Yarn formed from core sheath filaments and production thereof
The present invention relates to the yarn silk and the production technology thereof that are formed by the two component long filaments of core-skin type, the core silk and the skin silk of the two component long filaments of this core-skin type all are by being crushed to.
Two component long filaments of core-skin type and production technology thereof are widely known.For example, in document EP-A-O 011954, just point out:, must adopt special spinning equipment for avoiding when peel filament content is very low, occurring producing the phenomenon of one-component long filament.Although by adopting above-mentioned spinning equipment, can avoid producing the one-component long filament, but the yarn silk of making by the two component long filaments of core-skin type, still there is very big fluctuation inevitably in peel filament content in the long filament, even comprise the part that does not have some peel filament contents so that in the finished product gauze in the two component long filaments of core-skin type peel filament content fluctuate significantly.
Experimental results show that: with the spinning machine described in document EP-A-O 011954, import with 85: 15 volume ratio as described core silk of example and skin wire material, but in the yarn silk, the two component long filaments of the core-skin type of peel filament content about 15% (even the peel filament content fluctuation is thought of as ± 10%) be no more than 15%, general even less.The peel filament content of the two component long filaments of other core-skin type has higher (percent by volume reaches 30%) or lower (percent by volume is below 5%) in the yarn silk.
Under a certain control method, also can not in the yarn silk, obtain one or more one-component long filament with above-mentioned technology.The generation of one-component long filament by sheer chance can not guarantee in yarn silk cross section it is an one-component long filament and also be still an one-component long filament in yarn filament length degree direction.Opposite is, from the length direction of yarn silk, an one-component long filament can become the two component long filaments of a core-skin type, and vice versa.
The great fluctuation process of peel filament content makes the every threads in the yarn silk have different performances, that is to say that the performance difference of the long filament in the yarn silk is very big, and this is unfavorable.
Basically say, the yarn silk of being made up of the two component long filaments of core-skin type should have the ideal performance (intensity, contraction, elongation, birefringence etc.) of core-wire material material, and the skin silk then improves other performances (with adhesion, stainability, use fastness, anti-chemical and the anti-mechanicalness etc. of other materials) of yarn silk.In existing processes, for the fluctuation that keeps peel filament content in limited range, and holding core wire material performance is roughly even, is necessary for 20% or more more at the average external volume content of the two whole cross sections of component long filament of core-skin type epithelium silk.
The purpose of this invention is to provide novel, the better yarn silk of forming by the two component long filaments of core-skin type (it may comprise the one-component long filament) of performance, but the core silk and the skin silk of the two component long filaments of core-skin type are to be made through extruding by spinning polymer, and at least almost all the two component long filaments of core-skin type all have complete skin silk.This kind yarn silk guarantees to utilize preferably the characteristic of core-skin two-component materials, and the characteristic that can not lose the skin wire material.
Another object of the present invention provides a kind of technology that produces this kind yarn silk, and it guarantees that the yarn silk has the uniformity preferably, can and give the ratio that the state of establishing is divided into order component long filament and the two component long filaments of core-skin type in control simultaneously.The long-pending content of skin filament in the two component long filaments of core-skin type even also be comparatively uniform being lower than at 20% o'clock.
When the two component long filaments of every core-skin type have its corresponding two component long filament cumulative volumes (when the percentage P% that the two component long filaments of the core-skin type of the peel filament content of % of S ± 0.1S) account for the two component long filaments of the whole core-skin types of yarn silk met following condition simultaneously, this purpose can reach:
P≤100
S≥0.5
P≥30+(0.1S)
8
S ± 0.1S item represents that P depends on that having the long-pending content of skin filament in the two component long filaments of whole core-skin types is the two component long filament amounts of the core-skin type of the S% of the two component long filament cumulative volumes of its corresponding core-skin type.Peel filament content is determined on the basis of ± 10% scope.Because above-mentioned condition must meet simultaneously, therefore have only when P is not more than 100% and could set the S value.
Particularly according to yarn silk of the present invention, wherein
P≥40+7(0.1S)
8
As be preferably
P≥50+100(0.1S)
8
Excellent performance is then arranged.
