POLYMER COMPOSITION HAVING DELAYED CRYSTALLIZATION BEHAVIOR, ADDITIVE COMPOSITION THAT INFLUENCES THE CRYSTALLIZATION BEHAVIOR, METHOD FOR REDUCING THE CRYSTALLIZATION POINT AND/OR THE CRYSTALLIZATION SPEED, AND USE OF AN ADDITIVE COMPOSITION

Abstract

The invention relates to a polymer composition, which contains or consists of a matrix of at least one thermoplastic polymer capable of crystallization and, incorporated therein, at least one azine dye and at least mono-, di-, tri-, and/or tetravalent metal salt. Said polymer composition is characterized in that the crystallization point thereof is considerably reduced in comparison with polymer compositions having no additives or a composition containing only an azine dye or a metal salt as an additive. The invention further relates to a corresponding additive composition for the crystallization and/or for the lowering of the crystallization point of thermoplastic polymers or polymer compositions capable of crystallization.

Claims

1-20. (canceled)

21. A polymer composition, comprising or consisting of a) a matrix made of at least one crystallisable, thermoplastic polymer, b) at least one azine dye, and c) at least one mono-, bi-, tri- and/or tetravalent metal salt, selected from the group consisting of metal chlorides, metal bromides and metal pseudohalogenides, mixtures thereof, and combinations thereof.

22. The polymer composition according to claim 21, wherein the at least one azine dye is selected from the group consisting of phenazine dyes, oxazine dyes, thiazine dyes, and bisazine dyes.

23. The polymer composition according to claim 21, wherein the at least one azine dye is selected from the group consisting of nigrosines and indulines.

24. The polymer composition according to claim 21, wherein the at least one mono-, bi-, tri- and/or tetravalent metal salt is selected from the group consisting of alkali metal salts and alkaline earth metal salts.

25. The polymer composition according to claim 21, wherein the weight ratio of the at least one azine dye to the at least one mono-, bi-, tri- and/or tetravalent metal salt is from 1:99 to 99:1.

26. The polymer composition according to claim 25, wherein the at least one crystallisable, thermoplastic polymer of the polymer matrix is selected from the group consisting of a) polymers of olefins or diolefins, b) polyacetals, c) polyphenylene oxides and blends with polystyrene or polyamides, d) polyamides, e) polyimides, polyamide imides, polyetherimides, polyesterimides, poly(ether)ketones, polyarylsulphones, polyphenylensulphide, polybenzimidazoles, and polyhydantoins, f) polyesters made of aliphatic or aromatic dicarboxylic acids or diols or from hydroxycarboxylic acids, and g) mixtures, combinations or blends of two or more of the previously mentioned polymers, and blends with amorphous polymers.

27. The polymer composition according to claim 25, wherein the polymer matrix consists of a polymer selected from the group consisting of polyamides and polyesters.

28. The polymer composition according to claim 21, comprising or consisting of a) 99.98 to 80.00 parts by weight of a matrix made of at least one crystallisable, thermoplastic polymer, b) 0.01 to 10 parts by weight of at least one azine dye, and c) 0.01 to 10 parts by weight of at least one mono-, bi-, tri- and/or tetravalent metal salt, the parts by weight of components a) to c) adding up to 100 parts by weight.

29. The polymer composition according to claim 21, comprising or consisting of a) 99.98 to 80.00 parts by weight of a matrix made of at least one polyamide or polyester, b) 0.01 to 10 parts by weight of at least one nigrosine, and c) 0.01 to 10 parts by weight of at least one alkali- or alkaline earth metal halogenide or -pseudohalogenide, the parts by weight of components a) to c) adding up to 100 parts by weight.

30. The polymer composition according to claim 21, wherein, in addition to components a) to c), it comprises at least one additive selected from the group consisting of UV absorbers, light stabilisers, stabilisers, hydroxylamines, benzofuranones, metal deactivators, filler deactivators, nucleation agents, impact strength enhancers, flame retardants, plasticisers, lubricants, rheology modifiers, chain lengtheners, processing aids, pigments, colourants, optical brighteners, antimicrobial active substances, antistatic agents, slip agents, antiblocking agents, coupling means, dispersants, compatibilisers, oxygen collectors, acid collectors, marking means, anti-fogging means, filler/reinforcing materials and mixtures and combinations of at least two of the previously mentioned additives.

