KR20220041560A - Polyphenylene sulfide sea-island type twisted yarn and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a polyphenylene sulfide sea-island yarn to provide excellent stretching processability and dry heat shrinkage and a manufacturing method thereof. According to the present invention, the method comprises: a spinning step of composite-spinning with a sea component containing a soluble polyester resin and an island component containing a polyphenylene sulfide resin; a cooling step of cooling the spun sea-island yarn; a first winding step of winding the cooled sea-island yarn to produce an unstretched yarn; a stretching and twisting step of stretching and twisting the wound unstretched yarn by using two or more roller and performing non-contact heat treatment at 130 to 200℃; a shrinkage step of shrinking the stretched sea-island yarn at an overfeed rate of 0.7 to 0.99 and performing non-contact heat treatment at 200 to 400℃; and a second winding step of winding the shrunken sea-island yarn.

Description

Polyphenylene sulfide sea-island false-twisted yarn and manufacturing method thereof

The present invention relates to polyphenylene sulfide sea-island false-twisted yarn and a method for manufacturing the same, and more particularly, polyphenylene sulfide sea-island false-twisted yarn comprising polyphenylene sulfide (PPS) resin in an island component and false-twisting, and its manufacturing method It relates to a manufacturing method.

Polyphenylene sulfide fiber has various markets such as battery separators, dust collector filters, and automotive interior materials, as well as interior areas such as wallpaper, curtains, sofas, and bedding, industrial protective clothing, and protective clothing for protective gloves. In recent years, as the demand for chemical resistance and flame-retardant function increases, its use is increasing.

In particular, it is a filter material used for filters in filter cloth dust collectors, and is generally made from polyphenylene sulfide fibers, unlike non-woven fabrics made of glass fiber (Glass), meta-aramid (MA), Teflon (PTFE), polyimide (PI), etc. The manufactured nonwoven fabric is attracting attention as a heat-resistant filter material due to the excellent heat resistance, chemical resistance, low absorption characteristics, and shape stability of polyphenylene sulfide fibers.

Ultrafine fibers are fibers developed to make full use of a very soft and soft touch, and by dividing the spun fibers, fine fibers of up to 0.001 denier can be made. It is mainly used for high value-added textile products such as artificial leather, artificial suede, automobile interior materials, and case covers. Post-processing conditions ranging from punching and impregnation to raising are very diverse and complex.

Methods for producing microfibers include mono-component spinning, multi-component spinning (composite spinning), air jet spinning, flash spinning, and the like. Single-component spinning is a method of directly spinning fibers of a desired fineness, and has the advantage of reducing manufacturing cost by not going through the post-microfine process, but there is a limit to the ultrafine fineness of nano units in terms of facilities. Multi-component spinning can produce sea-island-type, split-type, and multi-layer fibers, and sea-island fibers are called extraction-type fibers. It is possible to manufacture 0.01 denier fiber by the extraction method, and has the advantage of small diameter deviation. Air jet spinning is the most excellent process for producing fine fibers by extruding a polymer melt through a nozzle, manufacturing fibers using heated high-speed air, and then stacking them irregularly in a collector to form a non-woven fabric structure. Flash spinning melts and extrudes a polymer such as propylene and evaporates the solvent immediately after detention, so that each fiber is collected in fibril form on a moving screen to form a network structure.

Currently, most of the sea-island microfibers are manufactured using polyester, nylon, or copolyester. However, in certain fields such as automobile interior materials, fiber materials with heat resistance are preferred for stability in case of emergency. In recent years, the use of polyphenylene sulfide (PPS) fiber as a material for interior materials with heat resistance is increasing as the limit of the amount of flame retardant additive used, national regulations on halogen flame retardants, and user expectations increase.

The sea-island polyphenylene sulfide microfine fibers with such heat resistance have a large amount of impurities remaining in the resin, unlike polyester or nylon, which are commonly used in the resin itself. Due to the side reaction caused by the . Accordingly, the process yield is very low, resulting in high process costs, and supply is not smooth compared to market demand.

