FIBER REINFORCED PROFILED OBJECT

Abstract

The invention relates to an elongate profiled object having a cross section, the object comprising a peripheral wall, forming a hollow profile extending in a longitudinal direction, wherein at least part of the peripheral wall is provided with a reinforcement layer extending in at least the longitudinal direction of the elongate profiled object, wherein the reinforcement layer comprises a tape or a laminate of tapes, wherein the reinforcement layer has a thickness of at least 0.6 mm and the tape is made of a first thermoplastic composition, which is a fiber reinforced thermoplastic composition comprising a flame retardant, wherein the elongate profiled object is made of a second thermoplastic composition.

Claims

1. An elongate profiled object having a cross section, the object comprising a peripheral wall, forming a hollow profile extending in a longitudinal direction, wherein at least part of the peripheral wall is provided with a reinforcement layer extending in at least the longitudinal direction of the elongate profiled object, wherein the reinforcement layer comprises a tape or a laminate of tapes, wherein the reinforcement layer has a thickness of at least 0.6 mm and the tape is made of a first thermoplastic composition, which is a fiber reinforced thermoplastic composition comprising a flame retardant, wherein the elongate profiled object is made of a second thermoplastic composition.

2. The elongate profiled object according to claim 1, wherein the tape in the reinforcement layer is a tape comprising a plurality of sheathed continuous multifilament strands, wherein each of the sheathed continuous multifilament strands comprises a core that extends in the longitudinal direction and a polymer sheath which intimately surrounds said core, wherein each of the cores comprises an impregnated continuous multifilament strand comprising at least one continuous glass multifilament strand, wherein the at least one continuous glass multifilament strand is impregnated with an impregnating agent, wherein the polymer sheath consists of a thermoplastic polymer composition comprising the flame retardant.

3. The elongate profiled object according to claim 1, wherein the tape in the reinforcement layer is a fiber-reinforced composite comprising: a matrix material including a thermoplastic polymer composition comprising the flame retardant; and a non-woven fibrous region comprising a plurality of continuous fibers dispersed in the matrix material; wherein the width and the length of the non-woven fibrous region are substantially equal to the width and the length, respectively, of the fiber-reinforced composite; wherein the non-woven fibrous region has a mean relative fiber area coverage (RFAC) (%) of from 65 to 90 and a coefficient of variance (COV) (%) of from 3 to 20; and wherein each of the plurality of continuous fibers is substantially aligned with the length of the fiber-reinforced composite.

4. The elongate profiled object according to claim 1, wherein the reinforcement layer is the laminate of tapes.

5. The elongate profiled object according to claim 1, wherein the reinforcement layer has a thickness of at least 0.8 mm and/or at most 5.0 mm.

6. The elongate profiled object according to claim 1, wherein the flame retardant in the first thermoplastic composition is a mixture of an organic phosphate compound, an organic phosphoric acid and a zinc oxide; wherein the weight ratio of phosphate compound to phosphoric acid compound is from 1:0.01 to 1:2 and wherein the zinc oxide is present in an amount of from 2-10 wt. % based on the weight of the flame retardant.

7. The elongate profiled object according to claim 1, wherein the second thermoplastic composition comprises a flame retardant; wherein the weight ratio of phosphate compound to phosphoric acid compound is from 1:0.01 to 1:2 and wherein the zinc oxide is present in an amount of from 2-10 wt. % based on the weight of the flame retardant.

8. The elongate profiled object according to claim 1, wherein the elongate profiled object further comprises a thermoplastic polymer film provided over the tape or the laminate of tapes.

9. The elongate profiled object according to claim 8, wherein the thermoplastic polymer film comprises a flame retardant; wherein the weight ratio of phosphate compound to phosphoric acid compound is from 1:0.01 to 1:2 and wherein the zinc oxide is present in an amount of from 2-10 wt. % based on the weight of the flame retardant.

10. The elongate profiled object according to claim 8, wherein the thermoplastic polymer film has a thickness of 0.5 to 1.5 mm.

11. The elongate profiled object according to claim 1, wherein the elongate profiled object has a flame retardancy of at least class D as determined by SBI test according to EN13823:2014.

12. The elongate profiled object according to claim 1, wherein the first thermoplastic composition and/or the second thermoplastic composition comprises a polyolefin.

13. A method for manufacturing the elongate profiled object according to claim 1, the method comprising: molding a second thermoplastic polymer composition to provide an elongate profiled object having a peripheral wall forming a hollow profile extending in a longitudinal direction; and providing a reinforcement layer at at least part of the peripheral wall.

