Polymeric Materials

Abstract

A liquid formulation for addition to a polymeric material comprises a vehicle, an additive (e.g. a colourant) and carbonyl bis (1-caprolactan)). The liquid formulation may be used to colour melt spun fibre (e.g. PET or polyamide).

Claims

1-36. (canceled)

37. A liquid formulation for addition to a polymeric material, said liquid formulation comprising a vehicle, an additive and carbonyl bis (1-caprolactan)) (herein referred to as CBC).

38. A formulation according to claim 37, wherein said vehicle has a flash point of at least 285 C., a % weight retention of greater than 85 wt % and a number average molecular weight in the range 750-1250 g/mol; and/or wherein said vehicle is a liquid at STP, has a boiling point at atmospheric pressure of 760 mmHg of greater than 300 C. and less than 1150 C. and a melting point of less than 0 C.

39. A formulation according to claim 37, wherein said vehicle includes a moiety OCOR.sup.50 wherein R.sup.50 includes at least 5 CH.sub.2 moieties and includes less than 24 CH.sub.2 moieties; and the sum of the number of CH.sub.2 moieties in all R.sup.50 groups of moieties OCOR.sup.50 is at least 15.

40. A formulation according to claim 37, wherein said vehicle is selected from groups (A) to (I) defined as follows: Group APentaerythritol tri or tetra esters where the ester is derived or derivable from reaction of pentaerythritol with a carboxylic acid with a carbon chain length of C.sub.12 to C.sub.22; Group BAlkoxylated pentaerythritol tri or tetra esters where the ester is derived or derivable from the reaction of an alkoxylated pentaerythritol with a carboxylic acid with a carbon chain length of C.sub.12 to C.sub.22; Group CDipentaerythritol penta or hexa esters where the ester is derived from the reaction of dipentaerythritol with a carboxylic acid with a carbon chain length of C.sub.5 to C.sub.18; Group DAlkoxylated dipentaerythritol penta or hexa esters where the ester is derived or derivable from the reaction of an alkoxylated dipentaerythritol with a carboxylic acid with a carbon chain length of C.sub.5 to C.sub.16; Group ETrimethylolpropane triesters where the ester is derived or derivable from the reaction of trimethylolpropane with a carboxylic acid with a carbon chain length of C.sub.8 to C.sub.22; Group FAlkoxylated trimethylolpropane triesters where the ester is derived or derivable from the reaction of an alkoxylated trimethylolpropane with a carboxylic acid with a carbon chain length of C.sub.8 to C.sub.22; Group GEsters of the tri-carboxylic acid of general formula: ##STR00015## where R.sup.9, R.sup.10 and R.sup.11 independently represent a hydrogen atom, an ester group or an optionally-substituted, preferably unsubstituted, alkyl group; Group HAliphatic dicarboxylic acid species containing between 2 and 22 carbon atoms in the main structural backbone; Group IFatty acid diesters of hydroxyl terminated polyester plasticisers derived from adipic acid and an alky diol; acetylated monoglycerides from hydrogenated castor oil; and ethoxylated fatty acid diesters.

41. A formulation according to claim 40, wherein said vehicle is selected from Group A.

42. A formulation according to claim 37, wherein said vehicle is of general formula ##STR00016## wherein each R.sup.20 independently represents a C.sub.11 to C.sub.21 optionally-substituted, linear or branched, saturated or unsaturated alkyl group; and R.sup.21 comprises a moiety R.sup.20COO or an hydroxy group.

43. A formulation according to claim 37, wherein said vehicle is a pentaerythritol tetra ester.

44. A formulation according to claim 37, wherein said vehicle is pentaerythritol tetraisostearate.

45. A formulation according to claim 37, wherein said liquid formulation includes at least 2 wt % of CBC; and/or includes less than 25 wt % of CBC.

46. A formulation according to claim 37, wherein said liquid formulation includes: 30-80 wt % of one or more vehicles; 5-60 wt % of one or more colourants; 3-25 wt % of CBC.

47. A formulation according to claim 37, wherein said liquid formulation includes: 30-80 wt % of a pentaerythritol tetra ester; 5-60 wt % of one or more colourants; 2-25 wt % of CBC.

48. A formulation according to claim 37, wherein, in said liquid formulation, the ratio of the total weight of colourants divided by the weight of CBC is at least 2 and is less than 10.

