EP3700969A1

EP3700969A1 - Method for dyeing elastomer particle foams

Info

Publication number: EP3700969A1
Application number: EP18789179.1A
Authority: EP
Inventors: Frank Prissok; Michael Harms
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2017-10-26
Filing date: 2018-10-25
Publication date: 2020-09-02
Also published as: WO2019081644A1; MX2020004316A; JP2021500460A; CA3080255A1; CN111263787A; RU2020117049A; KR20200070377A; TW201932520A; RU2020117049A3; BR112020006291A2; US20200270806A1

Abstract

The invention relates to a method for producing dyed foamed particles consisting of an elastomer (E), at least having the steps of providing foamed particles made of at least one elastomer (E) and bringing the particles into contact with a mixture (MF) containing a dye (F) and a carrier liquid (TF), thereby obtaining dyed foamed particles, wherein the carrier liquid (TF) has a polarity which is suitable for a sorption of the carrier liquid into the elastomer. The invention additionally relates to dyed foamed particles which are obtained or can be obtained according to such a method and to the use of the dyed foamed particles according to the invention for producing molded bodies, in particular shoe soles, parts of the shoe sole, bicycle saddles, upholstery, mattresses, underlays, handles, protective films, floor coverings, and components for automobile interiors or exteriors.

Description

Process for coloring elastomeric particle foams

description

The present invention relates to a process for the preparation of colored foamed particles consisting of an elastomer (E), comprising at least the provision of foamed particles of at least one elastomer (E), and contacting the particles with a mixture (M) containing a dye ( F) and a carrier liquid (TF) to give colored foamed particles, wherein the carrier liquid (TF) has a

Polarity, which is suitable that a sorption of the carrier liquid takes place in the elastomer. Furthermore, the present invention relates to colored foamed particles obtained or obtainable by such a process and to the use of the colored foamed particles according to the invention for the production of moldings, in particular of

Shoe soles, parts of a shoe sole, bicycle saddles, upholstery, mattresses, pads, handles, protective films, floor coverings, and components in the automotive interior and exterior.

Foams, especially particle foams, have long been known and widely described in the literature, e.g. in Ullmann's "Encyklopadie der technischen Chemie", 4th Edition, Volume 20, pp. 416-418.

Highly elastic, closed-cell foams, such as thermoplastic polyurethane particle foams, which are produced by autoclaving or by the extruder process, show good mechanical properties and in some cases good rebound resilience. Also

Hybrid foams of particles of thermoplastic elastomers and system foam or binders are known. Depending on the foam density, the method of manufacture and the

Matrix material can be a total of a relatively wide level of rigidity mapped. Also by a subsequent treatment of the foam such as tempering the properties of the foam can be influenced.

Particle foams (or particle foams, particle foam) and shaped articles based thereon on the basis of thermoplastic polyurethane or other elastomers are known (for example WO 94/20568, WO 2007/082838 A1, WO2017030835, WO 2013/153190 A1 WO2010010010) and can be used in a variety of ways.

Particle foams or foam particles based on thermoplastic polyurethane, also referred to herein as TPU, are disclosed in WO 94/20568. A disadvantage of the TPU foams described in WO 94/20568 A1 is the high energy consumption in the production and processing. It is applied a water vapor pressure of 4.5 bar to 7 bar at temperatures of 145 ° C to 165 ° C. Furthermore, WO 94/20568 A1 describes expanded, ie foamed, TPU particles which can be processed into shaped parts. These TPU foam particles are produced at temperatures of 150 ° C and higher and, according to the examples, have a bulk density between 55 and 180 g / L, which is disadvantageous during transport and storage of these particles because of the increased space requirement. WO 2007/082838 A1 discloses an expandable, preferably particulate, blowing agent-containing thermoplastic polyurethane, wherein the thermoplastic polyurethane has a Shore hardness between A 44 and A 84. The Shore hardness of the TPU is measured on the compact, ie non-expanded TPU. In addition, WO 2007/082838 A1 discloses processes for the production of expandable, preferably particulate, propellant-containing thermoplastic polyurethane and also processes for the production of expanded polymer

thermoplastic polyurethane and process for the production of foam based on thermoplastic polyurethane, and thus obtainable foams or expanded thermoplastic polyurethanes.

Particle foam or particle foam in the context of the present invention refers to a foam in the form of a particle, wherein the average diameter of the particle foam is between 0.2 to 20, preferably 0.5 to 15 and in particular between 1 to 12 mm. For non-spherical, e.g. elongated or cylindrical particle foam is meant by diameter the longest dimension.

For many applications it is desirable to use colored foamed particles to obtain colored shaped articles. From the state of the art, for example, the bonding or foaming of particle foams by means of (colored) polyurethane binders or

Polyurethane system foaming known (WO 2008/087078 A1). However, particles coated with colored, crosslinked binders can no longer be welded thermoplastically.

The prior art also discloses the production of foamed particles from mass-colored TPU. However, the coloring of these mostly black particles is poor because the color intensity of the coloring changes with the density of the particles. High density particles appear darker, those with lower density appear lighter. A coating of the molded parts made of foamed particles, for example, with a thermoplastic polyurethane is also possible and durable, but the molded body obtained thereby always a homogeneous coloring (WO 2015/165724 A1). The mixing of different colored particles is not possible.

In principle, it is also possible to colorize a granulate before foaming and to produce a particle foam. For this purpose, dyes must be used which have a very high temperature resistance in order to be used in the extrusion process can. However, this method has the disadvantage that the color intensity changes with the density of foam. Since the individual particles of a foam charge usually have certain density differences, the color is usually not homogeneous. On the other hand, it comes in the foaming impurities and expensive cleaning steps are necessary.

One object of the present invention was therefore to provide foam particles or shaped bodies produced from foam particles, the particles being simple can be colored and then processed, for example, in a molding machine to produce products. In addition, it was an object of the present invention to provide foam particles, or to develop a method that a

Coloring of the foam particles regardless of the manufacturing process allows this and allows high flexibility of the production facilities by first colorless, so uncoloured, particles are produced, which can be specifically dyed and further processed in a downstream process.

According to the invention this object is achieved by a process for the preparation of colored foamed particles consisting of an elastomer (E), at least comprising the

steps

(i) providing foamed particles of at least one elastomer (E), (ii) contacting the particles with a mixture (M) containing a dye (F) and a carrier liquid (TF) to give dyed foamed particles, the carrier liquid ( TF) has a polarity suitable for sorption of the carrier liquid into the elastomer.

The process according to the invention comprises the steps (i) and (ii). According to step (i), foamed particles of at least one elastomer (E) are provided. According to step (ii) of the method according to the invention, the particles are brought into contact with a mixture (M) containing a dye (F) and a carrier liquid (TF) to give dyed foamed particles. It is important in the context of the present invention that the foamed particles provided according to step (i) in accordance with step (ii) with the

Mixture (M) are brought into contact, that the dye contained in the mixture (M) can be absorbed by the particles. For example, the mixture (M) can be used in the form of a solution, an emulsion or a dispersion.