14. A tape comprising a plurality of sheathed continuous multifilament strands, wherein each of the sheathed continuous multifilament strands comprises a core that extends in the longitudinal direction and a polymer sheath which intimately surrounds said core, wherein each of the cores comprises an impregnated continuous multifilament strand comprising at least one continuous glass multifilament strand, wherein the at least one continuous glass multifilament strand is impregnated with an impregnating agent, wherein the polymer sheath consists of a thermoplastic polymer composition comprising a flame retardant.

15. A fiber-reinforced composite comprising: a matrix material including a thermoplastic polymer composition comprising a flame retardant; and a non-woven fibrous region comprising a plurality of continuous fibers dispersed in the matrix material; wherein the width and the length of the non-woven fibrous region are substantially equal to the width and the length, respectively, of the fiber-reinforced composite; wherein the non-woven fibrous region has a mean relative fiber area coverage (RFAC) (%) of from 65 to 90 and a coefficient of variance (COV) (%) of from 3 to 20; and wherein each of the plurality of continuous fibers is substantially aligned with the length of the fiber-reinforced composite.

Description

EXAMPLES

Materials Used

[0169] A heterophasic propylene copolymer having a melt flow rate of 66 dg/min as measured according to ISO1133 at 230° C./2.16 kg was used (PP1). The amount of ethylene-propylene copolymer in the heterophasic propylene copolymer (RC) was 18.5 wt %. The amount of ethylene in the ethylene-propylene copolymer (RCC2) was 55 wt % and the total ethylene amount in the heterophasic propylene copolymer (TC2) was 10 wt %. The matrix was a propylene homopolymer having a melt flow rate as measured according to ISO1133 at 230° C. was 156 dg/min, the melt flow rate of the ethylene-propylene copolymer as calculated as described herein was 1.5 dg/g.

[0170] As continuous glass multifilament strand a glass roving containing a sizing agent, which roving has a diameter of 19 micron and a tex of 3000 (tex means grams glass per 1000 m) was used. Its amount based on the sheathed continuous multifilament strand is indicated herein as GF (wt %).

[0171] As a coupling agent (CA) Exxelor PO1020, a maleic anhydride functionalized homo polypropylene, which is commercially available from Exxon Mobile, was used.

[0172] As an impregnating agent (IA), a highly branched polyethylene wax having a viscosity of 49 mPa.Math.s as measured according to ASTM D 3236-15 at 100° C. was used (Dicera 13082 Paramelt).

[0173] As a thermal stabilizer (TS), Irganox® B 225 was used, which is commercially available from BASF and which is a blend of 50 wt % tris(2,4-ditert-butylphenyl)phosphite and 50 wt % pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate].

[0174] As a UV stabilizer, Sabostab UV 119, a hindered amine light stabilizer (HALS) from CIBA which is commercially available from BASF, was used.

[0175] As a flame retardant (FR), ADK STAB FP-2200S, commercially available from Adeka Palmarole was used. This material is a mixture comprising piperaxine pyrophosphate, phosphoric acid compound and zinc oxide.

Step 1. Preparation of Tape

Method 1

Step 1-1. Preparation of Sheathed Continuous Multifilament Strands (Wire-Coating)

[0176] Single sheathed continuous multifilament strands were prepared using the amount of different ingredients as given in Table 1 using the wire coating process as described in details in the examples of WO2009/080281A1.

[0177] As a first step, the impregnating agent was molten and mixed at a temperature of 160° C. and applied to the continuous glass multifilament strands after unwinding from the package, by using a wax impregnation unit as described in WO2014/053590 A1.

[0178] The PP1 was fed to the main feeder, the additives (HALS, CA, TS) are mixed and fed to the additives feeder while the FR was fed to the side feeder of a 75 mm twin screw extruder (manufactured by Berstorff, screw L/D ratio of 34) at a temperature of about 250° C. to obtain a molten polypropylene matrix composition.

[0179] The molten polypropylene matrix composition was then used to sheath the impregnated continuous glass multifilament strands using an extruder-head wire-coating die having a die-hole of 2.8 mm. The sheathing step was performed in-line directly after the impregnating step.

[0180] The line speed for impregnating and sheathing was 60 m/min. After cooling, strands were wound onto bobbins. The length of the obtained strands was approximately 400 m long.

