be a polymer or an oligomer that contains only a single type of repeat unit. A copolymer or a cooligomer may be a polymer or an oligomer that contains two types of repeat units. A terpolymer or a teroligomer may be a polymer or an oligomer that contains three types of repeat units. With regard to the copolymer, the cooligomer, the terpolymer, and the teroligomer the different types of repeat units may be organized along the backbone in different ways. There may be a controlled arrangement of the different repeat units, a statistical distribution of the different repeat units, and/or a longer sequence of one specific repeat unit alternating a longer sequence of a different specific repeat unit.

Preferably the two different types of repeat units in the copolymer or the cooligomer are organized in blocks such that the copolymer or the cooligomer is a block copolymer or block cooligomer. More preferably the first type of repeat unit is non-polar and preferably comprises only C and H atoms. Preferably the second type of repeat unit is polar and comprises more than <NUM> wt. -% of heteroatoms based on the total weight of the repeat unit, wherein a heteroatom is any atom excluding C and H. These block copolymers and block oligomers may have the advantage that the migration of the organic aromatic coloring agent into the synthetic polar-polymer material is enhanced due to the formation of micelles and kind of channels in the synthetic polar-polymer material. Therefore, using these block copolymers and/or block cooligomers may lead to a more homogenous coloring of the synthetic polar-polymer material. These block copolymers and block oligomers may be produced by (living) radical polymerization and or radical oligomerization and/or by using coordinative polymerization methods with metal complex catalysts.

The synthetic polar-polymer or mixture thereof may be selected from the group comprising:.

Other synthetic polar-polymer of amorphous copolyester that can be used are known under the tradename Akestra <NUM>, <NUM> and <NUM>. The above named synthetic polar-polymers may be used alone or in a mixture of two or more.

With regard to hydroxyl-functional dendritic polyesters that can be suitable used as a polar polymers, these molecules may be produced using polyalcohol cores, hydroxy acids and technology based on captive materials. The dendritic structures may be formed by polymerization of the particular core and <NUM>,<NUM>-dimethylol propionic acid (Bis-MPA). The base products that may be obtained are hydroxyl-functional dendritic polyesters. They may be fully aliphatic and may consist only of tertiary ester bonds. They may provide excellent thermal and chemical resistance. Extensive branching also improves reactivity, lowers viscosity and results in balanced mechanical properties. The hydroxyl-functional dendritic polyesters may be known under the trade name Boltorn®. The following dendritic polymers may be used as non-limiting examples: Boltorn® H20 <NUM> terminal hydroxyl groups, nominal molecular weight of <NUM>/mol, Boltorn® H2004 <NUM> terminal hydroxyl groups, nominal molecular weight of <NUM>/mol, Boltorn® H311 <NUM> terminal hydroxyl groups, nominal molecular weight of <NUM>/mol, Boltorn® P500 Formulated bimodal product with terminal hydroxyl groups, nominal molecular weight <NUM>/mol, Boltorn® P1000 formulated bimodal product with terminal hydroxyl groups, nominal molecular weight <NUM>/mol, Boltorn® U3000 modified with unsaturated fatty acid, nominal molecular weight <NUM>/mol, Boltorn® W3000 modified with non-ionic groups and unsaturated fatty acid, nominal molecular weight <NUM>/mol.

With regard to the polyester based copolymers that can be suitable used as a polar polymers, these may further include but not limited to a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from <NUM>-(hydroxymethyl)cyclohexylmethyl-<NUM>'-(hydroxymethyl)cyclohexane carboxylate represented by the following chemical formula <NUM> and a residue derived from <NUM>,<NUM>-(oxybis(methylene)bis) cyclohexane methanol represented by the following chemical formula <NUM>. <CHM>
<CHM>.

The compounds of chemical formula <NUM> and <NUM> can be copolymerized with aromatic dicarboxylic acid may be one or more selected from a group consisting of terephthalic acid, dimethyl terephthalate, cyclic dicarboxylic acid, isophthalic acid, adipic acid, azelaic acid, naphthalene dicarboxylic acid, and succinic acid.

The diol-derived residue of the copolymers may further include a residue derived from one or more other diols selected from a group consisting of <NUM>,<NUM>-cyclohexane dimethanol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-propanediol, <NUM>,<NUM>-hexanediol, <NUM>,<NUM>-cyclohexanediol, <NUM>,<NUM>-cyclohexanediol, <NUM>,<NUM>-cyclohexane dimethanol, <NUM>,<NUM>-cyclohexane dimethanol, <NUM>,<NUM>-dimethylpropane-<NUM>,<NUM>-diol (neopentyl glycol), ethylene glycol, and diethylene glycol. A content of the diol derived residues of the residue derived from <NUM>-(hydroxymethyl)cyclohexylmethyl <NUM>'-(hydroxymethyl)cyclohexane carboxylate, the residue derived from <NUM>,<NUM>-(oxybis(methylene)bis) cyclohexane methanol, and other diol-derived residues may be about <NUM> to <NUM> mol% based on <NUM> mol% of the dicarboxylic acid co-monomer.

The synthetic polar-polymer may also comprise the polyester based copolymers used in a mixture with polyethylene terephthalate (PET). The mixture may consist of <NUM> to <NUM> wt. -% of PET and <NUM> to <NUM> wt. -% of the polyester based copolymers, in order that both components add up to <NUM> wt. Additionally or alternatively the compounds according to chemical formulas <NUM> and <NUM> may be used as co-monomers together with a further diol-component, e.g. ethylene glycol, in the preparation of the polyester based copolymers.

The polyester based copolymer may be prepared by reacting the dicarboxylic acid including the aromatic dicarboxylic acid with the diol including <NUM>-(hydroxymethyl)cyclohexylmethyl <NUM>'-(hydroxymethyl)cyclohexane carboxylate represented by chemical formula <NUM> and <NUM>,<NUM>-(oxybis(methylene)bis) cyclohexane methanol represented by chemical formula <NUM> to perform an esterification reaction and a polycondensation reaction. In this case, other diols such as <NUM>,<NUM>-cyclohexane dimethanol, ethylene glycol, diethylene glycol, or the like, as described above may be further reacted, such that a polyester based copolymer further including other diol-derived residues may be prepared.

With regard to the polyether, these may comprise but not limited to compounds that contain at least one polyethyleneglycol moiety and at least one fatty acid moiety coupled to the polyethyleneglycol moiety. The polyethyleneglycol moiety may contain <NUM> to <NUM> ethyleneglycol repeating units. The fatty acid moieties may be saturated or unsaturated and may contain <NUM> to <NUM> carbon atoms, preferably <NUM> to <NUM> carbon atoms. Examples of these fatty acid moieties are oleate, laureate, stearate, palmitate and ricinoleate. A specific preferred example may be ethoxylated sorbitan ester.

The ethoxylated sorbitan ester comprises a sorbitan group which is substituted by four polyethylene glycol substituents. The ethoxylated sorbitan ester may preferably comprise <NUM> to <NUM> ethylene glycol repeating units, preferably <NUM> to <NUM> ethylene glycol repeating units, more preferably between <NUM> and <NUM> repeating units. At least one of the ethylene glycol substituents in the ethoxylated sorbitan ester is connected via an ester bond to a fatty acid moiety. Preferably, at least two of the ethylene glycol substituents in the ethoxylated sorbitan ester are connected via an ester bond to a fatty acid moiety; more preferably at least three of the ethylene glycol substituents are connected via an ester bond to a fatty acid moiety. The fatty acid moieties may be saturated or unsaturated and may contain <NUM> to <NUM> carbon atoms, preferably <NUM> to <NUM> carbon atoms.

Examples of these fatty acid moieties are oleate, laureate, stearate and palmitate. Most preferred are ethoxylated sorbitan esters comprising four polyethylene glycol substituents and wherein the ester comprises between <NUM> and <NUM> ethylene glycol repeating units and wherein three of the ethylene glycol substituents are connected to oleate, laurate or stearate groups.

Examples of ethoxylated sorbitan esters that can be used as polar-polymer are polyoxyethylene (<NUM>) sorbitane monolaurate, polyoxyethylene (<NUM>) sorbitane dilaurate, polyoxyethylene (<NUM>) sorbitane trilaurate, polyoxyethylene (<NUM>) sorbitane mono-oleate, polyoxyethylene (<NUM>) sorbitane di-oleate, polyoxyethylene (<NUM>) sorbitane tri-oleate, polyoxyethylene (<NUM>) sorbitane monostearate, polyoxyethylene (<NUM>) sorbitane distearate, polyoxyethylene (<NUM>) sorbitane tristearate, and polyoxyethylene (<NUM>) sorbitan monooleate, also known as Polysorbate <NUM> and E433.

With respect to the synthetic polar-oligomer and according to another embodiment the synthetic polar-oligomer or mixture thereof may be selected from the group comprising:.

