Polyamide molding compositions with improved optical properties and use of colorants therein

Abstract

Disclosed is a method of reducing a haze value in molding compositions including use of colorants selected from anthraquinone colorants, benzimidazolone colorants and perinone colorants. The molding compositions include at least one polyamide and at least one compound of the general formula (I) ##STR00001##
where x is 1, 2 or 3; R1 and R2 are mutually independently selected from hydrogen, linear C1-C7-alkyl, branched C3-C10-alkyl, unsubstituted or substituted C3-C12-cycloalkyl, unsubstituted or substituted C3-C12-cycloalkyl-C1-C4-alkyl, unsubstituted or substituted aryl and unsubstituted or substituted aryl-C1-C4-alkyl; and Z is selected from C3-C10-alkanediyl, unsubstituted or substituted arylene, unsubstituted or substituted arylene-C1-C4-alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted heteroarylene-C1-C4-alkylene-heteroarylene, unsubstituted or substituted C5-C8-cyclo-alkylene, unsubstituted or substituted C5-C8-cycloalkylene-C1-C4-alkylene-C5-C8-cycloalkylene, unsubstituted or substituted heterocycloalkylene and unsubstituted or substituted heterocycloalkylene-C1-C4-alkylene-heterocycloalkylene.

Claims

1. A method of reducing a haze value, the method comprising: using colorants selected from anthraquinone colorants, benzimidazolone colorants and perinone colorants, in molding compositions comprising at least one polyamide and at least one compound of the general formula (I) ##STR00013## wherein x is 1, 2 or 3; R.sup.1 and R.sup.2 are mutually independently selected from hydrogen, linear C.sub.1-C.sub.7-alkyl, branched C.sub.3-C.sub.10-alkyl, unsubstituted or substituted C.sub.3-C.sub.12-cycloalkyl, unsubstituted or substituted C.sub.3-C.sub.12-cycloalkyl-C.sub.1-C.sub.4-alkyl, unsubstituted or substituted aryl and unsubstituted or substituted aryl-C.sub.1-C.sub.4-alkyl, and Z is selected from C.sub.3-C.sub.10-alkanediyl, unsubstituted or substituted arylene, unsubstituted or substituted arylene-C.sub.1-C.sub.4-alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted heteroarylene-C.sub.1-C.sub.4-alkylene-heteroarylene, unsubstituted or substituted C.sub.5-C.sub.8-cyclo-alkylene, unsubstituted or substituted C.sub.5-C.sub.8-cycloalkylene-C.sub.1-C.sub.4-alkylene-C.sub.5-C.sub.8-cyclo-alkylene, unsubstituted or substituted heterocycloalkylene and unsubstituted or substituted heterocycloalkylene-C.sub.1-C.sub.4-alkylene-heterocycloalkylene; wherein the haze value is reduced by at least 10%, determined by ASTM D1003 with a layer thickness of 1.27 mm in comparison with a reference polyamide composition without the colorants.

2. The method according to claim 1, wherein the quantity used of the colorants is from 10 to 1000 ppm, based on the entire molding composition.

3. The method according to claim 1, wherein the ratio by weight in which the colorants are used in relation to the at least one compound of the general formula (I) is in the range from 1:1 to 1:1000.

4. The method according to claim 1, characterized in that the colorants are dyes, pigments or mixtures of these.

5. The method according to claim 1, wherein the colorant is a benzimidazolone colorant.

6. A molding composition comprising: as component A, at least one polyamide; as component B, from 0.1 to 2% by weight of at least one compound of the general formula (I), ##STR00014## where x is 1, 2 or 3; R.sup.1 and R.sup.2 are mutually independently selected from hydrogen, linear C.sub.1-C.sub.7-alkyl, branched C.sub.3-C.sub.10-alkyl, unsubstituted or substituted C.sub.3-C.sub.12-cycloalkyl, unsubstituted or substituted C.sub.3-C.sub.12-cycloalkyl-C.sub.1-C.sub.4-alkyl, unsubstituted or substituted aryl and unsubstituted or substituted aryl-C.sub.1-C.sub.4-alkyl, and Z is selected from C.sub.3-C.sub.10-alkanediyl, unsubstituted or substituted arylene, unsubstituted or substituted arylene-C.sub.1-C.sub.4-alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted heteroarylene-C.sub.1-C.sub.4-alkylene-heteroarylene, unsubstituted or substituted C.sub.5-C.sub.8-cyclo-alkylene, unsubstituted or substituted C.sub.5-C.sub.8-cycloalkylene-C.sub.1-C.sub.4-alkylene-C.sub.5-C.sub.8-cyclo-alkylene, unsubstituted or substituted heterocycloalkylene and unsubstituted or substituted heterocycloalkylene-C.sub.1-C.sub.4-alkylene-heterocycloalkylene; and as component C, from 10 to 1000 ppm of at least one colorant selected from anthraquinone colorants, benzimidazolone colorants and perinone colorants and mixtures thereof, where the quantities are based on the entire molding composition.

