Composite Yarn, Manufacturing Process and Textile Surface Comprising Such a Yarn

Abstract

A composite yarn comprising a continuous multifilament core yarn incorporated in a matrix, is characterized in that the matrix comprises at least one polymer material and at least one reinforcing filler, the reinforcing filler being formed from functionalized particles, said particles having a median size (d.sub.v50) of less than 40 μm.

A process for manufacturing such a composite yarn, comprises at least one step of depositing, by coating or extrusion, a matrix comprising a polymer and a reinforcing filler, onto a core yarn.

A textile surface comprises at least one such composite yarn.

Claims

1-25. (canceled)

26. A process for manufacturing a composite yarn comprising a continuous multifilament core yarn incorporated in a matrix, said process comprising at least one step of depositing, by coating or extrusion, a matrix comprising a polymer material and a reinforcing filler formed from functionalized particles, onto a core yarn.

27. The process according to claim 26, wherein the reinforcing filler is dispersed throughout the polymer before depositing.

28. The process according to claim 26, wherein some of the filler is present in the inter-filament interstices of the core yarn.

29. The process according to claim 26, wherein the depositing step is performed by coating with a plastisol on the filaments of the core yarn.

30. The process according to claim 26, further comprising at least one coating step, on the composite yarn manufactured at the depositing step by coating or extrusion, of at least one layer of polymer material in which is dispersed at least one reinforcing filler, onto the composite yarn obtained in the depositing step.

31. The process according to claim 30, wherein the coating step is performed by coating with a plastisol or by extrusion of a compound.

32. The process according to claim 30, wherein the coating step is performed by extrusion-coating of a composite yarn obtained in the depositing step with a compound in which is dispersed at least one reinforcing filler.

33. The process according to claim 30, wherein the layer of polymer material further comprises at least one fire-retardant filler.

34. A composite yarn obtained by the process according to claim 26, comprising a continuous multifilament core yarn incorporated in a matrix, wherein the matrix comprises at least one polymer material and at least one reinforcing filler, the reinforcing filler being formed from functionalized particles.

35. The composite yarn according to claim 34, wherein the composite yarn has a titer of 135-140.

36. The composite yarn according to claim 34, wherein the continuous multifilament core yarn has a torsion within the range of from 20 to 40 rounds per meter.

37. The composite yarn according to claim 34, wherein the average diameter of each of the filaments of the core yarn is within the range from 3.5 μm to 13 μm.

38. The composite yarn according to claim 34, wherein the ratio between the median size (d.sub.v50) of the reinforcing particles and the diameter of each of the filaments of the core yarn is in the range from 0.15:1 to 12:1.

39. The composite yarn according to claim 34, wherein the weight percentage of reinforcing filler present in the composite yarn is within the range of 0.5 to 30%.

40. The composite yarn according to claim 34, wherein the amount of fire-retardant filler in the composite yarn is more than 1.5% and less than 7.5% by weight.

41. The composite yarn according to claim 34, wherein the composite yarn comprises a continuous multi-filament core yarn and a matrix, the matrix comprising: (i) at least one polymer material, the polymer being chosen from the group consisting of PVCs, polyacrylates, polyolefins, polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers and polyamides, and (ii) at least one reinforcing filler, the reinforcing filler being constituted by particles dispersed in the polymer material of the matrix and present in the inter-filament interstices of the core yarn, said particles being functionalized, the composite yarn further comprising a flame-retardant filler in an amount of approximately 0.5 to 5% by weight.

42. The composite yarn according to claim 34, wherein the composite yarn comprises a continuous multi-filament core yarn and a matrix, the matrix comprising: (i) at least one polymer material, the polymer being chosen from the group consisting of PVCs, polyacrylates, polyolefins, polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers and polyamides, and (ii) at least one reinforcing filler, the reinforcing filler being constituted by particles dispersed in the polymer material of the matrix and present in the inter-filament interstices of the core yarn, said particles being functionalized, the composite yarn further comprising a flame-retardant filler in an amount of approximately 5 to 15% by weight.

43. The composite yarn according to claim 34, wherein the Mohs hardness of the particles constituting the reinforcing filler is in the range from 1 to 5.5.

