METHOD FOR DYEING ELASTOMER PARTICLE FOAMS

Abstract

The present invention relates to a process for producing colored foamed particles consisting of an elastomer (E), at least comprising the providing of foamed particles made of at least one elastomer (E), and the contacting of the particles with a mixture (MF) comprising a dye (F) and a carrier fluid (TF) to obtain colored foamed particles, wherein the carrier fluid (TF) has a polarity suitable for sorption of the carrier fluid into the elastomer. The present invention further relates to cpspolored foamed particles obtained or obtainable by such a process, and to the use of the colored foamed particles of the invention for production of shaped bodies, especially of footwear soles, parts of a footwear sole, bicycle saddles, cushions, mattresses, underlays, handles, protective films, floor coverings, and components in the automotive interior and exterior sector.

Claims

1-15. (canceled)

16. A process for producing colored foamed particles consisting of an elastomer (E), the process comprising: (i) providing foamed particles made of at least one elastomer (E), (ii) contacting the particles with a mixture (M) comprising a dye (F) and a carrier fluid (TF) to obtain colored foamed particles, wherein the carrier fluid (TF) has a polarity suitable for sorption of the carrier fluid into the elastomer (E), and the carrier fluid (TF) has an E.sub.T(30) value of not less than 150 kJ/mol.

17. The process according to claim 16, wherein the mixture (M) is a solution, emulsion or dispersion.

18. The process according to claim 16, wherein the carrier fluid (TF) has a boiling point in the range from 80 C. to 300 C.

19. The process according to claim 16, wherein the carrier fluid (TF) is selected from the group consisting of glycols and of esters of citric acid and glycerol esters.

20. The process according to claim 16, wherein the dye (F) is selected from the group consisting of liquid dyes and solid pigments.

21. The process according to claim 16, wherein the elastomer (E) is a thermoplastic block copolymer.

22. The process according to claim 16, wherein the elastomer (E) is selected from the group consisting of thermoplastic polyurethanes, polyetheresters, polyesteresters and polyetheramides

23. Colored foamed particles obtained by a process comprising: (i) providing foamed particles made of at least one elastomer (E), (ii) contacting the particles with a mixture (M) comprising a dye (F) and a carrier fluid (TF) to obtain colored foamed particles, wherein the carrier fluid (TF) has a polarity suitable for sorption of the carrier fluid into the elastomer (E), and the carrier fluid (TF) has an E.sub.T(30) value of not less than 150 kJ/mol.

24. The particles according to claim 23, wherein the elastomer (E) is selected from the group consisting of thermoplastic polyurethanes, polyetheresters, polyesteresters and polyetheramides.

25. Colored foamed particles obtained by the process according to claim 16.

26. A process for producing a shaped body, comprising employing the foamed particles according to claim 23.

27. The process according to claim 26, wherein the shaped body is produced by fusion or bonding of the particles to one another.

28. The process according to claim 26, wherein the shaped body is a footwear sole, part of a footwear sole, a bicycle saddle, a cushion, a mattress, underlay, handle, protective film, or a component in the automotive interior and exterior sector.

29. A process, comprising employing the foamed particles according to claim 23 in balls and sports equipment or as floor covering and wall paneling.

Description

EXAMPLES

[0242] 1. Feedstocks: [0243] 1.1 E-TPU1: [0244] (Infinergy 32-100 U10) expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming pelletized TPU1 under pressure and at high temperature, particle weight 32 mg, bulk densities 110 g/L. [0245] 1.2 E-TPU2: [0246] (Infinergy X1125-130U000) expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming pelletized TPU1 under pressure and at high temperature, particle weight 25 mg, bulk densities 130 g/L. [0247] 1.3 E-TPU3: [0248] expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming pelletized TPU2 under pressure and at high temperature, particle weight 32 mg, bulk densities 90 g/L. [0249] 1.4 E-TPU4: [0250] expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming pelletized TPU1 under pressure and at high temperature, particle weight 5 mg, bulk densities 110 g/L. [0251] 1.5 E-TPU5: [0252] expanded, partly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming pelletized TPU3 under pressure and at high temperature, particle weight 32 mg, bulk densities 90 g/L. [0253] 1.6 TPU1: [0254] thermoplastic polyether polyurethane having a Shore hardness of 80 A based on PTHF1000, butane-1,4-diol, 4,4-MDI [0255] 1.7 TPU2: [0256] thermoplastic polyether polyurethane having a Shore hardness of 70 A based on PTHF1000, butane-1,4-diol, 4,4-MDI [0257] 1.8 TPU3: [0258] thermoplastic polyether polyurethane having a Shore hardness of 96 A based on PTHF1000, bisphenol A-started polyether polyol, butane-1,4-diol, 4,4-MDI [0259] 1.9 Adhesive 1: [0260] Elastopave 6550/101 from BASF Polyurethanes GmbH, compact, 2-component polyurethane system. [0261] 1.10 Dyes: [0262] Usable dyes are in principle all available colorants. Soluble or liquid dyes penetrate into the particles and color them throughout; insoluble dyes such as pigments are fixed on the surface. [0263] For identification, the dyes were first dissolved in a 1% solution in ethanol and the change in pH was determined. The dyes used are summarized in tables 1 and 2.