7. The molding composition according to claim 6, which comprises at least 60% by weight of component A.

8. The molding composition according to claim 7, which comprises at least 80% by weight of component A.

9. The molding composition according to claim 8, which comprises at least 90% by weight of component A.

10. The molding composition according to claim 6, wherein the quantity of component B is from 0.2 to 1.7% by weight.

11. The molding composition according to claim 10, wherein the quantity of component B is from 0.5 to 1.5% by weight.

12. The molding composition according to claim 6, wherein the quantity of component C is from 20 to 500 ppm.

13. The molding composition according to claim 12, wherein the quantity of component C is from 50 to 200 ppm.

14. The molding composition according to claim 6, wherein the ratio by weight of component C to component B is from 1:1 to 1:1000.

15. The molding composition according to claim 14, wherein the ratio by weight of component C to component B is from 1:5 to 1:700.

16. The molding composition according to claim 15, wherein the ratio by weight of component C to component B is from 1:10 to 1:500.

17. The molding composition according to claim 6, wherein Z in the compound of the general formula (I) is trans-1,4-cyclohexylene.

18. The molding composition according to claim 17, wherein in the compound of the general formula (I) R.sup.1 and R.sup.2 are identical and are selected from hydrogen, tert-butyl, 1,1-dimethylpropyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and 1-adamantyl, Z is trans-1,4-cyclohexylene and x is 1.

19. The molding composition according to claim 6, wherein the colorant is a benzimidazolone colorant.

20. A process for the production of molding compositions according to claim 6, which comprises mixing, with one another, components A, B and C and optionally other ingredients.

21. A method of producing fibers, films, or moldings, the method comprising using the molding compositions according to claim 6.

22. A fiber, film or molding made of a molding composition according to claim 6.

Description

EXAMPLES

(1) The following components were used:

(2) Component A:

(3) Polyamide 6 (PA 6) with intrinsic viscosity IV 150 ml/g, measured on a 0.5% by weight solution in 96% by weight sulfuric acid at 25° C. in accordance with ISO 307. Ultramid® B27 from BASF SE was used.

(4) Component B:

(5) (4-Ureidocyclohexyl)urea

(6) The synthesis of component B is described in WO 2013/139802.

(7) Component C:

(8) TABLE-US-00001 Com- Pigment/Dye ponent Trade name Class index No. CAS No. Name C1 Macrolex Red 5B Anthraquinone Solvent Red 52 81-39-0 3-Methyl-6-[(4-methylphenyl)amino]-3H- dibenzo[f,ij]isoquinoline-2,7-dione C2 Oracet Blue 700 FA Anthraquinone Solvent Blue 132 110157-96-5 Precise structure not disclosed C3 Macrolex Green 5B Anthraquinone Solvent Green 3 128-80-3 1,4-Bis(4-methylanilino)anthracene-9,10-dione C4 PV-Echtorange 6RL Benzimidazolone Pigment Orange 68 42844-93-9 [1,3-Dihydro-5,6-bis[[(2-hydroxy-1-naphthyl) methylene]amino]-2H-benzimidazol-2- onato(2-)N5,N6,O5,O6]nickel C5 Macrolex Red E2G Perinone Solvent Red 179 89106-94-5 14H-Benzo[4,5]isoquino[2,1-a]perimidin-14-one CV1 Oracet YW 160 Monoazo, chromate Solvent Yellow 21 5601-29-6 Hydrogen bis[2-[(4,5-dihydro-3-methyl-5-oxo-1- complex phenyl-1H-pyrazol-4-yl)azo]benzoato]chromate CV2 Keyplast FL Yellow Perylene Solvent Green 5 79869-59-3 Isobutyl 5-(4-isobutoxycarbonyl-1-naphthyl)4- Green 7G methylnaphthalene-1-carboxylate CV3 Hostasol Yellow 3G Naphthalinnide Solvent Yellow 98 12671-74-8 1H-Thioxantheno[ 2,1,9-def]isoquinoline- (aminoketone) 27870-92-4 1,3(2H)dione, 2-octadecyl- CV4 Hostasol Red GG Benzanthrone Solvent Orange 63 16294-75-0 14H-Anthra[2,1,9-mna]thioxanthen-14-one