With regard to the oligoester based cooligomers that can be suitable used as a polar oligomers, these may further include but not limited to a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from <NUM>-(hydroxymethyl)cyclohexylmethyl-<NUM>'-(hydroxymethyl)cyclohexane carboxylate represented by the following chemical formula <NUM> and a residue derived from <NUM>,<NUM>-(oxybis(methylene)bis) cyclohexane methanol represented by the following chemical formula <NUM>. <CHM>
<CHM>.

The compounds of chemical formula <NUM> and <NUM> can be cooligomerized with aromatic dicarboxylic acid may be one or more selected from a group consisting of terephthalic acid, dimethyl terephthalate, cyclic dicarboxylic acid, isophthalic acid, adipic acid, azelaic acid, naphthalene dicarboxylic acid, and succinic acid.

The diol-derived residue of the cooligomers may further include a residue derived from one or more other diols selected from a group consisting of <NUM>,<NUM>-cyclohexane dimethanol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-propanediol, <NUM>,<NUM>-hexanediol, <NUM>,<NUM>-cyclohexanediol, <NUM>,<NUM>-cyclohexanediol, <NUM>,<NUM>-cyclohexane dimethanol, <NUM>,<NUM>-cyclohexane dimethanol, <NUM>,<NUM>-dimethylpropane-<NUM>,<NUM>-diol (neopentyl glycol), ethylene glycol, and diethylene glycol. A content of the diol derived residues of the residue derived from <NUM>-(hydroxymethyl)cyclohexylmethyl <NUM>'-(hydroxymethyl)cyclohexane carboxylate, the residue derived from <NUM>,<NUM>-(oxybis(methylene)bis) cyclohexane methanol, and other diol-derived residues may be about <NUM> to <NUM> mol% based on <NUM> mol% of the dicarboxylic acid co-monomer.

The synthetic polar-oligomer may also comprise the oligoester based cooligomers used in a mixture with oligoethylene terephthalate (PET). The mixture may consist of <NUM> to <NUM> wt. -% of PET and <NUM> to <NUM> wt. -% of the oligoester based cooligomers, in order that both components add up to <NUM> wt. Additionally or alternatively the compounds according to chemical formulas <NUM> and <NUM> may be used as co-monomers together with a further diol-component, e.g. ethylene glycol, in the preparation of the oligoester based cooligomers.

The oligoester based cooligomer may be prepared by reacting the dicarboxylic acid including the aromatic dicarboxylic acid with the diol including <NUM>-(hydroxymethyl)cyclohexylmethyl <NUM>'-(hydroxymethyl)cyclohexane carboxylate represented by chemical formula <NUM> and <NUM>,<NUM>-(oxybis(methylene)bis) cyclohexane methanol represented by chemical formula <NUM> to perform an esterification reaction and a oligocondensation reaction. In this case, other diols such as <NUM>,<NUM>-cyclohexane dimethanol, ethylene glycol, diethylene glycol, or the like, as described above may be further reacted, such that a oligoester based cooligomer further including other diol-derived residues may be prepared.

With regard to the oligoether these may comprise but not limited to compounds that contains at least one oligoethyleneglycol moiety and at least one fatty acid moiety coupled to the oligoethyleneglycol moiety. The oligoethyleneglycol moiety may contain <NUM> or <NUM> ethyleneglycol repeating units.

The fatty acid moieties may be saturated or unsaturated and may contain <NUM> to <NUM> carbon atoms, preferably <NUM> to <NUM> carbon atoms.

Examples of these fatty acid moieties are oleate, laureate, stearate, palmitate and ricinoleate. Examples of compound that contain at least one polyethyleneglycol moiety and at least one fatty acid moiety coupled to the polyethyleneglycol moiety include PEG <NUM> di-oleate, PEG <NUM>-distearate, PEG <NUM> dioleate, PEG <NUM> distearate, PEG <NUM> monooleate, PEG <NUM> monoricinoleate, PEG <NUM> monostearate.

A specific preferred example may be ethoxylated sorbitan oligoester. The ethoxylated sorbitan oligoester comprises a sorbitan group which is substituted by four oligoethylene glycol substituents. The ethoxylated sorbitan ester may preferably comprise <NUM> to <NUM> ethylene glycol repeating units, preferably <NUM> to <NUM> ethylene glycol repeating units, more preferably between <NUM> and <NUM> repeating units. At least one of the ethylene glycol substituents in the ethoxylated sorbitan ester is connected via an ester bond to a fatty acid moiety. Preferably, at least two of the ethylene glycol substituents in the ethoxylated sorbitan ester are connected via an ester bond to a fatty acid moiety; more preferably at least three of the ethylene glycol substituents are connected via an ester bond to a fatty acid moiety. The fatty acid moieties may be saturated or unsaturated and may contain <NUM> to <NUM> carbon atoms, preferably <NUM> to <NUM> carbon atoms.

Examples of these fatty acid moieties are oleate, laureate, stearate and palmitate. Most preferred are ethoxylated sorbitan esters comprising four oligoethylene glycol substituents and wherein the ester comprises between <NUM> and <NUM> ethylene glycol repeating units and wherein three of the ethylene glycol substituents are connected to oleate, laurate or stearate groups.

The polar additive may be solid at <NUM>. The polar additive may not be a dye. The polar additive may be solid at <NUM> and is not a dye. The polar additive may be solid at <NUM> and is not a dye, is selected different from the dispersing agent and is selected different from the solubilizer.

In connection to the polar-additive and according to an another embodiment the polar-additive having a Mw about ≥ <NUM> and < <NUM>/mol may be selected from the group comprising aliphatic acids CH<NUM>-[CH<NUM>]n-COOH acids (n about ≥ <NUM>), amino acids, carboxylic acid amide, hydroxyl acids, fatty acids, aliphatic or aliphatic/aromatic aldehydes and ketones, esters, pentaerythritol, pentaerythritol dimers, pentaerythritol trimers, pentaerythritol ester preferably carboxylic acid ester, benzoic acid esters comprising benzylbenzoat or phenylbenzoat, phenylether, alcohols and polyvalent alcohols, preferably glycerine, amines, wherein the polar-additive is selected different to the organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ <NUM>/mol to about ≤ <NUM>/mol; and preferably the polar-additive having a Mw about ≥ <NUM> and < <NUM>/mol is containing a heteroatom selected from N, O, S and/or halogene. Preferably, halogens may be selected from the group comprising Cl, Br and I.

The carboxylic acid amide may comprise a compound according to formula C<NUM>H<NUM>(NHC(O)R<NUM>)<NUM>, wherein R<NUM> is a fatty acid moiety comprising <NUM>-<NUM> carbon atoms. The fatty acid moieties may be saturated or unsaturated. When the amount of carboxylic acid amide is too high the colored polar-polymer material may show blooming. Blooming i.e. discolorations may be caused by phase separation of the material's components. It may be caused by incompatibilities of the polar-additive with the polar-polymer and/or with the polar-polymer material.

Pentaerythritol may comprise a compound according to formula C(CH<NUM>OR)<NUM>, wherein R may be H, or wherein R may be a fatty acid moiety comprising <NUM>-<NUM> carbon atoms. The fatty acid moieties can be saturated or unsaturated. R may be also another moiety like ether, amide and/or urethane. As Pentaerythritol Perstorp Charmor PM <NUM> may be used.

Furthermore the polar additive may be an ether. Ether these may comprise but not limited to compounds that contains at least one ethyleneglycol moiety and at least one fatty acid moiety coupled to the ethyleneglycol moiety.

Examples of compound that contains at least one ethyleneglycol moiety and at least one fatty acid moiety coupled to the polyethyleneglycol moiety include PEG <NUM>-monostearate, PEG <NUM> monolaurate.

The carboxylic acid ester may comprise a compound according to the following chemical formula <NUM>:
<CHM>
wherein R<NUM> is an alkyl group comprising <NUM>-<NUM> carbon atoms and Z is hydrogen or a group according to the formula C(O)R<NUM>, wherein R<NUM> is an alkyl group comprising <NUM>-<NUM> carbon atoms. R<NUM> may be the same or different and is an alkyl group comprising <NUM>-<NUM> carbon atoms, preferably <NUM>-<NUM> carbon atoms, more preferably <NUM>-<NUM> carbon atoms. R<NUM> is an alkyl group comprising <NUM>-<NUM> carbon atoms, preferably <NUM>-<NUM> carbon atoms, more preferably <NUM>-<NUM> carbon atoms. Non-limiting examples of the carboxylic acid ester are triethylcitrate, tributylcitrate, trihexylcitrate, acetyltributylcitrate (ATBC; R<NUM> = C<NUM>H<NUM>, Z = CH<NUM>CO), propanoyltributylcitrate, acetyltrihexylcitrate and butanoyltriethylcitrate.