31. The polymer composition according to claim 21, wherein the at least one azine dye and/or the at least one mono-, bi-, tri- and/or tetravalent metal salt is incorporated by means of a master batch with respect to the polymer composition, identical to the matrix made of the at least one crystallisable material.

32. The polymer composition according to claim 21, wherein, in comparison to a polymer composition which comprises no azine dye and/or a mono-, bi-, tri- and/or tetravalent metal salt, the crystallisation point thereof is reduced, the crystallisation speed thereof is lower and/or the crystallisation behaviour thereof is delayed.

33. An additive composition for delaying crystallisation of crystallisable, thermoplastic polymers or polymer compositions, consisting of or comprising a) at least one azine dye and b) at least one mono-, bi-, tri- and/or tetravalent metal salt, selected from the group consisting of metal chlorides, metal bromides and metal pseudohalogenides and mixtures or combinations thereof.

34. The additive composition according to claim 33, wherein the at least one azine dye is selected from the group consisting of phenazine dyes, oxazine dyes, thiazine dyes and bisazine dyes.

35. The additive composition according to claim 33, wherein the at least one mono-, bi-, tri- and/or tetravalent metal salt is selected from the group consisting of alkali metal salts and alkaline earth metal salts.

36. The additive composition according to claim 33, wherein the weight ratio of the at least one azine dye to the at least one mono-, bi-, tri- and/or tetravalent metal salt is from 1:99 to 99:1, the additive composition being generally free of transition metal halogenides.

37. A method for delaying crystallisation, for reducing the crystallisation speed, and/or for lowering the crystallisation temperature of a crystallisable, thermoplastic polymer, in which an additive composition is: added to a polymer matrix, comprising or consisting of at least one crystallisable, thermoplastic polymer, the polymer matrix is transferred into the melt and subsequently cooled, or incorporated in a polymer matrix in the molten state, comprising or consisting of at least one crystallisable, thermoplastic polymer, and subsequently is cooled; wherein the additive composition consists of or comprises: a) at least one azine dye and b) at least one mono-, bi-, tri- and/or tetravalent metal salt, selected from the group consisting of metal chlorides, metal bromides, and metal pseudohalogenides, and mixtures or combinations thereof.

38. The method according to claim 37, wherein the additive composition or individual components of the additive composition are introduced in the form of a master batch or concentrate, the master batch comprising a matrix made of at least one crystallisable, thermoplastic polymer, in which master batch the additive composition, which is identical to the matrix of the polymer composition, is present.

39. A method of producing a moulded part from the polymer composition claim 21, which involves injection moulding, extrusion, a generative manufacturing method, a 3D printing method, a deep-drawing- or blow-moulding method.

Description

EXAMPLE 1-11

[0086] A polyamide 6 (Alphalon 27, Grupa Azoty ATT Polymers GmbH) was mixed with various nigrosines and/or metal salts in the melt. The compositions are described in Table 1. The processing in the melt was implemented with a synchronous twin-screw extruder (Thermo Scientific Process 11). The speed of rotation of the screws was 450 1/min, with a throughput of 800 g/h and a melt temperature of 260° C. The hot melt was then cooled in a water bath and subsequently strand-granulated.

[0087] Thermal analysis of the compounds was carried out by means of dynamic differential calorimetry (DSC). For examining the melt- and crystallisation behaviour, a DSC 822e (Mettler-Toledo AG) with a constant nitrogen throughflow of 20 ml 1/min and nitrogen cooling was used. The temperature and the heat flow were calibrated with indium and zinc. The sample quantity was always 5 mg with a deviation of ±0.1 mg. An aluminium crucible was used. The samples were heated at 10° C. min-1 from 0° C. to 270° C. and kept there for 3 min. Thereafter, the sample was cooled again to 0° C. at 10° C. min-1. This cycle was repeated twice. Analysis of the characteristic values of melting temperature Ts, peak crystallisation temperature T.sub.PC and crystallisation enthalpy ΔHc (J/g) was undertaken with reference to the second heating and cooling cycle. The characteristic value T.sub.PC, relevant to the invention, is represented in Table 1 for all examples.