44. A textile comprising at least one composite yarn according to claim 34.

45. The textile according to claim 44, wherein the textile is selected from sunblinds, sun-blocking textiles, sun-screening textiles, sun-shielding textiles, and combinations thereof.

Description

EXAMPLES

Example 1

[0115] Two composite yarns according to one embodiment were manufactured, from PVC plastisol, by coating a non-flame-retardant matrix comprising silanized glass microbeads as reinforcing filler, followed by coating with a flame-retardant layer itself also containing silanized glass microbeads as reinforcing filler on a core yarn. The core yarn was composed of a textile glass yarn from two different sources. The silanized glass beads had a hardness of 5.5 Mohs. They were spherical and had an average diameter of 20 μm, with a d.sub.v50 of 30 μm, a d.sub.v10 of 15 μm and a d.sub.v90 of 80 μm, as measured for example by laser particle size measurement using a Malvern Masterizer 2000 Instrument machine.

[0116] A control composite yarn was also made on the basis of the teaching of patent EP 0900294, with two successive coatings of the same PVC plastisol on the same core yarn.

[0117] 1. Composite Yarns According to One Embodiment of the Invention

[0118] Core Yarns: Textile Glass Yarns

[0119] The textile glass yarns are characterized by the chemical composition of the silionne, their titer expressed in tex, the diameter and the number of filaments of which the yarn is composed, their torsion and the type of sizing used:

[0120] Since the sizing is the protective coating deposited immediately after spinning the silionne, the final use of the textile glass yarn conditions the chemical nature of the sizing.

[0121] Two types of core yarn were used, respectively, for the two composite yarns according to the embodiment: [0122] A specific textile glass yarn specially developed for the “PVC coating” application (and thus more expensive) bearing a specific sizing compatible with PVC coating (silane based sizing TD52M sold by the company Vetrotex, of unknown proprietary composition) and also a high torsion (52 turns per meter, i.e. “1.3Z”); it was also used for the control composite yarn; [0123] a standard textile glass yarn (torsion 28 turns per meter, i.e. “0.7Z”) covered with a starch-based sizing.

[0124] PVC Plastisols According to One Embodiment

[0125] In each case, the core yarn was coated using a first non-flame-retardant coating containing silanized glass microbeads and then a second sparingly flame-retardant coating also containing silanized glass microbeads. The compositions of the two plastisols used are given in Tables 1 and 2 below.

[0126] Plastisol 1 (Matrix)

TABLE-US-00001 TABLE 1 Plastisol composition Component in PHR (per % weight function Component hundred resin) composition Plasticizer Benzoate/dioctyl 56.5 31.4% terephthalate Heat Liquid stabilizer of Ba/Zn 5.9 3.3% stabilizer type Inorganic Silanized glass beads 17.6 9.8% filler (Microperl ® 050-20 from the company Sovitec) PVC resin PB1302 from the 100.0 55.6% company Kem-one (emulsion polymerized PVC resin of K-Wert* 67) Total 180.0 100.0% *Fikentscher constant, representing the molecular mass of the polymer

[0127] The RV-type Brookfield viscosity of this plastisol was: 1200 mPa.Math.s (measured with a No. 3 spindle at 23° C.).

[0128] The temperature of the yarn exiting the coating line was: 125° C.

[0129] Plastisol 2 (Layer)

TABLE-US-00002 TABLE 2 Plastisol composition Component in PHR (per % weight function Component hundred resin) composition Plasticizer Benzoate/dioctyl terephthalate 45.0 23.1% Heat stabilizer Liquid stabilizer of Ba/Zn type 5.0 2.6% PVC resin 1 EXT from the company Vinnolit 20.0 10.3% (suspension polymerized PVC resin of K-Wert 66) Flame- Zinc hydroxystannate (Flamtard 10.0 5.1% retardant 1 H from the company William Blythe) Flame- Ceramic (Adrafoc CR-B from 5.0 2.6% retardant 2 the company Adrafoc) Flame- Alumina trihydrate (Sh 30 from 5.0 2.6% retardant 3 the company Alteo) Opacifier Sachtolit L zinc sulfide from the 10.0 5.1% company Sachleben Inorganic filler Silanized glass beads 15.0 7.7% (Microperl ® 050-20 from the company Sovitec) PVC resin 2 PB1302 from the company 80.0 41.0% Kem-one (emulsion PVC resin of K-Wert 67) Total 195.0 100.0%

[0130] The RV-type Brookfield viscosity of this plastisol was: 1350 mPa.Math.s (measured with a No. 3 spindle at 23° C.).

