FOAMED INJECTION MOULDED ARTICLE

Abstract

The invention is directed to a foamed injection moulded article comprising a foam composition obtained by foaming high density polyethylene having a quotient of melt strength and apparent viscosity >2 cN/K.Math.Pa.Math.s wherein the melt strength is determined as described in ISO 16790:2005 and the apparent viscosity is determined as described in ISO 11443:2014.

Claims

1-15. (canceled)

16. A method of manufacturing a foamed injection moulded article, the method comprising: a) chain branching a high density polyethylene by electron beam irradiation, the high density polyethylene having MI (melt index) in the range between ≥1 and ≤100, and density in the range between ≥930 and ≤985 kg/m.sup.3, resulting in a chain branched high density polyethylene having MI in the range between ≥0.01 and ≤50, density in the range between ≥930 and ≤985 kg/m.sup.3, a gel fraction less than 5%, and a quotient of melt strength and apparent viscosity >2cN/k.Math.Pa.Math.s and ≥30 cN/k.Math.Pa.Math.s, wherein MI is measured according ISO1133-1:2011 at a temperature of 190° C. at a load of 2.16 kg, the density is measured at a temperature of 23° C. according ISO1183-1:2012, the gel fraction is determined according to ASTM D2765-11, the melt strength is determined as described in ISO 16790:2005 and the apparent viscosity is determined as described in ISO 11443:2014; and b) physical injection moulding foaming a foam composition at a temperature between 120° C. and 140° C., the foaming composition comprising the chain branched high density polyethylene and a physical blowing agent comprising isobutane, isobutane with CO.sub.2, nitrogen, or pure CO.sub.2, and/or a fluorohydrocarbon.

17. The method of claim 16, wherein the article comprises two compact skins and a foamed core between the compact skins.

18. The method of claim 17, wherein the high density polyethylene has MI in the range between ≥7 and ≤100, and density in the range between ≥930 and ≤985, and chain branching the high density polyethylene takes place via electron beam irradiation, thereby forming the chain branched high density polyethylene with characteristics MI in the range between ≥0.01 and ≤10, density in the range between ≥930 and ≤985 kg/m.sup.3, and a gel fraction less than 5%.

19. The method of claim 17, wherein the high density polyethylene has MI in the range between ≥10 and ≤100, and density in the range between ≥935 and ≤970 kg/m.sup.3, and chain branching the high density polyethylene takes place via electron beam irradiation, thereby forming the chain branched high density polyethylene with characteristics MI in the range between ≥0.1 and ≤10, density in the range between ≥935 and ≤970 kg/m.sup.3, and a gel fraction less than 5%.

20. The method of claim 17, wherein the high density polyethylene has MI in the range between ≥12 and ≤50, and density in the range between ≥940 and ≤970 kg/m.sup.3, and chain branching the high density polyethylene takes place via electron beam irradiation, thereby forming the chain branched high density polyethylene with characteristics MI in the range between ≥0.1 and ≤10, density in the range between ≥940 and ≤970 kg/m.sup.3, and a gel fraction less than 3%.

21. The method of claim 17, wherein a ratio between a thickness of the foamed core and a total thickness of the article is between 0.20 and 0.95.

22. The method of claim 21, wherein a ratio between a thickness of the foam core and a total thickness of the article is between 0.4 and 0.9.

23. The method of claim 16, wherein the foam core has a density ranging between between ≥100 and ≤600 kg/m.sup.3.

Description

[0092] According to a preferred embodiment of the invention the foamed injection moulded article comprises a foam composition obtained by foaming high density polyethylene (HDPE) having a quotient of melt strength and apparent viscosity >2 cN/k.Math.Pa.Math.s wherein the melt strength is determined as described in ISO 16790:2005 using a capillary rheometer with a drawing device that pulls the molten polymer from the capillary die at a constant flow rate and at increasing drawing velocity wherein the capillary rheometer is operated at a temperature of 190° C., the preheating time is 300 seconds, the piston speed is 0.049 mm/s ,the barrel diameter is 12 mm, the capillary has a length of 40 mm , the diameter is 2 mm and the entrance angle is 180° (flat), the take-off wheels operate at an initial speed of 1.8 mm/s and an acceleration of 1.2 mm/s.sup.2and the apparent viscosity is determined as described in ISO 11443:2014 using the same capillary rheometer and the same test conditions as for the determination of the melt strength and wherein the apparent viscosity [Pa.Math.s] is defined as the quotient of the apparent shear stress and the apparent shear rate and wherein the high density polyethylene (HDPE) has [0093] MI (melt Index) In the range between ≥0.01 and ≤50 [0094] density in the range between ≥930 ands ≤985 kg/m.sup.3and [0095] a gel fraction less than 5%.