In addition, polyphenylene sulfide fibers are fibers with a high shrinkage rate, and research to lower the shrinkage rate is in progress due to a problem in that fairness and productivity are lowered due to the shrinkage rate in post-processing.

The present invention was invented to solve the problems of the prior art as described above, and provides a manufacturing method for producing polyphenylene sulfide sea-island false-twisted yarn having excellent drawing processability and dry heat shrinkage by controlling the temperature in the drawing step after spinning into the sea-island yarn aim to do

Another object of the present invention is to provide a method for manufacturing polyphenylene sulfide sea-island false-twisted yarn having excellent drawing processability and dry heat shrinkage by performing a shrinkage step after drawing.

Another object of the present invention is to provide a polyphenylene sulfide sea-island false-twist yarn having a crimp produced by the above manufacturing method.

In order to solve the above problems, the present invention provides a method for producing a polyphenylene sulfide sea-island false twist yarn, comprising: a spinning step of complex spinning with a sea component containing a soluble polyester resin and an island component containing a polyphenylene sulfide resin; a cooling step of cooling the spun sea-island yarn; a first winding step of winding the cooled island-in-the-sea yarn to produce an undrawn yarn; a stretching and false twisting step of stretching and false twisting the wound undrawn yarn using two or more rollers, and performing a non-contact heat treatment at 130 to 200°C; shrinking the stretched sea-island yarn at an over feed rate of 0.7 to 0.99 and non-contact heat treatment at 200 to 400° C.; and a secondary winding step of winding the contracted island-in-the-sea yarn.

In addition, in the false stretching step, there is provided a method for manufacturing polyphenylene sulfide sea-island false twisted yarn, characterized in that stretching is performed at a draw ratio of 1.5 to 4 times.

In addition, there is provided a method for manufacturing polyphenylene sulfide sea-island false-twisted yarn, characterized in that the sea-island yarn is contracted at an over feed rate of 0.75 to 0.95 in the shrinking step.

In addition, there is provided a method for producing polyphenylene sulfide sea-island false-twisted yarn, characterized in that the non-contact heat treatment temperature in the shrinkage step is 250 ~ 360 ℃.

In addition, there is provided a polyphenylene sulfide sea-island false-twisted yarn, characterized in that produced by the above manufacturing method.

In addition, there is provided a polyphenylene sulfide sea-island false-twisted yarn, characterized in that the dry heat shrinkage of the sea-island yarn is 1 to 5%.

In addition, there is provided a polyphenylene sulfide sea-island false-twisted yarn, characterized in that the creep rate of the sea-island yarn is 20% or more.

As described above, the method for producing polyphenylene sulfide sea-island yarn according to the present invention includes a sea component containing a soluble polyester resin and an island component containing polyphenylene sulfide resin. This has the effect of improving the drawing processability and dry heat shrinkage of the polyphenylene sulfide sea-island yarn.

In addition, there is an effect of providing a polyphenylene sulfide microfiber having a crimp through the polyphenylene sulfide sea-island false twist yarn produced by the above manufacturing method.

1 is a view showing a process diagram of a method for manufacturing polyphenylene sulfide sea-island false-twisted yarn according to the present invention.
2 is a diagram schematically illustrating a second process of the method for manufacturing polyphenylene sulfide sea-island false twisted yarn according to the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. First, it should be noted that in the drawings, the same components or parts are denoted by the same reference numerals as possible. In describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the gist of the present invention.

As used herein, the terms 'about', 'substantially' and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and serve to enhance the understanding of the present invention. To help, precise or absolute figures are used to prevent unfair use by unconscionable infringers of the stated disclosure.