Furthermore, as polar-additive <NUM>-(hydroxymethyl)cyclohexylmethyl-<NUM>'-(hydroxymethyl)cyclohexane carboxylate represented by the chemical formula <NUM>, <NUM>,<NUM>-(oxybis(methylene)bis) cyclohexane methanol represented by the chemical formula <NUM>, and mixtures thereof may be used:
<CHM>
<CHM>.

As already mentioned above, the synthetic polar-polymer material that is colored may comprise a composition of a non-polar-polymer having a Mw about ≥ <NUM>/mol. In connection to this non-polar-polymer having a Mw about ≥ <NUM>/mol and according to an another embodiment the non-polar-polymer may be selected from the group of polyalkylene polymers, polyalkylene copolymers, polyakylene block copolymers. The non-polar-polymer may be preferably selected from of polymeric aliphatic or aromatic hydrocarbons, preferably polyalkylene polymers, polyalkylene co- and terpolymer with random or block-structure; and more preferred from polyethylen (PE), polypropylene (PP), polybutene (PB), polystyrene, polyisobutylene, polybutadiene, polyisoprene. Preferably the non-polar-polymer may have a wt. -% of heteroatoms below <NUM> wt. -% with respect to the mass of the non-polar-polymer.

The organic aromatic coloring agent is not a chemical reactive dye. That means the organic aromatic coloring agent as used in the present invention doesn't covalently bond to a component of the polymer material that is colorized by the organic aromatic coloring agent. In this context forming no chemical covalent bond means that the organic aromatic coloring agent does not form a covalent sigma bond, covalent double bound, covalent triple bond or any other chemical covalent bond with the synthetic polar-polymer material or with a component of the synthetic polar polymer material.

The organic aromatic coloring agent for example adsorbs and/or absorbs to the polar-polymer component.

The organic aromatic coloring agent may have a molecular weight Mw in the range of about ≥ <NUM>/mol to about ≤ <NUM>/mol, preferably the organic aromatic coloring agent has a molecular weight Mw in the range of about ≥ <NUM>/mol to about ≤ <NUM>/mol, and more preferably the organic aromatic coloring agent has a molecular weight Mw in the range of about ≥ <NUM>/mol to about ≤ <NUM>/mol.

The organic aromatic coloring agent may absorb light in the visible spectrum; therefore it may appear to be colored for a human observer. Furthermore it may also be possible that the organic aromatic coloring agent absorbs light in the UV or in the infrared region of the electromagnetic spectrum. In this case the organic aromatic coloring agent may not appear to have a visible color to a human observer. It may also be possible that the organic aromatic coloring agent is a stabilizer to prevent the oxidation, chain fission, uncontrolled recombination and/or cross-linking reaction that are caused by photo-oxidation of the synthetic polar polymer material. The synthetic polar polymer material may become weathered by the direct or indirect impact of heat and ultraviolet light. This effect may be hindered by hindered amine light stabilizers (HALS).

Furthermore, the solubility of the organic aromatic coloring agent in water may be low. According to an another embodiment the organic aromatic coloring agent may have a solubility in water at <NUM> of about ≤ <NUM>/l and > <NUM>/l, preferably about ≤ <NUM>/l and > <NUM>/l, more preferably about ≤ <NUM>/l and > <NUM>/l.

The organic aromatic coloring agent comprises at least <NUM> to <NUM> aromatic six-membered rings, or at least <NUM> to <NUM> aromatic six-membered rings and at least <NUM> to <NUM> five-membered rings. Furthermore, the aromatic coloring agent has at least <NUM> to <NUM> aromatic six-membered rings and the organic aromatic coloring agent may comprises at least on heteroatom selected from N, O, S, Br.

Preferably the organic aromatic coloring agent is selected from the group comprising the following chemical formulas A1 to A10 according to table <NUM>:.

Regarding the chemical formula A7, the methoxy group -[OCH<NUM>] may be an alternative for the hydroxyl group -[OH] on the aromatic moiety, that is not part of the anthraquinone ring system.

Further the organic aromatic coloring agent may be selected from the group comprising Bis(<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-piperidyl)sebacat, methyl <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-piperidyl sebacate, <NUM>,<NUM>'-Thiobis(<NUM>-tert-octylphenolato)-n-butylamine nickel(II), N-(<NUM>-Ethoxyphenyl)-N'-(<NUM>-ethylphenyl)-ethlyene diamide. The organic aromatic coloring agent may include UV-absorbers form the company European Additives GmbH and the light stabilizers from the company MPI Chemie B.

Preferably the organic aromatic coloring agent is selected from the group comprising the coloring agents known under the trademark BEMACRON S/SE/E from CHT Germany GmbH, or from Dystar Pte Ltd. Preferably the organic aromatic coloring agent is selected from the group comprising BEMACRON Yellow S-6GF, BEMACRON Yellow S-<NUM>, BEMACRON Yellow Brown S-2RFl, BEMACRON Orange S-g, BEMACRON Scarlet S-gFl, BEMACRON Scarlet S-BWFl, BEMACRON Rubine S-2GFL, BEMACRON Violet S-3Rl, BEMACRON Violet S-BlF, BEMACRON Blue S-Bgl, BEMACRON Blue S-BB, BEMACRON Turquoise S-gF, BEMACRON Navy S-2gl, BEMACRON Navy S-<NUM>, BEMACRON Black S-<NUM>, BEMACRON Black S-T, BEMACRON Yellow SE-Rdl, BEMACRON Yellow SE-lF, BEMACRON Orange SE-Rdl, BEMACRON Red SE-<NUM>, BEMACRON Pink SE-REl, BEMACRON Red SE-3B, BEMACRON Red SE-Rdl, BEMACRON Blue SE-lF, BEMACRON Blue SE-Rdl, BEMACRON Navy SE-RlX, BEMACRON Black SE-RlX, BEMACRON Black SE-Rd2R, BEMACRON Yellow E-3gl, BEMACRON Red E-FB1, BEMACRON Blue E-FB1, and BEMACRON Black E-R.

More preferably the organic aromatic coloring agent is selected from the group comprising BEMACRON Black E-R, BEMACRON Yellow S-6GF, BEMACRON Rubine S-2GFL, BEMACRON Blue RS, BEMACRON Blue E-FBL <NUM>, BEMACRON Red E-FBL, BEMACRON Blue S-BGL, BEMACRON Yellow E-3gl, BEMACRON Lumin. Yellow SEL-<NUM>, and BEMACRON Lumin.

Preferably the aromatic coloring agent may not comprise a phthalocyanine.

The dispersing agent may be selected from the group comprising at least one:.

The polyacrylate polymers may be preferably selected from the Efka® <NUM> series from BASF SE.

The dispersing agent may contain tertiary nitrogen compounds.

A dispersing agent that can be suitable used may be a substance that holds two or more immiscible liquids or solids in suspension, e.g., water and the organic aromatic coloring agent. Dispersing agents which may be used include ionic dispersing agent, non-ionic dispersing agent, or mixtures thereof. Typical ionic dispersing agents are anionic dispersing agents, including amine salts or alkali salts of carboxylic, sulfamic or phosphoric acids, for example, sodium lauryl sulfate, ammonium lauryl sulfate, lignosulfonic acid salts, ethylene diamine tetra acetic acid (EDTA) sodium salts and acid salts of amines such as laurylamine hydrochloride or poly(oxy-<NUM>,<NUM> ethanediylphenyl)alpha-sulfo-omega-hydroxy ether with phenol <NUM>-(methylphenyl)ethyl derivative ammonium salts; or amphoteric, that is, compounds bearing both anionic and cationic groups, for example, lauryl sulfobetaine; dihydroxy ethylalkyl betaine; amido betaine based on coconut acids; disodium N-lauryl amino propionate; or the sodium salts of dicarboxylic acid coconut derivatives. Typical non-ionic dispersing agents include but not limited to ethoxylated or propoxylated alkyl or aryl phenolic compounds, such as, octylphenoxypolyethyleneoxyethanol or poly(oxy-<NUM>,<NUM>-ethanediyl)alpha-phenyl-omega-hydroxy, styrenated. An another dispersing agent may be a mixture of C<NUM>-C<NUM> and C<NUM>-C<NUM> ethoxylated unsaturated fatty acids and poly(oxy-<NUM>,<NUM>-ethanediyl)alpha-sulfo-omega-hydroxy ether with phenol <NUM>-(methylphenyl)ethyl derivative ammonium salts and poly(oxy-<NUM>,<NUM>-ethanediyl), alpha-phenyl-omega-hydroxy, styrenated.

Exemplary nonionic dispersing agents, also named nonionic tenside, that can be used in the aqueous dispersed coloring solution are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing <NUM> to <NUM> carbon atoms in the alkyl chain, more particularly the fatty acid methyl esters.

The nonionic low alkoxylated alcohol dispersing agents can be used to reduce surface tension, wet the soil particulate to allow penetration of the use solution, separation of the soil.

