Rigid and ductile polyamide-based transparent composition and use thereof

Abstract

The invention relates to the use of at least one impact modifier having a refractive index IR.sub.1 in a polyamide matrix consisting of a mixture of amorphous polyamide and semicrystalline polyamide, said matrix having a refractive index IR2, the difference in absolute value of IR.sub.1-IR.sub.2 not exceeding 0.006, to produce a transparent composition having a fatigue strength, under the fatigue test referred to as notched “Ross-Flex”, greater than 50 000 at −10° C.

Claims

1. A transparent composition comprising at least one impact modifier having a refractive index RI.sub.1 dispersed in a polyamide matrix comprising a mixture of at least one amorphous polyamide and at least one semi-crystalline polyamide, said polyamide matrix having a refractive index RI.sub.2, the difference in absolute value RI.sub.1-RI.sub.2 being less than or equal to 0.006, said transparent composition having a resistance in the notched Ross Flex fatigue test of greater than 50,000 at −10° C., wherein the Ross Flex test used is ASTM D1052 09(2014), the sample is notched, and the fold angle is 60°, wherein the transparent composition has a transparency such that the transmittance at 560 nm on a plate 2 mm thick is greater than or equal to 75% determined according to standard ISO 13468-2:2006, wherein said impact modifier represents from 17 to 27% of the total weight of the composition, wherein the transparent composition is free of polyether block amide (PEBA), wherein the impact modifier is a polymer having a flexural modulus less than 100 MPa measured according to the ISO 178 standard and Tg below 0° C. measured according to the standard 11357-2 near the inflection point of the DSC thermogram.

2. The transparent composition according to claim 1, wherein said transparent composition has a fatigue test resistance of greater than 100,000 at 23° C.

3. The transparent composition according to claim 1, wherein said matrix mixture comprises, by weight, the total being equal to 100%: 55 to 75% by weight of at least one semi-crystalline polyamide wherein each semi-crystalline polyamide has a mean number of carbon atoms relative to the nitrogen atom greater than 9, said semi-crystalline polyamide having formula A/Z wherein, A is a repeating aliphatic unit chosen from a unit obtained from the polycondensation of at least one aminocarboxylic acid and a unit obtained from the polycondensation of at least one lactam or a unit X-Y obtained from the polycondensation: of at least one diamine, said diamine being selected from a linear or branched aliphatic diamine, and a cycloaliphatic diamine, and at least one dicarboxylic acid, said dicarboxylic acid being chosen from: an aliphatic diacid and a cycloaliphatic diacid, said diamine and said dicarboxylic acid comprising from 4 to 36 carbon atoms, and Z represents a repeating aliphatic unit as defined for A but different than A and is included at from 0 to 20% relative to the sum A+Z; 25 to 45% by weight of an amorphous polyamide.

4. The transparent composition according to claim 3, wherein the proportion of Z=0.

5. The transparent composition according to claim 1, wherein said transparent composition further comprises from 0 to 5% of at least one additive selected from the group consisting of stabilizers, colorants, plasticizers, and whitening agents.

6. The transparent composition according to claim 1, wherein said transparent composition further comprises from 0 to 10% by weight of at least one fluidifying agent, wherein said fluidifying agent is a processing aid to aid in processing or demolding.

7. The transparent composition according to claim 1, wherein said transparent composition comprises, by weight, the total being equal to 100%: from 65 to 83% of said mixture of at least one amorphous polyamide and at least one semi-crystalline polyamide, from 17 to 27% of at least one impact modifier, optionally, from 0 to 5% of at least one additive selected from the group consisting of stabilizers, colorants, plasticizers, and whitening agents, optionally, from 0 to 10% by weight of at least one fluidifying agent, wherein said fluidifying agent is a processing aid to aid in processing or demolding, said amorphous polyamide being in sufficient proportion for the transparent composition to be sufficiently rubber at low temperature, and has an impact resistance with a T.sub.RG<0° C. as determined according to standard ISO 179 1eA.

8. The transparent composition according to claim 1, wherein the transparent composition has a Haze less than or equal to 25% in Haze units, measured according to standard ASTM D1003-97.

9. The transparent composition according claim 1, wherein the semi-crystalline polyamide is an aliphatic polyamide.

10. The transparent composition according to claim 9, wherein the aliphatic semi-crystalline polyamide is selected from the group consisting of PA11, PA12, PA1010, and PA1012.

11. The transparent composition according to claim 10, wherein the aliphatic semi-crystalline polyamide is PA11 and the amorphous polyamide is 11/B10, B being bis-(3-methyl-4-aminocyclohexyl)-methane.