1 is a view showing a process diagram of a method for manufacturing polyphenylene sulfide sea-island false twisted yarn according to the present invention, and FIG. 2 is a view briefly showing a second process of the method for manufacturing polyphenylene sulfide sea-island false twisted yarn according to the present invention.

The present invention relates to a polyphenylene sulfide sea-island false-twisted yarn composed of an island component containing a polyphenylene sulfide resin as a sea component containing a water-soluble polyester resin.

Polyphenylene sulfide resin forming the island component is a crystalline engineering plastic having a relative viscosity of 0.1 to 10, and has high heat resistance and excellent mechanical properties, chemical resistance, electrical properties and dimensional stability. Examples of applications include electric/electronic parts, automobile parts, and mechanical parts.

In addition, polyphenylene sulfide (Polyphenylene sulfide) resin may be a linear, cross-linked, semi-cross-linked polymer, but is preferably a linear, weight average molecular weight (Mw) of 2,000 ~ 8,000, melt flow index (melt flow index) 20 ~ 150g/10min can be used.

In addition, using the mechanical and chemical durability, which is the characteristic of polyphenylene sulfide, black coloration is required for use as an automobile interior material. can be excellent. It is preferable to use the original dyeing process to express the basic colors such as black, indigo, and brown.

The sea component is formed of a soluble polyester resin, and then the soluble polyester resin is dissolved through reduction processing to form the polyphenylene sulfide sea-island yarn of the present invention into polyphenylene sulfide microfibers.

The soluble polyester resin is currently used in many fields and is a polymer resin that can be used in various fields with the advantage of being easily soluble in an alkaline solution. will be able to use

In particular, 0.1 to 1 mol% of dimethyl-5-sulfo isophthalate phosphonium salt (DMSP) or di(β-hydroxyethyl group)-sulfoisophthalate phosphonate based on terephthalic acid or a derivative thereof 90-95 wt% of a polyester resin containing Di(β-hydroxyethyl)-5-sulfo isophthalate phosphonium salt (DHSP) and 2-5 mol% of 5-sodium sulfoisophthalic acid (DMS) and water A water-soluble polyester resin containing 5 to 10% by weight of a water-soluble polyalkylene oxide having an average molecular weight of 400 to 20,000 may be used.

A soluble poly formed of polyalkylene oxide and a polyester-based resin containing the dimethyl-5-sulfoisophthalate phosphonium salt (DMSP) or di(β-hydroxyethyl group)-sulfoisophthalate phosphonium salt (DHSP) By using the ester resin, the strength of the manufactured yarn can be increased, and the improvement of the strength will increase the melt spinning property and reduce the thread cutting phenomenon in the yarn processing.

Using only dimethyl-5-sulfoisophthalate phosphonium salt (DMSP) or di(β-hydroxyethyl group)-sulfoisophthalate phosphonium salt (DHSP) by using the 5-sodium sulfoisophthalic acid (DMS) together Since the amount of dimethyl-5-sulfo isophthalate phosphonium salt (DMSP) or di(β-hydroxyethyl group)-sulfo isophthalate phosphonium salt (DHSP) used can be reduced, cost reduction can be expected.

The polyphenylene sulfide sea-island yarn of the present invention formed of the island component and the sea component as described above is preferably formed in an area ratio of the island component and the sea component of 2:8 to 8:2, and when the sea component is dissolved, polyphenylene of the island component The sulfide microfiber may preferably have a single yarn fineness of 0.5 denier or less.

As described above, the polyphenylene sulfide sea-island yarn according to the present invention includes a spinning step, a cooling step, a first winding step, a stretching and false twisting step, a shrinking step, and a second winding step, as shown in FIG. 1, the first process of manufacturing undrawn yarn (POY) through the spinning step, the cooling step, and the first winding step, and the undrawn yarn through the stretching false twisting step, the shrinking step, and the second winding step as shown in FIG. It will be possible to improve the manufacturing processability and the physical properties of the false twisted yarn even with polyphenylene sulfide by manufacturing it in a two-step process of the second process of manufacturing the drawn yarn (FDY).

