KR0140074B1 - Yarns made from core-seed filaments and preparation methods thereof - Google Patents

Abstract

All core-sheath filaments in the yarn, the ratio A (%) of core-sheath filaments with (M ± 0.1M)% of the sheath content in the volume before and after each core-sheath filament at the same time, simultaneously and simultaneously The core of the core-sheath filament by extruding a spinnable polymer with or without additional single component filaments, characterized by meeting the conditions A≤100, M≥0.5 and A≥30 + (0.1M) ⁸ F) a sheath obtained from which at least almost all core-sheath filaments consist of a core-sheath filament having a complete sheath.

Description

Yarns made from core-seed filaments and preparation methods thereof

The present invention relates to yarns formed from core-seed filaments in which the cores and seeds of the core-seed filaments are formed by extrusion and methods of making the same.

Core-seed filaments and methods for their preparation are well known. For example, European Patent Application No. 0 011 954 teaches that a special spinning device is needed to prevent the formation of homofilaments even at low seed content. Despite the use of known spinning devices to prevent the formation of homopyramids, it is possible to prevent the formation of core-seed filaments with significantly different seed content, including uniform cross-sections with no seed content in the yarns produced. It is impossible to prevent the seed content of the core-filt filaments of the resulting yarn from varying widely.

As a result of the experiment, when using the spinning apparatus described in EP 0 011 954 and using a feed with a volume ratio of 85:15 of core and seed material as described in the examples of the present invention, Among the core-seed filaments of the genus, the seed content of about 15% is 15% or less, and generally less, even when the seed content variation rate is ± 10%. The seed content of the other core-seed filaments of the obtained yarn is higher (up to 30% by volume) or lower (up to 5% by volume).

It is not possible to obtain at least one homopyrament in the yarn in a controlled manner using known methods. Homopyraments are created by chance and there is no guarantee that homopyramids that are identifiable in the cross section of the yarn are identifiable in the yarn direction. On the other hand, the homopyramids turn into core-seed filaments in the linear direction of yarns, and conversely, the core-seed filaments may turn into homopyramids.

If the seed content is large, all the filaments in the yarn have different characteristics. This means that the properties of yarn filaments are very different from each other, which is undesirable.

Basically, a yarn made of core-seed filaments should have the desired properties of the core material (e.g. strength, shrinkage, elongation and birefringence), while the seed has other properties of the yarn (e.g. adhesion to other materials, stainability, handling fastness) Performance and chemical resistance and mechanical resistance). In existing processes, the average seed content should be at least 20% by volume in order to keep the variation of the seed content within a certain range and to keep the properties of the core material somewhat uniform based on the entire cross section of the core-seed filament.

It is an object of the present invention to extrude a spinnable polymer to form a core and seed of a core-seed filament, wherein at least nearly all core-seed filaments are composed of a core-seed filament having a complete seed and a single component filament (homopyrament) It is to provide a new and better performance yarn that can include. The yarn should make better use of the properties of the core-seed material without degrading the properties of the seed material.

It is another object of the present invention to provide a method for manufacturing yarns which allows the uniformity of yarns to be good and the ratio of single component filaments and core-seed filaments (bicomponent filaments) can be set in a controlled and predictable manner. will be. The seed content of the core-seed filaments should be more uniform, even at 20% by volume or less.

This aim is to achieve a ratio A of core-seed filaments of which the seed content of each core-seed filament among all core-seed filaments in the yarn is (M ± 0.1M)% based on the total volume of these particular core-seed filaments. Achievement is achieved when%) meets all of the following conditions:

A is less than or equal to 100%

M is 0.5 or more,

A is greater than 30 + (0.1M) 8%.

The term M ± 0.1M is defined by taking into account all core-seed filaments having a seed content of M volume% based on the total volume of a particular core-seed filament, with the seed content M based on a ± 10% range. It means to be decided. Since all of the above conditions must be met, M can only be estimated at values where A is less than 100%.

