Polymer composition for high-heat application comprising thermo-releasable substance

Abstract

The invention relates to a polymer composition suitable for high-heat application comprising: a. At least one polymer 1 having a solubility parameter P1; b. A thermo-releasable substance being a liquid at 200 C. and having a solubility parameter sub in an amount of at least 0.1 wt % with respect to the total amount of composition; and wherein the amount of thermo-releasable substance is in the range from 0.5 wt % to 70 wt % with respect to the polymer 1; wherein =(subP1).sup.2 is in the range from 0.5 to 24.0 and wherein the solubility parameter is calculated by the software package Synthia, Materials Studio v.6.0.0 2011, based on the method by J. Bicerano, Prediction of Polymer Properties, Marcel Dekker, 3rd Ed, 2002, ISBN 0-8247-0821-0; Chapter 5, and in which the E-modulus of the composition as measured according to method ISO 527-1 at 200 C. is at least 50 MPa. The invention also relates to personal care devices and hair-straighteners comprising this polymer composition.

Claims

1. A polymer composition suitable for high-heat application comprising a melt-blend mixture of: (a) at least one polymer 1 having a solubility parameter P1; (b) a thermo-releasable substance having a solubility parameter sub which is a liquid at 200 C., wherein the thermo-releasable substance is mixed with the at least one polymer 1 in an amount which is at least 0.1 wt % based on total weight of the composition and in an amount which is in a range from 0.5 wt % to 70 wt % based on weight of the polymer 1; wherein the composition exhibits a =(subP1).sup.2 which is in a range from 0.5 to 24.0 and has an E-modulus measured according to method ISO 527-1 at 200 C. of at least 50 MPa.

2. The polymer composition according to claim 1, wherein is in the range from 1.0 to 20.0.

3. The polymer composition according to claim 1, wherein the E-modulus of the composition is at least 70 MPa at 200 C. measured according to method ISO 527-1.

4. The polymer composition according to claim 1, wherein the E-modulus of the composition is at least 90 MPa at 200 C. measured according to method ISO 527-1.

5. The polymer composition according to claim 1, wherein the amount of thermo-releasable substance is present in the range from 0.5 wt % to 30 wt % based on the total weight of the composition.

6. The polymer composition according to claim 1, wherein the thermo-releasable substance is selected from the group consisting of polydimethylsiloxane, linear parafins, natural oils and combinations thereof.

7. The polymer composition according to claim 1, wherein the thermo-releasable substance comprises a natural oil selected from the group consisting of avocado oil, argan oil, camealia oil, sunflower oil, macadamia nut oil, safflower oil, apricot kernel oil and combinations thereof.

8. The polymer composition according to claim 1, wherein the polymer 1 is at least one selected from the group consisting of thermoplastic polyesters, syndiotactic polystyrene, styrene maleic anhydride copolymers, polybutylene naphthalate and polyamides.

9. The polymer composition according to claim 1, wherein the composition further comprises a semi-crystalline polymer with a melting temperature of at least 10 C. above an application temperature, which is selected from the group consisting of polyethylene terephthalate, polyamides, polystyrenes, polybutylene naphthalate (PBN) and polyethylene naphthalate (PEN).

10. The polymer composition according to claim 9, wherein the polymer 1 is a polybutylene terephthalate-co-dimer fatty acid and the thermo-releasable substance comprises a natural oil selected from the group consisting of avocado oil, argan oil, camealia oil, sunflower oil and combinations thereof.

11. The polymer composition according to claim 1, wherein the polymer 1 is a polybutylene terephthalate-co-dimer fatty acid and the thermo-releasable substance comprises a natural oil selected from the group consisting of avocado oil, argan oil, camealia oil, sunflower oil and combinations thereof and the further polymer is polyethyleneterephthalate.

12. The polymer composition according to claim 1, wherein is in the range from 1.0 to 15.0.

13. The polymer composition according to claim 1, wherein is in the range from 1.0 to 10.0.

14. A personal care device comprising a surface for contacting hair, wherein the surface of the device is made from the polymer composition according to claim 1.

15. The personal care device according to claim 14, wherein the surface for contacting hair is operated at a temperature of at least 100 C.