According to a further embodiment, the present invention therefore relates to a method as described above, wherein the mixture (M) is a solution, emulsion or dispersion.

Surprisingly, it has been found that foamed particles of an elastomer, in particular foamed particles of thermoplastic elastomers, can be coated with a mixture of pigments and / or dyes with a compatible carrier liquid which is absorbed by the elastomer in a short time. From the coated particles, single or multi-colored components can be produced by means of steam, HF or microwave welding, which have a permanent coloration.

The mixture (M) is prepared from the carrier liquid (TF) and the dye (F) by methods known per se. It has been found that a good coloration can be achieved if the carrier liquid used (TF) has a polarity which is suitable for sorption of the

Carrier liquid in the elastomer takes place. Suitable carrier liquids are known per se to the person skilled in the art. Suitable examples are those liquids which have a boiling point in the range of 80 ° C to 300 ° C. Such liquids are also used, for example, in the production of elastomers (E) as plasticizers.

In the context of the present invention, the carrier liquid is liquid at room temperature.

According to a further embodiment, the present invention therefore relates to a method as described above, wherein the carrier liquid has a boiling point in the range of 80 ° C to 300 ° C.

In the context of the present invention, the carrier liquid is preferably a colorless liquid. More preferably, the carrier liquid in the context of the present invention is not harmful to health and non-corrosive, more preferably non-oxidizing. Preferably, the carrier liquid in the scope of the present invention has no free acid groups.

One scale commonly used to determine the polarity of liquids is the ET (30) scale. The Ei (30) value is defined as the transition energy of the longest wavelength Vis / NIR absorption band in a solution with the negative solvatochromic Reichardt dye (Betain 30) under normal conditions in kcal-mol ^-1 . The He ^N value is the one on the

Polarity extrema tetramethylsilane (= 0) and water (= 1) normalized egg (30) value.

For example, the carrier liquid (TF) used according to the invention has an E _T (30) value of greater than or equal to 150 kJ / mol, preferably in the range from 150 to 250 kJ / mol, particularly preferably in the range from 200 to 250 kJ / mol.

According to a further embodiment, the present invention therefore relates to a method as described above, wherein the carrier liquid (TF) has a Ετ (30) value greater than or equal to 150 kJ / mol.

Suitable carrier liquids are, for example, selected from the group consisting of acetone, 1-butanol, dibutyl ether, diethylene glycol, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, acetic acid ester, ethyl acetate, water, ethanol, ethylene glycol, ethylene glycol dimethyl ether, 2-propanol (isopropyl alcohol) , 3-methyl-1-butanol (isoamyl alcohol), 2-methyl-2-propanol (fe-butanol), methyl ethyl ketone (butanone, propanol, propylene carbonate (4-methyl-1,3-dioxol-2-one), triethylene glycol, Triethylene glycol dimethyl ether (triglyme), glycerol ester, phthalic acid ester, adipic acid ester, citric acid ester,

Polyethylene glycols, polypropylene glycols. As a carrier liquid in particular glycols and esters are suitable. Those based on mono-, di- or trialcohols, such as ethanol, propanol, butanol, ethylene glycol, butanediol, glycerol and of mono- or dicarboxylic acid having 1 to 8 C atoms, such as acetic acid, adipic acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid.

According to a further embodiment, the present invention therefore relates to a method as described above, wherein the carrier liquid is selected from the group consisting of glycols and esters of citric acid and glycerol esters. In the context of the present invention is suitable as a carrier liquid, for example

Triacetin, a glycerol ester.

In the context of the present invention, mixtures of various

Carrier liquids are used.

In the context of the present invention, the mixture (M) is used in an amount which is sufficient to wet the foamed particles used at least 80%, preferably at least 90%, more preferably 100%. In the context of the present invention, the mixture (M) is preferably used in an amount in the range of 0.1 to 10% by weight, more preferably in an amount in the range of 0.2 to 5% by weight, particularly preferably in the range of 0.3 up to 3% by weight, in each case based on the weight of the foamed particles used. In the context of the present invention, the shape and size of the used

Foamed particles vary widely. According to the invention, the shape of the particles may be, for example, a tetrahedron, cylinder, sphere, lens or polyhedron such as cubes or octahedrons. The foamed particles are preferably at least approximately spherical and usually have an average diameter at the narrowest point of 1 mm to 20 mm, preferably 2 mm to 12 mm and in particular 3 mm to 10 mm.

The contacting according to step (ii) takes place for a time sufficient to allow sorption of the mixture (M) on the particle or in the elastomer. The mixture (M) is applied to the particles by, for example, mixing, spraying, tumbling or other conventional methods.

Usually, the impregnation time in the context of the present invention is less than or equal to 1 hour, for example less than or equal to 30 minutes, more preferably less than or equal to 10 minutes. In the context of the present invention, the process is preferably conducted such that the dye used penetrates into the foamed particles and remains close to the surface in the particles. For example, the dyes may have a penetration of greater than Ι Ομηη, especially greater than Ι ΟΟμηη, especially greater than 500μηι.

In the context of the present invention, it is also possible to achieve a homogeneous distribution of the dye in the particle by a suitable choice of the reaction conditions, such as, for example, the type of dye used or the duration of the contacting. The distribution of the dye or the penetration depth can be determined, for example, by measuring under a microscope, preferably an electron microscope, at a gate of the particle

According to the invention, the particles are brought into contact with the mixture (M) and, for example, stirred. In this case, the mixture (M) is finely distributed on the surface of the particles by the choice of the carrier liquid (TF) and adheres to this preferably. In the further treatment, for example when the particles are heated, the carrier liquid, for example, also penetrates the particles and thus does not interfere with the adhesion between the individual particles when they are processed into shaped bodies. In the present invention, the carrier liquid can fix the dye on the surface of the foamed particles. However, it is also possible that the

Carrier liquid entrains the dye in the foam particles and both components remain in the foam particles. According to a further embodiment, the present invention therefore relates to a method as described above, wherein the carrier liquid is introduced into the dye in the foam particles and both components remain in the foam particles.

In the context of the present invention, the mixture (M) contains at least one dye. In the context of the present invention, per se known pigments and

Dyes are used. Suitable are both liquid and solid dyes or pigments, provided that a sufficient miscibility with the carrier liquid (TF) is given, so that a mixture (M) is obtained. According to a further embodiment, the present invention therefore relates to a method as described above, wherein the dye is selected from the group consisting of liquid dyes and solid pigments.

The amount of dye used and the concentration of the dye in the mixture (M) can vary widely. The amount used or concentration of

Dye can be adjusted to adjust the color intensity of the colored particles. Preferably, the dye in the mixture (M) is in an amount in the range of 0.1 to 50 % By weight, more preferably in the range from 1 to 30% by weight, particularly preferably in the range from 2 to 20% by weight, in each case based on the total mixture (M).

