Injection-molded automotive body parts based on polyaryletherketone (PAEK)

Abstract

本発明は、ポリマーブレンド(PB)から製造されたものであるか又はこのポリマーブレンド(PB)を含有するポリマー部品を含む自動車車体部品であって、ポリマーブレンド(PB)が、·45.0~65.0重量%の少なくとも1種のポリアリールエーテルケトン(PAEK)と、·少なくとも1種の非晶質熱可塑性ポリマー(ATP)と、·1.0~15.0重量%の、タルク、窒化ホウ素、マイカ、黒鉛、グラフェン、及び前記無機フィラーの2種以上の組み合わせからなる群の中で選択される少なくとも1種の無機フィラーと、·任意選択的な、最大14.0重量%の少なくとも1種のプラスチック添加剤、特に着色剤、耐衝撃性改良剤、紫外線安定剤、熱安定剤、酸化防止剤、内部潤滑剤及び / 又は外部潤滑剤、難燃剤、帯電防止剤、アンチブロッキング剤、並びにそれらの組み合わせからなる群の中で選択されるプラスチック添加剤と、を含むか又はこれらからなり、PAEKとATPの合計割合が85.0~96.0重量%であり、これらの割合が、ポリマーブレンド(PB)の総重量に対する重量%で示されており、前記ポリマーブレンド(PB)が、少なくとも20.0J / gの溶融熱(Hm)を示す、自動車車体部品に関する。

Claims

1. Automobile body parts that are manufactured from a polymer blend (PB) or include polymer parts containing the polymer blend (PB), wherein the polymer blend (PB) is - 45.0 to 65.0% by weight of at least one polyaryl ether ketone (PAEK), (i) having a glass transition temperature Tg of at least 180°C, and (ii) at least one amorphous thermoplastic polymer (ATP) selected from the group consisting of polyphenylsulfone (PPSU), polyethersulfone (PES), polysulfone (PSU), polyetherimide (PEI), and two or more combinations of the aforementioned polymers, - At least one inorganic filler selected from the group consisting of two or more combinations of talc, boron nitride, mica, graphite, graphene, and inorganic fillers, in an amount of 1.0% to 15.0% by weight, - A choice of at least one plastic additive, up to 14.0% by weight, particularly selected from the group consisting of colorants, impact modifiers, UV stabilizers, heat stabilizers, antioxidants, internal lubricants and / or external lubricants, flame retardants, antistatic agents, antiblocking agents, and combinations thereof, This includes or consists of these: The combined percentage of PAEK and ATP is between 85.0% by weight and 96.0% by weight. These proportions are expressed as weight % of the total weight of the polymer blend (PB), The polymer blend (PB) has a heat of fusion (H) of at least 20.0 J / g, preferably at least 40.0 J / g. ｍ ) indicates, Tg and Hm were measured by DSC according to ASTM D3418-03. Automotive body parts.

2. The automobile body part according to claim 1, wherein the amorphous thermoplastic polymer (ATP) is selected from the group consisting of polyphenylsulfone (PPSU), polyethersulfone (PES), polysulfone (PSU), and two or more combinations of the polymer.

3. The polymer blend (PB) has a linear thermal expansion coefficient (CLTE) of 57×10 －６ °C －１ or less, preferably 55×10 －６ °C －１ or less, preferably 50×10 －６ °C －１ or less, preferably 45×10 －６ °C －１ or less, more preferably 40×10 －６ °C －１ or less, and the linear thermal expansion coefficient (CLTE) is measured from 0°C to 100°C in accordance with ASTM E831. The automotive body part according to claim 1 or 2.

4. The automotive body part according to claim 1 or 2, wherein the polymer blend (PB) exhibits an absorbed fracture energy of 30.0 J or more, preferably 50.0 J or more, preferably 55.0 J or more, and preferably 60.0 J or more, and the absorbed fracture energy is calculated at a position 50% from the maximum load and measured at -15°C on a 10.16 cm × 10.16 cm × 0.32 cm test plate in accordance with ASTM D3763.

5. The automotive body part according to any one of claims 1 to 4, wherein the polymer blend (PB) exhibits a heat distortion temperature at 1.82 MPa of at least 170°C, preferably at least 180°C, and most preferably at least 190°C, as measured according to ASTM D648.

6. The automotive body part according to any one of claims 1 to 5, wherein the polymer blend (PB) exhibits a tensile modulus of at least 3000 MPa, preferably at least 3500 MPa, and preferably at least 4000 MPa, as measured in accordance with ISO 527.

7. The polymer blend (PB) has a pressure of 150 Pa·s or less, and a pressure of 5000s. －１ An automobile body part according to any one of claims 1 to 6, wherein the melt viscosity is measured at 400°C, and the viscosity is measured using a capillary rheometer in particular in accordance with ASTM D3835.

8. The total proportion of the inorganic filler is, 4.0% to 15% by weight; or 4.0% to 12.0% by weight, preferably 4.0% to 10.0% by weight, or 6.0% to 10.0% by weight The automobile body part according to any one of claims 1 to 7.