16. The personal care device according to claim 14, wherein the device is a hair-straightener.

17. A hair-straightener comprising a sleeve made from the polymer composition according to claim 1.

Description

EXAMPLES

(1) Materials Used

(2) Polymers:

(3) PA-6=polyamide-6=Akulon K125 or Akulon K122 of DSM PA-66=polyamide-6,6=S222 of DSM PA-4,10=polyamide-4,10=EcoPaxx Q150MS of DSM SPS=Syndiotactic Polystyrene (Idemitsu Chemicals Europe, Xarec 90ZC, Xarec 300ZC, Xarec 142ZE) PET (A02 36)=polyethyleneterephthalate=Arnite A02 306 of DSM PET (5018)=polyethyleneterephthalate=Arnite BAGA 5018 of DSM PBT=polybutyleneterephthalate=Arnite T04 200 of DSM PBT-Eco=polybutyleneterephthalate-co-dimerfattyacid 20% DFA of DSM (Melt volume rate=3) PBT-Eco-2=polybutyleneterephthalate-co-dimerfattyacid 20% DFA of DSM (Melt volume rate=25) PBT-Eco-3=polybutyleneterephthalate-co-dimerfattyacid 40% DFA of DSM (Melt volume rate=40) PBT-E=polybutyleneterephthalate-co-polytetramethyleneoxide=Arnitel EL740 (Melt volume rate=15) PE-MA=Maleic Anhydride Modified Ethylene-Alpha Olefin Copolymer=Bondyram 7103 of Polyram SMA 08250=styrenemaleicanhydride copolymer=XIRAN SZ 08250 of Polyscope Polymers B.V. PBN-D=polybutylenenaphthanate-co-dimerfattyacid amide=experimental product of DSM PC=polycarbonate=Xantar 19R of DSM SAN 581=Poly(styrene-co-acrylonitrile) (75 wt % styrene and 25 wt % acrylonitrile) of Sabic. Comp=Compatibilizer for PA with SPS: acid modified poly(phenylene ether) CX-1, FA-PPE (Idemitsu Kosan Co., Ltd)
Thermo-Releasable Substances (Abbreviated Sub): Argan Oil=product code 50 3808 1 of DSM Nutritional Products Avocado oil=Persea Gratissima oil, Avoaodo oil RBD, code 266554 of IMCD Sunflower oil=product code 1665N of Volatile Camealia Oleifera Seed Oil=Cropure Yuchayu-LQ-(JP), product code SV70391 of Croda Jojoba oil=Simmondsia Chenensis Seed Oil=Cropure Jojoba of Croda Macadamia nut oil CPRBD, code 266526 of IMCD Safflower oil RBDW, code 266969 of IMCD Apricot Kernel oil RBDW, code 266559 of IMCD
Other Additives: I-1076=stabilizer Irganox1076 of Ciba (BASF) Glass=3B CS173-x11 of Owens Corning Carbon 1)=Expanded Graphite (C-Therm 01) Carbon 2)=99.25% Expanded Graphite (C-Therm 01) and 0.75% Carbon Black (Black pearls 800) Carbon 3)=Expanded Graphite (Ecophit GFG1200) Carbon 4)=95% Graphite (Ecophit GFG1200) and 5% Carbon black (Timcal Ensaco260G)
Abbreviations: bdl=below detection limit nd=not determined
Preparing Compositions

(4) Various compositions were made according to the tables below. The compositions were compounded on twin screw extruders like ZSK30/44D at a processing temperature being at least equal to the highest of Tg or Tm of the polymer of the composition. After the mixing the hot polymer composition string was cooled in a water bath or cooling belt and cut into granules suitable for injection molding.

(5) Injection Molding

(6) Injection molding was performed at an Engel 110, a machine with 110 ton maximum clamping force with a screw diameter of 30 mm. On this machine 1201201 mm.sup.3 plates were produced of almost all compositions using plate 1201201 mm.sup.3, for some materials also mechanical test bars were produced on the Engel 110, for these test bars plate ISO 527-1A pr.80*10*4 2v. was used. From the plates plaques were cut to determine the release of the thermo-releasable substance from the composition when used on the straightener. Test bars (dog-bone) were used to produce stress-strain curves of various compositions.

(7) Thermal Stability of Polymer Plaque

(8) In order to determine the thermal stability of the plaque it was fixed to a straightener and set at 200 C. When no visual melting or deformation of the plaque was observed within about 10 minutes the stability was judged as OK, and these compositions are considered suitable for high-heat application.

(9) Qualitative Release Inspection

(10) In order to judge qualitatively whether a plaque of exhibited release of the thermo-releasable substance at higher temperature, the plaques were fixed to a straightener and set at 200 C. After 5 min it was visually inspected if release of thermo-releasable substance was visible. Qualitative release was present when drops of thermo-releasable substance were visual or could be detected by wiping with fingers.

(11) Quantitative Release Inspection:

(12) In order to quantify the release of the thermo-releasable substance from the plate to hair, the following test method was used.