According to predetermined purposes, the yarn silk may be selected to be have at least 60% two component long filaments of core-skin type have (the long-pending content of the skin filament of % of S ± 0.1S), the volume % of S is herein:
S≤9%
Perhaps select for use have at least the two component long filaments of 70% core-skin type have (peel filament content of % of S ± 0.1S), the volume % of S is herein:
1%≤S≤7%
Perhaps select for use and have at least the two component long filaments of 75% core-skin type that the (peel filament content of % of S ± 0.1S) is arranged.The volume % of S is herein: 3%≤S≤6%.
Surprisingly some properties of these yarn silks improve significantly, for example, yarn silk intensity of the present invention (CN/dtex) is apparently higher than the existing yarn silk intensity made from two component long filaments of core-skin type and the one-component long filament only made with core silk polymer.
According to the present invention, the long filament in the yarn silk can have in fact any known cross sectional shape.For example, the long filament that is used for tyre cord is had circular cross-section,, can preferably adopt the trifoil cross-section long filament if emphasize visual effect, for example just very desirable for carpet silk.
The property of yarn silk, for example adhesion is worked as long filament, two component long filaments of core-skin type particularly, when having the trifoil cross-section, this characteristic is just more outstanding.
The composition of core silk and skin silk polymer, particularly Yi Xia composition is suitable:
Core Si Pisi
Poly terephthalic acid second two (alcohol) ester nylon 66(PA66)
(PET)
Poly terephthalic acid second two (alcohol) ester nylon 66(PA66) and poly-(m
(PET)-the dimethylbenzene adipamide) mixture
Nylon 46 (PA46) nylon 66(PA66)
Full-bodied poly terephthalic acid second two low viscous poly terephthalic acid second two
(alcohol) ester (PET) (alcohol) ester (PET)
Poly terephthalic acid second two (alcohol) ester poly terephthalic acid second two (alcohol) ester
(PET) (PET) support with poly-difluoroethylene
(PVDF) mixture
PEN (PEN) nylon 66(PA66)
PEN (PEN) nylon 46 (PA46)
More desirable combination is:
Core Si Pisi
Poly terephthalic acid second two (alcohol) ester polyether sulfone
(PET) (PES)
High visocity nylon 6 6(PA66) low viscosity nylon 66(PA66)
High visocity nylon 6 (PA6) low viscosity nylon 6(PA6)
Poly terephthalic acid second two (alcohol) ester polytetrafluoroethylene (PTFE)
(PET)
Core Si Pisi
Poly terephthalic acid second two (alcohol) ester polyimides
(PET)
Poly terephthalic acid second two (alcohol) ester polyphenylene sulfide (PPS)
(PET)
Poly terephthalic acid second two (alcohol) ester polypropylene (PP)
(PET)
Poly terephthalic acid second two (alcohol) ester poly terephthalic acid second two (alcohol) ester
(PET) (PET) and polytetrafluoroethylene (PTFE)
(PTFE) mixture
Poly terephthalic acid second two (alcohol) ester poly terephthalic acid second two (alcohol) ester
(PET) (PET) and poly-(m-dimethylbenzene oneself
Two acid diamides) mixture
Nylon 6(PA6) polypropylene (PP)
Nylon 6(PA6) poly-difluoroethylene support (PVDF)
Yarn silk according to the present invention has a lot of use.
Making the sewing thread that the core silk makes with polymer (PET, PA66, PA6) commonly used can coat with heat-resistant polymer, and this just goes for very high sewing velocity.With rope bundle or net that the yarn silk is made, Pi Si can improve its chemically-resistant, UV resistant and heat resistance.
When the yarn silk was used for strengthening elastomer, as tyre cord, it was to be used for fortified tyre, transmission belt or conveyer belt, and the Pi Sineng of the two component long filaments of core-skin type promotes the adhesion between core silk and the elastomer.Equally, for fibre reinforced plastics, the method strengthens the adhesion between yarn and the plastics.
During as the carpet yarn silk, the stainability that the Pi Sike of the two component long filaments of core-skin type promotes long filament, even when the core silk contained the high conduction material for strengthening antistatic property, its color was very gloomy often, also is difficult to dye other colors.Because the core silk is different with the shrinkage of skin wire material, uses this yarn silk to be made into carpet, after Overheating Treatment, the yarn silk of carpet that is made into or textiles will produce significantly and curl so.The heterogeneous yarn silk has improved the scattering property of light.The correct skin wire material of the two component long filaments of core-skin type of selecting has improved carpet and the combustibility of textiles and the contamination property of being made by the two component long filaments of these core-skin types widely, and is same, reduced mouldy and rotten.