The alkoxylated alcohol dispersing agents mentioned above includes end caped alkoxylated alcohol dispersing agents.

Exemplary nonionic low alkoxylated alcohol dispersing agents that can be used are alkoxylated alcohols containing <NUM> to <NUM> ethylene oxide groups (<NUM>-4EO), <NUM> to <NUM> butylene oxide groups (<NUM>-4BO), <NUM> to <NUM> propylene oxide groups (<NUM>-4PO), end caped alkoxylated alcohol dispersing agents thereof or mixtures thereof.

Advantageously low alkoxylated alcohols useful according to the invention are particularly primary and/or branched alcohols, preferably containing <NUM> to <NUM> carbon atoms, and containing <NUM> to <NUM> ethylene oxide groups (<NUM>-4EO), <NUM> to <NUM> butylene oxide groups (<NUM>-4BO), <NUM> to <NUM> propylene oxide groups (<NUM>-4PO), end caped alkoxylated alcohol dispersing agents thereof or may contain a mixture. The alcohol radical may be linear, branched, or may contain a mixture.

Exemplary nonionic higher alkoxylated alcohol dispersing agents suitable for use in the aqueous dispersed coloring solution are alkoxylated alcohols containing <NUM> to <NUM> ethylene oxide groups (<NUM>-40EO), butylene oxide groups (<NUM>-40BO), propylene oxide groups (<NUM>-40PO), preferably <NUM> to <NUM> ethylene oxide groups (<NUM>-30EO), butylene oxide groups (<NUM>-30BO), propylene oxide groups (<NUM>-30PO), further preferred <NUM> to <NUM> ethylene oxide groups (<NUM>-20EO), butylene oxide groups (<NUM>-20BO), propylene oxide groups (<NUM>-20PO), more preferred <NUM> to <NUM> ethylene oxide groups (<NUM>-10EO), butylene oxide groups (<NUM>-10BO), propylene oxide groups (<NUM>-10PO), and most preferred <NUM> ethylene oxide groups (8EO), butylene oxide groups (8BO), propylene oxide groups (8PO) groups, end caped alkoxylated alcohol dispersing agents thereof, or mixtures thereof.

Advantageously higher alkoxylated alcohols useful in the composition of the invention are particularly linear and/or branched alcohols, preferably containing <NUM> to <NUM> carbon atoms, and <NUM> to <NUM> ethylene oxide groups (<NUM>-40EO), butylene oxide groups (<NUM>-40BO), propylene oxide groups (<NUM>-40PO), preferably <NUM> to <NUM> ethylene oxide groups (<NUM>-30EO), butylene oxide groups (<NUM>-30BO), propylene oxide groups (<NUM>-30PO), further preferred <NUM> to <NUM> ethylene oxide groups (<NUM>-20EO), butylene oxide groups (<NUM>-20BO), propylene oxide groups (<NUM>-20PO), more preferred <NUM> to <NUM> ethylene oxide groups (<NUM>-10EO), butylene oxide groups (<NUM>-10BO), propylene oxide groups (<NUM>-10PO), and most preferred <NUM> ethylene oxide groups (8EO), butylene oxide groups (8BO), propylene oxide groups (8PO), end caped alkoxylated alcohol dispersing agents thereof, or may contain a mixture. The alcohol radical may be linear, branched, or may contain a mixture.

Particularly preferred are higher alkoxylated alcohols, preferably alcohol ethoxylates with linear or branched radicals of alcohols with <NUM> to <NUM> carbon atoms, e.g. from coco-, palm-, tallow- or oleyl alcohol, containing <NUM> to <NUM> carbon atoms, and <NUM> to <NUM> ethylene oxide groups (<NUM>-40EO), butylene oxide groups (<NUM>-40BO), propylene oxide groups (<NUM>-40PO), preferably <NUM> to <NUM> ethylene oxide groups (<NUM>-30EO), butylene oxide groups (<NUM>-30BO), propylene oxide groups (<NUM>-30PO), further preferred <NUM> to <NUM> ethylene oxide groups (<NUM>-20EO), butylene oxide groups (<NUM>-20BO), propylene oxide groups (<NUM>-20PO), more preferred <NUM> to <NUM> ethylene oxide groups (<NUM>-10EO), butylene oxide groups (<NUM>-10BO), propylene oxide groups (<NUM>-10PO), and most preferred <NUM> ethylene oxide groups (8EO), butylene oxide groups (8BO), propylene oxide groups (8PO), end caped alkoxylated alcohol dispersing agents thereof, or may contain a mixture. However, most preferred is isotridecyl alcohol in the composition of the invention with 6EO to 14EO, 6PO to 14PO, 6BO to 14BO, preferably 7EO to 10EO, 7PO to 10PO, 7BO to 10BO, and most preferred 8EO, 8PO, 8BO, or may contain a mixture.

According to the present invention higher alkoxylated alcohols can be used with 5EO, 6EO, 7EO, 8EO, 9EO, 10EO, 11EO, 12EO, 13EO, 14EO, 15EO, 16EO,17EO, 18EO, 19EO, 20EO, 21EO, 22EO, 23EO, 24EO or 25EO, 5PO, 6PO, 7PO, 8PO, 9PO, 10PO, 11PO, 12PO, 13PO, 14PO, 15PO, 16PO,17PO, 18PO, 19PO, 20PO, 21PO, 22PO, 23PO, 24PO or 25PO, 5BO, 6BO, 7BO, 8BO, 9BO, 10BO, 11BO, 12BO, 13BO, 14BO, 15BO, 16BO,17BO, 18BO, 19BO, 20BO, 21BO, 22BO, 23BO, 24BO or 25BO, end caped alkoxylated alcohol dispersing agents thereof, or may contain a mixture.

Exemplary higher alkoxylated alcohols with 5EO to 40EO, preferably 6EO or 30EO, further preferred 7EO to 20EO, more preferred 8EO to 10EO and most preferred 8EO; 5PO to 40PO, preferably 6PO or 30PO, further preferred 7PO to 20PO, more preferred 8PO to 10PO and most preferred 8PO; 5BO to 40BO, preferably 6BO or 30BO, further preferred 7BO to 20BO, more preferred 8BO to 10BO and most preferred 8BO include C<NUM>-C<NUM>-alcohols; C<NUM>-C<NUM>-alcohols, C<NUM>-C<NUM>- alcohols, C<NUM>-C<NUM>-alcohols, end caped alkoxylated alcohol dispersing agents thereof, and mixtures thereof, as well as mixtures of C<NUM>-C<NUM>-alcohols and C<NUM>-C<NUM> -alcohols, end caped alkoxylated alcohol dispersing agents thereof, and most preferred is a C<NUM>-alcohol.

In addition to these nonionic dispersing agents, fatty alcohols containing more than <NUM> EO, <NUM> PO, <NUM> BO may also be used. Examples of such fatty alcohols are tallow fatty alcohol containing <NUM> EO, <NUM> EO, <NUM> EO or <NUM> EO, <NUM> PO, <NUM> PO, <NUM> PO or <NUM> PO, <NUM> BO, <NUM> BO, <NUM> BO or <NUM> BO and end caped alkoxylated alcohol dispersing agents thereof.

The degrees of 5EO to 40EO, 5PO to 40PO, 5BO to 40BO preferably 6EO or 30EO, 6PO or 30PO, 6BO or 30BO,further preferred 7EO to 20EO, 7PO to 20PO, 7BO to 20BO,more preferred 8EO to <NUM> EO, 8PO to <NUM> PO, 8BO to <NUM> BO and most preferred 8EO, 8PO, 8BO alkoxylation mentioned are statistical mean values, which for a special product, may be either a whole number or a fractional number. However, more preferred, the degrees of 5EO to 40EO, 5PO to 40PO , 5BO to 40BO preferably 6EO or 30EO, 6PO or 30PO , 6BO or 30BO further preferred 7EO to 20EO, 7PO to 20PO , 7BO to 20BO, more preferred 8EO to <NUM> EO, 8PO to <NUM> PO, 8BO to <NUM> BO and most preferred 8EO, 8PO, 8BO alkoxylation mentioned may be either a whole number or a fractional number. Most preferred, the degrees of 5EO to 40EO, 5PO to 40PO, 5BO to 40BO, preferably 6EO or 30EO, 6PO or 30PO, 6BO or 30BO, further preferred 7EO to 20EO, 7PO to 20PO, 7BO to 20BO, more preferred 8EO to <NUM> EO, 8PO to 10PO, 8BO to 10BO and most preferred 8EO, 8PO, 8BO. The alkoxylation grade mentioned may be a whole number.

Preferred higher alkoxylated alcohols have a narrow homolog distribution (narrow range ethoxylates, NRE).