(9) Structural Formulae:

(10) TABLE-US-00002 B C1 C2 Precise structure not disclosed C3 C4 C5 CV1 CV2 0 CV3 CV4

(11) Processing:

(12) Production of PA 6 Composition (AB)

(13) 99.0% by weight of Ultramid B27 were compounded under nitrogen with 1.0% by weight of compound B in a conical twin-screw extruder (DSM Xplore, 15cc). In order to obtain a reference sample, the pure polyamide, i.e. with no addition of component B, was processed in the same manner. The following parameters were used:

(14) residence time: 3 min

(15) barrel temperature: 260° C.

(16) melt temperature: 240° C. to 245° C.

(17) rotation rate: 100 rpm

(18) Masterbatch Production by Compounding (MB1-MB9):

(19) In order to achieve better dispersion of the dyes in the polymer, first a masterbatch of each colorant (components C1-C5 and CV1-CV4) was produced in Ultramid B27, the concentration of dye being 2.94% by weight. For this, the polyamide pellets were compounded under nitrogen with the colorant in a conical twin-screw extruder (DSM Xplore, 15cc). In order to obtain a reference sample, the pure polyamide, i.e. with no addition of component C, was processed in the same manner. The following parameters were used:

(20) residence time: 3 min

(21) barrel temperature: 260° C.

(22) melt temperature: 240° C. to 245° C.

(23) rotation rate: 100 rpm

(24) Production of Experimental Examples:

(25) The experimental examples were produced by compounding the polyamide pellets or the polyamide composition AB under nitrogen with the respective color masterbatches (MB1-MB9) in a conical twin-screw extruder (DSM Xplore, 15cc). In order to obtain a reference sample, the pure polyamide, i.e. without additions, was processed in the same manner. The following parameters were used:

(26) residence time: 3 min

(27) barrel temperature: 260° C.

(28) melt temperature: 240° C. to 245° C.

(29) rotation rate: 100 rpm

(30) Processing by Injection Molding:

(31) The compounded polymers were processed by injection molding in a 10 cc DSM micro-injection-molding apparatus. For this, the molten compounded material was charged directly under nitrogen into the cylinder of the injection-molding machine. The melt was then injected into a polished rectangular mold measuring (30 mm×30 mm×1.27 mm). The following parameters were used:

(32) mold: polished plaque: 30 mm×30 mm×1.27 mm

(33) mold temperature: 60° C.

(34) cylinder temperature: 260° C.

(35) injection pressure: 10 to 12 bar

(36) Test Methods:

(37) Optical Properties: Haze and Transmittance

(38) Haze and transmittance were measured at room temperature by using a haze-gard plus tester (BYK, Gardner®, illumination CIE-E). The measurement was made in accordance with ASTM D1003 in the version valid in 2017. The haze values were measured 24-48 h after injection molding.

(39) Formulations for Masterbatch Production

(40) TABLE-US-00003 A B C1 C2 C3 C4 C5 CV1 CV2 CV3 CV4 (% by (% by (% by (% by (% by (% by (% by (% by (% by (% by (% by Example wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) MB1 97.06 — 2.94 — — — — — — — — MB2 97.06 — — 2.94 — — — — — — — MB3 97.06 — — — 2.94 — — — — — — MB4 97.06 — — — — 2.94 — — — — — MB5 97.06 — — — — — 2.94 — — — — MB6 97.06 — — — — — — 2.94 — — — MB7 97.06 — — — — — — — 2.94 — — MB8 97.06 — — — — — — — — 2.94 — MB9 97.06 — — — — — — — — — 2.94