TABLE-US-00001 TABLE 1 Composition details of sheathed continuous multifilament strands produced using method 1A Wire coating Non-FR tape FR tape PP1 (wt %) 26.24 21.87 GF (wt %) 60.30 60.30 CA (wt %) 3.00 3.00 Impregnating 10.00 5.00 agent (wt %) UV stabilizer 0.06 0.06 (wt %) Thermal 0.40 0.40 stabilizer (wt %) FR (wt %) 0.00 9.37

Step 1-2. Preparation of Tapes from Sheathed Continuous Multifilament Strands Produced in Step 1-1

[0181] In this step, tapes were prepared using the strands obtained in step 1-1. First, the strands were put from the bobbin onto an unwinder and then they were unwound from the unwinder. Subsequently, strands were rolled onto a metal cylinder covered with a Teflon® layer to prevent sticking of the strands on the surface of cylinder. Then, the cylinder was placed into an oven having a temperature of 172° C. After the temperature of the strand surface reached 172° C. and all the sheath had melted and all strands were merged together (as observed visually), the cylinder was taken out of the oven and placed in an open area for 1.5 hours to achieve free air cooling. The tape obtained was then again placed into an oven having a temperature of 172° C. and weights were placed onto the tape. After the temperature reached 172° C. the heating of the oven was shut down and the tape was obtained by slow cooling.

[0182] After the slow cooling, the tape was consolidated by using a double belt press machine (KFK-XL 1900 from Meyer, RutzDouble) to improve tape quality. This machine has four heating zones with a length of 4.5 m and two cooling zones with a length of 3.5 m. The tape was placed on the bottom belt. The belt speed was set to 2 m/min, a belt gap of 2.3 mm and the belt temperature was set to 190° C. On average, the thickness of tape obtained after using the double belt press was 1.7 mm.

Method 2

[0183] Tapes were prepared from sheathed continuous multifilament strands according to the method as described in WO2016/142784A1 On average, the thickness of tape obtained was 0.5 mm.

TABLE-US-00002 TABLE 2 The composition of the sheathed continuous multifilament strands produced using method 2. Uni-directional Non-FR FR tape tape tape PP1 (wt %) 36.24 16.24 GF (wt %) 60.30 60.30 Coupling 3.00 3.00 agent (wt %) Impregnating 0.00 0.00 agent (wt %) UV stabilizer 0.06 0.06 (wt %) Thermal 0.40 0.40 stabilizer (wt %) FR (wt %) 0.00 20

Step 2. Preparation of the Construction Profile

[0184] The construction profile was extruded at a temperature of 170-195° C. and a line speed of 0.35 m/min. The die dimensions resulted in a product with sheet thickness 55+/−1.0 mm, top/bottom layer with wall thickness 3.2 mm and rib thickness 2.0+/−0.2 mm, width 237+/−3 mm.

[0185] Two types of construction profiles were prepared:

[0186] one containing a flame retardant and the other not containing a flame retardant.

[0187] The flame retardant (FR profile) construction profiles were prepared from a composition containing:

[0188] −50 wt % SABIC® STAMAX 60YM240, which is a 60 wt % long glass fiber concentrate commercially available from SABIC. The glass fibres are chemically coupled to the PP matrix [0189] 25 wt % SABIC® PP 83MF10, which is a heterophasic propylene copolymer having a melt flow rate of 1.8 dg/min as measured according to ISO1133 (2.16 kg, 230° C.) [0190] 25 wt % ADK STAB FP-2100 JC

[0191] The non-flame retardant (non-FR profile) construction profiles were prepared from a composition containing: [0192] 50 wt % SABIC® STAMAX 60YM240, which is a 60 wt % long glass fiber concentrate commercially available from SABIC. The glass fibres are chemically coupled to the PP matrix [0193] 50 wt % SABIC® PP 83MF10, which is a heterophasic propylene copolymer having a melt flow rate of 1.8 dg/min as measured according to ISO1133 (2.16 kg, 230° C.)

Step 3. Application of the Tape onto the Construction Profile

[0194] The tapes prepared in step 1 according to method 1 and 2 were laminated onto the construction profile as prepared in step 2 using a double belt press machine ((KFK-XL 1900 from Mayer, RutzDouble). The belt temperature was set to 200° C., the belt gap was set to 59 mm and the belt speed was set to 2 m/min. Each construction profile had a dimension of 237 mm width and 3 m length. Two types of construction profiles were used: FR profile and non-FR profile. Table 4 below summarizes the composition of the construction profile, the method to prepare and the composition of the tape, the number of tape layers applied to the contruction profile, the tape direction and the (sum of the) thickness of the tape(s). In Ex 3, after the tapes were provided, 0.8 mm of a film made of a composition consisting of 60 wt % of polypropylene, 20 wt % of talc and 20 wt % of ADK STAB FP-2200S was provided thereon.