[0096] and the high density polyethylene (HDPE) has been obtained by chain branching, preferably electron beam Irradiation , high density polyethylene (HDPE) having [0097] MI in the range between ≥1 and ≤100 and [0098] density in the range between ≥930 and ≤985 kg/m.sup.3.

[0099] WO 9824836 discloses an article of manufacture comprising a foamed high density polyethylene wherein said polyethylene, prior to foaming, has a density of at least 0.93 g/cc, a melt strength of 5 to 20 grams and a melt viscosity, at 0.1 rad/s, of 4 to 10 (kPa.Math.s); wherein after foaming, the density of the foamed polyethylene is at least 20% less than said at least 0.93 g/cc density. WO 9824836 does not disclose or indicate values for the apparent viscosity. The melt viscosity at 0.1 rad/s of HDPE according to the present invention is higher than 10 kPa.Math.s.

[0100] WO 0064967 is directed to a process for forming articles consisting of foamed HDPE having an original density, prior to foaming, of at least 0.94 g/cc, comprising treating said HDPE, prior to foaming, with a peroxide. This process provides a peroxide treated high density polyethylene (whereas in contrast the present invention is directed to an irradiated high density polyethylene). HDPE has a low shear viscosity which is at least about 1.25 times the viscosity of the untreated HDPE measured at 0.1 rad./sec. and a high shear viscosity which is less than about 3.0 times the viscosity of the untreated HDPE measured at 100 rad./sec; admixing the peroxide treated HDPE with a blowing agent; and foaming the peroxide treated HDPE to form a closed cell foam product which exhibits a density reduction, as a result of foaming of over 20%. As shown by the comparative example the quotient of the melt strength and apparent viscosity is less than 2 cN/k.Math.Pa.Math.s. HDPE foam made with peroxide modified HDPE according to WO 0064967 has a higher density and a higher open cell content then HDPE foam made with HDPE according to the present invention.

[0101] The invention will be elucidated by means of the following non-restrictive examples.

EXAMPLES

[0102] Electron beam irradiation of HDPE granules was carried out at using a 10 MeV Rhodotron. In order to improve the homogeneity of irradiation dose, HDPE was packed into bags of 600×450×100 mm.sup.3 containing 12.5 kg HDPE granules. The 100 mm thick bags were radiated with the target irradiation dose on two sides in order to further improve the homogeneity of the irradiation dose.

[0103] The irradiated HDPE was characterized by the following measurements:

[0104] The melt strength was measured according ISO 16790:2005 using a Göttfert Rheograph 6000 In combination with a Rheotens 71.97. The equipment specifications are: [0105] Oven diameter of 12 mm. [0106] Capillary 40/2 (l/d), length 40 mm, diameter 2 mm, entrance angle 180° (flat). [0107] Pressure transducer: max 200 bar.

[0108] The test conditions were as follows: the rheograph was filled in less than one minute and the sample preheating time was 300 seconds. The measuring temperature was 190° C. The speed of the piston was 0.049 mm/s corresponding to a throughput of 5.5 mm.sup.3/s and apparent shear-rate of 7 s.sup.−1. The drawing device (Rheotens 71.97) was operated at an acceleration of 1.2 mm/s.sup.2 and a velocity of 1.8 mm/s. The melt strength is expressed in cN.

[0109] The apparent viscosity was measured according ISO11443:2014 using the Göttfert Rheograph 6000 and the test conditions being described for the determination of the melt strength. The apparent viscosity is defined as the quotient of the apparent shear stress and the apparent shear rate being 7 s.sup.−1. The apparent shear stress is calculated from pressure drop [kPa] times the capillary diameter in mm divided by 4 times the length of the capillary in mm. The apparent shear rate (1/s) is calculated from the throughput (mm/s) divided by 6.28 times the diameter (mm) to the power of 3. The apparent viscosity is usually expressed in kPa.Math.s.

[0110] The melt index was measured according ISO1133-1:2011 at a temperature of 190° C. and at 2.16 kg.

[0111] The density of the compression moulded HDPE disks was measured at a temperature of 23° C. according to ISO1183-1:2012 after at least one day of conditioning.