The first process is a process for producing undrawn yarn (POY) through a spinning step, a cooling step, and a first winding step. It is a step of complex spinning in the form of island-in-the-sea yarns to form fibers. Using a general island-in-the-sea composite spinning device, the spinning temperature will be about 270~350℃.

The cooling step is a step of cooling the spun island-in-the-sea yarn, and sufficiently cools the island-in-the-sea yarn before winding so that fibers do not adhere to each other in the winding process. It is preferable that it is below ℃, and more preferably, it is 10-20 ℃.

In the cooling step, if the cooling temperature is too low or exceeds 20° C., the degree of crystallinity of the spun island-in-the-sea yarn may be lowered, and thus spinning processability and physical properties of the island-in-the-sea yarn may be deteriorated.

The first winding step is a step of winding the cooled island-in-the-sea yarn, and it is preferable to wind the undrawn yarn at a winding speed of 1500-2500 m/min.

If the winding speed of the first winding step is too low, the elongation rate is too low, and a trimming phenomenon may occur in the second process thereafter, thereby reducing fairness. The physical properties of the sea-island yarn may be deteriorated because cooling is not smooth in the sea.

The second process is a process of manufacturing an undrawn yarn into a drawn yarn (FDY) through a drawing false twist step, a shrinkage step, and a secondary winding step, and is carried out through a plurality of rollers.

The second process is, for example, as shown in FIG. 2 , the undrawn yarn is wound with the roller 100 and the stretching false-twisting rollers 210 and 230 for stretching, the contraction roller 250 for shrinking by giving an op-feed, and the winding-up roller 300 for winding. can be carried out with

The stretching false twist step is a step of giving twist to the island-in-the-sea yarn while stretching the undrawn yarn using two or more rollers, and stretching at a speed of 300 to 500 m/min is preferable to suppress the yarn breakage during stretching. .

In the stretching and false twisting step, it may be preferable to conduct non-contact heat treatment at 130 to 200° C. to facilitate crimp formation due to false twist.

In the stretching and false twisting step, contact heat treatment through a roller cannot be continuously heat treated during stretching and false twisting, and since the uniformity of the crimp may be deteriorated due to the heated roll furnace, non-contact heat treatment may be preferable.

The non-contact heat treatment in the stretching false twist step may be performed through a first heat plate 310 as shown in FIG. 2 , and it is preferable to continuously heat treatment during the stretching false twist step.

If the non-contact heat treatment temperature in the stretching false twisting step is too low or too high, the crystallinity of the polyphenylene sulfide resin may proceed too slowly or rapidly, so that the strength of the sea-island yarn may decrease during stretching. Higher strength can be maintained.

In the stretching false-twisting step, the stretching ratio may be adjusted in consideration of the stretching ratio in the first process, but if the stretching ratio is too large, stretching processability may be deteriorated. Therefore, it is preferable to stretch by about 1.5 to 4 times.

The shrinking step is a step of shrinking the drawn island-in-the-sea yarn at an over feed rate of 0.7 to 0.99, and is performed between the last drawing roller and the next roller in the drawing false twist step. That is, in FIG. 2 , it is a step between the last stretching roller 230 and the shrinking roller 250 .

The shrinking step is performed consecutively with the stretching false twist step, and the final drawing roller relaxes the sea-island yarn in a high temperature state to an overfeed rate of 0.7 to 0.99 to induce contraction of the sea-island yarn, thereby lowering the shrinkage of the sea-island yarn. .

In order to achieve a low dry heat shrinkage of the polyphenylene sulfide sea-island yarn of the present invention through the shrinking step, it is preferable to shrink the sea-island yarn at an overfeed rate of 0.75 to 0.95 in the shrinking step. More preferably, the overfeed ratio is 0.90 or less.

In addition, in the shrinkage step, a non-contact heat treatment is performed at 200 to 400°C.