Further dispersing agents include alkoxylated long chain fatty acid amides where the fatty acid has <NUM>-<NUM> carbon atoms and the amide group is alkoxylated with <NUM>-<NUM> ethylene oxide, propylene oxide and/or butylene oxide units.

A further class of nonionic dispersing agents, which can be used in the aqueous dispersed coloring solution, is that of the alkyl polyglycosides (APG). Suitable alkyl polyglycosides satisfy the general Formula RO(G)z where R is a linear or branched, particularly <NUM>-methyl-branched, saturated or unsaturated aliphatic radical containing <NUM> to <NUM> and preferably <NUM> to <NUM> carbon atoms and G stands for a glycose unit containing <NUM> or <NUM> carbon atoms, preferably glucose. The degree of oligomerization z is a number between <NUM> and <NUM> and preferably between <NUM> and <NUM>.

Silicone containing nonionic dispersing agents, such as the ABIL B8852 or Silwet <NUM>, can also be used. An exemplary silicone-containing dispersing agent is silicone polybutane.

Examples of amine oxide dispersing agents include: dimethyldodecylamine oxide, dimethyltetradecylamine oxide; ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, lauryl dimethyl amine oxide, bis- (<NUM>-hydroxyethyl) dodecylamine oxide, bis- (<NUM>-hydroxyethyl)-<NUM>-dodecoxy-<NUM>- hydroxypropyl amine oxide, (<NUM>-hydroxypropyl) methyltetradecylamine oxide, dimethyloleyamine oxide, dimethyl- (<NUM>-hydroxydodecyl) amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.

Additional nitrogen-containing dispersing agents include ethoxylated primary alkyl amines where the alkyl group has <NUM>-<NUM> carbon atoms and the amine is ethoxylated with <NUM>-<NUM> ethylene oxide units.

Additionally, non-ionic dispersing agents derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine are also useful. For example, there are compounds containing from <NUM>% to <NUM>% of polyoxyethylene by weight and having a molecular weight from <NUM>,<NUM> to <NUM>,<NUM> resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product from ethylene diamine and excess propylene oxide wherein the base has a molecular weight on order of <NUM>,<NUM>-<NUM>, <NUM>.

Suitable nonionic dispersing agents include the polyoxyethylene-polyoxypropylene condensates, which are sold by BASF under the trade name 'Pluronic', polyoxyethylene condensates of aliphatic alcohols/ethylene oxide condensates having from <NUM> to <NUM> moles of ethylene oxide per mole of coconut alcohol; ethoxylated long chain alcohols sold by Shell Chemical Co. under the trade name 'Neodol', polyoxyethylene condensates of sorbitan fatty acids, alkanolamides, such as the monoalkoanolamides, dialkanolamides and the ethoxylated alkanolamides, for example coconut monoethanolamide, lauric isopropanolamide and lauric diethanolamide; and amine oxides for example dodecyldimethylamine oxide.

Further exemplary non-ionic dispersing agents include alkylphenol alkoxylates, and amine oxides such as alkyl dimethylamine oxide or bis (<NUM>- hydroxyethyl) alkylamine oxide.

The additional nonionic dispersing agents can be provided in the aqueous dispersed coloring solutionin an amount of ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, preferably ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, further preferred ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, and more preferred <NUM> wt. -% to <NUM> wt. -%, based on the weight of all components of the total composition.

It should be understood that the addition of a nonionic dispersing agent to the aqueous dispersed coloring solution can be omitted.

Exemplary anionic dispersing agents, also named nonionic tenside, that can be used include organic carboxylates, organic sulfonates, organic sulfates, organic phosphates and the like, particularly linear alkylaryl sulfonates, such as alkylarylcarboxylates, alkylarylsulfonates, alkylarylphosphates, and the like. These classes of anionic dispersing agents are known within as linear alkyl benzyl sulfonates (LABS), alpha olefin sulfonates (AOS), alkyl sulfates, and secondary alkane sulfonates.

The anionic dispersing agents can be provided in the aqueous dispersed coloring solutionin an amount of ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, preferably ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, further preferred ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, and more preferred <NUM> wt. -% to <NUM> wt. -%, based on the weight of all components of the total composition.

It should be understood that the addition of an anionic dispersing agent to the aqueous dispersed coloring solution can be omitted.

In a preferred embodiment of the aqueous dispersed coloring solution comprises a cationic dispersing agent, also named cationic tenside.

Suitable cationic dispersing agents include quaternary ammonium compounds having the formula of RR'R" R‴N+X-, where R, R', R" and R‴ are each a C<NUM>-C<NUM> alkyl, aryl or arylalkyl group that can optionally contain one or more P, O, S or N heteroatoms, and X is F, Cl, Br, I or an alkyl sulfate. Additional preferred cationic dispersing agents include ethoxylated and/or propoxylated alkyl amines, diamines, or triamines.

Each of R, R', R" and R‴ can independently include, individually or in combination, substituents including <NUM> to <NUM> carbon atoms, preferably <NUM> to <NUM> carbon atoms, and more preferably, <NUM> to <NUM> carbon atoms.

Each of R, R', R" and R‴ can independently be linear, cyclic, branched, saturated, or unsaturated, and can include heteroatoms such as oxygen, phosphorous, sulfur, or nitrogen. Any two of R, R', R" and R‴ can form a cyclic group. Any one of three of R, R', R" and R‴ can independently can be hydrogen. X is preferably a counter ion and preferably a non-fluoride counter ion. Exemplary counter ions include chloride, bromide, methosulfate, ethosulfate, sulfate, and phosphate.

In an embodiment, the quaternary ammonium compound includes alkyl ethoxylated and/or propoxylated quaternary ammonium salts (or amines). Preferably, the alkyl group contains between about <NUM> and about <NUM> carbon atoms and can be saturated and/or unsaturated. The degree of alkoxylation is preferably between about <NUM> and about <NUM>, and/or the degree of propoxylation is preferably between about <NUM> and about <NUM>. In an embodiment, the quaternary ammonium compound includes an alkyl group with about <NUM> to about <NUM> carbon atoms and a degree of alkoxylation between about <NUM> and about <NUM>.

The cationic dispersing agents can be provided in the aqueous dispersed coloring solutionin an amount of ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, preferably ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, further preferred ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, and more preferred <NUM> wt. -% to <NUM> wt. -%, based on the weight of all components of the total composition.

It should be understood that the addition of a cationic dispersing agent to the aqueous dispersed coloring solution can be omitted.

The aqueous dispersed coloring solution is preferably free of amphoteric dispersing agents.

Examples of suitable amphoteric dispersing agents include capryloamphopropionate, disodium lauryl B-iminodipropionate, and cocoamphocarboxypropionate, and disodium octylimino dipropionate.

The amphoteric dispersing agents can be provided in the composition in an amount of ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, preferably ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, further preferred ≥ <NUM> wt. -% to ≤ <NUM> wt. -%, and more preferred <NUM> wt. -% to <NUM> wt. -%, based on the weight of all components of the total composition.

It should be understood that the addition of an amphoteric dispersing agent to the aqueous dispersed coloring solution can be omitted.

The solubilizer is selected different to the dispersing agent and may be used in addition to the dispersing agent. The solubilizer is at least partially soluble at <NUM>° C and may be selected from the group comprising a C<NUM> to C<NUM> alcohol, C<NUM> to C<NUM> organic acid, C<NUM> to C<NUM> ketone, C<NUM> to C<NUM> aldehyde, C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> ester, alkylene glycol alkyl ether, glycol alkyl ether,; preferably glycol and glycol oligomers, ethanol, acetone, formic or acetic acid, dimethylformamide or dimethylsulfoxide.

Furthermore, the solubilizer may be a compound according to the following formula R'-[(O(CH<NUM>)m)n-]OH, wherein R' is an ethyl, propyl or butyl radical, m is <NUM>, <NUM> or <NUM>, and n is <NUM>, <NUM> or <NUM>, with the proviso that where R' is butyl m is <NUM> or <NUM>. The solubilizer may be selected from the group consisting of ethylene glycol butyl ether, diethylene glycol ethylether, diethylene glycol butylether, propylene glycol propylether, dipropylene glycol propyl ether and tripropylene glycol propylether.

Furthermore, the solubilizer may be a compound according to the following formula H-[(O(CH<NUM>)m)n-]OH, where m is <NUM>, <NUM> or <NUM> and n is <NUM>, <NUM>, or <NUM>. The solubilizer may be selected from the group consisting of diethylene glycol, triethylene glycol and <NUM>,<NUM> butanediol. Preferably the solubilizer forms a homogenous solution with water.

The carrier agent is selected different to the dispersing agent and the solubilizer and may be used in addition to the dispersing agent.