TABLE-US-00001 TABLE 1 Compositions and crystallisation temperatures of compositions according to the invention and comparative examples W T.sub.PC Example Additives [%] [° C.] Comparative example 1 — 0 186.9 Comparative example 2 nigrosine A 0.5 181.2 Comparative example 3 nigrosine A 1.5 178.3 Comparative example 4 nigrosine A 3.0 180.4 Comparative example 5 nigrosine B 0.5 176.9 Comparative example 6 nigrosine B 3.0 176.3 Comparative example 7 lithium chloride 0.5 180.7 Comparative example 8 lithium chloride 1.5 168.8 Comparative example 9 lithium chloride 3.0 152.5 Comparative example 10 lithium benzoate 0.5 184.9 Comparative example 11 lithium benzoate 3.0 178.6 Example 1 according to the nigrosine A/lithium 0.5 175.6 invention chloride 1:2 Example 2 according to the nigrosine A/lithium 3.0 143.0 invention chloride 1:2 Example 3 according to the nigrosine A/lithium 0.5 172.6 invention chloride 1:1 Example 4 according to the nigrosine A/lithium 1.5 163.4 invention chloride 1:1 Example 5 according to the nigrosine A/lithium 3.0 145.3 invention chloride 1:1 Example 6 according to the nigrosine A/lithium 0.5 179.0 invention chloride 2:1 Example 7 according to the nigrosine A/lithium 3.0 151.0 invention chloride 2:1 Example 8 according to the nigrosine B/lithium 0.5 157.2 invention chloride 1:1 Example 9 according to the nigrosine B/lithium 3.0 149.8 invention chloride 1:1 Example 10 according to the nigrosine A/lithium 0.5 174.8 invention benzoate 1:1 Example 11 according to the nigrosine A/lithium 3.0 169.7 invention benzoate 1:1 T.sub.PC: crystallisation temperature; w: mass proportion of the additive(s) Nigrosine A: NIGROSINBASE BA01 (LANXESS Deutschland GmbH) Nigrosine B: NUBIAN ® BLACK TN-870 (ORIENT CHEMICAL INDUSTRIES CO., LTD.) Lithium chloride: lithium chloride AnalaR NORMAPUR ® ACS (VWR International GmbH) Magnesium chloride: magnesium chloride water-free for the synthesis (Merck KGaA) Lithium benzoate: lithium benzoate 99% (SIGMA-ALDRICH CHEMIE GmbH)

[0088] The examples according to the invention surprisingly show a significantly reduced crystallisation temperature at the same concentrations in comparison to the comparative examples which comprise only one of the two components of the examples according to the invention.

EXAMPLE 12-15

[0089] A polyamide 6 (Alphalon 27, Grupa Azoty ATT Polymers GmbH) was mixed with nigrosine and/or metal salt with different method parameters in the melt. The processing in the melt was implemented with a synchronous twin-screw extruder (Thermo Scientific Process 11). The method parameters are documented in Table 2. The hot melt was then cooled in a water bath and subsequently strand-granulated. The compositions are described in Table 3. For the tests, a weight proportion of 0.5% by weight of the anti-nucleation agents was chosen.

TABLE-US-00002 TABLE 2 Method parameters Test Melt temperature Speed of rotation Throughput setting [° C.] [rpm−1] [gh−1] 1 240 450 1,000 2 260 150 1,000 3 260 450 1,000 4 260 750 1,000

[0090] Thermal analysis of the compounds was carried out according to the description for example 1-11. The characteristic value T.sub.PC, relevant to the invention, is illustrated in Table 3 for all examples.