In the context of the present invention can be used as dyes, for example

Metal complex dyes are used which have good solubility in polar solvents, such as Neozapon® dyes. It is also possible to use cationic dyes which have good solubility in alcohols and glycol ethers. Suitable dyes are, for example, Basonyl® dyes. Also suitable are, for example, commercially available dyes, for example under the trade names Neozapon® Black X55, Neozapon® Black X51, Neozapon® Red 335,

Neozapon® Yellow 141, Neozapon® Red 471, Neozapon® Blue 807, Neozapon® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl® Red 545 liquid, Basonyl® Red 555 liquid, Basonyl® Green 830 liquid, Basonyl® Blue 636, Basantol® Yellow 099 liquid, Basantol® Black X82 liquid, Neptune Yellow 075, Heliogen® Blue L 6930, Basacid® Orange 282 liquid, Basacid® Yellow 093 liquid, Isopur SU 12021/91 1 or Reaktint Yellow X15 available dyes.

Dyes selected from the group consisting of Neozapon® Black X55, Neozapon® Red 335, Neozapon® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl® Red 545 liquid, Basonyl® Red are preferred in the context of the present invention 555 liquid, Basonyl® Green 830 liquid, Basonyl® Blue 636, and Neptun Yellow 075 used. More preferably, a dye selected from the group consisting of Basonyl® Blue 644, Basonyl® Red 545, Basonyl® Green 830 and Neozapon® black X55, and Neptun Yellow 075 is used.

According to the invention foamed particles are used, which consist of at least one

Elastomer (E) exist. According to the invention, the particles can be open-celled or

be closed-celled. For example, the closed cell density of the foam is greater than 60%, determined according to DIN ISO 4590: 2016. In the context of the present invention, the foamed particles preferably have a closed shell.

The elastomer (E) can vary within wide limits. Suitable, for example

thermoplastic elastomers such as thermoplastic block copolymers. suitable

Thermoplastic elastomers are known per se to the person skilled in the art. For example, the thermoplastic elastomer may be a thermoplastic polyurethane, a thermoplastic

Polyetheramide, a polyether ester, a polyester ester or a thermoplastic styrene butadiene block copolymer. Particularly suitable are within the scope of the present

Invention thermoplastic polyurethanes, polyether esters, polyester esters and polyether amides.

According to a further embodiment, the present invention therefore relates to a method as described above, wherein the elastomer is a thermoplastic block copolymer. According to a further embodiment, the present invention therefore relates to a method as described above, wherein the elastomer is selected from the group consisting of thermoplastic polyurethanes, polyether esters, polyester esters and polyetheramides.

The thermoplastic elastomers used to produce the foam particles have for example a Shore hardness in the range of 30A to 82D, preferably in the range of 65A to 96A, determined according to DIN 53505. For example, the thermoplastic elastomers used have an elongation at break of greater than 50%, preferably in the range from 200 to 800%, measured according to DIN EN ISO 527-2.

Mixtures of two or more elastomers can also be used according to the invention. Suitable thermoplastic polyether esters and polyester esters can be prepared by all conventional processes known from the literature by transesterification or esterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 carbon atoms or esters thereof with suitable aliphatic and aromatic diols and polyols (cf., "Polymer Chemistry ", Interscience Publ., New York, 1961, p.1 1 1-127; Kunststoffhandbuch, Volume VIII, C. Hanser Verlag, Munich 1973 and Journal of Polymer Science, Part A1, 4, pages 1851 -1859 (1966)) Suitable aromatic dicarboxylic acids include, for example, phthalic acid, iso and

Terephthalic acid or its esters. Suitable aliphatic dicarboxylic acids include but are not limited to e.g. Cyclohexane-1, 4-dicarboxylic acid, adipic acid, sebaconic acid, azelaic acid and

Decanedicarboxylic acid as saturated dicarboxylic acids and maleic acid, fumaric acid,

Aconitic acid, itoconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as

unsaturated dicarboxylic acids.

Suitable diol components are, for example, diols of the general formula HO- (CH 2) n -OH, where n = 2 to 20, such as ethylene glycol, propanediol (1, 3), butanediol (1, 4) or hexanediol (1, 6 ) Polyetherols of the general formula HO- (CH 2) n -O- (CH 2) m -OH, where n is equal to or different than m and n or m = 2 to 20, unsaturated diols and polyetherols such as butenediol (1, 4) ; Diols and polyetherols containing aromatic moieties; as well as polyesterols.

In addition to the carboxylic acids mentioned or their esters and the alcohols mentioned, all other common representatives of these classes of compounds can be used to provide the polyether esters and polyester esters used according to the invention.

The thermoplastic polyether amides can be used according to all known, literature

Process by reaction of amines and carboxylic acids or their esters are obtained. Amines and / or carboxylic acid also contain ether units of the type ROR, where R = organic radical (aliphatic and / or aromatic). In general, monomers of the following classes of compounds are used: HOOC-R'-NH 2, where R 'can be aromatic and aliphatic, preferably containing ether units of the type ROR, where R = organic radical (aliphatic and / or aromatic); aromatic dicarboxylic acids, including, for example

Phthalic acid, iso- and terephthalic acid or their esters and aromatic dicarboxylic acids containing ether units of the type R-O-R, where R = organic radical (aliphatic and / or aromatic); aliphatic dicarboxylic acids, inter alia e.g. Cyclohexane-1, 4-dicarboxylic acid, adipic acid, sebaconic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids and also maleic acid, fumaric acid, aconitic acid, itoconic acid,

Tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated and aliphatic dicarboxylic acids containing ether units of the type R-O-R, where R = organic radical (aliphatic and / or aromatic); Diamines of the general formula H2N-R "-NH2, where R" can be aromatic and aliphatic, preferably containing ether units of the type R-O-R, where R = organic radical (aliphatic and / or aromatic); Lactams, such as ε-caprolactam, pyrrolidone or laurolactam; as well as amino acids.

In addition to the carboxylic acids mentioned or their esters and the amines mentioned, lactams and amino acids, all other common representatives of these

Classes of compounds can be used to provide the polyetheramine used according to the invention.

The thermoplastic elastomers having a block copolymer structure used according to the invention preferably contain vinylaromatic, butadiene and isoprene and also polyolefin and vinylic units, for example ethylene, propylene and vinyl acetate units. Preference is given to styrene-butadiene copolymers.

The thermoplastic elastomers having a block copolymer structure, polyetheramides, polyether esters and polyester esters used according to the invention are preferably selected such that their melting points are <300 ° C., preferably <250 ° C., in particular <220 ° C.

The thermoplastic elastomers having a block copolymer structure, polyetheramides, polyether esters and polyester esters used according to the invention may be partially crystalline or amorphous.

Thermoplastic polyurethanes are also known from the prior art. They are usually prepared by reacting a polyisocyanate composition with a

Obtained polyol composition, wherein the polyol composition usually comprises a polyol and a chain extender.

In the context of the present invention, thermoplastic polyurethanes are usually used which are prepared by reacting a polyisocyanate composition with a

Polyol composition obtained or are available.

The expanded particles of the invention can be, for example, by suspension or extrusion processes directly or indirectly via expandable particles and foaming in produce a Druckvorschäumer with steam or hot air. Suitable methods are known per se to the person skilled in the art.