(41) Formulations for Production of Compounded Materials

(42) TABLE-US-00004 A AB MB1 MB2 MB3 MB4 MB5 MB6 MB7 MB8 MB9 (% by (% by (% by (% by (% by (% by (% by (% by (% by (% by (% by Example wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) wt.) V1 100 V2 99.74 0.26 V3 99.48 0.52 V4 99.74 0.26 V5 99.48 0.52 V6 99.74 0.26 V7 99.48 0.52 V8 99.74 0.26 V9 99.48 0.52 V10 99.74 0.26 V11 99.48 0.52 V12 99.74 0.26 V13 99.48 0.52 V14 99.74 0.26 V15 99.48 0.52 V16 99.74 0.26 V17 99.48 0.52 V18 99.74 0.26 V19 99.48 0.52 V20 100 1 99.74 0.26 2 99.48 0.52 3 99.74 0.26 4 99.48 0.52 5 99.74 0.26 6 99.48 0.52 7 99.74 0.26 8 99.48 0.52 9 99.74 0.26 10 99.48 0.52 V21 99.74 0.26 V22 99.48 0.52 V23 99.74 0.26 V24 99.48 0.52 V25 99.74 0.26 V26 99.48 0.52 V27 99.74 0.26 V28 99.48 0.52

(43) Results:

(44) Composition of Experimental Examples:

(45) TABLE-US-00005 Haze Transmittance Plaque, wall Haze A B Dye thickness change [% by [% by concentration 1.27 mm relative to Example wt.] wt.] Colorant [ppm] [%] [%] reference V1 100 — none 100 78 Reference V2 100 — C1 69 97.5 39.8  −2.5% V3 100 — C1 156 96.7 26.7  −3.3% V4 100 — C2 69 92 40  −8.0% V5 100 — C2 156 87 26 −13.0% V6 100 — C3 69 92 35  −8.0% V7 100 — C3 156 88 21 −12.0% V8 100 — C4 69 96.6 58.7  −3.4% V9 100 — C4 156 96.6 47.2  −3.4% V10 100 — C5 69 96 43  −4.0% V11 100 — C5 156 93 30  −7.0% V12 100 — CV1 69 94 60  −6.0% V13 100 — CV1 156 93 54  −7.0% V14 100 — CV2 69 96.5 82.7  −3.5% V15 100 — CV2 156 97.2 82.3  −2.8% V16 100 — CV3 69 97.3 82.8  −2.7% V17 100 — CV3 156 97 81.5  −3.0% V18 100 — CV4 69 99.6 45.1  −0.4% V19 100 — CV4 156 98.1 35.1  −1.9% V20 99 1 none 21.9 77.7 Reference 1 99 1 C1 69 15.4 41.7 −29.7% 2 99 1 C1 156 13.8 24.7 −37.0% 3 99 1 C2 69 17.2 55.8 −21.5% 4 99 1 C2 156 12.6 40.7 −42.5% 5 99 1 C3 69 13.7 49.5 −37.4% 6 99 1 C3 156 12 33.7 −45.2% 7 99 1 C4 69 16.8 53.6 −23.3% 8 99 1 C4 156 15.9 42 −27.4% 9 99 1 C5 69 16 56.3 −26.9% 10 99 1 C5 156 9.8 43 −55.3% V21 99 1 CV1 69 17.6 66.8 −19.6% V22 99 1 CV1 156 19.7 71.3 −10.0% V23 99 1 CV2 69 27.5 77.3   25.6% V24 99 1 CV2 156 28.7 76.9   31.1% V25 99 1 CV3 69 27.2 76.1   24.2% V26 99 1 CV3 156 31.1 74.4   42.0% V27 99 1 CV4 69 24.3 45.5   11.0% V28 99 1 CV4 156 27.9 32.3   27.4%

(46) Inventive examples 1 to 10: addition of component C to the polyamide composition AB leads to a relative haze decrease of at least 20% at 69 ppm and at least 25% at 156 ppm content of component C. Non-inventive examples are polyamide compositions made of component A and component C (without component B), and also polyamide compositions made of components A and CV, and also A, B and CV. The relative haze decrease in each of these is less than 20% at 69 ppm of component C or CV and less than 25% at 156 ppm of component C or CV.

(47) As is apparent from the inventive examples and the comparative examples, anthraquinone colorants, benzimidazolone colorants and perinone colorants are suitable for improving the optical properties of the molding compositions. Other colorants, for example chromate complexes, perylene dyes, naphthalimide dyes or benzanthrone dyes, led to no, or to inadequate, improvement of optical properties.