[0112] SABIC HDPE type CC3054 with a melt index of 27.5 (190° C., 216 kg) is used as a raw material. Table 1 and Table 2 show characteristics of electron beam irradiated HDPE type CC3054 (HDPE I, HDPE II) as compared to the values for unmodified HDPE type CC 3054 (HDPE A) and HOPE type 3H671 (HDPE B).

TABLE-US-00001 TABLE 1 Characteristics of electron beam irradiated HDPE (HDPE I, HDPE II) and comparative examples (HDPE A and HDPE B) Irradiation dose Melt index Density Gel fraction HDPE resin kGy (190° C., 2.16 kg) kg/m.sup.3 % HDPE I 30 1.8 950 0.8 HDPE II 40 0.4 950 1.0 HDPE A 0 27.5 953 n.a. HDPE B 0 2.1 954 n.a.

TABLE-US-00002 TABLE 2 Melt strength and apparent viscosity of electron beam irradiated HDPE (HDPE I, HDPE II) and comparative examples (HDPE A and HDPE B) Ratio between melt Irradiation Apparent strength and dosis Melt strength viscosity apparent viscosity HDPE resin kGy cN kPa .Math. s cN/kPa .Math. s HDPE I 30 15.4 2.9 5.3 HDPE II 40 13.9 2.5 5.6 HDPE A 0 0.2 0.32 0.63 HDPE B 0 1.2 2.5 0.5
Injection moulding foaming of HDPE was carried using an injection moulding machine type Engel DUO 1350H-1350M-450 with MuCell technology for foaming. This machine was equipped with a Variotherm; the mould can be heated and cooled down in a controlled manner during an injection cycle. Furthermore the mould can be opened after the injection phase of the process. The foam injection moulded plate produced on this machine has a length of 400 mm, a width of 200 mm and a minimal thickness of 3 mm with upstanding edges. The technical machine specifications are given in Table 3.

TABLE-US-00003 TABLE 3 Injection moulding machine specification for Engel DUO 450 Combi M Parameter Unit Value Injection unit with MuCell technology — — Single Screw diameter mm 60 L/D ratio — 24 Maximum injection volume cm.sup.3 450 Maximum injection pressure bar 1800 Maximum processing temperature ° C. 450 Clamping force kN 4500 Clamping unit — Hydraulic Minimum dimension mm 400 Maximum dimension mm 1200

[0113] Talc is added as a nucleating agent. Nitrogen is used as physical blowing agent. Hydrocerol is used as both a chemical blowing agent and a nucleating agent. Table 4 provides information with respect to additives.

TABLE-US-00004 TABLE 4 Nucleating agent and blowing agents. Chemical Commercial name name Master batch Schulman Talc 50% in LDPE Nucleating agent PBHFPE50T Clariant ITP473 Hydrocerol 65% in LDPE Nucleating agent N.sub.2 Nitrogen — Physical blowing agent Clariant CF40E Hydrocerol 40% in LDPE Chemical blowing agent

[0114] Table 5, and Table 6 show the machine settings for respectively physical foaming and chemical foaming of mould HDPE.

TABLE-US-00005 TABLE 5 Machine settings for injection moulding foaming using MuCell technology (physical foaming), Variotherm and mould opening Comparative Comparative Parameter Unit Example I Example II Example III Example A Example B HDPE type HDPE I HDPE I HDPE II HDPE A HDPE B Nitrogen weight % 0.5 0.5 0.5 0.15 0.3 Talc weight % 2 2 2 2 2 ITP473 weight % 0 1 1 1 1 Melt temperature ° C. 210 210 210 210 200 Dosing volume cm.sup.3 400 400 400 400 400 Injection time s 4.6 4.6 4.6 4.5 4.5 Active cooling s 10 10 10 10 10 started Cooling time in s 60 60 60 60 60 mould Delay time (time s 1 1 1 1 1 to mould opening) Variotherm hot ° C. 120 120 120 120 110 Variotherm cold ° C. 40 40 40 30 40

TABLE-US-00006 TABLE 6 Machine settings for injection moulding foaming using a chemical blowing agent (CF40E) and a fixed cold mould (no Variotherm, no mould opening). Comparative Parameter Unit Example V Example C HDPE type HDPE I HDPE A CF40E weight % 2.0 2.0 Melt temperature ° C. 220 220 Dosing volume cm.sup.3 500 500 Injection time s 0.75 0.75 Cooling time in mould s 160 160

[0115] The total density of the foam injection moulded plates Is determined by the immersion method, also referred to as Archimedes method. The density is expressed in kg/m.sup.3.