With respect to result of the coloring process it may be advantages when the aqueous dispersed coloring solution further comprises a carrier agent. According to an another embodiment the aqueous dispersed coloring solution may comprise in addition a carrier agent, wherein the carrier agent is preferably selected from the group comprising aromatic esters such as phthalic acid esters, , polyphenylether, phenoles, aromatic alcohols, aromatic ketones, aryl halides, such as halogenized benzene, halogenzide toluene; N-alkylphthalimide, methylnaphthaline, diphenyle, diphenylethere, naphtholether, and oxybiphenyle. Preferably the carrier agent does not form a homogenous solution with water. The carrier agent may decrease the time that is used for coloring and/or enhance the penetration capacity of the organic aromatic coloring agent.

It may be preferred that the temperature of the aqueous dispersed coloring solution is adjusted according to specific properties of the synthetic polar-polymer material. For example the temperature of the aqueous dispersed coloring solution exposed to the outer surface of the synthetic polar-polymer material may be adjusted such that the temperature of the aqueous dispersed coloring solution is higher or same than the glass-transition temperature Tg of the synthetic polar-component of the synthetic polar-polymer material to be colored; and/or the aqueous dispersed coloring solution exposing the synthetic polar-polymer material may have a temperature lower than the heat deflection temperature of the synthetic polar-polymer material to be colored. This may have the advantages that distortion or deforming of the synthetic polar-polymer material may be avoided.

The heat deflection temperature also called heat distortion temperature may be the temperature at which synthetic polar-polymer material deforms under a specified load. It may be determined by the following test procedure outlined in ASTM D648. The test specimen is loaded in three-point bending in the edgewise direction. The outer fiber stress used for testing is either <NUM> MPa or <NUM> MPa, and the temperature is increased at <NUM>/min until the specimen deflects <NUM>.

As already mentioned, during the coloring process the outer surface of the synthetic polar-polymer material is exposed to the aqueous dispersed coloring solution. According to preferred embodiment the step of exposing the outer surface of the synthetic polar-polymer material to the aqueous dispersed coloring solution may comprises:.

The specific way how the outer surface of the synthetic polar-polymer material is exposed to the aqueous dispersed coloring solution may be dependent on the article made of the synthetic polar-polymer material. For example if the article has the form of a bottle, the article may be dipped into the aqueous dispersed coloring solution in such a fashion that the inner surface of the bottle may not be exposed to the aqueous dispersed coloring solution. However, for other forms of the article made of the synthetic polar-polymer material it may be advantageous to flow coat the outer surface of the synthetic polar-polymer material with the aqueous dispersed coloring solution.

In order to achieve a homogenous coloring result and according to an another embodiment the step of exposing the outer surface of the synthetic polar-polymer material to the aqueous dispersed coloring solution may comprise.

These method steps may increase and/or homogenize the migration of the organic aromatic coloring agent into the synthetic polar-polymer material.

Furthermore, the synthetic polar-polymer material, which is exposed to the aqueous dispersed coloring solution, may have a temperature in the range of about ≥ <NUM>° C to about ≤ <NUM>° C, preferably the synthetic polar-polymer material, which is exposed to the aqueous dispersed coloring solution, may have a temperature about ≥ <NUM>° C and lower than the heat deflection temperature of the synthetic polar-polymer material. It may be preferably that the synthetic polar-polymer material may have a temperature that corresponds to the temperature of the aqueous dispersed coloring solution +/- <NUM>.

Therefore the temperature difference between the synthetic polar-polymer material and the aqueous dispersed coloring solution may not be higher than <NUM>. This may reduce unwanted effects in the synthetic polar-polymer material caused by a fast increase or decrease of the temperature.

Furthermore it may be preferable that the synthetic polar-polymer material may have a temperature lower than the heat deflection temperature of the synthetic polar-polymer material. Preferably the synthetic polar-polymer material does not deflect and/or deform when exposed to the conditions of the aqueous dispersed coloring solution.

It may be advantageous that the synthetic polar-polymer material may be partially cooled while being exposed to the aqueous dispersed coloring solution. For example if the synthetic polar-polymer material has the form of a bottle, the bottle may be dipped into the aqueous dispersed coloring solution in such a fashion that the inner surface of the bottle may not be exposed to the aqueous dispersed coloring solution. In this case the inner surface of the bottle may be cooled, while the outer surface of the bottle is exposed to the aqueous dispersed coloring solution.

It may be advantageous to expose the synthetic polar-polymer material to the aqueous dispersed coloring solution right after the synthetic polar-polymer material is formed in a manufacturing process. According to the above and to another preferred embodiment the synthetic polar-polymer material may be formed in a molding process, a compression molding process, an extruding process, a thermoforming process, a blowing process and/or a 3D-printing process, thereafter exposed to the aqueous dispersed coloring solution; preferably the synthetic polar-polymer material may be directly exposed, without cooling, to the aqueous dispersed coloring solution.

The synthetic polar-polymer material may be further formed in a compression molding, an injection molding, a rotational molding, an extrusion, an injection and/or extrusion blow molding, and/or casting process. The method of forming the synthetic polar-polymer material may not be critical to the method of reversibly and selectively coloring the synthetic polar-polymer material. Furthermore it may be possible that the synthetic polar-polymer material may be formed in another manufacturing process including all other manufacturing processes not explicitly listed here for the manufacturing of plastic parts.

According to an another embodiment the synthetic polar-polymer material, preferably at least one outer surface of the synthetic polar-polymer material, may be exposed to the aqueous dispersed coloring solution for about ≥ <NUM> second to about ≤ <NUM> minutes, preferably about ≥ <NUM> seconds to about ≤ <NUM> minutes, in addition preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, and also preferred about ≥ <NUM> seconds to about ≤ <NUM> minute, or about ≥ <NUM> seconds to about ≤ <NUM> seconds. However it is preferred that the synthetic polar-polymer material, preferably at least one outer surface of the synthetic polar-polymer material, may be exposed to the aqueous dispersed coloring solution for about ≥ <NUM> second to about < <NUM> minutes, preferably about ≥ <NUM> seconds to about ≤ <NUM> minutes, in addition preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, and also preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, or about ≥ <NUM> seconds to about ≤ <NUM> minutes.

In general the outer surface of a synthetic polar-polymer material is completely colored at about ≥ <NUM> second to about < <NUM> minutes, preferably about ≥ <NUM> seconds to about ≤ <NUM> minutes, in addition preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, and also preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, or about ≥ <NUM> seconds to about ≤ <NUM> minutes, that means the colorized surface of the synthetic polar-polymer material has a color defined by the organic aromatic coloring agent or mixtures thereof.

The synthetic polar-polymer material may be withdrawn at a specific rate from the aqueous dispersed coloring solution, including a rate sufficient to effect a coloring gradient. Therefore, the portion of the synthetic polar-polymer material that remains in the aqueous dispersed coloring solution longest may contain the most organic aromatic coloring agent per unit volume so that it exhibits the darkest color tint.

The thickness of the layer that is colored may be about <NUM>% to about <NUM>% for a single layer, or about <NUM>% to about <NUM>% for a multilayer, regardless of the total thickness, or about <NUM> to about <NUM>, or preferably about <NUM>% to about <NUM>%. The thickness of the layer that is completely colored may be about <NUM> to about <NUM>, more preferably about <NUM> to about <NUM>.

According to one embodiment the layer thickness of the synthetic polar-polymer material that is colorized by the method according to the present invention may be about ≥ <NUM>, preferably of about ≥ <NUM> to about ≤ <NUM>, preferably the synthetic polar-polymer material is homogenously colored.

According to one embodiment the layer thickness of the synthetic polar-polymer material that is colorized by the method according to the present invention may be about ≥ <NUM>, preferably of about ≥ <NUM> to about ≤ <NUM>, with a coloring grade of <NUM>% to ≤ <NUM>%, preferably ≥ <NUM> % to ≤ <NUM>%.

It is not always the case that the additivated layer is completely colored. For a PET preform, the total thickness of the layer is may be about <NUM>, but the dye penetrates only about <NUM> to about <NUM>.

In furniture applications, the layer is <NUM>% colorized of a thickness of <NUM>, or the layer is <NUM>% colorized of a thickness of <NUM>. The thickness and % of colorization is depending on the article that is colorized by a method according to the invention.

Even with multilayer parts, with short dyeing times, it may happen that the dye does not penetrate the entire colorable layer, only the top layer of the part is colored, although the thickness of the additivated layer is significantly larger.

The layer thickness of the polar-polymer material that is colored by the process according to the invention may be about ≥ <NUM> to about ≤ <NUM>, preferably about ≥ <NUM> to about ≤ <NUM>, further preferred about ≥ <NUM> to about ≤ <NUM>, also preferred about ≥ <NUM> to about ≤ <NUM>, in addition preferred about ≥ <NUM> to about ≤ <NUM> and furthermore preferred about ≥ <NUM> to about ≤ <NUM>, wherein the colorized layer of the synthetic polar-polymer material has a color defined by the organic aromatic coloring agent or mixtures thereof used.