In particular, in the yarn according to the invention, the property is excellent in the condition that A is 40 + 7 (0.1M) ⁸ %, preferably A is 50 + 100 (0.1M) ⁸ % or more.

Depending on the intended use, the proportion of core-seed filaments having a seed content of M ± 0.1 M% by volume where M is 9 vol% or less is greater than or equal to 60%, or the seed content is M ± 0.1M, wherein M is not less than 1% by volume and not more than 7% by volume] of core-seed filaments having a ratio of 70% or more of core-seed filament, or a seed content of M ± 0.1M, wherein M is 3% by volume or more and 6% by volume It is preferable to provide a yarn having a core-seed filament ratio of 75% or more.

Surprisingly, it has been found that the special properties of these yarns are significantly improved. For example, the strength (cN / dtex) of the yarns according to the invention is clearly higher than that of existing yarns composed of core-seed filaments and that of single component yarns consisting solely of core polymers.

The filaments of the yarns according to the invention can have virtually any known cross sectional shape. For example, a filament with a circular cross section is preferred for tire cords, while a cross section is preferably trilobal, for example, when focusing on visual effects that can be woven into carpet yarns.

Special properties of yarns [eg; Adhesion] is particularly enhanced when the cross section of the filament, in particular the core-seed filament, is trilobal.

Suitable polymer blends for the cores and seeds are in particular the following polymers:

Core seed

Polyethylene terephthalate Nylon 66 (PA 66) (PET)

Polyethylene terephthalate Nylon 66 (PA 66) and poly

(PET) a mixture of (m-xylyleneadipamide)

Nylon 46 (PA 46) Nylon 66 (PA 66) low viscosity polyethylene

High Viscosity Polyethylene Terephthalate (PET)

Terephthalate (PET)

Polyethylene terephthalate (PET) Polyethylene terephthalate (PET)

Mixtures of Polyvinylene Difluoride (PVDF)

Polyethylene naphthalate (PEN) Nylon 66 (PA 66)

Polyethylene naphthalate (PEN) Nylon 46 (PA 46)

Further preferred combinations are as follows:

Core seed

Polyethylene terephthalate (PET) Polyether sulfone (PES)

High viscosity nylon 66 (PA 66) Low viscosity nylon 66 (PA 66)

High viscosity nylon 6 (PA 6) Low viscosity nylon 6 (PA 6)

Polyethylene terephthalate (PET) Polytetrafluoroethylene (PTFE)

Polyethylene terephthalate (PET) Polyimide

Polyethylene terephthalate (PET) Polyphenylene sulfide (PPS)

Polyethylene terephthalate (PET) Polypropylene (PP)

Polyethylene terephthalate (PET) Polyethylene terephthalate (PET)

Mixture of polytetrafluoroethylene (PTFE)

Polyethylene terephthalate (PET) Polyethylene terephthalate (PET)

Mixture of poly (m-xylyleneadipamide)

Nylon 6 (PA 6) Polypropylene (PP)

Nylon 6 (PA 6) Polyvinylene difluoride (PVDF)

The yarns according to the invention are used in many products.

Sewing threads formed using conventional polymers (PET, PA 66, PA 6) in the core can be wrapped using high heat resistant polymers and are suitable for high speed sewing. In the case of yarns and nets made of yarns, the seed can enhance chemical resistance, UV resistance and heat resistance.

In the case of reinforced elastomeric sprays (eg, tire cords) used in reinforced compression tires, drive belts or conveyor belts, the seed of the core-seed filaments may promote adhesion between the core and the elastomer. Similar to fiber reinforced plastics, this method promotes adhesion between yarns and plastics.