The particle foams according to the invention generally have a bulk density of from 50 g / l to 200 g / l, preferably from 60 g / l to 180 g / l, particularly preferably from 80 g / l to 150 g / l. Bulk density is measured analogously to DIN ISO 697, using a 10 l volume vessel instead of a 0.5 l volume vessel in determining the above values, unlike the standard, especially for the low density, high mass foam particles a measurement with only 0.5 l volume is too inaccurate.

As stated above, the diameter of the particle foams is between 0.5 to 30;

preferably 1 to 15 and in particular between 3 to 12 mm. For non-spherical, e.g.

elongated or cylindrical particle foam is meant by diameter the longest dimension.

According to the invention, the method may comprise further steps, for example

Temperature treatments. It is also possible within the scope of the present invention for further coatings or additives to be applied to the foamed particles.

Suitable methods are known per se to the person skilled in the art.

In another aspect, the present invention also relates to colored foamed particles obtained or obtainable by a process as described above. Thus, the present invention relates to colored foamed particles obtained or obtainable by a process comprising at least the steps

(i) providing foamed particles of at least one elastomer (E),

(ii) contacting the particles with a mixture (MF) containing a dye (F) and a carrier liquid (TF) to give dyed foamed ones

Particles, wherein the carrier liquid (TF) has a polarity which is suitable that a sorption of the carrier liquid takes place in the elastomer.

With regard to the preferred embodiments, reference is made to the above statements. In particular, the present invention relates to colored particles as described above, wherein the elastomer is selected from the group consisting of thermoplastic polyurethanes, polyether esters, polyester esters and polyetheramides.

The production of the particle foams can be carried out by the usual methods known in the prior art

a. Providing the elastomer; b. Impregnation of the elastomer with a propellant under pressure; c. Expand the elastomer by means of pressure drop.

The amount of blowing agent is preferably 0.1 to 40, in particular 0.5 to 35 and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of the amount of the elastomer used.

Embodiment of the above method comprises

a. Providing the elastomer in the form of granules;

b. Impregnation of the granules with a propellant under pressure;

c. Expand the granules by means of pressure drop. Another embodiment of the above-mentioned method comprises a further step: a. Providing the elastomer in the form of granules;

b. Impregnation of the granules with a propellant under pressure;

c. Reducing the pressure to normal pressure without foaming the granules, if necessary by prior reduction of the temperature

d. Foaming of the granules by a temperature increase. In this case, the granulate preferably has an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granulate, for example via dynamic image analysis with the use of an optical measuring apparatus named PartAn 3D from Microtrac).

The individual granules generally have an average mass in the range from 0.1 to 50 mg, preferably in the range from 4 to 40 mg and more preferably in the range from 7 to 32 mg. This average mass of the granules (particle weight) is determined as an arithmetic mean by weighing 3 times each of 10 granular particles.

An embodiment of the above method comprises impregnating the granules with a propellant under pressure and then expanding the granules in step (b) and (c): b. Impregnating the granules in the presence of a propellant under pressure at elevated temperatures in a suitable closed reaction vessel (e.g., autoclave);

c. sudden relaxation without cooling.

In this case, the impregnation in step (b) can be carried out in the presence in the presence of water and optionally suspension aids or only in the presence of the blowing agent and absence of water.

Suitable suspension aids are, for example, water-insoluble inorganic stabilizers, such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and Surfactants, such as sodium dodecylarylsulfonate. They are usually used in amounts of 0.05 to 10 wt .-%, based on the elastomer.

The impregnation temperatures are in the range of 100-200 ° C., depending on the selected pressure, the pressure in the reaction vessel being between 2 and 150 bar, preferably between 5 and 100 bar, more preferably between 20 and 60 bar, the impregnation time is general 0.5 to 10 hours.

The performance of the process in suspension is known to those skilled in the art and e.g.

described in detail in WO 2007/082838.

When carrying out the process in the absence of the blowing agent, it must be ensured that the aggregation of the polymer granulate is avoided. Suitable propellants for carrying out the process in a suitable closed reaction vessel are e.g. organic liquids and gases used in the

Processing conditions in a gaseous state, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases and inorganic gases, and these can also be combined. suitable

Hydrocarbons are, for example, halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons. Preferred organic blowing agents are saturated, aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms, such as butane or pentane.

Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide or mixtures of the abovementioned gases.

In a further embodiment, the impregnation of the granules with a propellant under pressure comprises processes and subsequent expansion of the granules in steps (b) and (c):

b. Impregnation of the granules in the presence of a blowing agent under pressure at elevated temperatures in an extruder;

c. Granulation of the mass leaving the extruder under conditions which prevent uncontrolled foaming.

Suitable propellants in this process variant are volatile organic compounds having a boiling point at atmospheric pressure of 1013 mbar from -25 to 150, in particular -10 to 125 ° C. Well suited are hydrocarbons (preferably halogen-free), especially C4-10 alkanes, for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably iso-pentane. Further possible blowing agents are also sterically more demanding compounds or functionalized hydrocarbons such as alcohols, ketones, esters, ethers and organic carbonates, In this case, the elastomer is mixed in step (b) in an extruder while melting with the blowing agent under pressure, which is fed to the extruder. The

propellant-containing mixture is under pressure, preferably with moderately controlled

Counter pressure (e.g., underwater granulation) is squeezed and granulated. In this case, the melt strand foams and granules give the particle foams.

The implementation of the process via extrusion is known to the person skilled in the art and e.g. described in detail in WO 2007/082838 and WO 2013/153190 A1.

Suitable extruders are all conventional screw machines, in particular

Single screw and twin screw extruders (e.g., ZSK type from Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roll extruders, e.g. in Saechtling (ed.), plastic paperback, 27.

Edition, Hanser-Verlag Munich 1998, chap. 3.2.1 and 3.2.4 are described. The extruder is usually operated at a temperature at which the MATERIAL is in the form of a melt, for example at 120 ° C. to 250 ° C., in particular 150 to 210 ° C. and a pressure after the addition of the blowing agent of 40 to 200 bar, preferably 60 to 150 bar, particularly preferably 80 to 120 bar to ensure homogenization of the blowing agent with the melt.

In this case, the implementation can be carried out in an extruder or an arrangement of one or more extruders. For example, in a first extruder, the

Components are melted and blinded, and a propellant is injected. In the second extruder, the impregnated melt is homogenized and adjusted the temperature and or the pressure. If, for example, three extruders are combined with one another, the mixing of the components and the injection of the blowing agent can likewise be subdivided into two different process parts. If, as preferred, only one extruder is used, then all process steps will melt, mix, inject the

Propellant, homogenization and adjusting the temperature and or pressure in an extruder performed.

Alternatively, as described in WO 2014150122 or WO 2014150124 A1

Methods from the granules directly the corresponding, possibly even already dyed

Particle foam produced by soaking the appropriate granules with a supercritical fluid is removed from the supercritical fluid followed by

(a) immersing the article in a heated fluid or

(β) irradiating the article with energetic radiation (e.g., infrared or

Microwave irradiation). Suitable supercritical fluids are, for example, those described in WO 2014/150122 or described, for example carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen. The supercritical fluid may also contain a polar fluid having a Hildebrand solubility parameter equal to or greater than 9 MPa ^1/2 .