(13) The test was performed on two injection molded plates of 30901 mm. The two plates were attached to heating plates of a Philips straightener HP 8339 with Kapton tape, to allow maximum contact surface between the plate and the heating plates of the straighteners. The straightener was heated to 200 C. Hair swatches were used as test material being 1.5 cm wide, 23 cm free length held together with by a glued part which was not pulled through the straightener (Klebetresse dicht aus Euro-Natur-Haar, remis, Farbe 6/0, Kerling International Haarfabrik GmbH, item number 826500). The hair swatch was pulled 10 times through the straightener in approximately 10 seconds per pull after which the straightener was kept on and a 15 minutes pause was applied without the hair being in proximity of the straightener. This procedure was repeated twice, thus resulting in a single hair swatch being pulled through the straightener 30 times. During the last pull, the swatch was twisted and put in a flask after cutting off the glued part of the swatch.

(14) 4 ml THF (Tetrahydrofuran VWR, chromanorm, prod. code 28559.320) was added to the flask with the swatch and the flask was closed and put on rollers for 15 minutes to allow extraction of the oil from the hair swatch. After these 15 minutes, 1 ml THF/oil mixture was put in a GPC vial for injection on GPC.

(15) GPC Setup

(16) Waters HPLC pump type 515 (flow 1.0 ml/min) Waters autosampler 717plus (injection volume was set at 100 l) Waters column oven, temperature was set to 50 C. Column set: 2 PL-gel Mixed E-columns from PSS Differential Refractive Index detector, Waters 2414

(17) System was controlled by software of Waters, Empower. Calibration for determination of released thermo-releasable substance was done by injection of known amounts of thermo-releasable substance. The detection limit for the thermo-releasable substance on hair determination method is 0.08 mg oil/4 ml THF.

(18) The resulting chromatogram was integrated and compared to a calibration curve of the same thermo-releasable substance mixture resulting in an amount of released thermo-releasable substance in mg from two plates to the hair swatch (1,5 cm wide, 23 cm long hair swatch).

(19) This procedure constituted one treatment. This treatment was repeated and release of thermo-releasable substance was measured during treatment no 5 and treatment no 10. The data are shown in the tables below.

(20) TABLE-US-00003 TABLE 3 Experiments with various thermo-releasable substances Release at sub sub P1 P2 visual 200 C. [mg] Experi- wt % wt % sub Poly- wt % P1 Poly- wt % P2 Comp (sub sub 1st 5th ment on on (J/ mer on (J/ mer on (J/ wt I-1076 P1).sup.2 on treat- treat- no sub total P1 cm.sup.3).sup.1/2 1 total cm.sup.3).sup.1/2 2 total cm.sup.3).sup.1/2 % wt % (J/cm.sup.3) plaque ment ment 1 Sun- 20.1 41.8 17.4 SPS 28 19.52 PA- 48 24.2 2.9 1.0 4.7 yes 29 0.9 flower (90ZC) 4, 10 2 Avo- 20.1 41.8 17.3 SPS 28 19.52 PA- 48 24.2 2.9 1.0 5.0 yes 25 2.5 cado (90ZC) 4, 10 3 Argan 20.1 41.8 17.4 SPS 28 19.52 PA- 48 24.2 2.9 1.0 4.5 yes 25 0.7 (90ZC) 4, 10 4 Jo- 20.1 41.8 17.0 SPS 28 19.52 PA- 48 24.2 2.9 1.0 6.2 yes 1) 1) joba (90ZC) 4, 10 C_1 Argan 10 10.1 17.4 PA-6 89 25.14 1.0 60 no 0.1 bdl (K125) C_2 PDMS 2 2.0 14.2 PA-6 98 25.14 120 no 2) nd (K122) C_3 PDMS 0.5 0.5 14.2 PA-66 99.5 25.14 120 no 2) nd (S222) 1) = Quantitative analytical method (GPC) not adequate for this oil but after heating oil was visival on polymer sleeve 2) = Quantitative analytical method (GPC) not adequate for this oil but after heating no oil was visual at polymer sleeve, IR analysis of sleeve was inconclusive

(21) TABLE-US-00004 TABLE 4 Experiments with one polymer Release at Sub = 200 C. Argan [mg] thermal oil (sub 1st 5th 10th stability Experiment = 17.4 Polymer P1 I-1076 P1).sup.2 treat- treat- treat- at no wt % 1 wt % (J/cm.sup.3).sup.1/2 wt % (J/cm.sup.3) ment ment ment 200 C. 5 5 PBN-D 94.0 19.6 1.0 4.7 0.81 0.20 0.14 Yes 6 17 SPS (142ZE) 82.0 19.5 1.0 4.5 6.40 0.80 0.70 Yes 7 29 SPS (142ZE) 70.0 19.5 1.0 4.5 12.40 0.80 0.10 Yes 8 29 SPS (330ZC) 70.0 19.5 1.0 4.5 7.10 0.70 0.10 Yes 9 29 SPS (90ZC) 70.0 19.5 1.0 4.5 13.20 1.60 0.30 Yes C_4 7.5 PA-4, 10 91.5 24.2 1.0 46.2 bdl bdl nd Yes C_5 15 PBT-Eco 84.0 18.8 1.0 1.8 0.80 nd nd No