TABLE-US-00003 TABLE 3 Compositions and crystallisation temperatures of compositions according to the invention and comparative examples Test T.sub.PC Example Additives setting [° C.] Comparative example 12 — 1 187.1 Comparative example 13 — 2 186.7 Comparative example 1 — 3 186.9 Comparative example 14 — 4 186.7 Comparative example 15 nigrosine A 1 182.2 Comparative example 16 nigrosine A 2 179.8 Comparative example 2 nigrosine A 3 181.2 Comparative example 17 nigrosine A 4 181.2 Comparative example 18 lithium chloride 1 182.0 Comparative example 19 lithium chloride 2 182.3 Comparative example 7 lithium chloride 3 180.7 Comparative example 20 lithium chloride 4 180.2 Example 12 according to the nigrosine A/lithium 1 177.8 invention chloride 1:1 Example 13 according to the nigrosine A/lithium 2 177.4 invention chloride 1:1 Example 14 according to the nigrosine A/lithium 3 175.1 invention chloride 1:1 Example 15 according to the nigrosine A/lithium 4 179.3 invention chloride 1:1 T.sub.PC: crystallisation temperature Nigrosine A: NIGROSINBASE BA01 (LANXESS Deutschland GmbH) Lithium chloride: lithium chloride AnalaR NORMAPUR ® ACS (VWR International GmbH)

[0091] The examples according to the invention show surprisingly, even with different process conditions, a significantly reduced crystallisation temperature in comparison to the comparative examples which comprise only one of the two components of the examples according to the invention.

EXAMPLE 16-17

[0092] A polyamide 6 (Alphalon 27, Grupa Azoty ATT Polymers GmbH) was mixed with nigrosine and/or metal salt in the melt. The nigrosine was used as raw material and in the form of a polyamide 6 master batch, with 20% by weight of nigrosine. The compositions are described in Table 4.

[0093] The compound- and also the master batch production were effected according to the description for example 1-11.

[0094] Thermal analysis of the compounds was carried out according to the description for example 1-11. The characteristic value T.sub.PC, relevant to the invention, is illustrated in Table 4 for all examples.

TABLE-US-00004 TABLE 4 Compositions and crystallisation temperatures of compositions according to the invention and comparative examples W T.sub.PC Example Additives [%] [° C.] Comparative example 1 — 0 186.9 Comparative example 2 nigrosine A 0.5 181.2 Comparative example 4 nigrosine A 3.0 180.4 Comparative example 7 lithium chloride 0.5 180.7 Comparative example 9 lithium chloride 3.0 152.5 Comparative example 21 nigrosine A - MB20 0.5 178.6 Comparative example 22 nigrosine A - MB20 3.0 176.8 Example 3 according to the nigrosine A/lithium 0.5 172.6 invention chloride 1:1 Example 5 according to the nigrosine A/lithium 3.0 145.3 invention chloride 1:1 Example 16 according to the nigrosine A - MB20/lithium 0.5 174.0 invention chloride 1:1 Example 17 according to the nigrosine A - MB20/lithium 3.0 144.2 invention chloride 1:1 T.sub.PC: crystallisation temperature; w: mass proportion of the additive(s) Nigrosine A: NIGROSINBASE BA01 (LANXESS Deutschland GmbH) Lithium chloride: lithium chloride AnalaR NORMAPUR ® ACS (VWR International GmbH)

[0095] The examples according to the invention surprisingly show, even with incorporation of a component in the form of a master batch, a significantly reduced crystallisation temperature at the same concentrations in comparison to the comparative examples which comprise only one of the two components of the examples according to the invention.

EXAMPLE 18-19

[0096] A polyamide 6 (Alphalon 27, Grupa Azoty ATT Polymers GmbH) was mixed with nigrosine and/or metal salt in the melt. The compositions are described in Table 5. All compounds were stabilised with 0.15% by weight of Irgafos 168 (BASF SE), 0.15% by weight of Irganox 1098 (BASF SE) and 0.2% by weight of Ceasit AV/PA (Baerlocher GmbH).

[0097] Processing in the melt was implemented with a synchronous twin-screw extruder (Leistritz MIC 27 GL/44D). The speed of rotation of the screws was 300 1/min, with a throughput of 5 kg/h and a melt temperature of 260° C. The hot melt was then cooled in a water bath and subsequently strand-granulated.

[0098] Thermal analysis of the compounds was carried out according to the description for example 1-11. The characteristic value T.sub.PC, relevant to the invention, is illustrated in Table 5 for all examples.