[0131] The temperature of the yarn at the outlet of the coating line was: 135° C.

[0132] Plastisols 1 and 2 contain no viscosity reducer. This absence of viscosity reducer is one advantage, which is very beneficial for the conservation of the plastisol and participates in reducing the emission of VOCs during the production of the composite yarn.

[0133] Two composite yarns were thus obtained according to one embodiment, the characteristics of which are given in Table 3 below.

TABLE-US-00003 TABLE 3 Type of base yarn ECG 75 0.7Z ECG 75 1.3Z Torsion Z28 Z52 Sizing Starch standard Specific (B12) (TD52M) Titer of the yarn after the 1.sup.st 108 tex 110 tex coating Titer of the yarn after the 2.sup.nd 135 tex 140 tex coating Breaking strength of the coated 50N 54N yarn (measured using a tensile testing machine with jaws specific for the yarn, at a tensile speed of 50 mm/min)

[0134] 2. Control Yarn

[0135] A control yarn, of reference 165 tex, was made according to the recommendations of patent EP 0900294, starting with the core yarn which is a specific textile glass yarn, specially developed for the PVC coating of specific sizing type TD52M sold by the company Vetrotex and of high torsion (52 turns per meter) similar to that used for one of the two composite yarns according to the embodiment. Only two successive coatings were performed with the same plastisol. The composition of the plastisol used is given in Table 4 below.

TABLE-US-00004 TABLE 4 Plastisol composition in % weight Component PHR (per % compo- function Component hundred resin) sition Plasticizer Diisodecyl phthalate 45.43 24.2% (DIDP) Heat stabilizer Liquid stabilizer of 4.96 2.6% Ba/Zn type PVC resin EXT from the company 20 10.6% Vinnolit Flame-retardant 1 Antimony trioxide (Triox 7.65 4.1% from the company PLC) Flame-retardant 2 Zinc borate 7.64 4.1% Flame-retardant 3 Alumina hydrate 7.65 4.1% Opacifier Zinc sulfide (ZnS) in a 3.10 1.7% plasticizer of DIDP terephthalate type in a 70/30 ratio (weight/weight) PVC resin PB1302 from the 80 42.7% company Kem-one Lubricant Wacker ® AK 50 silicone 0.93 0.5% oil from the company Wacker Chemie Diluent (viscosity C.sub.11-C.sub.13 isoparaffinic 10.08 5.4% reducer) fraction Isopar ® L from the company Exxon Total 187.44 100.0%

[0136] The RV-type Brookfield viscosity of this plastisol was: 1300 mPa.Math.s (measured with a No. 3 spindle at 23° C.). This value was obtained with the addition of 5.4% of a volatile viscosity reducer, the presence of which generated VOCs during the transformation of the plastisol.

[0137] The temperature of the yarn at the outlet of the coating line was: 135° C.

[0138] 3. Results

[0139] The three composite yarns and the corresponding textiles obtained by the same operation for the weaving of these composite yarns had the characteristics given, respectively, in Tables 5 and 6 below.

TABLE-US-00005 TABLE 5 Composite yarn A Composite yarn Control according to the B according to composite embodiment the embodiment yarn C Titer of the core yarn 68 tex 68 tex 68 tex Diameter of each of the 9 μm 9 μm 9 μm filaments Reference of the core ECG 75 0.7Z ECG 75 1.3Z ECG 75 1.3Z yarn Torsion of the core yarn Z28 Z52 Z52 Sizing of the core yarn Starch standard Specific Specific (B12 from the (TD52M from (TD52M from company NAG) the company the company Vetrotex) Vetrotex) Titer of the composite 108 tex 110 tex — yarn after the 1.sup.st coating Titer of the composite 135 tex 140 tex 166 tex yarn after the 2.sup.nd coating Breaking strength of the 50N 54N 42N final composite yarn (measured with a, as one example of the type of machine that can be used for this assessment, at a tensile speed of 50 mm/min),