A kind of Pi Sineng of hydrophobic material makes the two component long filament protection against the tide of core-skin type effectively.This makes textile limit interested in especially yarn silk of the present invention, also can go spinning as the mixture of polymers of the component of skin silk with pigment, produces solution dyed long filament.
If yarn silk of the present invention is used for supatex fabric, selective polymer can be promoted chemical resistance rightly, for example is used to filter the supatex fabric of dirt.Equally also can obtain ion-exchange performance, perhaps influence flammable degree.
Purpose of the present invention also reaches in the technology of producing the yarn silk by the present invention.(EP-A-O 011954) under normal conditions, core silk component is imported through first spinning plate to the second spinning plate with many independent silk streams, and between first and second piece spinning plate, the skin silk component that the independent silk stream of every core silk component is all imported just there coats, two kinds of components fuse and carry out spinning, stretch and reel, it is characterized in that: around the independent silk stream of core silk component, skin silk component affords flow resistance at least.
According to technology of the present invention, can realize one-step technology (not reeling in the middle of not having) or multistep processes technology (reeling in the middle of having).
A suitable Fluistor is a special woven wire, one hole is all arranged silk stream place separately at each.In addition, captured whole spaces between first and second spinning plate as woven wire, this is very favourable.Also can adopt other Fluistors, for example porous plate.Adopt woven wire even under the big relatively spinning plate situation of application, two distances between the spinning plate are consistent, because woven wire also plays a part division board.
Under the state that control is simply arranged, also may make each threads in the two component long filaments of the core-skin type of producing have different peel filament contents.For this purpose, can select different resistances to the Pi Siliu of each root core silk stream.If resistance is selected very greatly, make the skin wire material can not be coated on the corresponding core silk stream, consequently produce simple one-component long filament.
The X sieve mesh silk screen of the particularly commercial general R.V.S trade mark of suitable woven wire, wherein X is from 30 to 500, and R.V.S is a kind of stainless steel trade mark, and the X sieve mesh represents that woven wire every inch on two directions has the X one metal wire.Knit wire diameter into the net and be 0.5 to 0.025mm.
Flow resistance can be determined that permeability K is determined by following formula by the permeability of Fluistor
K=- (ηV)/(δP/δX)
The viscosity of η fluid (Pa.S) in the formula
The V fluid is by the speed (m/sec) of Fluistor
δ P/ δ X is at the barometric gradient (N/m of flow direction
3)
In view of the above, infiltrative unit is m
2
The permeability K of Fluistor preferably is selected in 10
-11To 3 * 10
-10m
2Between.
Especially curiously, not only can be used for melt spinning according to technology of the present invention, and also can be used for solvent spinning, use is united in perhaps above-mentioned two kinds of spinning.For example two kinds of components all can be spun into by melt spinning or solvent spinning.Yet also such example can be arranged, core silk component is by melt spinning production, and skin silk component is by solvent spinning production.Solution spins and is meant that spinning solution is made up of the polymer that is dissolved in the solvent, and molten spinning is the polymer spray silk with fusion.
If first and second spinning plate has only a spinneret orifice separately, can be in order to producing the two component mono filaments of core-skin type according to technology of the present invention, and one layer thickness skin silk is very uniformly arranged at its circumference and along its length direction.
The present invention is further set forth for embodiment with reference to the accompanying drawings.
Fig. 1 represents that the field , And that yarn silk of the present invention is showed compares with existing processes;
Fig. 2 represents the process chart of production yarn silk of the present invention;
The spinning plate schematic diagram that the existing technology of Fig. 3 is used;
The spinning plate schematic diagram of Fig. 4 process application of the present invention;
The structure chart of Fig. 5, Fig. 6 presentation graphs 4 spinning plate;
The partial cross section of the yarn silk of the existing explained hereafter of Fig. 7;
The partial cross section of Fig. 8 yarn silk of the present invention.