Single Burning Item Test

[0195] The single burning item (SBI) test (method EN 13823:2014) is considered as a regulatory test that building/construction products should go through before being classified based on their flame retardant properties.

Procedure

[0196] The procedure of the SBI test involves exposing the specimen to a diffusive flame of 30 kW. This flame is provided by burning propane in a diffusion gas burner. The test specimen includes two samples, each with dimensions of 1.5 m×1.0 m and 1.5 m×0.5 m. The two samples are mounted at a right angle, which creates a corner to form a specimen. The specimen is mounted on a floor and then placed on a trolley, as can be seen in the Figure below. The time of exposure to the flame is 20 minutes. A hood is used to collect the combustion gases. Smoke production is measured by attenuation of a light signal which is introduced in the exhaust duct. There are differential pressure probes, gas sample probes and thermocouples in the system for measurement purposes. At the end of the test various parameters can be determined. [0197] Heat release rate, measured in kW [0198] Fire growth rate (FIGRA) based on heat release, measured in W/s [0199] Total heat release in the first 10 minutes (THR600s), measured in MJ [0200] Total smoke production (TSP), measured in m2 [0201] Smoke growth rate (SMOGRA), measured in m2/s2 [0202] Lateral flame spread (LFS) to the end of the long wing, which is visually observed [0203] Burning droplets and particles, which are visually observed

Classification

[0204] Based on the test results, the test specimen can be classified into class A2, B, C and D. The criteria that determines the class of a test specimen is shown in the table below.

TABLE-US-00003 TABLE 3 classification according to SBI test performed according to EN 13823:2014 Flaming droplets/ particles Main classification Smoke classification classification Class Criteria Class Criteria Class Criteria A1 No contribution to fire — — — — A2 FIGRA ≤ 120 W/s s1 SMOGRA ≤ 30 m.sup.2/s.sup.2 d0 No flaming LFS < edge of specimen TSP.sub.600s ≤ 50 m.sup.2 droplets or THR.sub.600s ≤ 7.5 MJ particles B FIGRA ≤ 120 W/s s1 SMOGRA ≤ 30 m.sup.2/s.sup.2 d0 No flaming LFS < edge of specimen TSP.sub.600s ≤ 50 m.sup.2 droplets or THR.sub.600s ≤ 7.5 MJ particles C FIGRA ≤ 250 W/s s2 SMOGRA ≤ 180 m.sup.2/s.sup.2 d1 No flaming LFS < edge of specimen TSP.sub.600s ≤ 200 m.sup.2 droplets or THR.sub.600s ≤ 15 MJ particles persisting < 10 s D FIGRA ≤ 750 W/s s3 — d2 —

[0205] For the experimentals as provided herein, the single burning item (SBI) test method was performed according to EN 13823:2014.

TABLE-US-00004 TABLE 4 Profiles provided with tapes made by Method 1 CE1 CE2 CE3 Ex. 1 Profile FR or Non-FR FR FR FR non-FR tape — — Non-FR FR # layers 0 0 1   1   Direction Cross/uni uni Uni of layers Layer 1.8 1.8 thickness (mm) results FAIL FAIL FAIL Class C

[0206] As can be seen from the results in the above Table, the article of the invention (Ex. 1) comprising a flame retardant tape passes class C of the SBI test, whereas articles not containing flame retardant in the tape do not (CE1, CE2, CE3). In addition, it can also be seen from the Table 4, that the presence of a flame retardant tape on the construction profile is needed for passing the class C SBI test.

TABLE-US-00005 TABLE 5 Profiles provided with tapes made by Method 2 CE1 CE2 CE4 CE5 Ex. 2 Ex. 3 Profile Non-FR FR Non-FR FR FR FR tape FR FR FR FR # layers 0 0 1   1   2   2   Direction — — Cross Cross Cross Cross of layers Layer — — 0.5 0.5 1.0 1.0 thickness (mm) Cover Yes film (0.8 mm) results FAIL FAIL FAIL FAIL Class D Class C

[0207] As can be seen from the Results, the article of the invention (Ex. 2, Ex. 3) comprising flame retardant tapes passes class D respectively class C of the SBI test, whereas articles with thinner or no tapes do not (CE1, CE2, CE4, CE5).