Here, the supercritical fluid or the heated fluid may also contain a dye, whereby a dyed, foamed article is obtained.

Another object of the present invention is a molded article produced from the particle foams according to the invention.

Shaped articles can be produced from the foamed particles dyed according to the invention, for example by welding them together in a closed mold under the action of heat. For this purpose, for example, the particles are filled into the mold and, after closing the mold, initiates steam or hot air, whereby the particles expand further and weld together to the foam, preferably with a density in the range of 8 to 600 g / l. The foams can be semi-finished products, such as plates, profiles or webs, or finished moldings with simple or complicated geometry. Accordingly, the term includes foam, semi-finished foam products and foam moldings.

According to a further aspect, the present invention also relates to a method for producing a shaped article from the colored foamed particles according to the invention or to the use of the colored foamed particles for producing a shaped article. In this case, the shaped body can be produced from the foam particles according to the invention in a manner known per se. A suitable method is, for example, welding by means of steam, hot air or high-energy radiation.

The preparation of the corresponding moldings can be known to the person skilled in the art

Methods are done. A preferred method for producing a

Foam molding comprises the following steps:

(a) introducing the particle foams according to the invention in a corresponding form,

(b) fusing the particle foams according to the invention from step (a).

The fusing in step (b) is preferably carried out in a closed mold, wherein the fusing by gases such as water vapor, hot air (as described for example in EP1979401 B1

described) or energetic radiation (microwaves or radio waves) can take place.

The temperature at the fusing of the particle foam is preferably below or close to the melting temperature of the polymer from which the particle foam was made. For the common polymers is therefore the temperature for fusing the particle foam between 100 ° C and 180 ° C, preferably between 120 and 150 ° C.

In this case, temperature profiles / residence times can be determined individually, e.g. in analogy to the methods described in US20150337102 or EP2872309B1.

The welding via energetic radiation is generally carried out in the frequency range of microwaves or radio waves, if necessary in the presence of water or other polar liquids, e.g. polar group-containing, microwave-absorbing

Hydrocarbons (such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols) and may be prepared in analogy to those described in EP3053732A or US Pat

WO2016 / 146537 described method.

Accordingly, according to a further embodiment, the present invention also relates to the use of the foamed particles as described above, wherein the production of the shaped body takes place by means of welding or adhesive bonding of the particles to one another. According to a further embodiment, the present invention also relates to the use of foamed particles as described above for producing a shaped body by welding the particles by means of superheated steam, hot air, heat radiation, electromagnetic radiation, such as radio frequency radiation, microwave radiation, NIR radiation, infrared radiation.

The temperature in the welding of the expanded particles is preferably between 100 ° C and 140 ° C. The present invention thus also relates to processes for the production of foam based on thermoplastic polyurethane, wherein the expanded thermoplastic polyurethane according to the invention is welded by means of steam at a temperature between 100 ° C and 140 ° C to form a shaped body.

The invention also provides the use of the expanded particles for the production of foams, as well as foams, obtainable from the expanded particles.

According to a further aspect, the present invention also relates to shaped articles obtainable or obtained according to the process according to the invention for producing a shaped article as described above. Such moldings have in addition to good mechanical

Features a high elongation at break. Accordingly, according to a further embodiment, the present invention also relates to a shaped body as described above, wherein the shaped body has an elongation at break of greater than 100%, determined according to DIN 53504.

According to a further aspect, the present invention also relates to the use of the foam particles or foam particles according to the invention obtainable or obtained according to a method according to the invention for the production of shoe soles, bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in components in Automotive interior and exterior area, in balls and

Sports equipment or as a floor covering, in particular for sports surfaces, athletics tracks, Sports halls, children's playgrounds and sidewalks. Furthermore, the present invention relates to the use of the colored foamed particles according to the invention or of foamed particles obtainable by a method according to the invention for use in balls and sports equipment or as a floor covering and wall cladding, in particular for sports surfaces,

Athletics tracks, sports halls, children's playgrounds and sidewalks.

The invention further relates to the use of an inventive

Particle foam for the production of a molded article for shoe midsoles,

Shoe insoles, shoe combination soles, bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in automotive interior and exterior components, in balls and sports equipment or as a floor covering, in particular for sports surfaces, track athletics, sports halls, children's playgrounds and sidewalks ,

It is also advantageous that the foams according to the invention can be easily recycled thermoplastically. For this purpose, for example, the foamed materials are extruded using an extruder with a degassing device, wherein the extrusion may optionally precede a mechanical comminution. Thereafter, they can be re-processed into foams in the manner described above. Further embodiments of the present invention are the claims and the

To take examples. It is understood that the above and the

hereinafter explained features of the invention

The subject matter / method / uses can be used not only in the particular combination specified, but also in other combinations, without departing from the scope of the invention. So z. Also, the combination of a preferred feature with a particularly preferred feature, or a non-further characterized feature with a particularly preferred feature, etc. implicitly encompasses, even if this combination is not explicitly mentioned. Listed below are exemplary embodiments of the present invention, which are not limitative of the present invention. In particular, the

The present invention also provides such embodiments which result from the following references and combinations thereof.

1 . Process for the preparation of dyed foamed particles consisting of an elastomer (E), comprising at least the steps

(i) providing foamed particles of at least one elastomer (E),

Contacting the particles with a mixture (M) containing a dye (F) and a carrier liquid (TF) to give dyed foamed particles, wherein the carrier liquid (TF) has a polarity suitable that a

Sorption of the carrier liquid takes place in the elastomer.

2. Method according to embodiment 1, wherein the mixture (M) is a solution, emulsion or dispersion.

3. The method according to any one of embodiments 1 or 2, wherein the carrier liquid has a boiling point in the range of 80 ° C to 300 ° C. 4. The method according to any one of embodiments 1 to 3, wherein the carrier liquid has an ET (30) value of greater than or equal to 150 kJ / mol.

5. The method according to any one of embodiments 1 to 4, wherein the carrier liquid

is selected from the group consisting of glycols and esters of citric acid and glycerol esters.

6. The method according to any one of embodiments 1 to 5, wherein the carrier liquid

Triacetin is. 7. The method according to any one of embodiments 1 to 6, wherein the dye is selected from the group consisting of liquid dyes and solid pigments.

8. The method according to any one of embodiments 1 to 7, wherein the dye is selected from the group consisting of metal complex dyes and cationic dyes.