By the two group part filament yarns of core-skin type of the present invention, the zone that represents among Fig. 1 becomes and should be readily appreciated that. Among the figure, abscissa is the volume % of peel filament content, and vertical coordinate is that its peel filament content is the two groups of the core-skin type part shared percentage P% of long filament of S ± 0.1S in the two group part long filaments of whole core-skin types of yarn silk. The area that mark with hatching for indicating " existing technology " distributed areas that existing technology is possible. In view of this, adopt existing technology to be easy to just can produce the yarn silk that is made up of the two group part long filaments of the core-skin type that contains 25% peel filament content, wherein, the peel filament content of the two group part long filaments of whole core-skin types all is 25%. Otherwise, when by peel filament content being two group part long filaments of 10% core-skin type when forming the yarn silk, only have the two group part of core-skin type long filaments of 5% that 10% peel filament content is arranged. Its uniformity of yarn silk provided by the invention obviously improves. Curve A is corresponding to the condition of claim 1 among Fig. 1, and curve B is corresponding to the bar of claim 2 Part, and curve C is corresponding to the condition of claim 3.
Fig. 2 is the process flow diagram of producing the yarn silk according to the present invention. 1 represents filament spinning component among the figure, and it is connecting spinning plate parts 2 with flange, and these spinning plate parts will elaborate at Fig. 3,4,5 and 6 specification. The flow process of filament spinning component more than 1 is extruder and the molten thread (not shown in FIG.) of commonly using. Leave from assembly 1, the two group part long filaments of core-skin type or one-component long filament 8 are through a cooling chamber 7 that is provided with cooling-air 9. Long filament rolls 5 by a spin finishing, assembles together , And at the there plurality of threads and from then on enters into the district 3,4 that stretches, and then perfect yarn silk is wound up on the bobbin 6.
Fig. 3 is the detail drawing that existing technology is used spinning plate, and wherein 10 is first spinning plate, and 11 is second spinning plate. The melting of core silk is flowed through the hole 12 of first spinning plate 10 and is entered second spinning plate 11, or rather, enters into 13 of funnel shape. Pi Sisi stream flows between the spinning plate 10 and 11, thus coat every from the hole the 12 core silks that come out flow. At this, the independent silk stream of every of core silk component is coated by skin silk component, and two components are connected and enter spinneret orifice 14 and be extruded out through funnel hole 13 then. In Pi Siliu coats the zone of core silk stream, second spinning plate 11 boss 15 is arranged.
Fig. 4 has provided the spinning plate structure that is used for technology of the present invention briefly, and 20 is first spinning plate, and 21 is second spinning plate. Core silk component is introduced into and enters a spray silk passage 22 through a cone seat hole 26, and on second spinning plate 21, link to each other with spray silk passage 22 be a spray passage 23. Skin silk component is evenly distributed between spinning plate 20 and 21 by annular channel 28, and the space between the spinning plate 20 and 21 is filled up by a woven wire, and gets through fully at spray silk passage 22 and 23 places. Like this, skin silk component goes to coat core silk component from annular channel 28 through woven wire 27. At this, woven wire acts on skin silk component just as a flow resistance device. Core silk and skin silk component are united by hole 24 and are extruded out.
Fig. 5 and Fig. 6 are according to technology of the present invention used spinning plate entity, and Fig. 5 is one vertical Section, Fig. 6 are the cross sections. Passage 32 guiding core silk component stream are to first spinning plate 20, this moment, skin silk component represented through its continuity part with dashed lines of passage 33(, because passage 33 extends to beyond the plane) and continuity part 34 pass first spinning plate 20 and enter into circular passage (not showing) between first and second spinning plate. Between first spinning plate 20 and second spinning plate 21 a flow resistance device is arranged, it plays a part division board simultaneously between first and second spinning plate 20,21. 31 expression alignment pins, 30 expression sealing rings. Packing ring 35 between passage plate 29 and first spinning plate is in order to prevent the leakage of skin silk component.
Fig. 7 is the part sectioned view of the two group part filament yarns of the core-skin type of existing explained hereafter. The 37th, skin silk, the 36th, core silk. Can find out that the two area change scope of skin silk and core silk between each long filament is very big. At the length direction of one filament, the area change scope of Pi Si and core silk is also very big.
Fig. 8 is the corresponding topical profile according to the silk yarn of explained hereafter of the present invention. The uniformity of core silk area 38 and Pi Si area 39 is very noticeable.
When illustrated embodiments, will further specify the present invention.
Embodiment 1-9(sees Table 1)
Example 1-9 shows the excursion that can produce the yarn silk according to the present invention.
Example 1-3 SMIS silk polymer adopts has the polyester of typical case's weaving with silk relative viscosity (the 1g polyester is dissolved in the m-cresols of 100g, measures) in the time of 25 ℃.The polyester of example 4-6, its low relative viscosity are applicable to industrial silk, and the polyester of routine 7-9 has high viscosity, for example is applicable to tyre cord or sewing threads.In all cases, the skin wire material is all used nylon 66(PA66).