The non-contact heat treatment in the shrinking step can be performed through a heat plate like the stretching false twist step, and as shown in FIG. 2, the second heat plate 330 is continuously heat treated during the shrinking step. It would be desirable to form it so that

The non-contact heat treatment in the shrinking step is a step of fixing the crimp formed in the stretching and false twisting step, and is performed at a high temperature. It is preferable that the non-contact heat treatment is performed at 200 to 400° C., and more preferably, the non-contact heat treatment is performed at 250 to 360° C.

The second winding step is a winding step of winding the contracted polyphenylene sulfide sea-island yarn.

The polyphenylene sulfide sea-island false twisted yarn according to the present invention produced by the first process of producing undrawn yarn (POY) by spinning as described above and the second process of producing undrawn yarn into drawn yarn (FDY) is cooled in the cooling step Polyphenylene sulfide sea-island false-twisted yarn with a low dry heat shrinkage rate can be manufactured by controlling the overfeed rate in the shrinkage step and controlling the overfeed rate in the shrinkage step by controlling the temperature and controlling the drawing temperature in the drawing step.

In addition, by maintaining the crimp formed by false twist by the non-contact heat treatment of the stretching and false twisting step, and fixing the crimp by the non-contact heat treatment of the shrinking step, the crimp is formed and microfibers can be manufactured.

It will be preferable that the polyphenylene sulfide sea-island yarn of the present invention has a dry heat shrinkage rate of 1 to 5% at 180°C and a crimp rate of 20% or more.

The polyphenylene sulfide sea-island false-twisted yarn of the present invention is manufactured from polyphenylene sulfide microfibers and has high heat resistance and chemical resistance in industrial fields such as battery separators, dust collector filters, automobile interior materials, industrial protective clothing, protective clothing fields of protective gloves, curtains, It can be used in various fields such as sofas and interior fields of bedding.

Hereinafter, the present invention will be described by way of examples. The following examples are only for a more accurate understanding of the present invention, and do not limit the protection scope of the present invention.

◈ How to measure

* Relative viscosity is determined by dissolving the sample in a solvent (5:5 weight ratio mixed solution of phenol and ethane tetrachloride) at a concentration of 0.5% and using an Ubbelohde type viscosity tube set in a constant temperature bath adjusted to a constant volume of solution. Calculate the flow time (sec) of and find the relative viscosity by the flow time (sec) of the same volume of solvent.

* Dry heat shrinkage: 180℃ shrinkage, length change before and after 1 hour heat treatment (%)

* Crimp rate:

(1) Apply a load of 600g, measure L1, heat it in hot water (98.5℃), and let it dry naturally for 4 hours.

(2) Measure L2 after applying a load of 600 g and leaving it for 1 minute. Remove 600g load and leave for 5 minutes, then measure L3

Total Crimp Ratio = (L2-L3)/L1 *100

◎ Preparation Example 1: Dry heat shrinkage according to the orbital rate

Using a polyphenylene sulfide resin having a relative viscosity of 0.3 as an island component, and using a polyphenylene sulfide resin having a relative viscosity of 0.3 as a sea component, a polyphenylene sulfide resin copolymerized with 2% by weight of polyethylene glycol having a molecular weight of 20,000 is used as a sea component. Undrawn yarn was prepared by supplying island component spinnerets to a sea-island type composite spinning spinneret with 37 spinnerets, performing composite spinning at 290°C, cooling to 15°C, and first winding at a speed of 2,000 m/min.

The prepared undrawn yarn was false-twisted while stretching to double the draw ratio using the same device as in FIG. 2, and the shrinkage step was performed with an overfeed ratio of 0.75 to 1.0, and the polyphenylene sulfide sea-island false-twisted yarn was prepared by secondary winding.