9. The automobile body part according to any one of claims 1 to 8, wherein the proportion of PAEK is 45.0% by weight to 60.0% by weight, or 45.0% by weight to 57.0% by weight.

10. The automobile body part according to any one of claims 1 to 9, wherein the total proportion of PAEK and ATP is at least 88.0% by weight, preferably at least 90.0% by weight.

11. The automobile body part according to any one of claims 1 to 10, wherein the proportion of the plastic additive is a maximum of 10.0% by weight.

12. The automobile body part according to any one of claims 1 to 11, wherein the PAEK is selected from the group consisting of PEEK, PEEK-PEDEK, PEKK, PEK, PEEKK, PEKEKK, and two or more combinations of the polymer.

13. The automobile body part according to any one of claims 1 to 12, wherein the PAEK is PEEK.

14. PEEK is present in at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%, of the repeating units, most preferably all of the repeating units, of formula (J'-A): 【Chemistry 1】 The automobile body part according to claim 12 or 13, wherein the polymer is a repeating unit.

15. The automobile body panel according to any one of claims 12 to 14, wherein the melt viscosity of the PEEK, as measured at a temperature of 400°C and a shear rate of 1000 1 / s according to ASTM D3835, is 50 Pa₂s to 500 Pa₂s, preferably 100 Pa₂s to 350 Pa₂s.

16. PPSU is present in at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%, of the repeating units, most preferably all of the repeating units, in the form of formula (L''): 【Chemistry 2】 Repeating unit (R ＰＰＳＵ An automobile body part according to any one of claims 1 to 15, wherein the polymer is a polymer.

17. The automobile body part according to any one of claims 1 to 16, wherein the melt flow rate (MFR) of the PPSU, measured at 365°C under a load of 5.0 kg according to ASTM D1238, is 20.0 to 50.0 g / 10 min, preferably 25.0 g / 10 min to 40.0 g / 10 min.

18. PES is present in at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%, of the repeating units, most preferably all of the repeating units, which is formula (O''): 【Transformation 3】 Repeating unit (R ＰＥＳ An automobile body part according to any one of claims 1 to 17, wherein the polymer is a polymer.

19. The automobile body part according to any one of claims 1 to 18, wherein the melt flow rate (MFR) of the PES, measured at 380°C with a load of 2.16 kg according to ASTM D1238, is 20.0 to 120.0 g / 10 min, preferably 50.0 g / 10 min to 90.0 g / 10 min.

20. The automobile body part according to any one of claims 1 to 19, wherein all the components of the polymer blend (PB) are blended together to preferably form a uniform blend.

21. The automobile body part according to any one of claims 1 to 20, wherein the polymer blend (PB) is based on a combination of PEEK + PPSU or PEEK + PPSU + PES, particularly a combination of PEEK and PPSU, or a combination of PEEK, PPSU and PES.

22. The aforementioned polymer blend (PB) - At least one type of PEEK in an amount of 45.0% to 65.0% by weight, - At least one amorphous PPSU having a glass transition temperature Tg of at least 180°C, - At least one inorganic filler selected from the group consisting of talc, boron nitride, mica, graphite, graphene, and two or more combinations of the aforementioned inorganic fillers, in an amount of 1.0% to 15.0% by weight, - At least one plastic additive selected from the group consisting of colorants, impact modifiers, UV stabilizers, heat stabilizers, antioxidants, internal lubricants and / or external lubricants, flame retardants, antistatic agents, antiblocking agents, and combinations thereof, in an optional amount of up to 14.0% by weight, This includes or consists of these: The combined percentage of PEEK and PPSU is between 85.0% by weight and 96.0% by weight. Automobile body part according to any one of claims 1 to 21.

23. The aforementioned polymer blend (PB) - At least one type of PEEK in an amount of 45.0% to 65.0% by weight, - At least one amorphous PPSU having a glass transition temperature Tg of at least 180°C and at least one amorphous PES having a glass transition temperature Tg of at least 180°C, - At least one inorganic filler selected from the group consisting of talc, boron nitride, mica, graphite, graphene, and two or more combinations of the aforementioned inorganic fillers, in an amount of 1.0% to 15.0% by weight, - A choice of at least one plastic additive, up to 14.0% by weight, particularly selected from the group consisting of colorants, impact modifiers, UV stabilizers, heat stabilizers, antioxidants, internal lubricants and / or external lubricants, flame retardants, antistatic agents, antiblocking agents, and combinations thereof, This includes or consists of these: The total percentage of PEEK, PES, and PPSU is between 85.0% by weight and 96.0% by weight. Automobile body part according to any one of claims 1 to 21.

24. The automobile body part according to claim 23, wherein the proportion of PPSU is less than 10.0% by weight, or between 1.0% by weight and 10.0% by weight.

25. The automobile body part according to any one of claims 1 to 24, wherein the inorganic filler is a plate-shaped inorganic filler.