49. A formulation according to claim 37, wherein, in said liquid formulation, said CBC includes particles having a 1 m or greater median particle diameter; and/or the median particle diameter is 200 m or less.

50. A method of introducing an additive into a polymeric material, the method comprising: (i) selecting a polymeric material; (ii) contacting the polymeric material with said additive, carbonyl bis (1-caprolactam) (CBC) and vehicle; and (iii) melt-processing said polymeric material.

51. A method according to claim 50, wherein said vehicle is selected from groups (A) to (I) defined as follows: Group APentaerythritol tri or tetra esters where the ester is derived or derivable from reaction of pentaerythritol with a carboxylic acid with a carbon chain length of C.sub.12 to C.sub.22; Group BAlkoxylated pentaerythritol tri or tetra esters where the ester is derived or derivable from the reaction of an alkoxylated pentaerythritol with a carboxylic acid with a carbon chain length of C.sub.12 to C.sub.22; Group CDipentaerythritol penta or hexa esters where the ester is derived from the reaction of dipentaerythritol with a carboxylic acid with a carbon chain length of C.sub.5 to C.sub.18; Group DAlkoxylated dipentaerythritol penta or hexa esters where the ester is derived or derivable from the reaction of an alkoxylated dipentaerythritol with a carboxylic acid with a carbon chain length of C.sub.5 to C.sub.16; Group ETrimethylolpropane triesters where the ester is derived or derivable from the reaction of trimethylolpropane with a carboxylic acid with a carbon chain length of C.sub.8 to C.sub.22; Group FAlkoxylated trimethylolpropane triesters where the ester is derived or derivable from the reaction of an alkoxylated trimethylolpropane with a carboxylic acid with a carbon chain length of C.sub.8 to C.sub.22; Group GEsters of the tri-carboxylic acid of general formula: ##STR00017## where R.sup.9, R.sup.10 and R.sup.11 independently represent a hydrogen atom, an ester group or an optionally-substituted, preferably unsubstituted, alkyl group; Group HAliphatic dicarboxylic acid species containing between 2 and 22 carbon atoms in the main structural backbone; Group IFatty acid diesters of hydroxyl terminated polyester plasticisers derived from adipic acid and an alky diol; acetylated monoglycerides from hydrogenated castor oil; and ethoxylated fatty acid diesters.

52. A formulation according to claim 37, wherein said liquid formulation includes: 40-70 wt % of pentaerythritol tetraisostearate; 20-50 wt % of one or more colourants; 3-20 wt % of CBC.

53. A liquid formulation for addition to a polymeric material, said liquid formulation comprising a vehicle, an additive and carbonyl bis (1-caprolactan)) (herein referred to as CBC), wherein said vehicle is selected from groups (A) to (I) defined as follows: Group APentaerythritol tri or tetra esters where the ester is derived or derivable from reaction of pentaerythritol with a carboxylic acid with a carbon chain length of C.sub.12 to C.sub.22; Group BAlkoxylated pentaerythritol tri or tetra esters where the ester is derived or derivable from the reaction of an alkoxylated pentaerythritol with a carboxylic acid with a carbon chain length of C.sub.12 to C.sub.22; Group CDipentaerythritol penta or hexa esters where the ester is derived from the reaction of dipentaerythritol with a carboxylic acid with a carbon chain length of C.sub.5 to C.sub.18; Group DAlkoxylated dipentaerythritol penta or hexa esters where the ester is derived or derivable from the reaction of an alkoxylated dipentaerythritol with a carboxylic acid with a carbon chain length of C.sub.5 to C.sub.16; Group ETrimethylolpropane triesters where the ester is derived or derivable from the reaction of trimethylolpropane with a carboxylic acid with a carbon chain length of C.sub.8 to C.sub.22; Group FAlkoxylated trimethylolpropane triesters where the ester is derived or derivable from the reaction of an alkoxylated trimethylolpropane with a carboxylic acid with a carbon chain length of C.sub.8 to C.sub.22; Group GEsters of the tri-carboxylic acid of general formula: ##STR00018## where R.sup.9, R.sup.10 and R.sup.11 independently represent a hydrogen atom, an ester group or an optionally-substituted, preferably unsubstituted, alkyl group; Group HAliphatic dicarboxylic acid species containing between 2 and 22 carbon atoms in the main structural backbone; Group IFatty acid diesters of hydroxyl terminated polyester plasticisers derived from adipic acid and an alky diol; acetylated monoglycerides from hydrogenated castor oil; and ethoxylated fatty acid diesters; and wherein said liquid formulation includes: 30-80 wt % of one or more of said vehicles; 5-60 wt % of one or more colourants; 3-25 wt % of CBC.