According to an another embodiment the synthetic polar-polymer material, preferably at least one outer surface of the synthetic polar-polymer material, may be exposed to the aqueous dispersed coloring solution for about ≥ <NUM> second to about ≤ <NUM> minutes, preferably about ≥ <NUM> seconds to about ≤ <NUM> minutes, in addition preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, and also preferred about ≥ <NUM> seconds to about ≤ <NUM> minute, or about ≥ <NUM> seconds to about ≤ <NUM> seconds; wherein the layer thickness of the polar-polymer material that is colored by the process according to the invention is about ≥ <NUM> to about ≤ <NUM>, preferably about ≥ <NUM> to about ≤ <NUM>, further preferred about ≥ <NUM> to about ≤ <NUM>, also preferred about ≥ <NUM> to about ≤ <NUM>, in addition preferred about ≥ <NUM> to about ≤ <NUM> and furthermore preferred about ≥ <NUM> to about ≤ <NUM>, wherein the colorized layer of the synthetic polar-polymer material has a color defined by the organic aromatic coloring agent or mixtures thereof used.

However it is preferred that the synthetic polar-polymer material, preferably at least one outer surface of the synthetic polar-polymer material, may be exposed to the aqueous dispersed coloring solution for about ≥ <NUM> second to about < <NUM> minutes, preferably about ≥ <NUM> seconds to about ≤ <NUM> minutes, in addition preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, and also preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, or about ≥ <NUM> seconds to about ≤ <NUM> minutes; wherein the layer thickness of the polar-polymer material that is colored by the process according to the invention is about ≥ <NUM> to about ≤ <NUM>, preferably about ≥ <NUM> to about ≤ <NUM>, further preferred about ≥ <NUM> to about ≤ <NUM>, also preferred about ≥ <NUM> to about ≤ <NUM>, in addition preferred about ≥ <NUM> to about ≤ <NUM> and furthermore preferred about ≥ <NUM> to about ≤ <NUM>, wherein the colorized layer of the synthetic polar-polymer material has a color defined by the organic aromatic coloring agent or mixtures thereof used.

The result of the coloring process may be influenced by the pH of the aqueous dispersed coloring solution. Preferably the aqueous dispersed coloring solution may have a pH in the acidic range. According to an another embodiment the aqueous dispersed coloring solution has a pH in the range of about ≥ <NUM> and about ≤ <NUM>, preferably a pH in the range of about ≥ <NUM> and about ≤ <NUM>; in addition preferred a pH in the range of about ≥ <NUM> and about ≤ <NUM> and also preferred a pH in the range of about ≥ <NUM> and about ≤ <NUM>. It may be possible to reduce the pH of the aqueous dispersed coloring solution by adding acetic acid to the aqueous dispersed coloring solution.

It is surprising that the colorizing speed of the synthetic polar-polymer material can be significant increased by a pH < <NUM>. The colorizing speed of the synthetic polar-polymer material seems to be highest at a pH range of the aqueous dispersed coloring solution of about ≥ <NUM> and about < <NUM>, in particular at a pH range of about ≥ <NUM> and about < <NUM>.

For example at a pH range of about ≥ <NUM> and about ≤ <NUM> of the aqueous dispersed coloring solution, the colorizing time for colorizing a layer thickness of the polar-polymer material that is colored by the process according to the invention can be of about ≥ <NUM> to about ≤ <NUM>, preferably about ≥ <NUM> to about ≤ <NUM>, further preferred about ≥ <NUM> to about ≤ <NUM>, also preferred about ≥ <NUM> to about ≤ <NUM>, in addition preferred about ≥ <NUM> to about ≤ <NUM> and furthermore preferred about ≥ <NUM> to about ≤ <NUM>, is < <NUM> minutes, preferably about ≥ <NUM> seconds to about ≤ <NUM> minutes, in addition preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, and also preferred about ≥ <NUM> seconds to about ≤ <NUM> minutes, or about ≥ <NUM> seconds to about ≤ <NUM> minutes.

In other words, the coloring process is rather fast. By changing the duration of the exposure the migration depth of the migration of the organic aromatic coloring agent into the synthetic polar-polymer material and/or the concentration of the organic aromatic coloring agent in the synthetic polar-polymer material may be varied. Therefore, the color appearance of the colored synthetic polar-polymer material may also vary according to the duration of exposure. For example the color of a colored synthetic polar-polymer material that has been exposed to the aqueous dispersed coloring solution for < <NUM> minutes may be more intense than the color of a colored synthetic polar-polymer material that has been exposed to the aqueous dispersed coloring solution for ≤ <NUM> minutes.

In another preferred embodiment the aqueous dispersed coloring solution may comprise:.

The polar-polymer material can comprise at least one or more layers. For example the polar-polymer material can comprises a multi-layer. The layers may be differently composed. One layer of the polymer material may have a content of polar components and non-polar polymers, wherein the content of the polar components are less than about <NUM> wt. -%, preferably about < <NUM> wt. -%, further preferred about ≤ <NUM> wt. -% and in addition preferred about < <NUM> wt. -% or about < <NUM> wt. -% and about ≥ <NUM> wt. -%, preferably about ≥ <NUM> wt. -%, more preferably preferably about ≥ <NUM> wt. -% of non-polar components, such as non-polar polymer and/or non-polar oligomer cannot be colorized by the method according to the present invention.

The advantage is that a two layer polar-polymer material, such as a bottle, wherein the outer surface directed outwards is of a polar-polymer material comprises about ≥ <NUM> wt. -%, preferably about ≥ <NUM> wt. -%, more preferably ≥ <NUM> wt. -%, of polar components, such as synthetic polar polymer, synthetic polar oligomer and/or polar additive, can be colored by the method according to the invention, where else the inner layer facing to the inside of the bottle, which is a layer comprising less than about <NUM> wt. -%, preferably about < <NUM> wt. -%, further preferred about < <NUM> wt. -% and in addition preferred about < <NUM> wt. -%, and more preferably < <NUM> wt. -%, or about ≥ <NUM> to < <NUM> wt. -% of a polar component and about ≥ <NUM> wt. -%, preferably about ≥ <NUM> wt. -%, more preferably about ≥ <NUM> wt. -% to about < <NUM> wt. -% of non-polar components, such as non-polar polymer and/or non-polar oligomer, cannot be colorized by the method according to the present invention.

Therefore it is possible to color for example a multilayer package, wherein only the outer layer is colored. Thus the inner layer, that is supposed to be in contact to the filling of the package may be free of the organic aromatic coloring agent.

According to an embodiment a synthetic polar-polymer material may comprises at least two layers, wherein at least a first layer is of a polar-polymer material, that comprises about ≥ <NUM> wt. -%, further ≥ <NUM> wt. -%, preferably ≥ <NUM> wt. -%, of polar components, such as synthetic polar polymer, synthetic polar oligomer and/or polar additive, and is colorizable, where else the second layer comprising less than about <NUM> wt. -%, preferably about < <NUM> wt. -%, further preferred about < <NUM> wt. -% and in addition preferred about < <NUM> wt. -%, more preferably less than <NUM> wt. -% or about ≥ <NUM> to < <NUM> wt. -% of a polar component and about ≥ <NUM> wt. -%, preferably about ≥ <NUM> wt. -% to about ≤ <NUM> wt. -% of at least one non-polar component, such as non-polar polymer and/or non-polar oligomer, cannot be colorized.

This is very useful for containers where the inner surface comes into contact with foodstuffs, such as beverages, fruits or there like, because the inner non-polar surface of that container is not colored by the method according to the invention so that the foodstuff cannot be contaminated by the coloring agent of the outer polar surface layer.

According to an another embodiment the article may be selected from the group comprising a sheet, a foil, a tube, a container, a part, a bottle, a non-woven fabric, and preferably the article may be selected from the group comprising computer face-plates, keyboards, bezels and cellular phones, color coded packaging and containers of all types, including ones for industrial components, residential and commercial lighting fixtures and components therefor, such as sheets, used in building and in construction, tableware, including plates, cups and eating utensils, small appliances and their components, optical and sun-wear lenses, as well as decorative films including such films that are intended for use in film insert molding. Preferably the article may not be selected from the group comprising a fiber, a woven fabric, and a knitted fabric.

With regard to further advantages and technical features of the method for reversible and selective coloring the synthetic polar-polymer material it is referred to the colored synthetic polar-polymer material, to the article comprising at least one colored synthetic polar-polymer material, the examples and the further description.

The present invention further relates to the colored synthetic polar-polymer material, wherein the synthetic polar-polymer material, preferably the outer surface of the synthetic polar-polymer material, is colored by the above described method. This is not only an easy way for coloring a synthetic polar-polymer material but allows also for decoloring of the colored synthetic polar-polymer material.