TABLE-US-00005 TABLE 5 Compositions and crystallisation temperatures of compositions according to the invention and comparative examples W T.sub.PC Example Additives [%] [° C.] Comparative example 23 — 0 188.5 Comparative example 24 nigrosine B 0.5 180.4 Comparative example 25 nigrosine B 1.5 173.9 Comparative example 26 lithium chloride 0.5 184.4 Comparative example 27 lithium chloride 1.5 178.2 Example 18 according to the nigrosine B/lithium 0.5 173.5 invention chloride 1:1 Example 19 according to the nigrosine B/lithium 1.5 172.9 invention chloride 1:1 T.sub.PC: crystallisation temperature; w: mass proportion of the additive(s) Nigrosine B: NUBIAN ® BLACK TN-870 (ORIENT CHEMICAL INDUSTRIES CO., LTD.) Lithium chloride: lithium chloride AnalaR NORMAPUR ® ACS (VWR International GmbH)

[0099] The examples according to the invention surprisingly show, even on an enlarged processing scale and in the presence of stabiliser systems, a significantly reduced crystallisation temperature at the same concentrations in comparison to the comparative examples which comprise merely one of the two components of the examples according to the invention.

EXAMPLE 20-21

[0100] A polyamide 6 (Alphalon 27, Grupa Azoty ATT Polymers GmbH) was mixed with nigrosine and/or metal salt in the melt. The compositions are described in Table 6. All compounds were stabilised with 0.15% by weight of Irgafos 168 (BASF SE), 0.15% by weight of Irganox 1098 (BASF SE) and 0.2% by weight of Ceasit AV/PA (Baerlocher GmbH).

[0101] The compound production was effected according to the description for example 19-20.

[0102] From the compounds, test pieces of type 1A were produced according to DIN EN ISO 527-2. Production of the test pieces was effected following DIN EN ISO 294-1 with a Klöckner Ferromatik Desma injection moulding machine of the type FX 75-2F at 260° C.

[0103] The test pieces were conditioned with acceleration according to DIN EN ISO 1110. For this purpose, the test pieces were stored in an air conditioned cupboard for 10 days, in an atmosphere of (70±1°) C. and (62±1)% relative humidity (psychometric temperature difference of (10±3°) C.) until the test pieces had reached a moisture absorption of at least 95% of their equilibrium weight.

[0104] Thermal analysis of the compounds was carried out according to the description for example 1-11, except that the analysis was carried out on thin sections (300 μm) of the injection moulded and conditioned test pieces. The characteristic value T.sub.PC, relevant to the invention, is illustrated in Table 6 for all examples.

TABLE-US-00006 TABLE 6 Compositions and crystallisation temperatures of compositions according to the invention and comparative examples W T.sub.PC Example Additives [%] [° C.] Comparative example 28 — 0 189.1 Comparative example 29 nigrosine B 0.5 179.7 Comparative example 30 nigrosine B 1.5 174.0 Comparative example 31 lithium chloride 0.5 178.0 Comparative example 32 lithium chloride 1.5 173.2 Example 20 according to the nigrosine B/lithium 0.5 175.9 invention chloride 1:1 Example 21 according to the nigrosine B/lithium 1.5 166.9 invention chloride 1:1 T.sub.PC: crystallisation temperature; w: mass proportion of the additive(s) Nigrosine B: NUBIAN ® BLACK TN-870 (ORIENT CHEMICAL INDUSTRIES CO., LTD.) Lithium chloride: lithium chloride AnalaR NORMAPUR ® ACS (VWR International GmbH)

[0105] The examples according to the invention surprisingly show a significantly reduced crystallisation temperature even after processing in the injection moulding process in the same concentrations in comparison to the comparative examples which comprise merely one of the two components of the examples according to the invention.

EXAMPLE 22

[0106] A polyamide 6 (Alphalon 27, Grupa Azoty ATT Polymers GmbH) was mixed with nigrosine and/or metal salt in the melt. The compositions are described in Table 7. All compounds were stabilised with 0.15% by weight of Irgafos 168 (BASF SE), 0.15% by weight of Irganox 1098 (BASF SE) and 0.2% by weight of Ceasit AV/PA (Baerlocher GmbH). For the tests, a weight proportion of 1.5% by weight of the anti-nucleation agents was chosen.