[0116] The open cell content was determined using a gas pycnometer. Samples with a weight around 10 gram were taken. The pycnometer pressurizes the foam with nitrogen. Open cells in the foam are filled with nitrogen, while closed cells are not. Consequently, the volume of the foam that cannot be filled by the nitrogen gas equals the volume of the closed cells. The open cell content is defined as:

Open cell content=1−V.sub.pycn/V.sub.geo

V.sub.pycn=the sample volume measured by the pycnometer=closed cell volume

V.sub.geo=the geometric volume of the sample

[0117] Using Archimedes principle, the geometric volume of a sample is measured with a balance by determining the upward force of the sample while being submerged under water. Then the sample is placed in the pycnometer and the volume of the sample in nitrogen is measured. The pressurized nitrogen compresses the closed cells and reduces their volume. To measure the actual, not pressurized, closed cell volume the sample volume is determined at several pressures and the apparent volume at a pressure of 0 bar is determined by extrapolation.

[0118] The cellular morphology of the HDPE foams was visualized using scanning electron microscopy. Each sample was frozen with liquid nitrogen and fractured. The fractured surface was made conductive by sputtering deposition of gold and observed using a Jeol JSM-820 operating at 20 kV. The microstructure of the materials has been studied in one plane (machine direction, thickness direction). Three micrographs were taken with a magnification of ×30. The cell size was calculated using an image processing tool based on the software Image J. The fraction foam is defined as the quotient of the thickness of the foam layer and the total thickness. The fraction skin is defined as the quotient of the thickness of the two skin layers and the total thickness.

[0119] The flexural properties of the foam Injection moulded samples were determined using ISO 178:2010 as a guideline. Five tests per sample were conducted.

[0120] A sample width of 10 mm and a length of 80 mm was used. Following testing conditions were applied:

TABLE-US-00007 Support distance 50.65 mm Testing speed 2 mm/min Modulus between 0.05 and 0.25% strain Temperature 23° C.

[0121] The flexural rigidity (F) is defined as the product of the modulus (E) by the moment of inertia (I). The moment of inertia (I=width×thickness.sup.3/12) is influenced by the thickness of the specific test specimen, whereas the modulus is a material property. In order to compare samples correctly, the thickness used to determine the moment of inertia (I) is corrected for the weight per surface area of the test specimen assuming a linear relationship between the weight per surface area and thickness. In this way data for equal weight per surface area are compared. In this report, the flexural rigidity (F) Is calculated for a weight per surface area of 3 kg/m.sup.2(via correction in thickness) using the following formula:

[00001]$\mathrm{Flexural}\mathrm{rigidity}\left(F\right)=\mathrm{flexural}\mathrm{modulus}\left(E\right)\times \frac{\mathrm{width}\times {\mathrm{thickness}}^3}{12}$

[0122] The change in flexural rigidity upon foaming is calculated by dividing the flexural rigidity of a foam injection moulded sample by the flexural rigidity of the compact 3 mm thick material being 0.0285 N m.sup.2

[0123] The structural and flexural properties of foam injection moulded HDPE are shown in Table 7 and Table 8. Articles made with electron beam irradiated HDPE of this invention have a relative low density and open cell content as compared to the standard HDPE (Comparative examples). The articles made with electron beam irradiated HDPE have a flexural rigidity being at least a factor 3 higher than compact material with the same weight. Samples produced with standard HDPE only show a limited increase (less than factor 3) In flexural rigidity compared to compact material with the same weight.

TABLE-US-00008 TABLE 7 Structural and flexural properties of foam injection moulded plates produced with MuCell ®technology (physical foaming), Variotherm and mould opening as described in Table 5. Comparative Comparative Parameter Unit Example I Example II Example III Example A Example B Total density kg/m.sup.3 356 376 383 626 553 Open cell content % 16 30 30 90 16 Cell size μm 1386 121 156 — — Fraction foam — 0.81 0.89 0.88 0.76 0.82 Thickness mm 8.5 8.6 8.5 5.1 5.5 Flexural modulus N/mm.sup.2 412 306 351 759 556 Flexural rigidity — 7.2 4.6 4.9 2.4 2.6 change

TABLE-US-00009 TABLE 8 Structural and flexural properties of foam injection moulded plates using a chemical blowing agent (CF40E) and a fixed cold mould as described in Table 6. Comparative Parameter Unit Example IV Example C Total density kg/m.sup.3 481 577 Open cell content % 11 74 Cell size μm 153 188 Fraction foam — 0.78 0.89 Thickness mm 8.4 8.4 Flexural modulus N/mm.sup.2 455 387 Flexural rigidity change — 3.3 1.6