EP3700969A1 - Procédé pour colorer des mousses particulaires d'élastomère - Google Patents

Procédé pour colorer des mousses particulaires d'élastomère

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Publication number
EP3700969A1
EP3700969A1 EP18789179.1A EP18789179A EP3700969A1 EP 3700969 A1 EP3700969 A1 EP 3700969A1 EP 18789179 A EP18789179 A EP 18789179A EP 3700969 A1 EP3700969 A1 EP 3700969A1
Authority
EP
European Patent Office
Prior art keywords
particles
elastomer
foamed particles
carrier liquid
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP18789179.1A
Other languages
German (de)
English (en)
Inventor
Frank Prissok
Michael Harms
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3700969A1 publication Critical patent/EP3700969A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/236—Forming foamed products using binding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • 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
  • 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.
  • 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
  • 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.
  • TPU foams or foam particles based on thermoplastic polyurethane 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.
  • 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.
  • 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.
  • non-spherical, e.g. elongated or cylindrical particle foam is meant by diameter the longest dimension.
  • the prior art also discloses the production of foamed particles from mass-colored TPU.
  • 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.
  • 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.
  • 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.
  • this object is achieved by a process for the preparation of colored foamed particles consisting of an elastomer (E), at least comprising the
  • the process according to the invention comprises the steps (i) and (ii).
  • step (i) foamed particles of at least one elastomer (E) are provided.
  • 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.
  • M mixture
  • F dye
  • TF carrier liquid
  • Mixture (M) are brought into contact, that the dye contained in the mixture (M) can be absorbed by the particles.
  • the mixture (M) can be used in the form of a solution, an emulsion or a dispersion.
  • the present invention therefore relates to a method as described above, wherein the mixture (M) is a solution, emulsion or dispersion.
  • 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.
  • the carrier liquid is liquid at room temperature.
  • 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.
  • 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.
  • 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
  • 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.
  • the present invention therefore relates to a method as described above, wherein the carrier liquid (TF) has a ⁇ (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,
  • glycols polypropylene glycols.
  • glycols and esters are suitable.
  • 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.
  • 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.
  • the carrier liquid is selected from the group consisting of glycols and esters of citric acid and glycerol esters.
  • the carrier liquid is suitable as a carrier liquid, for example
  • Triacetin a glycerol ester
  • Carrier liquids are used.
  • 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%.
  • 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.
  • Foamed particles vary widely.
  • 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.
  • 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.
  • 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.
  • the process is preferably conducted such that the dye used penetrates into the foamed particles and remains close to the surface in the particles.
  • the dyes may have a penetration of greater than ⁇ ⁇ , especially greater than ⁇ ⁇ , especially greater than 500 ⁇ .
  • the dye in the particle 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
  • the particles are brought into contact with the mixture (M) and, for example, stirred.
  • 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.
  • 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.
  • the carrier liquid can fix the dye on the surface of the foamed particles.
  • Carrier liquid entrains the dye in the foam particles and both components remain in the foam particles.
  • 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.
  • the mixture (M) contains at least one dye.
  • the mixture (M) contains at least one dye.
  • 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 the dye in the mixture (M) can vary widely.
  • the amount used or concentration of the dye in the mixture (M) can vary widely.
  • Dye can be adjusted to adjust the color intensity of the colored particles.
  • 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).
  • 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,
  • 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.
  • foamed particles which consist of at least one
  • Elastomer (E) exist.
  • the particles can be open-celled or
  • the closed cell density of the foam is greater than 60%, determined according to DIN ISO 4590: 2016.
  • 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.
  • thermoplastic elastomers are known per se to the person skilled in the art.
  • 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
  • thermoplastic polyurethanes polyether esters, polyester esters and polyether amides.
  • 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.
  • 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.
  • 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.
  • 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, Kunststoff 1973 and Journal of Polymer Science, Part A1, 4, pages 1851 -1859 (1966))
  • Suitable aromatic dicarboxylic acids include, for example, phthalic acid, iso and
  • 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
  • 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.
  • thermoplastic polyether amides can be used according to all known, literature
  • R organic radical (aliphatic and / or aromatic).
  • Classes of compounds can be used to provide the polyetheramine used according to the invention.
  • 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.
  • 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.
  • 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.
  • thermoplastic polyurethanes are usually used which are prepared by reacting a polyisocyanate composition with a
  • 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 DruckvorJumer 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.
  • the diameter of the particle foams is between 0.5 to 30;
  • elongated or cylindrical particle foam is meant by diameter the longest dimension.
  • the method may comprise further steps, for example
  • the present invention also relates to colored foamed particles obtained or obtainable by a process as described above.
  • the present invention relates to colored foamed particles obtained or obtainable by a process comprising at least the steps