9. The method according to any one of embodiments 1 to 7, wherein the dye is selected from the group consisting of Neozapon® Black X55, Neozapon® Black X51, Neozapon® Red 335, Neozapon® Yellow 141, Neozapon® Red 471, Neozapon® Blue 807 , Neozapon® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl® Red 545 liquid, Basonyl® Red 555 liquid, Basonyl® Green 830 liquid, Basonyl® Blue 636,

Basantol® Yellow 099 liquid, Basantol® Black X82 liquid, Neptun Yellow 075, Heliogen® Blue L 6930, Basacid® Orange 282 liquid, Basacid® Yellow 093 liquid, Isopur SU

12021/91 1 or Reaktint Yellow X15. 10. The method according to any one of embodiments 1 to 7, wherein the dye is selected from the group consisting of Neozapon® Black X55, Neozapon® Red 335,

Neozapon® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl® Red 545 liquid, Basonyl® Red 555 liquid, Basonyl® Green 830 liquid, Basonyl® Blue 636, and Neptun Yellow 075.

1 1. The method according to any one of embodiments 1 to 7, wherein the dye is selected from the group consisting of Basonyl® Blue 644, Basonyl® Red 545, Basonyl® Green 830, Neozapon® black X55, and Neptun Yellow 075th 12. The method according to any one of embodiments 1 to 1 1, wherein the elastomer is a thermoplastic block copolymer. 13. The method according to any one of embodiments 1 to 12, wherein the elastomer

is selected from the group consisting of thermoplastic polyurethanes, polyether esters, polyester esters and polyetheramides.

14. The method according to any one of embodiments 1 to 13, wherein the elastomer

is selected from the group consisting of thermoplastic polyurethanes.

15. Colored foamed particles obtained or obtainable by a process comprising at least the steps of (i) providing foamed particles of at least one elastomer (E),

(ii) contacting the particles with a mixture (M) containing a dye (F) and a carrier liquid (TF) to obtain colored foamed particles, wherein the carrier liquid (TF) has a polarity suitable that a

Sorption of the carrier liquid takes place in the elastomer.

16. Particles according to embodiment 15, wherein the elastomer is selected from the group consisting of thermoplastic polyurethanes, polyether esters, polyester esters and polyetheramides.

17. Particles according to embodiment 15 or 16, wherein the mixture (M) is a solution, emulsion or dispersion. 18. Particles according to any one of embodiments 15 to 17, wherein the carrier liquid has a boiling point in the range of 80 ° C to 300 ° C.

19. Particles according to any one of embodiments 15 to 18, wherein the carrier liquid has an E _T (30) value of greater than or equal to 150 kJ / mol.

20. Particles according to any one of embodiments 15 to 19, wherein the carrier liquid

is selected from the group consisting of glycols and esters of citric acid and glycerol esters. 21. Particles according to any one of embodiments 15 to 20, wherein the carrier liquid

Triacetin is. Particles according to any of embodiments 15 to 21, wherein the dye is selected from the group consisting of liquid dyes and solid pigments. Particles according to any of embodiments 15 to 22, wherein the dye is selected from the group consisting of metal complex dyes and cationic dyes. Particles according to any of embodiments 15 to 22, wherein the dye is selected from the group consisting of Neozapon® Black X55, Neozapon® Black X51, Neozapon® Red 335, Neozapon® Yellow 141, Neozapon® Red 471, Neozapon® Blue 807, Neozapon ® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl®

Red 545 liquid, Basonyl® Red 555 liquid, Basonyl® Green 830 liquid, Basonyl® Blue 636, Basantol® Yellow 099 liquid, Basantol® Black X82 liquid, Neptun Yellow 075, Heliogen® Blue L 6930, Basacid® Orange 282 liquid, Basacid ® Yellow 093 liquid, Isopur SU

12021/91 1 or Reaktint Yellow X15. Particles according to any of embodiments 15 to 22, wherein the dye is selected from the group consisting of Neozapon® Black X55, Neozapon® Red 335,

Neozapon® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl® Red 545 liquid, Basonyl® Red 555 liquid, Basonyl® Green 830 liquid, Basonyl® Blue 636, and Neptun Yellow 075. Particles according to any of the embodiments 15 to 22, wherein the dye is selected from the group consisting of Basonyl® Blue 644, Basonyl® Red 545, Basonyl® Green 830, Neozapon® black X55, and Neptun Yellow 075. Particles according to any one of embodiments 1 to 13, wherein the Elastomer is selected from the group consisting of thermoplastic polyurethanes. Colored foamed particles obtained or obtainable by a method according to any of embodiments 1 to 14. Use of foamed particles according to any of embodiments 15 to 28 or foamed particles obtainable by a method according to any of embodiments 1 to 14 for producing a shaped article. Use according to embodiment 29, wherein the production of the shaped body takes place by means of welding or gluing the particles together. Use according to embodiment 29 or 30, wherein the shaped body a

Shoe sole, a part of a shoe sole, a bicycle saddle, a padding, a mattress,

Underlay, handle, protective film, a component in the automotive interior and exterior area is. Use of foamed particles according to any one of embodiments 15 to 28 or of foamed particles obtainable by a method according to any one of embodiments 1 to 14 in balls and sports equipment or as a floor covering and

Wall cladding, in particular for sports surfaces, athletic tracks, sports halls, children's playgrounds and sidewalks.

Process for the preparation of dyed foamed particles consisting of an elastomer (E), comprising at least the steps

(i) providing foamed particles of at least one elastomer (E),

Sorption of the carrier liquid takes place in the elastomer,

wherein the carrier liquid is selected from the group consisting of glycols and esters of citric acid and glycerol esters,

wherein the dye is selected from the group consisting of Neozapon® Black X55, Neozapon® Red 335, Neozapon® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl® Red 545 liquid, Basonyl® Red 555 liquid, Basonyl ® Green 830 liquid, Basonyl® Blue 636, and Neptun Yellow 075.

(i) providing foamed particles of at least one elastomer (E),

Sorption of the carrier liquid takes place in the elastomer,

wherein the carrier liquid is triacetin,

(i) providing foamed particles of at least one elastomer (E), (ii) contacting the particles with a mixture (M) containing a dye (F) and a carrier liquid (TF) to obtain colored foamed particles, wherein the carrier liquid (TF) has a polarity suitable that a

Sorption of the carrier liquid takes place in the elastomer,

wherein the dye is selected from the group consisting of Basonyl® Blue 644, Basonyl® Red 545, Basonyl® Green 830, Neozapon® black X55, and Neptun Yellow 075.

(i) providing foamed particles of at least one elastomer (E),

Sorption of the carrier liquid takes place in the elastomer,

wherein the carrier liquid is triacetin, and

(i) providing foamed particles of at least one elastomer (E),

Sorption of the carrier liquid takes place in the elastomer,

wherein the elastomer is selected from the group consisting of thermoplastic polyurethanes,

wherein the dye is selected from the group consisting of Neozapon® Black X55, Neozapon® Red 335, Neozapon® Orange 251, Basonyl® Green 830 liquid, Basonyl® Blue 644 liquid, Basonyl® Red 545 liquid, Basonyl® Red 555 liquid, Basonyl® Green 830 liquid, Basonyl® Blue 636, and Neptun Yellow 075.