TABLE-US-00006 TABLE 6 Composite yarn Composite yarn Control A according to B according to composite yarn the embodiment the embodiment C Textile 18 × 14 weave 18 × 14 weave 18 × 14 weave Weight of the textile 450 450 520 per m.sup.2 in g Thickness in mm of 0.67 0.67 0.75 the textile Opening factor of the 5.5% 5.5% 5.0% textile in % (measured with a spectrophotometer at 650 nm) Fire test class M1 M1 M1 according to standard NF P-92507 Visual evaluation of Weak Weak Strong the smoke during combustion UV stability according 7/8 7/8 7/8 to standard ISO 105B02 Mechanical strength Class 3 Class 3 Class 3 tests according to EN (>10 000 (>10 000 (>10 000 13561 cycles) cycles) cycles)

[0140] As seen in Tables 5 and 6, the properties of yarns A and B were revealed to be greater than those of the control yarn, irrespective of the core yarn (standard for yarn A or specific for yarn B). Tables 7 and 8 below reveal the differences in composition between the control yarn C and yarn B according to one embodiment made with the same core yarn. These results also apply to yarn A, which uses the same plastisols as yarn B and which is made with a textile glass yarn having an identical titer to that of the textile glass yarn used for making yarns B and C.

TABLE-US-00007 TABLE 7 Composite yarn according to the Control Component embodiment composite yarn Core yarn made of textile 50.4% 42.3% glass yarn Plasticizer 14.0% 14.8% Flame retardant(s)  1.9%  7.5% Inorganic reinforcing filler  4.5% — PVC 26.8% 32.5% Opacifier (zinc sulfide)  1.0%  1.0% Various additives  1.5%  1.9% TOTAL (weight %)  100%  100%

[0141] It was thus seen that yarn B according to one embodiment includes an amount of fire-retardant filler equal to about 25% (i.e., the ratio of 1.9% to 7.5%) by weight of the amount of fire-retardant filler of the control yarn C, for the same fire resistance class. Thus, the amount of fire-retardant filler was able to be reduced by about 75% to obtain a level of flame retardancy similar to that of the control composite yarn.

[0142] This leads to a significant drop in production costs. Thus, for the composite yarn according to the embodiment comprising a textile glass yarn as core yarn and a PVC plastisol, this results in a significant reduction in the costs of the PVC plastisol, of the order of 25% to 35%, to obtain a fire compliance result identical to that obtained according to the prior art, for example the class M1 according to the present example.

TABLE-US-00008 TABLE 8 Weight ratio of Composite Control composite components yarn B yarn C % sheath (matrix + layer) 50.5% 58.8% Plasticizer/core yarns 14.3% 14.7% Plasticizer/PVC 52.4% 45.4% Flame retardant/organic 4.5% 15.2% materials Mineral materials/organic 17.3% 17.2% materials Flame retardant/plasticizer 13.5% 50.5%

[0143] It was thus seen that yarn B according to the embodiment has a similar mineral materials/organic materials ratio (58.8% for the control yarn C; 50.5% maximum for yarn B), whereas the flame retardant/organic materials ratio is greatly reduced (15.2% for yarn C; 4.5% for yarn B). However, yarn B makes it possible to obtain the same level of fire performance.

[0144] In addition, the use of a reinforcing filler makes it possible to obtain higher mechanical properties (increase in the breaking strength of the yarn by 18.5%: 54 N for yarn B and 42 N for yarn C; see Table 5), whereas the overall level of plasticization of the two yarns is similar (14.7% for yarn C; 14.3% for yarn B; see Table 8), which ensures equivalent flexibility for the 2 yarns.

[0145] In sum, a composite yarn is disclosed wherein the use of particles in a matrix enables the material, by virtue of the particles that are incorporated therein, to be present in the inter-filament interstices of the core yarn. The particles interact both with the core yarn filaments and with the matrix polymer to provide one or more of the benefits described above, based on the disclosed parameters and the desired application.