According to another preferred embodiment the colored synthetic polar-polymer material may comprise at least one synthetic polar-component layer and at least one non-polar-component layer, wherein at least one layer or outer surface of the synthetic polar-component layer is colored by the above described method, wherein the non-polar-component layer is not colorable by the above described method. In other words the colored synthetic polar-polymer material may have a layered structure, comprising the synthetic polar-component layer and the non-polar-component layer. Only the synthetic polar-component layer may be colorable with the above described method but not the non-polar-component layer. Therefore, by adjusting the polarity of the different layers it may be possible to selectively color the desired layers while the other layers remain colorless.

As described above the coloring process is based on migration of the organic aromatic coloring agent into the synthetic polar-polymer material. By exposing the outer surface of the synthetic polar-polymer material to the aqueous dispersed coloring solution, the outer layer of the synthetic polar-polymer material gets colored. According to the above a colored synthetic polar-polymer material may be provided, wherein at least a layer thickness of about ≥ <NUM> of an outer layer of the colored synthetic polar-polymer material is homogenous colored. Homogeneous coloration of the outer layer of the synthetic polar-polymer material may be achieved by having the same amount of the organic aromatic coloring agent per area of the outer surface of the synthetic polar-polymer material. The organic aromatic coloring agent may be essentially homogenously distributed in the colored part or layer of the synthetic polar-polymer material, meaning that that for the eye of a human being the colored outer surface or the colored part or the colored layer of the synthetic polar-polymer material appear uniformly colored without color variations. The outer surface may be homogenously colored by migration of the organic aromatic coloring agent into the synthetic polar-polymer material up to certain migration depth. A migration depth further into the synthetic polar-polymer material may only further increase the opacity, darkness, and/or color depth of the color but not the homogeneity of the colored surface. The colored surface may be homogenously colored when no significant color fluctuations may be visible by the human eye. For a homogenously colored surface the color differences, given in ΔE*ab, according to the International Commission on Illumination (CIE), over the outer surface of the colored synthetic polar-polymer material may be about ≤ <NUM>.

According to an another embodiment the concentration of the organic aromatic coloring agent in at least one colored layer of the synthetic polar-polymer material, colored by the above described method, wherein the colored layer has a thickness of about ≥ <NUM>, may be <NUM> wt. -% to about ≤ <NUM> wt. -%, based on the total weight of said colored layer.

With regard to further advantages and technical features of the colored synthetic polar-polymer material it is referred to the method for reversible and selective coloring the synthetic polar-polymer material, the article comprising at least one colored synthetic polar-polymer material, the examples and the further description.

The present invention further relates to an article comprising at least one colored synthetic polar-polymer material as described above and colored by the method as described above. By using the above described method for reversible and selectively coloring an article may be provided having the advantages that the article may be decolored.

With regard to further advantages and technical features of the article it is referred to the method for reversible and selective coloring the synthetic polar-polymer material, the colored synthetic polar-polymer material, examples and the further description.

To summarize the above, the present invention solves an important object how to design a coloring process to be environmentally friendly.

Other example embodiments will be described in the following with reference to the examples. It has to be noted that the examples are only provided for illustration of the general concept by examples not defining the scope of protection of the invention. The examples are not drawn to scale. Features shall not be considered to be essential for the present invention because they are depicted in the examples.

The invention will be described in the following with reference to exemplary examples <NUM> to <NUM>.

A polar polymer material layer of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A5:
<CHM>
a dispersing agent of <NUM> Efka® <NUM> (acrylic block-copolymer) obtainable by BASF SE and <NUM> of a solubilizer of ethanol, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM>° C. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

The homogenous penetration depth of the organic aromatic coloring agent (formula A5) in the polar polymer material layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

A polar polymer material layer of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A5:
<CHM>
a dispersing agent of <NUM> Efka® <NUM> (acrylic block-copolymer) obtainable by BASF SE and <NUM> of a solubilizer of <NUM>-methoxy-<NUM>-propyl acetate, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM>° C at a pH of <NUM>. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

The homogenous penetration dept. of the organic aromatic coloring agent (formula A5) in the polar polymer material layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

A polar polymer material layer of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A5:
<CHM>
a dispersing agent of <NUM> Efka® PU <NUM> (is a modified polyurethane) obtainable by BASF SE and <NUM> of a solubilizer of ethanol, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM> C. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

The homogenous penetration depth of the organic aromatic coloring agent (formula A5) in the polar polymer material layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

A polar polymer material layer of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A5:
<CHM>
a dispersing agent of <NUM> Efka® PU <NUM> (is a modified polyurethane) obtainable by BASF SE and <NUM> of a solubilizer of <NUM>-methoxy-<NUM>-propyl acetate, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM> C. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

A polar polymer material layer of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A1:
<CHM>
a dispersing agent of <NUM> Efka® <NUM> (acrylic block-copolymer) obtainable by BASF SE and <NUM> of a solubilizer of ethanol, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM>° C. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

The homogenous penetration depth of the organic aromatic coloring agent (formula A1) in the polar polymer material layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

A polar polymer material layer of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A2:
<CHM>
a dispersing agent of <NUM> Efka® <NUM> (acrylic block-copolymer) obtainable by BASF SE and <NUM> of a solubilizer of <NUM>-methoxy-<NUM>-propyl acetate, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM>° C at a pH of <NUM>. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

The homogenous penetration depth of the organic aromatic coloring agent (formula A2) in the polar polymer material layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

A polar polymer material layer of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A3:
<CHM>
a dispersing agent of <NUM> Efka® PU <NUM> (is a modified polyurethane) obtainable by BASF SE and <NUM> of a solubilizer of ethanol, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM>° C. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

The homogenous penetration depth of the organic aromatic coloring agent (formula A3) in the polar polymer material layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

A polar polymer material layer of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A10:
<CHM>
a dispersing agent of <NUM> Efka® PU <NUM> (is a modified polyurethane) obtainable by BASF SE and <NUM> of a solubilizer of <NUM>-methoxy-<NUM>-propyl acetate, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM>° C. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

The homogenous penetration depth of the organic aromatic coloring agent (formula A10) in the polar polymer material layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

A polar polymer material layer of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) with a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A5:
<CHM>
a dispersing agent of <NUM> Efka® <NUM> (acrylic block-copolymer) obtainable by BASF SE, wherein the aqueous coloring solution contacting the polar polymer material has a temperature of <NUM>° C. The polar polymer material layer is exposed to the aqueous coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the polar polymer material layer is removed from the aqueous coloring solution and the colored polar polymer material layer is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals.

An article comprising two layers, wherein the first layer is a polar polymer material of a blend of <NUM> wt. -% HDPE (MFI <NUM>) and <NUM> wt. -% of poly ε-Caprolactone (MFI <NUM>-<NUM> and MW about <NUM>) and the second layer is a non-polar component layer comprising <NUM> wt. -% HDPE (MFI <NUM>). The article which has a length of <NUM>, height of <NUM> and width of <NUM> is placed in <NUM> of an aqueous coloring solution, wherein the aqueous coloring solution comprises <NUM> of an organic aromatic coloring agent having formula A1:
<CHM>
a dispersing agent of <NUM> Efka® <NUM> (acrylic block-copolymer) obtainable by BASF SE and <NUM> of a solubilizer of ethanol, wherein the aqueous displersed coloring solution contacts the first layer and the second layer and has a temperature of <NUM>° C. The article is exposed to the aqueous dispersed coloring solution for about <NUM> minutes at a pH of <NUM>. Thereafter the article is removed from the aqueous dispersed coloring solution and the article is rinsed with water of <NUM>° C at least <NUM> times to remove color residuals. The first layer, i.e. the polar polymer material layer is colored wherein the second layer i.e. the non-polar component layer is not colored. The homogenous penetration depth of the organic aromatic coloring agent (formula A1) in the first layer is at least <NUM> and the RGB: <NUM>/<NUM>/<NUM>.

Claim 1:
Method for reversible and selective coloring a synthetic polar-polymer material comprising the step:
exposing the outer surface of the synthetic polar-polymer material to an aqueous dispersed coloring solution, wherein
the aqueous dispersed coloring solution comprises:
- at least one organic aromatic coloring agent having a molecular weight Mw in the range of ≥ <NUM>/mol to ≤ <NUM>/mol, and wherein the organic aromatic coloring agent is not a chemical reactive dye, and wherein the coloring agent comprises at least <NUM> to <NUM> aromatic six-membered rings and comprises at least one heteroatom selected from N, O, S, halogens,
- at least one dispersing agent for dispersing the organic aromatic coloring agent in the aqueous solution, and
- optionally at least one solubilizer,
wherein the aqueous dispersed coloring solution exposing the synthetic polymer material has a temperature in the range of ≥ <NUM> to ≤ <NUM> and optionally a pH in the range of ≥ <NUM> and < <NUM>, and wherein the dispersing agent is selected different from the solubilizer.