38. A process for the preparation of colored foamed particles consisting of an elastomer (E), comprising at least the steps

(i) providing foamed particles of at least one elastomer (E), (ii) contacting the particles with a mixture (M) containing a dye (F) and a carrier liquid (TF) to give dyed foamed particles, the carrier liquid ( TF) has a polarity suitable that a

Sorption of the carrier liquid takes place in the elastomer,

wherein the elastomer is selected from the group consisting of thermoplastic

polyurethanes,

wherein the carrier liquid is triacetin,

39. A process for the preparation of colored foamed particles consisting of an elastomer (E), comprising at least the steps

(i) providing foamed particles of at least one elastomer (E),

Sorption of the carrier liquid takes place in the elastomer,

wherein the dye is selected from the group consisting of Basonyl® Blue 644, Basonyl® Red 545, Basonyl® Green 830, Neozapon® black X55, and Neptun Yellow 075. 40. Process for the preparation of dyed foamed particles consisting of an elastomer (E. ), at least comprising the steps

Sorption of the carrier liquid takes place in the elastomer,

wherein the carrier liquid is triacetin, and

wherein the dye is selected from the group consisting of Basonyl® Blue 644,

Basonyl® Red 545, Basonyl® Green 830, Neozapon® black X55, and Neptun Yellow 075.

41. Colored foamed particles obtained or obtainable by a process according to

one of the embodiments 33 to 40.

42. Foamed particles according to any one of embodiments 15 to 28 or 41, wherein the average diameter of the particle foams in the range of 0.5 to 15 mm.

43. A foamed particle according to any of embodiments 15 to 28 or 41, wherein the average diameter of the particle foams is in the range of 1 to 12 mm.

44. A process for the preparation of a shaped body of particle foams according to one of

Embodiments 15 to 28 or 41 comprising

(a) providing the foamed particles;

(b) Fusion of the particles.

45. The method according to embodiment 44, wherein the fusion in step (b) by means of

Steam, hot air or energy radiation takes place. 46. A method for producing a shaped article according to one of the embodiments 44 or 45 comprising

(a) introducing the particle foams into a corresponding shape,

(b) fusing the particle foams from step (a). 47. The method according to embodiment 46, characterized in that the fusion in step (b) takes place in a closed mold.

48. The method according to any one of embodiments 46 or 47, characterized in that the fusion in step (b) by means of steam, hot air or energy radiation takes place.

49. Shaped bodies obtainable or obtained according to a method according to one of

Embodiments 44 to 48. 50. Shaped body according to embodiment 49, wherein the shaped body a

Shoe midsole, shoe insole, shoe combination sole, bicycle saddle,

Bicycle tire, damping element, padding, mattress, pad, handle, protective film, a components in the automotive interior and exterior area, ball, or flooring, especially for sports surfaces, track athletics, sports halls, children's playgrounds and sidewalks.

51. Use of a particle foam according to one of the embodiments 41 to 43 for the production of a shaped article according to one of the embodiments 49 or 50.

The following examples are illustrative of the invention, but are in no way limiting as to the subject matter of the present invention.

EXAMPLES

1. Starting materials:

1.1 E-TPU1:

(Infinergy® 32-100 U10) expanded, predominantly closed-cell

Thermoplastic polyurethane-based foam particles obtained by foaming granulated TPU 1 under pressure and high temperature,

Particle weight 32mg, bulk densities 1 10 g / l.

1.2 E-TPU2:

(Infinergy® X1 125-130U000) expanded, predominantly closed-cell

Particle weight 25mg, bulk densities 130 g / l.

1 .3 E-TPU3:

expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming granulated TPU2 under pressure and high temperature, particle weight 32 mg, bulk density 90 g / l.

1 .4 E-TPU4:

expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming granulated TPU1 under pressure and high temperature, particle weight 5 mg, bulk densities 1 10 g / l.

1 .5 E-TPU5: expanded, partially closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming granulated TPU3 under pressure and high temperature, particle weight 32 mg, bulk density 90 g / l.

1.6 TPU 1:

Thermoplastic polyether polyurethane with a Shore hardness of 80A based on PTHF1000, 1,4 butanediol, 4,4 'MDI

1.7 TPU2:

Thermoplastic polyether polyurethane with a Shore hardness of 70A based on PTHF1000, 1,4 butanediol, 4,4 'MDI

1.8 TPU3:

Thermoplastic polyether polyurethane with a Shore hardness of 96A based on PTHF1000, bisphenol A-started polyether polyol, 1,4-butanediol, 4,4 'MDI

1.9 Glue:

Elastopave 6550/101 from BASF Polyurethanes GmbH, compact, 2-component polyurethane system.

1.10 Dyes:

As dyes, in principle, all available colorants can be used. Soluble or liquid dyes penetrate into the particles and color them through, insoluble dyes, as pigments are fixed on the surface.

The dyes were first dissolved in ethanol to identify 1% and the

Change in the pH value determined. The dyes used are summarized in Tables 1 and 2.

Table 1

Color pH solubility in ethanol 1%

1 Neozapon® Black X55 5.9 ++

2 Neozapon® Black X51 4.5 ++

3 Neozapon® Red 335 5.9 ++

4 Neozapon® Yellow 141 7.5 ++

5 Neozapon® Red 471 5.4 ++

6 Neozapon® Blue 807 6.7 ++

7 Neozapon® Orange 251 5.8 ++

8 Basonyl® Green 830 liquid 4.9 ++

9 Basonyl® Blue 644 liquid 5.4 ++

10 Basonyl® Red 545 liquid 5.1 ++

1 1 Basonyl® Red 555 liquid 2.6 ++ 12 Basonyl® Green 830 liquid 4.3 ++

13 Basonyl® Blue 636 4.3 ++

14 Basantol® Yellow 099 liquid 6.7 ++

15 Basantol® Black X82 liquid 6.2 ++

16 Neptune Yellow 075 7.5 +

17 Heliogen® Blue L 6930 6.5 + - sediment

18 Basacid® Orange 282 liquid 3,5 +

19 Basacid® Yellow 093 liquid 4,5 + - sediment

20 Isopur SU 12021/91 1

21 Reactint Yellow X15

Comparison measurement pure

Ethanol 4,5

Table 2

Solubility in coloring potential of triacetin 5% E-TPU particles

Color 1 d 5min 30min

1 Neozapon® Black X55 ++ ++ ++

2 Neozapon® Black X51 - + - + -

3 Neozapon® Red 335 + - + ++

4 Neozapon® Yellow 141 - - -

5 Neozapon® Red 471 + - -

6 Neozapon® Blue 807 - - -

7 Neozapon® Orange 251 + - + ++

8 Basonyl® Green 830 liquid ++ + ++

9 Basonyl® Blue 644 liquid ++ ++ ++

10 Basonyl® Red 545 liquid ++ + ++

1 1 Basonyl® Red 555 liquid + - + ++

12 Basonyl® Green 830 liquid + + +

13 Basonyl® Blue 636 + - + ++

14 Basantol® Yellow 099 liquid - - -

15 Basantol® Black X82 liquid + - -

16 Neptune Yellow 075 - + +

17 Heliogen® Blue L 6930 - + - + -

18 Basacid® Orange 282 liquid - + +

19 Basacid® Yellow 093 liquid - - -

20 Isopur SU 12021/91 1 + - - -

21 Reactint Yellow X15 ++ - - Rating Scale:

+++ = very good; + - = medium, - = very bad

2. Experimental procedure

2.1 Preparation of Impregnation Blends

60 g of the dyes (1 -21) are initially introduced into a roll glass, after the addition of 200 g of glycerol triacetate (triacetin) is added. After the glasses are tight

they were locked on a roller belt overnight

Room temperature moved. The resulting 30% solutions or dispersions of the colorants were then diluted depending on the desired color intensity with more triacetin.