  • the carrier liquid (TF) has a polarity which is suitable that a sorption of the carrier liquid takes place in the elastomer.
  • 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 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.
  • Another embodiment of the above-mentioned method comprises a further step: a. Providing the elastomer in the form of granules;
  • 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 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);
  • a suitable closed reaction vessel e.g., autoclave
  • 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.
  • 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.
  • 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.
  • the impregnation of the granules with a propellant under pressure comprises processes and subsequent expansion of the granules in steps (b) and (c):
  • 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.
  • blowing agents are also sterically more demanding compounds or functionalized hydrocarbons such as alcohols, ketones, esters, ethers and organic carbonates.
  • the elastomer is mixed in step (b) in an extruder while melting with the blowing agent under pressure, which is fed to the extruder.
  • propellant-containing mixture is under pressure, preferably with moderately controlled
  • Counter pressure e.g., underwater granulation
  • the melt strand foams and granules give the particle foams.
  • Suitable extruders are all conventional screw machines, in particular
  • Single screw and twin screw extruders e.g., ZSK type from Werner & Pfleiderer
  • co-kneaders e.g., ZSK type from Werner & Pfleiderer
  • Kombiplast machines e.g., MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roll extruders, e.g. in Saechtling (ed.), plastic paperback, 27.
  • 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.
  • the implementation can be carried out in an extruder or an arrangement of one or more extruders.
  • the implementation can be carried out in an extruder or an arrangement of one or more extruders.
  • the implementation can be carried out in a first 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
  • Particle foam produced by soaking the appropriate granules with a supercritical fluid is removed from the supercritical fluid followed by
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • Foam molding comprises the following steps:
  • step (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
  • energetic radiation microwaves or radio waves
  • 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.
  • the temperature for fusing the particle foam between 100 ° C and 180 ° C, preferably between 120 and 150 ° C.
  • 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
  • Hydrocarbons such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols
  • 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.
  • 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.
  • 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
  • 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.
  • 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
  • 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,
  • the invention further relates to the use of an inventive
  • the foams according to the invention can be easily recycled thermoplastically.
  • 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.
  • the present invention also provides such embodiments which result from the following references and combinations thereof.
  • Sorption of the carrier liquid takes place in the elastomer.
  • glycols and esters of citric acid and glycerol esters are selected from the group consisting of glycols and esters of citric acid and glycerol esters.
  • 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.
  • 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
  • thermoplastic polyurethanes is selected from the group consisting of thermoplastic polyurethanes, polyether esters, polyester esters and polyetheramides.
  • thermoplastic polyurethanes is selected from the group consisting of thermoplastic polyurethanes.
  • Sorption of the carrier liquid takes place in the elastomer.
  • thermoplastic polyurethanes polyether esters, polyester esters and polyetheramides.
  • 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®
  • 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.
  • Shoe sole a part of a shoe sole, a bicycle saddle, a padding, a mattress,
  • Wall cladding in particular for sports surfaces, athletic tracks, sports halls, children's playgrounds and sidewalks.
  • the carrier liquid is selected from the group consisting of glycols and esters of citric acid and glycerol esters,
  • 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.
  • carrier liquid is triacetin
  • 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.
  • the carrier liquid is selected from the group consisting of glycols and esters of citric acid and glycerol esters,
  • 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.
  • the carrier liquid is triacetin
  • 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.
  • thermoplastic polyurethanes wherein the elastomer is selected from the group consisting of thermoplastic polyurethanes,
  • the carrier liquid is selected from the group consisting of glycols and esters of citric acid and glycerol esters,
  • 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.
  • thermoplastic thermoplastic
  • carrier liquid is triacetin
  • 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.
  • thermoplastic polyurethanes wherein the elastomer is selected from the group consisting of thermoplastic polyurethanes,
  • the carrier liquid is selected from the group consisting of glycols and esters of citric acid and glycerol esters,
  • 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.
  • thermoplastic polyurethanes wherein the elastomer is selected from the group consisting of thermoplastic polyurethanes,
  • the carrier liquid is triacetin
  • 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.
  • Embodiments 15 to 28 or 41 comprising
  • step (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.
  • step (b) by means of steam, hot air or energy radiation takes place.
  • Shaped bodies obtainable or obtained according to a method according to one of
  • Thermoplastic polyurethane-based foam particles obtained by foaming granulated TPU 1 under pressure and high temperature,
  • Thermoplastic polyurethane-based foam particles obtained by foaming granulated TPU 1 under pressure and high temperature,
  • thermoplastic polyurethane obtained by foaming granulated TPU2 under pressure and high temperature, particle weight 32 mg, bulk density 90 g / l.
  • 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.
  • 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.
  • 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
  • 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 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
  • Table 3 lists the vapor pressures.
  • 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.
  • E-TPU5 foam particles 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
  • 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