For carpet yarns, the seeding of the core-seed filaments may contribute to enhancing the dyeability of the filaments even when high conductivity materials which enhance the antistatic properties are used as the core, although the colors are often very dark and difficult to dye using other dyes. Can be. If there is a shrinkage difference between the core and the seed in the material, such yarns can be used for the manufacture of carpets, and the crimp can be clearly given by heating the yarns in the processed carpet or fabric. Deformed section yarns improve light scattering. By suitably selecting the seed material for the core-seed filaments, the flammability grade and / or contamination properties of the carpet or fabric made from such core-seed filaments are significantly improved. Similarly, mold formation or rot can be reduced.

Hydrophobic seeds can effectively prevent the absorption of moisture by using core-seed filaments. This is of particular interest in the use of the yarns according to the invention in the field of textiles. It is also possible to spin the polymer mixture using colored pigments as seed components to obtain spin-dye (SPUN-DYE) core-seed filaments.

When the yarn according to the present invention is used in a nonwoven fabric (eg, a filter nonwoven fabric), the polymer can be appropriately selected to improve chemical resistance. It can also obtain ion exchange properties or affect flammability ratings.

It is also an object of the present invention to supply the core component to the second spinneret plate in a plurality of individual flows via the first spinneret plate, and to separate each core component between the first spinneret plate and the second spinneret plate. In a conventional method (EP-A-0 011 954) in which a stream is wrapped with a seed component supplied thereon, followed by simultaneous spinning, stretching and winding the two components, at least in the region around the individual flows of the core component, It can be achieved by the method of manufacturing yarns according to the invention characterized by being subjected to flow resistance.

The process according to the invention can be carried out in a one step method (with no intermediate winding step) or in a multi step method (with an intermediate winding step).

Suitable flow resistors are in particular wire mesh with one hole for each individual flow. It is advantageous if the wire mesh occupies the entire space between the first spinneret plate and the second spinneret plate except for the holes for the individual flows. In addition, other flow resistors such as porous plates can be used. In the case of using a wire mesh, since the wire mesh also acts as a separator, even in the case of a relatively large spinneret plate, the distance between the two spinneret plates can be kept the same everywhere.

In this way, simple and controlled methods can be used to obtain core-seed filaments with different seed content per filament. To achieve this goal, resistors for seed flow are chosen differently for each core flow. If the resistance chosen is so large that the seed material cannot cover a particular core flow, a single component filament is simply obtained.

Suitable wire meshes are in particular sold under the tradename roll type R.V.S x mesh, where x is from 30 to 500. R.V.S stands for stainless steel, the x mesh indicates the presence of x inches of wire in both directions of the mesh, and the diameter of the cross-woven wires forming the mesh is from 0.5 to 0.025 mm.

The flow resistance is obtained by the permeability of the flow resistor. The transmittance K is defined by the following equation.

ηV

K = -------

δp / δx

In the above formula,

η is the viscosity of the fluid (Pa.s),

V is the velocity (m / sec) of the fluid passing through the flow resistor,

δp / δx is the pressure gradient (N / m 3) in the flow direction.

Therefore, the unit of permeability is m 2.

The permeability K of the flow resistor used is preferably ¹ × ^{10 −11} to 3 × ^{10 −10} m 2.

It is particularly surprising that the process according to the invention can be used not only for melt spinning but also for solvent spinning or combinations thereof. For example, the two components can be formed by melt spinning or solvent spinning. However, for example, the core component may be obtained by melt spinning and the seed component may be obtained by solvent spinning. Solvent spinning refers to a spinning method for spinning a spinning solution composed of a polymer dissolved in a solvent, while melt spinning refers to a spinning method for spinning a molten polymer.

If there is only one spinneret orifice of the first spinneret plate and the second spinneret plate, the core according to the present invention has a very uniform thickness of the seed in the circumferential direction and the longitudinal direction of the core-seed motor filament. Seed monofilaments can be obtained.

The present invention will be further described by way of example with reference to the accompanying drawings.

Figure 1 shows the area developed using the yarn according to the invention in comparison with the prior art.

Figure 2 shows a working flow diagram for manufacturing the yarn according to the present invention.

3 is a schematic of the spinneret used in the prior art.