TABLE-US-00001 TABLE 1 Solubility in 1% Color pH solution in ethanol 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 ++ 11 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 Neptun 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 12021/911 21 Reaktint Yellow X15 Comparative measurement for 4.5 pure ethanol

TABLE-US-00002 TABLE 2 Solubility in 5% solution in Coloring potential triacetin of E-TPU particles Color 1 d 5 min 30 min 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 ++ + ++ 11 Basonyl Red 555 liquid + + ++ 12 Basonyl Green 830 liquid + + + 13 Basonyl Blue 636 + + ++ 14 Basantol Yellow 099 liquid 15 Basantol Black X82 liquid + 16 Neptun Yellow 075 + + 17 Heliogen Blue L 6930 + + 18 Basacid Orange 282 liquid + + 19 Basacid Yellow 093 liquid 20 Isopur SU 12021/911 + 21 Reaktint Yellow X15 ++

[0264] Assessment scale:

[0265] +++=very good; +=average; =very poor

[0266] 2. Experimental Procedure [0267] 2.1 Production of the impregnation mixtures [0268] A roller bottle is initially charged in each case with 60 g of the dyes (1-21), after the addition of 200 g of glycerol triacetate (triacetin). Once the bottles had been sealed tight, they were agitated on a roller belt at room temperature overnight. The 30% solutions or dispersions of the colorants obtained were then diluted with further triacetin according to the desired color intensity. [0269] 2.2 Impregnation of the particle foams [0270] (a) Laboratory scale [0271] 10 g of the E-TPU1-5 in each case were weighed into a roller bottle. After addition of 0.1 g of the color solutions 1-21, the roller bottle was firmly closed and agitated on a roller belt for 5 or 30 min in each case. [0272] Color intensity and colorability were assessed. [0273] (b) Pilot plant scale [0274] 12 kg of the E-TPU in each case were weighed into a 200 L lidded drum. After the color solutions had been added, the lidded drum was firmly closed and secured in a drum-hoop mixer. After agitation for 8 hours, the drum was removed from the mixer and opened. The colored particles were removed from the vessel; the colors were fixed firmly on the surface or had penetrated into the particles. [0275] 2.3 Production of particle foam slabs [0276] The colored foam particles were then fused in a molding machine from Kurtz ersa GmbH (Boost Foamer) to give square slabs having a side length of 200 mm and a thickness of 10 mm thickness by contacting with water vapor. The fusion parameters of the different materials were chosen such that the slab side of the final shaped article that faced the movable side (MII) of the mold had a minimum number of collapsed ETPU particles. Gap steaming was optionally also effected through the moving side of the mold. Regardless of the experiment, a cooling time of 100 s for a slab of thickness 10 mm from the fixed side (MI) and the moving side of the mold was always established at the end. The respective steaming conditions are dependent on the particle foam used; table 3 lists the vapor pressures.

TABLE-US-00003 TABLE 3 Gauge vapor pressures and times for fusion of the materials Gap Gap Gap Gap steaming steaming steaming steaming MI MI MII MII [bar] [s] [bar] [s] E-TPU1 1.8 10 1.8 10 E-TPU2 1.8 18 1.8 18 E-TPU3 1.4 10 1.5 10 E-TPU4 1.5 10 1.5 10 [0277] The quality of fusion of the slabs can be determined with the aid of various test methods. The results are summarized in Table 4.

TABLE-US-00004 TABLE 4 Results for various test methods on 10 mm slab 10% 50% Elongation Density of indentation indentation Tensile under the slab hardness hardness strength tensile Resilience E-TPU Color (g/cm.sup.3) (kPa) (kPa) (MPa) stress (%) (%) E-TPU1 1 0.253 78 365 1.17 150 70 E-TPU2 3 0.280 25 250 1.97 200 65 E-TPU3 8 0.204 15 195 1.11 215 68 E-TPU4 9 0.270 35 280 1.65 220 66 E-TPU1 12 0.250 76 360 1.20 160 70 E-TPU2 7 0.209 40 290 0.80 85 65 E-TPU2 3 0.210 40 295 0.80 80 65 E-TPU2 none 0.206 39 290 0.75 85 65 comparison [0278] Particle foam E-TPU5 was processed to give a molded slab by means of microwave radiation. [0279] 45 parts by weight of the colored E-TPU5 foam particles were introduced into a vessel together with 2.4 parts by weight of glycerol triacetate. By agitating the vessel, the E-TPU foam particles had been completely wetted with glycerol triacetate within 60 seconds. [0280] 47.4 grams of the wetted and still-loose individual particles were introduced into a microwaveable mold of dimensions 200 mm x 200 mm x 10 mm. Gentle pressure was exerted on the particles by means of a height-adjustable lid. This filled mold was positioned at a 30 angle on the outer edge of the laboratory microwave turntable and irradiated with a power of 400 watts for 40 seconds, the mold was rotated by 180 in the vertical axis and irradiated at 400 W for a further 40 seconds, then the mold was rotated by a further 90 in the vertical axis and then irradiated horizontally at 400 W for a further 40 seconds. The mold was removed from the microwave and cooled down to room temperature in a water bath. It was then possible to remove a fused slab of foam. [0281] 2.4 Bonding of colored E-TPU particles 60 g of foam particles of E-TPU1 colored with dye 7 and having a density of 110 g/L were mixed vigorously with 9% by weight of adhesive 1 in a plastic cup for 20 s and bonded in a metal mold to give a shaped foam body of thickness 10 mm. The slab obtained was intensely orange in color.

[0282] 3. Tests [0283] Indentation hardness in accordance with DIN EN ISO 3386 [0284] Resilience DIN 53512

LITERATURE CITED

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