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Abstract

La présente invention concerne un procédé pour la fabrication de particules moussées colorées, constituées par un élastomère (E), comprenant au moins la préparation de particules moussées en au moins un élastomère (E) et la mise en contact des particules avec un mélange (MF) contenant un colorant (F) et un liquide support (TF) avec obtention de particules moussées colorées, le liquide support (TF) présentant une polarité appropriée pour qu'une sorption du liquide support dans l'élastomère se produise. En outre, la présente invention concerne des particules moussées colorées, obtenues ou pouvant être obtenues selon un tel procédé ainsi que l'utilisation des particules moussées colorées selon l'invention pour la fabrication de corps façonnés, en particulier de semelles de chaussures, de parties d'une semelle de chaussures, de selles de vélo, de rembourrages, de matelas, de sous-couches, de poignées, de feuilles de protection, de revêtements de sol ainsi que de pièces pour l'intérieur et l'extérieur d'automobiles.
EP18789179.1A 2017-10-26 2018-10-25 Procédé pour colorer des mousses particulaires d'élastomère Withdrawn EP3700969A1 (fr)

Applications Claiming Priority (2)

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EP17198591 2017-10-26
PCT/EP2018/079293 WO2019081644A1 (fr) 2017-10-26 2018-10-25 Procédé pour colorer des mousses particulaires d'élastomère

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JP (1) JP2021500460A (fr)
KR (1) KR20200070377A (fr)
CN (1) CN111263787A (fr)
BR (1) BR112020006291A2 (fr)
CA (1) CA3080255A1 (fr)
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WO2022161995A1 (fr) 2021-01-29 2022-08-04 Basf Se Procédé de fabrication d'un materiau composite
WO2022161978A1 (fr) 2021-01-29 2022-08-04 Basf Se Construction d'un corps moulé pour pneus non pneumatiques
WO2022161994A1 (fr) 2021-01-29 2022-08-04 Basf Se Préparation pour corps moulé
WO2022161981A1 (fr) 2021-01-29 2022-08-04 Basf Se Matériau composite pour un corps moulé
WO2022248558A1 (fr) 2021-05-27 2022-12-01 Basf Se Matériau composite multicouche comprenant des granulés expansés
WO2023208987A1 (fr) 2022-04-27 2023-11-02 Basf Se Compactage local d'un matériau en mousse particulaire de e-tpu

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CN115702183A (zh) 2020-06-15 2023-02-14 巴斯夫欧洲公司 高机械性能、抗紫外线辐射良好和低起霜起雾的热塑性聚氨酯组合物

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WO2022161995A1 (fr) 2021-01-29 2022-08-04 Basf Se Procédé de fabrication d'un materiau composite
WO2022161978A1 (fr) 2021-01-29 2022-08-04 Basf Se Construction d'un corps moulé pour pneus non pneumatiques
WO2022161994A1 (fr) 2021-01-29 2022-08-04 Basf Se Préparation pour corps moulé
WO2022161981A1 (fr) 2021-01-29 2022-08-04 Basf Se Matériau composite pour un corps moulé
WO2022248558A1 (fr) 2021-05-27 2022-12-01 Basf Se Matériau composite multicouche comprenant des granulés expansés
WO2023208987A1 (fr) 2022-04-27 2023-11-02 Basf Se Compactage local d'un matériau en mousse particulaire de e-tpu

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RU2020117049A (ru) 2021-11-26
KR20200070377A (ko) 2020-06-17
CN111263787A (zh) 2020-06-09
JP2021500460A (ja) 2021-01-07
WO2019081644A1 (fr) 2019-05-02
RU2020117049A3 (fr) 2022-04-21
US20200270806A1 (en) 2020-08-27
BR112020006291A2 (pt) 2020-10-13
MX2020004316A (es) 2020-08-13
CA3080255A1 (fr) 2019-05-02

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