4 is a schematic of the spinneret required to carry out the method according to the invention.

5 and 6 show the structure of the spinneret of FIG.

7 is a partial cross section of a yarn according to the prior art.

8 is a partial cross section of a yarn according to the invention.

1 shows the areas accessible through the core-seed filament yarns according to the invention. In the figure, the abscissa is the seed content (% by volume) and the ordinate is the ratio A (%) of core-seed filaments with a seed content of M ± 0.1M of all core-seed filaments of the yarn. Possible distribution zones in the prior art are shown in the diagonal lines indicated by the prior art. In the prior art, it is easy to obtain yarns consisting of core-seed filaments with a seed content of 25% of all core-seed filaments, while 5% for yarns comprising a core-seed filament with a seed content of 10%. Only has a seed content of 10%. The present invention now provides yarns with clearly improved uniformity. Here, curve A corresponds to the conditions of claim 1, curve B corresponds to the conditions of claim 2, and curve C corresponds to the conditions of claim 3.

2 is a schematic view of a process showing a method for manufacturing a yarn according to the present invention. Here, (1) shows the spinneret pack with the spinneret plate combination 2 attached to the edge, which will be described in detail later with reference to FIGS. 3, 4, 5, and 6. The top of the spinneret pack 1 is a conventional extruder and a melting line (not shown). When exiting it, the spun core-seed filament or homopyrament 8 passes through the quench cell 7 to which the quench air 9 is supplied. The filaments pass through the roll 5 for spinning, where they are focused together, from there through the stretching devices 3, 4 and then wound into the bobbin 6 as a working yarn.

3 shows in detail the spinneret of the prior art, wherein 10 denotes the first spinneret plate and 11 denotes the second spinneret plate. The core melt flow passes through the hole 12 of the first spinneret plate 10 to the second spinneret plate 11, more precisely the goblet-shaped portion 13. The seed flow flows into the space between the spinneret plates 10, 11 to enclose each core flow exiting the hole 12. In this way, each individual flow of the core component is wrapped by the seed component, after which both components flow simultaneously through the goblet 13 into the spinneret orifice 14 and are extruded therefrom. A rise 15 is present in the second spinneret plate 11 in the region where the seed flow surrounds the core flow.

4 diagrammatically shows the structure of the spinneret used in the method according to the invention. The first spinneret plate is represented by (20) and the second spinneret plate is represented by (21). The core component is introduced into the die channel 22 through opening 26 and then connected to the channel 23 of the second spinneret plate 21. The seed component is distributed evenly between the spinneret plates 20, 21 through the annular channel 28 and the die channels 22, 23 are completely open in the spaces between the spinneret plates 20, 21. Is filled with a metal wire mesh 27 serving as a flow resistor. Thus, the seed component is supplied from the annular channel 28 to wrap the core component through the metal wire mesh 27. Here, the metal wire mesh acts on the seed component as a flow resistor. The core and seed components are extruded simultaneously through the holes 24.

5 and 6 show aspects of the spinneret used in the method according to the invention, in which FIG. 5 shows a longitudinal section and FIG. 6 shows a cross section. The channel 32 guides the core component in the direction of the first spinneret plate 20, while the seed component is shown in dashed lines as the channel 33 (continuous portions extend as the channel 33 extends out of the plane of the drawing). ], And its continuous portion 34 passes through an annular channel (not shown) between the first spinneret plate and the second spinneret plate through the first spinneret plate 20. Between the first plate 20 and the second plate 21, there is a metal wire mesh 27, which is a flow resistor that also acts as a separator between the first plate 20 and the second plate 21. Reference numeral 31 denotes a center pin and 30 denotes a suture. Bush 35 prevents seed components from escaping between channel plate 29 and first spinneret plate 20.

7 is a partial cross sectional view of a filament yarn of the prior art. The seed is represented by (37) and the core is represented by (36). Both core area and seed area vary widely per filament. The seed and / or core area also varies widely in the longitudinal direction of the individual filaments.