(22) TABLE-US-00005 TABLE 5 Experiments with two polymers Sub = Release at Argan sub P1 P2 200 C. [mg] oil wt % wt % wt % (sub 1st 5th 10th Experiment = 17.4 on polymer on P1 polymer on P2 Comp I-1076 P1).sup.2 treat- treat- treat- no wt % P1 1 total (J/cm.sup.3).sup.1/2 2 total (J/cm.sup.3).sup.1/2 wt % wt % (J/cm.sup.3) ment ment ment 10 7 17.5 PBT-Eco 33.0 18.8 PBT 59 18.8 1.0 1.8 0.5 0.1 0.1 11 1.5 5.0 PBT-E 28.5 19.2 PET 69 19.8 1.0 3.3 nd 0.2 0.1 12 9 33.3 SMA (08250) 18.0 19.9 PA-4, 10 72 24.2 1.0 6.4 0.2 0.2 0.1 13 22 44.0 SPS (142ZE) 28.0 19.5 PA-4, 10 46 24.2 3.0 1.0 4.5 12.5 1.6 0.6 14 21 42.0 SPS (90ZC) 29.0 19.5 PA-4, 10 46 24.2 3.0 1.0 4.5 20.5 3.4 0.7 15 10 35.7 SAN (581) 18.0 20.8 PA-4, 10 71 24.2 1.0 11.6 0.7 0.1 nd 16 8 18.2 PBT-Eco 36.0 18.8 PA-4, 10 55 24.2 1.0 1.8 0.7 0.5 nd 17 8 29.6 PC (19R) 19.0 19.3 PA-4, 10 72 24.2 1.0 3.7 0.3 nd nd C_6 15 46.9 PE-MA (7103) 17.0 17.3 PA-4, 10 67 24.2 1.0 0.0 bdl nd nd