In each above-mentioned example group, the core silk all is different with the output of skin silk Spinning pumps.Fluistor is P.V.S.60 silk screen (seeing routine 10-15 for details).Spinning plate will adopt Fig. 4-6 described.
Except not stretching, the two component long filaments of core-skin type are the technological process production with earlier figures 2.Process conditions and used polyester all are listed in the table 1.The two component long filaments of core-skin type that table 1 also is listed in the long-pending content of skin filament of S% (account for all having (S ± 0.1S) the two component long filaments of the core-skin type of the peel filament content of % all count) the percentage P% of corresponding long filament cumulative volume.The P(% that reports out) be to get the average that 10 cross sections draw at the variant point of corresponding yarn silk.
The P value has proved that its uniformity of yarn silk of producing according to the present invention is desirable.Simultaneously, the diameter D of the two component long filaments of single core-skin type also is uniformly in the yarn silk, because they are equally approximately (in the scope of D ± 0.1D).
Embodiment 10-15(sees Table 2)
Example 10-15 discusses the production of tyre cord and the mensuration of performance thereof.
For this purpose, core silk polymer employing relative viscosity is 2.04 polyester.The material of skin silk is selected nylon 66(PA66 for use in example 10 and 11), and in example 12 to 15, adopt the mixture (in table, marking the PA66+ additive) of poly-(the m-dimethylbenzene adipamide) of nylon 66 and 0.3% weight.This mixture has fabulous adhesiveness to rubber especially to polyester and to elastomeric material.
The component of every core silk and skin silk still adopts technology shown in Figure 2 once to use 900m/min without stretching, and another time is with the speed of 500m/min.Fluistor is to use the R.V.S.60 silk screen.This net is to be made into by stainless steel wire.Horizontal and vertical all be every inch 60 one metal wires.The steel wire diameter of this commercial general silk screen is 0.16mm.
Spinning plate will adopt Fig. 4-6 described.
In example 14 and 15, the long heating tube of 0.4m is placed directly in below the spinning plate, postpones the effect of cooling with test.Selection of technological conditions is listed in the table 2.
Yarn silk with gained stretches in stretching device then.This comprises that the yarn silk withdraws from from bobbin and enters first three roller stretching-machine and enter second three roller stretching-machine again, then thus through one section 10 meters long steam heater, the yarn silk is subjected to the processing of 250 ℃ of temperature at this, then the yarn silk enters the 3rd three roller stretching-machine , And and is keeping draw speed to reel.Seven roller organizational securities are held 75 ℃ temperature.
The yarn silk selected for use of the example 10-15 draw speed that stretches is when listed in table 3, and seven roller machine draw ratios are meant that the yarn silk is by obtainable draw ratio behind the seven roller machines in the table.Total stretch ratio is that the speed difference according to first and the 3rd three roller stretching-machines gets.
The performance of the yarn silk that obtains with the method is listed in " yarn silk " column of table 4.LASE 1%(N in the table) be meant the intensity (N) of yarn silk when bearing that to make its percentage elongation be 1% load, LASE 2% and LASE 5% also are same explanations.
/ 160 ℃ of HAS 4 ' are meant that the yarn silk is exposed to 160 ℃ of yarn silk hot air shrinkages that produce after following 4 minutes with the load of 5mN/tex.
Resulting yarn silk is respectively all with 1100(Z472) X2(S472) structure make tyre cord.The performance of this structure tyre cord is listed in the column that table 4 indicates cord equally.
The cord that obtains under this state will be coated with adhesive in the ordinary course of things.For this purpose, cord passed through one 150 ℃ stove continuously with the tension force of 5N in 120 seconds, then by solution, again at the stove that passed through 240 ℃ under the tension force of 5N in 45 seconds.Solution is grouped into by following one-tenth:
Soft water,
Sodium hydroxide solution,
Resorcinol,
Formaldehyde,
VP latex,
Ammoniacal liquor.
Listing in table 4 equally with the cord performance of the method processing indicates in the column of " polyfiber yarn immersion cord ".
P and S only refer to the yarn silk, so these numerical value do not have in the column of " cord " and " polyfiber yarn immersion cord ", and only list in the column of " yarn silk ".