12. The transparent composition according to claim 1, wherein the amorphous polyamide is a polyamide having formula A.sub.1/X.sub.1Y.sub.1 wherein: A.sub.1 is a repeating aliphatic unit chosen from a unit obtained from the polycondensation of at least one aminocarboxylic acid and a unit obtained from the polycondensation of at least one lactam or a unit obtained from the polycondensation of at least one aliphatic diamine and at least one aliphatic diacid, X.sub.1 is a cycloaliphatic diamine, and Y.sub.1 is a dicarboxylic acid, said dicarboxylic acid being chosen from an aliphatic diacid, a cycloaliphatic diacid and an aromatic diacid, said diamine and said diacid described in A.sub.1, X.sub.1, and Y.sub.1 comprising from 4 to 36 carbon atoms.

13. The transparent composition according to claim 12, wherein the amorphous polyamide is selected from the group consisting of 11/B10, 11/P10, 12/B10, 12/P10, 11/BI, 11/PI, 12/BI, and 12/PI, B being bis-(3-methyl-4-aminocyclohexyl)-methane and P being p-bis(aminocyclohexyl)-methane.

14. The transparent composition according to claim 1, wherein the impact modifier is chosen from styrene/ethylene-butene/styrene (SEBS) block copolymers.

15. The transparent composition according to claim 1, wherein the semi-crystalline polyamide and/or the amorphous polyamide is(are) partially or completely biosourced.

16. A transparent composition according to claim 1, comprising: from 73 to 83% by weight of a polyamide matrix having a refractive index RI.sub.2, from 17 to 27% by weight of at least one impact modifier having a refractive index RI.sub.1, said impact modifier not being PEBA, optionally, from 0 to 5% of at least one additive selected from the group consisting of stabilizers, colorants, plasticizers, and whitening agents, optionally, from 0 to 10% by weight of at least one fluidifying agent, wherein said fluidifying agent is a processing aid to aid in processing or demolding, the sum of the constituents being equal to 100% and the difference in absolute value RI.sub.1-RI.sub.2 being less than or equal to 0.006.

17. The transparent composition according to claim 16, wherein said polyamide matrix is a mixture comprising from 55 to 75% by weight of an aliphatic semi-crystalline polyamide and from 25 to 45% by weight of an amorphous polyamide.

18. The transparent composition according to claim 16, wherein the semi-crystalline polyamide is an aliphatic semi-crystalline polyamide selected from the group consisting of PA11, PA12, PA1010, and PA1012.

19. The transparent composition according to claim 18, wherein the aliphatic semi-crystalline polyamide is PA11 and the amorphous polyamide is 11/B10, B being bis-(3-methyl-4-aminocyclohexyl)-methane.

20. The transparent composition according to claim 16, wherein the amorphous polyamide is selected from the group consisting of 11/B10, 12/B10, 11/BI/BT, 11/BI, B being bis-(3-methyl-4-aminocyclohexyl)-methane.

21. The transparent composition as defined in claim 1, wherein said transparent composition is part of an article, wherein said article is selected from the group consisting of a sports article, eyewear, an electric and electronic article, a fiber, cloth, film, sheet, rod, tube, and an injected part, wherein said article is obtained by extrusion, injection, molding or thermoforming.

22. The transparent composition according to claim 21, wherein said article is obtained by injection, and wherein said article is selected from the group consisting of a sports article, a ski boot, a ski boot part, a rigid shoe with cleats, a part of rigid shoes with cleats, a soccer cleat, rugby cleat, football cleat, hockey footwear, a part of hockey footwear, a running shoe, a golf ball, a part of a golf ball, a lacrosse stick, a hockey article, a helmet, sport articles for protecting the head, shoulders, elbows, hands, knees, back or shins, helmets, gloves, shoulder pads, elbow pads, knee pads, shin guard, optical articles, goggles, a mask, protective goggles, and a ski mask.

23. The transparent composition as defined in claim 1, wherein said transparent composition is part of an article selected from the group consisting of, a part of a ski boot, a part of a roller boot, a part of hockey footwear, a ski boot, goggles, a mask, protective goggles, and a ski mask.

24. A method for forming an article from the transparent composition of claim 1, comprising a step of mixing said matrix, said impact modifier, optionally an additive and optionally a fluidifying agent, in a melt, in an extruder, at a temperature of between 230 and 330° C., to produce granules, said granules then injected at a temperature of between 230 and 330° C., on an injection press to produce the desired article, wherein said fluidifying agent is a processing aid to aid in processing or demolding, wherein said additive is selected from the group consisting of stabilizers, colorants, plasticizers, whitening agents, and mixtures thereof.

25. The transparent composition according to claim 1, wherein said amorphous polyamide has an impact resistance with a T.sub.RG<0° C. as determined according to standard ISO 179 1eA.

Description

EXAMPLES

(1) The semi-crystalline (PAsc) and amorphous (PAam) polyamides are prepared by polycondensation according to methods known to the person skilled in the art.