(23) TABLE-US-00006 TABLE 6 Experiments with two polymers and quantification of E-modulus sub Sub P1 P2 Experi- wt % wt % sub wt % P1 wt % P2 ment on on (J/ Polymer on (J/ Polymer on (J/ Comp. I1076 no Sub total P1 cm.sup.3).sup.1/2 1 total cm.sup.3).sup.1/2 2 total cm.sup.3).sup.1/2 wt % wt % 18 Argan 10.6 28.2 17.4 SPS(142ZE) 27.0 19.5 PA-4, 10 44.1 24.2 2.5 0.9 19 Argan 10.6 28.2 17.4 SPS(142ZE) 27.0 19.5 PA-4, 10 44.1 24.2 2.5 0.9 20 Argan 8.5 28.2 17.4 SPS(142ZE) 21.6 19.5 PA- 35.4 24.2 2 0.7 4, 10 21 Argan 8.5 28.2 17.4 SPS(142ZE) 21.6 19.5 PA- 35.4 24.2 2 0.7 4, 10 22 Argan 5.4 15.1 17.4 PBT-Eco 30.3 18.8 PBT 53.5 19.3 0 0.8 23 Avocado 4.7 14.9 17.3 PBT-Eco 26.8 18.8 PET 47.3 19.8 0 0.8 (5018) 24 Avocado 7.8 20.7 17.3 PBT-Eco 29.9 18.8 PET 43.0 19.8 0 0.8 (5018) 25 Avocado 4.7 14.9 17.3 PBT-Eco-2 26.8 18.8 PET 47.3 19.8 0 0.8 (5018) 26 Avocado 6.1 15.0 17.3 PBT- Eco-2 34.7 18.8 PET 40.8 19.8 0 0.8 (5018) 27 Mix-1 5.4 15.0 17.3 PBT-Eco 30.6 18.8 PET 43.1 19.8 0 0.7 (5018) 28 Mix-2 5.4 15.0 17.3 PBT-Eco 30.6 18.8 PET 43.1 19.8 0 0.7 (5018) 29 Mix-2 5.4 15.0 17.3 PBT-Eco 30.6 18.8 PET 43.1 19.8 0 0.7 (5018) 30 Mix-3 5.4 15.0 17.29 PBT-Eco 30.6 18.8 PET 43.1 19.8 0 0.7 (5018) 31 Mix-4 5.4 15.0 17.29 PBT-Eco 30.6 18.8 PET 43.1 19.8 0 0.7 (5018) 32 Mix-5 5.4 15.0 17.29 PBT-Eco 30.6 18.8 PET 43.1 19.8 0 0.7 (5018) C_7 Avocado 6.9 20.8 17.3 PBT-Eco 26.2 18.8 PBT 46.2 19.3 0 0.7 C_8 Avocado 13.3 32.5 17.3 PBT-Eco-3 27.6 18.8 PET(5018) 40.8 19.8 0 0.8 Release at 200 C. [mg] E-mod Experi- Car- Glass (sub 1st 5th at ment bon 3B P1).sup.2 treat- treat- 200 C. no wt % wt % (J/cm.sup.3) ment ment MPa 18 15.sup.3) 0 4.5 1.8 0.3 124 19 15.sup.4) 0 4.5 1.4 0.3 119 20 22.7.sup.3) 9.1 4.5 1.6 0.4 404 21 22.7.sup.4) 9.1 4.5 2.0 0.4 431 22 10.sup.3) 0 1.8 0.8 0.1 151 23 20.3.sup.1) 0 2.2 0.5 0.2 610 24 18.4.sup.1) 0 2.2 1.1 0.1 398 25 20.3.sup.1) 0 2.2 0.7 0.2 nd 26 17.5.sup.1) 0 2.2 0.8 0.2 nd 27 20.2.sup.2) 0 2.1 0.7 0.1 431 28 20.2.sup.2) 0 2.1 0.5 0.2 353 29 20.2.sup.1) 0 2.1 0.4 0.1 309 30 20.2.sup.1) 0 2.1 0.4 nd nd 31 20.2.sup.1) 0 2.1 0.3 nd nd 32 20.2.sup.1) 0 2.1 0.5 nd nd C_7 20.0.sup.1) 0 2.2 nd nd No thermal intregrity C_8 17.5.sup.1) 0 2.2 nd nd No thermal intregrity Sub Mix-1 = 95 wt % avocado/5 wt % argan oil Sub Mix-2 = 95 wt % avocado/2.5 wt % argan/2.5 wt % camealia oil Sub Mix-3 = 95 wt % avocado/2.5 wt % argan/2.5 wt % macadamia nut oil Sub Mix-4 = 95 wt % avocado/2.5 wt % argan/2.5 wt % safflower oil Sub Mix-5 = 95 wt % avocado/2.5 wt % argan/2.5 wt % apricot kernel oil Carbon.sup.1) = Expanded Graphite (C-Therm 01) Carbon.sup.2) = 99.25 wt % Expanded Graphite (C-Therm 01) and 0.75 wt % Carbon Black (Black pearls 800) Carbon.sup.3) = Graphite (Ecophit GFG1200) Carbon.sup.4) = 95 wt % Graphite (Ecophit GFG1200) and 5 wt % Carbon black (Timcal Ensaco260G)

(24) Table 3 clearly shows that with polymer compositions having a in the range from 0.5 to 24, release of thermo-releasable substance was visible on the plaque and the release could be quantified and was above 0. For polymer compositions with above 24, no release was visible and no release could be measured.

(25) Experiments 5 to 9 in table 4 all showed sufficient thermal stability at 200 C., which indicates that these compositions were suitable for high-heat application. Comparative example C-5 showed no sufficient thermal stability, which indicated that this composition was not suitable for high-heat application, and also indicates that the E-modulus of comparative example C-5 cannot reach 50 MPa at 200 C.

(26) Moreover, table 4 shows that with a polymer composition having a in the range from 0.5 to 24, but no thermal stability, release at 200 C. could not be measured more than once as these plates did not have sufficient mechanical integrity, and this also means that the E-modulus cannot reach 50 MPa at 200 C.

(27) Table 5 shows in experiments 10 to 17 polymer compositions having a in the range from 0.5 to 24.0 in which release was visible. Comparative example C_6 shows that with a below 0.5 no release of thermo-releasable substance was visible.

(28) Table 6 shows examples for which the E-modulus was quantified at 200 C. For examples 30 to 32 E-modulus was not measured, but they are expected to are similar to examples 27 to 29, as the same polymers were employed in the same amounts.

(29) For comparative examples C_7 and C_8 the thermal stability was so low, that no E-modulus could be measured at 200 C. The dog bone bars of these examples broke in the clamp at the start of the tensile experiment, and no release at 200 C. could be measured as these plates did not have sufficient mechanical integrity.