26. The inorganic filler is, - Arithmetic mean aspect ratio AR1 of 1 to 4 (AR1 represents the ratio a / b of the major axis a to minor axis b of an ellipse that best fits the shape of the filler particle, determined by scanning electron microscopy (SEM) on a large number of particles (especially at least 200); and / or - Arithmetic mean aspect ratio AR2 greater than 10.0 (AR2 is determined by scanning electron microscopy (SEM) on a large number of particles (especially at least 200) and represents the ratio a / c of ​​the major axis a of the ellipse that best fits the shape of the filler particle to the thickness c of the particle). An automobile body part according to any one of claims 1 to 25, characterized by having the following features.

27. The automobile body part according to any one of claims 1 to 26, wherein the inorganic filler exhibits a D50 of less than 100.0 microns or less than 50.0 microns, and D50 is the median of the size distribution in the volume obtained by laser diffraction measurement.

28. The automotive body part according to any one of claims 1 to 27, wherein the polymer blend (PB) exhibits one or more, preferably all, of the following properties: (a) The linear thermal expansion coefficient (CLTE) measured at 0°C to 100°C according to ASTM E831 is 50 × 10⁻⁶ －６ ℃ －１ Preferably 45 x 10 －６ ℃ －１ More preferably, 40 x 10 －６ ℃ －１ The following conditions must be met: (b) The absorbed fracture energy, calculated at 50% of the maximum load in accordance with ASTM D3763 and measured at -15°C on a 10.16 cm × 10.16 cm × 0.32 cm (4 inches × 4 inches × 0.125 inches) test plate, is 60.0 J or greater; (c) The thermal distortion temperature at 1.82 MPa, as measured according to ASTM D648, is at least 190°C; (d) The tensile modulus, as measured in accordance with ISO 527, is at least 3500 MPa.

29. An automobile body panel according to any one of claims 1 to 28, wherein layer (L) is in contact with the surface of the polymer component, and layer (L) is particularly composed of layer (L1) / (L2), where layer (L1) is an adhesive layer and layer (L2) is a layer that provides a visual effect and / or protection.

30. The automotive body part according to any one of claims 1 to 29, wherein the surface of the polymer part is pre-treated by a treatment selected from flame treatment, corona treatment, plasma treatment, mechanical polishing, and chemical treatment.

31. The automobile body part according to any one of claims 1 to 30, wherein the polymer part is flat and / or curved.

32. The automotive body part according to any one of claims 1 to 31, wherein the polymer part is a three-dimensional structure having length, width and thickness, and both the length L and width W are significantly larger than the thickness T, and L / T and W / T are particularly 100 or more, preferably 150 or more.

33. The automobile body part according to any one of claims 1 to 32, wherein the polymer part is a panel.

34. The automobile body part according to any one of claims 1 to 33, wherein the automobile body part is selected from the group consisting of a roof panel, a hood panel, a deck panel, a rear fender panel, a front fender panel, a quarter panel, a trunk lid, a rear hatch panel, a floor panel, and a door panel.

35. Use of a polymer blend (PB) according to any one of claims 1 to 28 for the manufacture of an automotive body part, particularly a polymer part of an automotive body part according to any one of claims 1 to 34.

36. The use according to claim 35, wherein the polymer component is flat and / or curved.

37. The use according to claim 35 or 36, wherein the polymer component has a three-dimensional structure having length, width and thickness, and both the length L and width W are significantly larger than the thickness T, and L / T and W / T are particularly 100 or more, preferably 150 or more.

38. The use according to any one of claims 35 to 37, wherein the polymer component is a panel.

39. The use according to any one of claims 35 to 38, wherein the automobile body part is selected from the group consisting of a roof panel, a hood panel, a deck panel, a rear fender panel, a front fender panel, a quarter panel, a trunk lid, a rear hatch panel, a floor panel, and a door panel.

40. Use of a polymer (P) for the manufacture of a polymer part according to any one of claims 1 to 28 of an automobile body part, or for the manufacture of an automobile body part according to any one of claims 1 to 34, wherein the polymer (P) is selected from the group consisting of polyaryl ether ketone (PAEK), polyphenyl sulfone (PPSU), polyether sulfone (PES), polysulfone (PSU), and polyetherimide (PEI).

41. A method for manufacturing a polymer part for an automobile body, comprising the step of injection molding a polymer blend (PB) according to any one of claims 1 to 28.

42. The method according to claim 41, wherein the polymer component is flat and / or curved.

43. The method according to claim 41 or 42, wherein the polymer component is a three-dimensional structure having length, width and thickness, and both the length L and width W are significantly larger than the thickness T, and L / T and W / T are particularly 100 or more, preferably 150 or more.

44. The method according to any one of claims 41 to 43, wherein the polymer component is a panel.

45. The method according to any one of claims 41 to 44, wherein the automobile body part is selected from the group consisting of a roof panel, a hood panel, a deck panel, a rear fender panel, a front fender panel, a quarter panel, a trunk lid, a rear hatch panel, a floor panel, and a door panel.

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