2.2 Impregnation of Particle Foams

(a) laboratory scale

10g each of the E-TPU1 -5 were weighed into a tumbler. After the addition of 0.1 g of the color solutions 1 -21, the roll glass was tightly closed and moved on a roll band for 5 or 30 minutes respectively.

The color intensity and colorability were evaluated.

(b) Pilot scale

Each 12 kg of E-TPU were weighed into a 2001 lidded cask. After adding the dye solutions, the lidded barrel was tightly closed and mounted on a Rhönradmischer. After 8 hours of movement, the barrel was removed from the mixer and opened. The colored particles were removed from the container, the colors were firmly fixed on the surface or penetrated into the particles.

2.3 Production of particle foam boards

The dyed foam particles were then welded on a molding machine from Kurtz ersa GmbH (Boost Foamer) to square plates with a side length of 200 mm and a thickness of 10 mm thickness by application of water vapor. The welding parameters of the different materials were chosen so that the plate side of the final molding, which was facing the movable side (MI I) of the tool, collapsed as few as possible ETPU particles. If necessary, the Spaltbedampfung was carried out by the movable side of the tool. Regardless of the experiment, a cooling time of 100 s was always set at the end for a 10 mm thick plate of the fixed (MI) and the movable side of the tool. The respective ones

Steaming conditions depend on the particle foam used, in

Table 3 lists the vapor pressures.

Table 3: Steam pressures and times for welding the materials

The weld quality of the panels can be determined by means of various test methods. The results are summarized in Table 4. Table 4: Results of various test methods on a 10 mm plate

The particle foam E-TPU5 was processed by means of microwave radiation to a mold plate.

Forty-five parts by weight of the colored E-TPU5 foam particles were placed in a vessel together with 2.4 parts by weight of glycerol triacetate. By shaking the vessel the E-TPU foam particles were completely within 60 seconds

Wets glycerol triacetate.

47.4 grams of wetted and still loose individual particles were in a

Microwaveable mold with the dimensions 200mm x 200mm x 10mm filled. A height-adjustable lid exerted light pressure on the particles. This filled shape was slanted at a 30 ° angle on the outer edge of the

Lab microwave oven turntable placed and irradiated for 40 seconds with a power of 400 watts, the mold was rotated by 180 ° in the vertical axis and irradiated for 400 seconds with 400 W, then the mold was rotated by another 90 ° in the vertical axis and now horizontally another 40 Seconds irradiated with 400W. The mold was removed from the microwave and placed in a water bath

Room temperature cooled. Subsequently, a welded together could

Foam sheet are removed.

Gluing of colored E-TPU particles

60 g of foam particles with Farbstoff7 colored E-TPU 1 with a density of 1 10 g / l were mixed with 9 wt .-% of adhesive intensively in a plastic cup 20s and glued in a metal mold to a foam molding of a thickness of 10mm. The resulting plate was intensely orange in color.

exams

Compressive hardness based on DIN EN ISO 3386

Rebound resilience DIN 53512

Quoted literature

Ullmanns "Encyklopadie der technischen Chemie", 4th Edition, Volume 20, pp. 416-418 WO 94/20568 A1

WO 2007/082838 A1

WO 2008/087078 A1

WO 2015/165724 A1

Polymer Chemistry, Interscience Publ., New York, 1961, p.1 1 1-127

Journal of Polymer Science, Part AI, 4, pages 1851-1859 (1966))

WO 2017/030835 A1

WO 2013/153190 A1

WO 2010/010010 A1

Saechtling (ed.), Plastic paperback, 27th edition, Hanser-Verlag Munich 1998, chap. 3.2.1 and 3.2.4

WO 2014/150122 A1

WO 2014/150124 A1

EP 1979401 B1

US 2015/0337102

EP 2872309 B1

EP 3053732 A

WO 2016/146537 A1

Claims

claims

1. A process for the preparation of colored foamed particles consisting of an elastomer (E), comprising at least the steps

(i) providing foamed particles of at least one elastomer (E),

(ii) contacting the particles with a mixture (M) containing a dye (F) and a carrier liquid (TF) to give colored foamed particles, the carrier liquid (TF) having a polarity suitable for sorption of the particles Carrier liquid in the elastomer (E) takes place.

2. The method according to claim 1, wherein the mixture (M) is a solution, emulsion or a dispersion.

3. The method according to any one of claims 1 or 2, wherein the carrier liquid (TF) has a boiling point in the range of 80 ° C to 300 ° C.

4. The method according to any one of claims 1 to 3, wherein the carrier liquid (TF) has an ET (30) value of greater than or equal to 150 kJ / mol.

5. The method according to any one of claims 1 to 4, wherein the carrier liquid (TF)

6. The method according to any one of claims 1 to 5, wherein the dye (F) is selected from the group consisting of liquid dyes and solid pigments.

7. The method according to any one of claims 1 to 6, wherein the elastomer (E) a

thermoplastic block copolymer.

8. The method according to any one of claims 1 to 7, wherein the elastomer (E) is selected from the group consisting of thermoplastic polyurethanes, polyether esters,

Polyester esters and polyetheramides.

9. Colored foamed particles obtained or obtainable by a process comprising at least the steps

(i) providing foamed particles of at least one elastomer (E), (ii) contacting the particles with a mixture (M) containing a dye (F) and a carrier liquid (TF) to obtain colored foamed particles, wherein the carrier liquid (TF) has a polarity suitable that

Sorption of the carrier liquid in the elastomer (E) takes place.

10. Particles according to claim 9, wherein the elastomer (E) is selected from the group consisting of thermoplastic polyurethanes, polyether esters, polyester esters and polyetheramides.

1 1. Colored foamed particles, obtained or obtainable by a process according to one of claims 1 to 8.

12. Use of foamed particles according to any one of claims 9 to 1 1 or of foamed particles obtainable by a process according to any one of claims 1 to 8 for the preparation of a shaped body.

13. Use according to claim 12, wherein the preparation of the molding by means of

Welding or bonding of the particles takes place together.

14. Use according to claim 12 or 13, wherein the molded body is a shoe sole, a part of a shoe sole, a bicycle saddle, a padding, a mattress, pad, handle, protective film, a component in the automotive interior and exterior area.

15. Use of foamed particles according to one of claims 9 to 11 or of foamed particles obtainable by a process according to one of claims 1 to 8 in balls and sports equipment or as floor covering and wall cladding,

especially for sports surfaces, track athletics, sports halls, children's playgrounds and sidewalks.