54. A formulation according to claim 53, wherein said liquid formulation includes 30-80 wt % of a pentaerythritol tetra ester.

55. A formulation according to claim 53, wherein said liquid formulation includes: 40-70 wt % of pentaerythritol tetraisostearate; 20-50 wt % of one or more colourants; 3-20 wt % of CBC.

56. A formulation according to claim 54, wherein, in said liquid formulation, the ratio of the total weight of colourants divided by the weight of CBC is at least 2 and is less than 10; and, in said liquid formulation, said CBC includes particles having a 1 m or greater median particle diameter; and a median particle diameter of 200 m or less.

Description

[0141] Specific embodiments of the invention will now be described, by way of example, with reference to FIG. 1 which is a schematic representation of a pilot fibre line.

[0142] In the following, firstly, tests used in assessing features associated with the process and products produced by the process are initially described. Then, Example 1 describes preparation of a carbon black dispersion which is used with varying amounts of carbonyl bis (1-caprolactam) (CBC) formulations in Examples 2 to 5 and with pyromellitic anhydride in comparative Example 6. The preparation and testing of fibre samples using different formulations, including those of Examples 2 to 5, are described in Examples 7 to 12. The preparation and testing of further formulations is described in Examples 13 to 16.

[0143] The following tests are referred to hereinafter:

Test 1Determination of Intrinsic Viscosity (IV)

[0144] The intrinsic viscosity of PET fibre samples was determined using ASTM D4603 at 30 C. (concentration of 0.5 wt/v; solvent 60/40 phenol/tetrachloroethane).

Test 2Determination of Fibre Tenacity

[0145] Using an Instron 3365 the tenacity of the fibre sample was determined at 20 C. and an extension rate of 250 mm/min (ASTM D885).

Test 3Determination of Die Head Pressure

[0146] A probe was inserted into the polymer melt after the melt pump and upstream of the spinneret to obtain die head pressure values.

Test 4Determination of Elongation

[0147] This was determined as described for Test 2

Example 1Carbon Black Liquid Dispersion

[0148] 400 g of carbon black (Monarch 430) was mixed under high shear with 503 g of pentaerythritol tetraisostearate sold as CRODAMOL PTIS, 95 g of Solplus K240 (hyperdispersant), 1 g Irganox 1010 (anti-oxidant) and 1 g of Doverphos (anti-oxidant) before being milled using 70% loaded 0.8 beads until the required particle size was achieved. A particle size of less than 5 m was required for the formulations to achieve good dispersion in the fibre, to increase shelf-life of the formulation and prevent sedimentation.

Examples 2 to 5Preparation of Formulations Containing Carbonyl Bis (1-Caprolactam) (CBC)

[0149] CBC in powder form (particle size less than 50 m) was blended into the carbon black formulation of Example 1 by high shear mixing at ambient temperature (21 C.). Varying amounts of CBC were incorporated as detailed in Table 1.

TABLE-US-00001 TABLE 1 Weight (g) of Example Example 1 Weight (g) No. formulation of CBC 2 100 10.00 3 100 13.33 4 100 16.67 5 100 20.00

Example 6 (Comparative)

[0150] Pyromellitic anhydride (PMDA), an additive previously used by Applicant, was blended with the black formulation of Example 1, instead of the CBC. The composition comprised 100 g of the formulation of Example 1 and 5 g of PMDA.

Examples 7 to 12Preparation of Fibre Samples

[0151] Apparatus for the preparation of the fibre samples, shown in FIG. 1, comprises a hopper 1 for feeding PET resin into an extruder. Liquid additive formulation is injected into molten PET at position 2 using injection apparatus 3. Die head pressure may be assessed at position 3. The mixture is spun into fibre via spinning head 4.

[0152] Partially orientated (POY) polyethylene terephthalate (PET), 165 dtex/48f, fibre was produced by melt extruding a sample of PET (Equipolymers C93), that had been dried for 4 hours at 170 C. through a 30 mm extruder (L/D ratio of 24/1) fitted with a cavity transfer mixer (CTM speed=90 rpm) and a 48 hole (hole diameter 0.4 mm) spin pack at 285 C. and 2.72 kg/hours. The extruded fibre was drawn from the spinneret using a Barmag ASW602 winder (winder speed 2,800 m/min). Table 2 records details of the fibres produced, die head pressures and tensile properties of the fibre measured in accordance with Tests 1 to 4.