8 shows a partial cross section of a yarn according to the invention. The uniformity of the core area 38 and the seed area 39 is noteworthy.

The present invention is further described with reference to the following examples.

[Examples 1 to 9]

Examples 1 to 9 show a variant range from which the yarn according to the invention can be obtained.

The core polymers used were polyesters having a typical relative viscosity (1 g of polymer in 100 g of m-cresol measured at 25 ° C.) in textile yarns in Examples 1 to 3, and low relative viscosity suitable for industrial yarns in Examples 4 to 6. Polyester having, in Examples 7 to 9, polyester having a high relative viscosity suitable for a tire cord or sewing thread. The seed material is nylon 66 (PA 66) in all cases.

Within each group of examples described above, the spinning pump throughput is variable for both the core and seed components. Flow resistance is roll type R.V.S. 60 mesh metal mesh (see Examples 10 to 15 for details).

The spinnerets used are shown in FIGS. 4 to 6.

Core-seed filaments are obtained by the method described above with reference to FIG. 2 except that they are not drawn. The process conditions and polymers used are shown in Table 1. Table 1 also shows the ratio A (%) of core-seed filaments whose seed content is M% by volume of the total volume, taking into account all core-seed filaments having a content of (M ± 0.1M)% in certain filaments]. Indicates. Reported A (%) is the average of the cross sections measured 10 times at various points of a particular yarn.

The A value represents the uniformity with which the yarn according to the invention can be made, and the diameter D of the individual core-seed filaments in the yarn can be very uniform because it is similar in the range of about (D ± 0.1D).

[Examples 10 to 15]

Examples 10 to 15 relate to the manufacture of various tire cords and the measurement of their properties.

Understanding this purpose The selected core polymer is a polyester with a relative viscosity of 2.04. The seed material selected was nylon 66 (PA 66) in Examples 10 and 11, and a mixture of nylon 66 and 0.3% by weight of poly (m-xylyleneadipamide) in Examples 12-15 [PA 66 + additive in table It is represented by]. The mixtures exhibit particularly good adhesion not only to polyesters but also to elastic materials, in particular rubbers.

Each core-seed blend is treated once at 900 m / min and once at 500 m / min using the method shown in FIG. 2 again without stretching. The flow resistor used was roll type R.V.S. 60 mesh metal wire mesh. Thus, the mesh is made of stainless steel wire. There are 60 iron wires per inch in both the longitudinal and transverse directions. The wire diameter of the commercially available mesh is 0.16 mm.

The spinnerets used are shown in FIGS. 4 to 6.

In Examples 14 and 15, a delayed quench effect is tested by placing a heating tube of 0.4 m length directly underneath the spinneret. The selected process conditions are shown in Table 2.

Then, the obtained yarn is stretched by the stretching apparatus. This included running the bobbin yarn as the first three godets. From three godets, the yarns are transferred to the second three godets via seven godets, from which the yarns are passed through a 10 m long steam treatment zone, treated with 250 ° C. steam, and the third yarns. It is passed through three godets, and then wound while maintaining a constant drawing speed. Seven godets are maintained at a temperature of 75 ° C.

The draw ratios and draw rates selected for the yarns of Examples 10-15 are shown in Table 3, where the draw ratios at the seven godets represent the draw ratios applied to the yarns passing through the seven godets. The figures for the total draw ratio are obtained from the speed difference between the first three Godets and the third three Godets.

The properties of the yarn obtained by this method are shown in the column '' of Table 4. In Table 4, LASE 1% (N) represents the strength (N) of yarn under load at a specific elongation of 1%. The same applies to LASE 2% and LASE 5%.

HAS 4 '/ 160 ° C represents the hot air shrinkage of the yarn exposed for 4 minutes at 160 ° C with a load of 5mN / tex.

The obtained yarns are each formed of a tire cord having a structure of 1100 (Z 472) X 2 (S 472). The characteristics of the tire cord of this structure are also shown in the item code column of Table 4.