Example 2

[0146] 1. Composite Yarns

[0147] One composite yarn according to one embodiment (D) was manufactured, from PVC plastisol, by two successive coatings of the same PVC plastisol coating containing flame-retardant particles and silanized glass microbeads as reinforcing filler on a core yarn. The core yarn is the standard textile glass yarn composed with a low torsion (28 rounds per meter) of Example 1 and a title of 68 tex. Two types of silanized glass beads were used. The silanized glass beads Microperl® had a hardness of 5.5 Mohs. They were spherical and had an average diameter of 20 μm, with a d.sub.v50 of 30 μm, a d.sub.v10 of 15 μm and a d.sub.v90 of 80 μm, as measured for example by laser particle size measurement using a Malvern Masterizer 2000 Instrument machine. The silanized glass beads Omicron® had a hardness of 5.5 Mohs. They were spherical and had an average diameter of 5 μm, with a d.sub.v50 of 7 μm, a d.sub.v10 of 2 μm and a d.sub.v90 of 15 μm, as measured for example by laser particle size measurement using a Malvern Masterizer 2000 Instrument machine.

[0148] One control composite yarn (E) was also used, which is a commercial product of the Applicant, made by two successive coatings of the same PVC plastisol on a core yarn. The core yarn is the specific textile glass yarn with a high torsion (52 rounds per meter) of Example 1 and a title of 68 tex. This commercial product has the best fire performance among the commercial products sold by the Applicant, thus meeting both the fire performance criteria “M1” of standard NF 92-503 and the fire performance criteria “B1” of standard DIN 4102-1.

[0149] The compositions of the plastisol used are given in Tables 9 and 10 below.

TABLE-US-00009 TABLE 9 Composite yarn according to the embodiment D Sheath sheath composition in sheath composition PHR (per composition in wt % of the Component hundred (PVC) in wt % of composite function Component resin) the sheath yarn Plasticizer 1 Benzoate dioctyl 37.0 20.2% 10.% terephtalate Plasticizer 2 PLF 290 from the 5.0 2.7% 1.4% company Thor Heat Liquid stabilizer of 3.0 1.6% 0.8% stabilizer Ba/Zn type Flame- Zinc 5.0 2.7% 1.4% retardant 1 hydroxystannate Flame- Alumina hydrate 10.0 5.5% 2.8% retardant 2 Flame- Phosphorous 5.0 2.7% 1.4% retardant 3 ceramic powders Inorganic Silanized glass 12.8 7.0% 3.6% filler 1 beads (Microperl ® 050-20 from the company Sovitec) Inorganic Silanized glass 3.2 1.7% 0.9% filler 2 beads (Omicron ® 110-P8 from the company Sovitec) Opacifier Zinc sulfide (ZnS) in 1.1 0.6% 0.3% a plasticizer of DIDP terephthalate type in a 70/30 ratio (weight/weight) PVC resin PB1302 from the 68 37.2% 19.0% company Kem-one PVC resin EXT from the 32 17.5% 8.9% company Vinnolit Fumed silica Wacker ® AK 50 0.8 0.4% 0.2% silicone oil from the company Wacker Chemie Total I 182.7 100.0% 50.7%

[0150] The RV-type Brookfield viscosity of this plastisol was: 900 mPa.Math.s (measured with a No. 3 spindle at 23° C.). The temperature of the yarn at the outlet of the coating line was: 155° C.

[0151] The title of the composite yarn D according to the embodiment thus obtained was 139 tex.

TABLE-US-00010 TABLE 10 Control composite yarn E Sheath Sheat composition in sheath composition PHR (per composition in wt % of the Component hundred (PVC) in wt % of composite function Component resin) the sheath yarn Plasticizer Diisodecyl phthalate 45.5 25.9% 15.2% (DIDP) Heat Liquid stabilizer of 5.0  2.8% 1.7% stabilizer Ba/Zn type Flame- Base on anti- 23.0 13.0% 7.8% retardant monytrioxide and zinc hydrostannate Opacifier Zinc sulfide (ZnS) in 1.1  0.6% 0.4% a plasticizer (terephthalate type) in a 70/30 ratio (weight/weight) PVC resin PB1302 from the 80 45.6% 26.8% company Kem-one PVC resin EXT from the 20 11.4% 6.7% company Vinnolit Lubricant Wacker ® AK 50 0.9  0.5% 0.3% silicone oil from the company Wacker Chemie Total 175.5  100% 58.8%

[0152] The RV-type Brookfield viscosity of this plastisol was: 1300 mPa.Math.s (measured with a No. 3 spindle at 23° C.). The temperature of the yarn at the outlet of the coating line was: 135° C.