[0153] Liquid formulations of Examples 1 to 6 were added to the melt stream at position 2 using a Flex-IM Colour Cart calibrated with a CM6000 controller unit. The formulations were dosed through high pressure braided cable into the injector system and then mixed into the melt stream using a cavity transfer mixer (speed 90 rpm).

[0154] Results are provided in Table 2. phr refers to parts by weight of the formulation used per hundred parts of resin.

TABLE-US-00002 TABLE 2 Dose rate of and Die CBC identity of Head Could content in formulation Pressure Tenacity Elongation IV fibre be the final Example No. used (bar) (cN/Dtex) (%) dL/g spun? fibre Example 7 0 52 2.11 110 0.659 Yes 0 (comparative) Example 8 3.0 phr 29 1.91 123 0.591 Yes 0 (comparative) Example 1 formulation Example 9 3.3 phr 43 1.90 109 0.642 Yes 0.3 phr Example 2 formulation Example 10 3.4 phr 47 1.95 105 0.673 Yes 0.4 phr Example 3 formulation Example 11 3.5 phr 54 1.99 101 0.700 Yes 0.5 phr Example 4 formulation Example 12 3.15 phr 47 No, 0 Comparative Example 6 filament formulation too stiff

[0155] Referring to Table 2, it is clear from comparative Example 8 that, at high levels of liquid colourant (about 3 phr), there is a significant reduction in die head pressure, an unacceptable increase in elongation and a reduction in IV of the fibre, compared to the uncoloured fibre of Example 7.

[0156] Additionally, comparative Example 12 shows that the addition of PMDA produces a recovery of die head pressure, close to that of the uncoloured fibre of Example 7, but it is not possible to spin the fibre because the melt strength is too stiff.

[0157] However, advantageously, Examples 9 to 11 show that addition of CBC leads to appreciable die head pressure which improves the stability of fibres during spinning and minimises broken filaments.

Example 13Preparation of Base Formulation Comprising CBC

[0158] 470 g of CBC was mixed under high shear with 450 g of PTIS and 80 g of Solplus K240 (hyperdispersant) before being milled using 70% loaded 0.8 beads until the required particle size was achieved. A particle size of less than 30 m was required for the formulations described below for example to increase shelf-life of the formulation and prevent sedimentation.

Examples 14 to 16Preparation of Fibre Samples

[0159] Partially orientated (POY) polyethylene terephthalate (PET), 128 dtex/72f, fibre was produced by melt extruding a sample of PET (Invista 5540) that had been dried for 4 hours at 170 C. through a 30 mm extruder (L/D ratio of 24/1) fitted with a Barmag Promix AC dynamic melt mixer and a 72 hole spin pack at 285 C. and 4.5 kg/hours. The extruded fibre was drawn from the spinneret using a WINGS-POY 1500/10 winder (winder speed 3,050 m/min).

[0160] Liquid formulations injected into the Promix AC were added to the melt stream at position 2 (FIG. 1) using a Barmag Inject AC pump. The formulations were dosed through high pressure braided cable into the injector system and then mixed into the melt stream using a Promix AC (speed=30 rpm).

[0161] Example 16 uses a blend of the Examples 1 and 13 formulations.

[0162] Results are provided in Table 3

TABLE-US-00003 TABLE 3 CBC base of Die head Example 1 Example 13 Pressure Tenacity Elongation Spinning Example No (phr) phr (bar) (cN/Dtex) (%) stability Example 14 0 0 149 2.53 133.2 good (comparative) Example 15 3.4 0 109 2.17 143.5 poor (comparative) (broken filaments) Example 16 3.4 0.6 154 2.24 130.7 good

[0163] The results in Table 3 show that, in the production of finer denier fibre (1.78 denier per filament) addition of 3.4 phr of Example 1 as per Example 15 led to a significant reduction in die-head spinning pressure and tensile properties; and, additionally, the stability of the spinning process was poor, there being many broken filaments. However, results for Example 16 show that use of CBC leads to die-head pressure similar to that observed for uncoloured fibre (Example 14), improved mechanical properties and a stable spinning process, with few broken filaments.

[0164] The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.