[0107] The compound production was effected according to the description for example 19-20.

[0108] Thermal analysis of the compounds was carried out by means of dynamic differential calorimetry (DSC) following DIN EN ISO 11357-7:2013-04. For examining the melt- and crystallisation behaviour, a DSC 822e (Mettler-Toledo AG) with a constant nitrogen throughflow of 20 ml/min and nitrogen cooling was used. The temperature and the heat flow were calibrated with indium and zinc. The sample quantity was always 5 mg with a deviation of ±0.1 mg. An aluminium crucible was used. The samples were heated at 50° C. min.sup.−1 from 0° C. to 250° C. and kept there for 10 min in order to melt all the crystallites. Thereafter, the samples were cooled at 100° C. min.sup.−1 to the relevant isothermal crystallisation temperatures and kept there until complete crystallisation of the samples. Isothermal crystallisation temperatures between 194 and 200° C., with a step width of 2° C., were used.

[0109] The ratio between the crystallinity at the time t and the crystallinity at the end of the crystallisation is termed relative crystallinity a. For each isothermal crystallisation temperature, the change of a as a function of time was plotted. The time until reaching the relative crystallinity of 0.5 (t.sub.0.5) is a measure of the isothermal crystallisation speed. The characteristic value t.sub.0.5, relevant to the invention, is illustrated in Table 7 as a function of the isothermal crystallisation temperature for all examples.

TABLE-US-00007 TABLE 7 Compositions and t.sub.0.5 of compositions according to the invention and comparative examples T.sub.i t.sub.0.5 Example Additives [° C.] [min] Comparative example 33 — 198 1.3 200 1.8 202 2.6 Comparative example 34 nigrosine B 196 9.7 198 11.1 200 15.0 Comparative example 35 lithium chloride 196 6.9 198 7.9 200 8.08 Example 22 according to the nigrosine B/lithium 194 11.0 invention chloride 1:1 196 15.1 198 23.9 T.sub.PC: crystallisation temperature; T.sub.i: isothermal crystallisation temperature; t.sub.0.5: time until reaching the relative crystallinity of 0.5 Nigrosine B: NUBIAN ® BLACK TN-870 (ORIENT CHEMICAL INDUSTRIES CO., LTD.) Lithium chloride: lithium chloride AnalaR NORMAPUR ® ACS (VWR International GmbH)

[0110] The examples according to the invention surprisingly show a significantly extended time until reaching the relative crystallinity of 0.5 at the same concentrations in comparison to the comparative examples which comprise only one of the two components of the examples according to the invention.

EXAMPLE 23

[0111] A polyamide 6.6 (Radipol A45, RADICI CHIMICA S.p.A.) was mixed with a nigrosine and/or a metal salt in the melt. The compositions are described in Table 8. Processing in the melt was implemented analogously to Example 1-11. The melt temperature was 285° C.

[0112] Thermal analysis of the compounds was carried out analogously to Example 1-11. The samples were heated at 10° C. min-1 from 0° C. to 300° C. and kept there for 3 min. Thereafter, the sample was cooled again to 0° C. at 10° C. min.sup.−1. This cycle was repeated twice. The characteristic value T.sub.PC, relevant to the invention, is illustrated in Table 8 for all examples.

TABLE-US-00008 TABLE 8 Compositions and crystallisation temperatures of compositions according to the invention and comparative examples W T.sub.PC Example Additives [%] [° C.] Comparative example 36 — 0 229.4 Comparative example 37 nigrosine A 3.0 218.0 Comparative example 38 lithium chloride 3.0 201.6 Example 23 according to the nigrosine A/lithium 3.0 191.1 invention chloride 1:1 T.sub.PC: crystallisation temperature; w: mass proportion of the additive(s) Nigrosine A: NIGROSINBASE BA01 (LANXESS Deutschland GmbH) Lithium chloride: lithium chloride AnalaR NORMAPUR ® ACS (VWR International GmbH)

[0113] The examples according to the invention surprisingly show a significantly reduced crystallisation temperature at the same concentrations in comparison to the comparative examples which comprise only one of the two components of the examples according to the invention.