[0153] The title of the control composite yarn E thus obtained was 165 tex.

[0154] 2. Results

[0155] The two composite yarns and the corresponding textiles obtained by the same operation for the weaving of these composite yarns had the characteristics given, respectively in Tables 11, 12 and 13 below.

TABLE-US-00011 TABLE 11 Control Composite yarn composite yarn D according to E the embodiment Textile 18 × 10 weave 21 × 11 weave Weight of the textile 462 455 per m.sup.2 in g Thickness in mm of 0.57 0.59 the textile Opening factor of the 1.2% 1.3% textile in % (measured with a spectrophotometer at 650 nm) Titer of the composite 165 139 yarn in tex Breaking strength of 38N 42N the final composite yarn (measured with a, as one example of the type of machine that can be used for this assessment, at a tensile speed of 50 mm/min),

[0156] Composite yarn D according to the embodiment gave textile surfaces having substantially similar weight, thickness and opening factors to that of the textile surface obtained by control composite yarn E, the mechanical properties of the two composite yarns are quite similar.

TABLE-US-00012 TABLE 12 Control Composite yarn composite yarn D according to E the embodiment % sheath (matrix +   59%   51% layer) % flame  7.8%  5.6% retardant/composite yarn % plasticizer/PVC 45.5%   42% % 15.2% 11.4% plasticizer/composite yarn % flame 15.4% 14.0% retardant/organic materials % mineral 15.9% 26.1% materials/organic materials on sheath % flame 50.5% 47.6% retardant/plasticizer

[0157] As seen in Tables 11 and 12, in comparison with the control yarn E, composite yarn D according to the embodiment has a slightly lower flame retardant/organic materials ratio (15.4% for control yarn E; 14% for composite yarn D), and a slightly lower flame retardant/plasticizer ratio (50.5% for control yarn E; 47.6% for composite yarn D).

TABLE-US-00013 TABLE 13 Control Composite yarn composite yarn D according to E the embodiment FIGRA.sub.0.2 in W/s 260 90 THP.sub.600 in MJ 0.80 0.20 Fire test class Cs3d0 Bs3d0 according to standard EN 13-501-1

[0158] The FIGRA parameter measures the speed of the energetic production during the combustion. FIGRA.sub.0.2 parameter provides the speed level to reach 0.2 MJ. The FIGRA.sub.0.2 value for Euroclass “B” is less or equal than 120 W/s.

[0159] The THP parameter measures the total energetic production during the combustion. The THP.sub.600 parameter provides the energetic production level reached at 600 s. The THP.sub.600 value for Euroclass “B” is less or equal than 7.5 MJ, whereas the THP.sub.600 for Euroclass “C” is less or equal than 15.MJ.

[0160] The FIGRA.sub.0.2 value obtained with the textile made from composite yarn D according to the embodiment reflects, compared to the textile made from control yarn E, a very sharp decrease in energy production during combustion (90 W/s against 260 W/s) although they have very similar physical characteristics. This level of performance (FIGRA.sub.0.2<100 W/s) cannot normally be achieved by glass-fiber-based textiles coated with plasticized PVC.

[0161] Therefore, only composite yarn D makes it possible to meet the requirements of Euroclass “B” of standard EN 13-501-1, the control yarn meeting only the requirement of Euroclass “C” of standard EN 13-501-1. However, the textile surface obtained by composite yarn D according to the embodiment has a greatly improved fire performance although it has a lower flame retardant content than the textile surface obtained by control yarn E (5.6% against 7.8%) and a slightly lower flame retardant/plasticizer ratio (47.6% against 50.5%).

[0162] To the knowledge of the Applicant, this is the first time that a composite yarn obtained by coating a flame retardant plastisol on a glass textile yarn can meet the requirements of Euroclass “B” of standard EN 13-501-1.