The cord obtained in this way is coated with an adhesive in a conventional manner. To achieve this goal, the cord is continuously passed through an oven at 150 ° C. for 120 seconds under a tension of 5N, then through a bath and 45 seconds at 240 ° C. under a tension of 5N. The bath contains the following ingredients:

Deionized Water,

Sodium hydroxide solution,

Resorcinol,

Formaldehyde,

VP latex,

ammonia,

The characteristics of the cord treated by this method are similarly shown in the item immersion cord column of Table 4.

Since the A and M values are the same for yarn, cord and immersion cord, they are shown only in each case.

Claims (19)

Of all core-seed filaments in the yarn, the ratio A (%) of core-seed filaments in which the seed content of each core-seed filament is (M ± 0.1M) (%) based on the total volume of these particular core-seed filaments ) Extrudes a spinnable polymer with or without additional single component filaments, characterized in that it satisfies all conditions wherein A is 100% or less, M is at least 0.5 and A is at least 30 + (0.1M) ⁸ %. Thereby obtaining cores and seeds of core-seed filaments and at least nearly all core-seed filaments consisting of core-seed filaments having complete seeds. 2. A yarn according to claim 1 wherein A is at least 40 + 7 (0.1M) ⁸ %. 2. A yarn according to claim 1 wherein A is at least 50 + 100 (0.1M) ⁸ %. The core-seed filament of claim 1, wherein the core-seed filament having a seed content of (M ± 0.1M), wherein M is 9 vol% or less, is at least 60% of the total core-seed filament. The core seed filament according to claim 1, wherein the core seed filament having a seed content of (M ± 0.1M), wherein M is 1 vol% or more and 7 vol% or less, is 70% or more of the total core-seed filaments. The core-seed filament of claim 1, wherein the core-seed filament having a seed content of (M ± 0.1M), wherein M is greater than or equal to 3% and less than or equal to 6% by volume, is at least 75% of the total core-seed filament. . 7. The yarn according to any one of claims 1 to 6, wherein the core of the core-seed filament consists of polyethylene terephthalate (PET) and the seed consists of nylon 66 (PA 66). The yarn according to any one of claims 1 to 6, wherein the core of the core-seed filament consists of PET and the seed consists of PA 66 and poly (m-xyleneadipamide). 7. The yarn according to any one of claims 1 to 6, wherein the core of the core-seed filament consists of PA 46 and the seed consists of PA 66. 7. The yarn according to any one of claims 1 to 6, wherein the core of the core-seed filament consists of high viscosity PET and the seed consists of low viscosity PET. 7. The yarn according to any one of claims 1 to 6, wherein the core of the core-seed filament consists of PET and the seed consists of a mixture of PET and PVDF. A seed which is fed into the second spinneret plate via the first spinneret plate in a plurality of individual flows, and the respective flow of each core component is fed to it between the first spinneret plate and the second spinneret plate. 12. A method of producing a yarn according to any one of claims 1 to 11 by wrapping it with components and then spinning, stretching and winding the two components together, wherein the seed component flows in at least a region around the individual flow of the core component. A method characterized by resisting. 13. The method of claim 12 wherein the flow resistor used is a metal wire mesh with one hole for each individual flow. The method according to claim 12 or 13, wherein the permeability of the flow resistor used is 10 ⁻¹¹ to 3 × ^{10 −10} m 2. The method of claim 13, wherein the density of the metal wire mesh is 30 to 500 wires / in. 13. A method according to claim 12, wherein the homofilament is produced by sufficiently high flow resistance for the purpose of producing the homofilament so that the seed component does not enclose the individual core flow. 13. The method of claim 12, characterized by melt spinning the seed and / or core components. 13. The method of claim 12, wherein the seed and / or core components are solvent sprayed. 13. The method of claim 12, wherein there is only one spinneret orifice in the first spinneret plate and the second spinneret plate.