(2) TABLE-US-00001 Ross Flex % impact Transmittance Number of cycles modifier 100 × @560 nm, Haze Flexural at break at (Kraton ® (PAsc/ΣPA) 2 mm (2 mm) modulus T.sub.RG 23° C./−10° C. - RI.sub.1- Ref 1901) (%) (%) (%) (MPa) (° C.) Notched - RI.sub.2 C1 7.5 50 83 — 1300 5 13,000/5,000 0.0045 C2 4 62 85 — 1250 23  7,000/3,000 0.0053 C3 10 50 83 — 1200 <0  8,000/3,000 0.0045 I1 10 70 75 — 1140 <0 >100,000/>50,000 0.0059 C4 10 78 71 — 1050 <0 >100,000/>50,000 0.0065 C5 12.5 34 82 — 1200 <0  7,000/4,000 0.0034 C6 12.5 50 84 — 1150 <0  8,000/3,000 0.0045 C8 15 18 83 — 1180 <0  5,000/2,000 0.0023 C9 15 50 82 — 1110 <0  30,000/10,000 0.0045 I2 15 63 79 — 1000 <0 >100,000/>50,000 0.0054 C10 15 82 69 — 980 <0 >100,000/>50,000 0.0067 I3 17.5 63 78 — 960 <0 >100,000/>50,000 0.0054 C11 20 35 83 — 1110 <0 12,000/2,500 0.0034 I4 20 66 77 — 940 <0 >100,000/>50,000 0.0056 C12 15 (Peba 100 <75 — 850 >0 >100,000/>50,000 >0.006 40ShD) C13 12 (Fusabond 55 <75 — 1100 <0 >100,000/>50,000 >0.006 493N) C14 21 (Fusabond 67 <75 — 940 <0 >100,000/>50,000 >0.006 493N) I5 20 66 76 22 950 <0 >100,000/>50,000 0.0056 I6 21 67 75 20 920 <0 >100,000/>50,000 0.0057 I7 25 62 75 17 910 <0 >100,000/>50,000 0.0053 C15 0 30 88 — 1300 >0  3,000/1,000 — C16 0 70 83 — 1200 >0  30,000/12000 — I8 21 67.5 77 20 960 <0 >100,000/>50,000 0.0057 I9 21 67.5 75 21 880 <0 >100,000/>50,000 0.0057 I10 25 64 75 19 910 <0 >100,000/>50,000 0.0055 I11 25 66 75 20 900 <0 >100,000/>50,000 0.0056 I12 25 68 75 21 890 <0 >100,000/>50,000 0.0058 I13 22.5 64 76 18 930 <0 >100,000/>50,000 0.0055 I14 22.5 66 76 19 930 <0 >100,000/>50,000 0.0056 I15 22.5 68 75 24 920 <0 >100,000/>50,000 0.0058

(3) The mixtures were created by a compounding method, using a twin-screw co-rotating extruder 40×D long (D=screw diameter and =18 mm), at a flow rate Q=7 kg/h, a screw rate of 300 rpm, and at a T=270° C.

(4) The flexural modulus is determined according to ISO 178:2010.

(5) The impact strength is obtained with the Charpy impact test conducted according to standard ISO 179 1eA.

(6) Therefore the rubber-glass transition (T.sub.RG) corresponds to the inflection point of the curve of impact strength as a function of temperature.

(7) The Ross Flex fatigue test is conducted in accordance with standard ASTM D1052 09(2014) with the modifications described above. Parts 2 mm thick, 150 mm long and 20 mm wide were made from the compositions of the invention (I.sub.n) or comparison compositions (C.sub.n). These parts have been notched V (1×1 mm wide and deep, with notch base radius of 0.25 mm), the fold angle is 60°, then conditioned for 7 days at 70° C. and 62% relative humidity. The number of cycles is 100/min.

(8) The samples are tested at 23° C. or −10° C.

(9) Through the “Ross Flex” test the number of times after which the part, folded at the height of the notch at 600 and at a temperature of 23° C. or −10° C., breaks. It is considered that the part meets the conditions of this test when the number of cycles is greater than or equal to 50,000.

(10) The Ross Flex results are expressed in numbers of cycles at break. Signifies not tested

(11) Transmittance is determined according to ISO 13468-2:2006.

(12) Haze is measured according to standard ASTM D1003-97.

(13) The shock modifier used is Kraton® FG 1901 (Kraton Polymers International), which is a maleic anhydride-grafted SEBS apart from composition C12 wherein a PEBA (11PTMG1000 (50/50)) with 40 Shore D is used, and compositions C13 and C14 wherein a Fusabond 493N (sold by DuPont), which is a maleic anhydride-modified ethylene copolymer.

(14) The sum of the percentage of impact modifier and mixture of semi-crystalline polyamide with the amorphous polyamide represents 100% in all the examples apart from examples 19 that correspond to I8 plus 2% by weight of Bruggolen® TP-P1507, the total being equal to 100%, and for examples 110-12 wherein there is 6% of oligomer PA11-mono NH.sub.2 having Mn=3000 g/mol, the total being equal to 100% and examples 13-115, wherein there is 4.5% of oligomer PA11-mono NH.sub.2 having Mn=3000 g/mol, the total being equal to 100%.

(15) The mixture of polyamides in the compositions of the invention is constituted of PAsc:PA11 and PAam:PA11/B10
ΣPA=% PAsc+% PAam.