The non-contact heat treatment in the stretching and false twisting step was performed at 180 ° C. and the non-contact heat treatment at 280 ° C in the shrinking step.

overfeed rate 0.75 0.8 0.85 0.9 0.95 One Dry heat shrinkage (%) 1.62 1.85 2.02 2.89 4.23 9.32

As shown in Table 1, as the overfeed rate increases, the dry heat shrinkage rate tends to decrease. When the overfeed rate is 0.75 to 0.95, it can be seen that the dry heat shrinkage rate is 5% or less, and when the overfeed rate is 0.9 or less, the dry heat shrinkage rate is large. can be seen to decrease

◎ Preparation Example 2: Dry heat shrinkage and crimp rate according to the non-contact heat treatment temperature in the shrinkage step

Although polyphenylene sulfide sea-island yarn was prepared as in Preparation Example 1, it was shrunk at an overfeed rate of 0.8 in the shrinkage step, and the non-contact heat treatment temperature was adjusted to 210 to 400° C. indicated.

Temperature (℃) 210 250 280 320 360 400 Dry heat shrinkage (%) 10.3 5.1 4.2 4.13 3.1 2.4 Crimp rate (%) 25.6 25.2 24.1 22 20 12.4

As shown in Table 2, it can be seen that the dry heat shrinkage rate and the crimp rate tend to decrease according to the non-contact heat treatment temperature in the shrinkage step.

When the non-contact heat treatment in the shrinkage step is 250 to 360° C., the dry heat shrinkage rate is about 5% or less, and the crimp rate is 20% or more, indicating that both the dry heat shrinkage rate and the crimp rate are in an excellent range.

◎ Examples 1 to 3, and Comparative Examples 1 to 3

Polyphenylene sulfide sea-island yarn was manufactured as in Preparation Example 1, but in the shrinkage step, the overfeed rate was adjusted to 0.8 to 1.0 and the non-contact heat treatment (second heat plate) temperature was adjusted to 280 to 400 ° C. was manufactured.

The overfeed rate, non-contact heat treatment temperature and dry heat shrinkage rate, and crimp rate of the shrinkage step of each Example and Comparative Example were measured and shown in Table 3.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 overfeed rate 0.8 0.8 0.9 One 0.8 second heat plate
Temperature (℃) 280 360 280 280 400 Dry heat shrinkage ℃%) 4.20 3.10 4.50 11.30 2.40 Crimp rate (%) 24.1 20.0 24.8 25.7 12.4

As shown in Table 3, Examples 1 to 3 have better dry heat shrinkage than Comparative Example 1 and superior crimp rate than Comparative Example 2, with an overfeed rate of 0.75~0.95, an overfeed rate of the shrinkage step, and a non-contact heat treatment temperature of 250~ It can be seen that Examples 1 to 3 prepared in the range of 360° C. have excellent physical properties with a dry heat shrinkage of 5% or less and a crimp rate of 20% or more.

Claims (7)

In the polyphenylene sulfide sea-island false twisted yarn manufacturing method,
A spinning step of complex spinning with a sea component containing a soluble polyester resin and an island component containing a polyphenylene sulfide resin;
a cooling step of cooling the spun sea-island yarn;
a first winding step of winding the cooled island-in-the-sea yarn to produce an undrawn yarn;
Stretching and twisting step of stretching and twisting the wound undrawn yarn using two or more rollers, and performing non-contact heat treatment at 130-200°C;
a shrinking step of shrinking the drawn sea-island yarn at an over feed rate of 0.7 to 0.99, and performing a non-contact heat treatment at 200 to 400° C.; and,
A method for manufacturing polyphenylene sulfide sea-island false-twisted yarn comprising a secondary winding step of winding the contracted island-in-the-sea yarn. According to claim 1,
The stretching false-twisting step is a method for producing a polyphenylene sulfide sea-island false-twisted yarn, characterized in that the stretching ratio is 1.5 to 4 times. According to claim 1,
A method for manufacturing polyphenylene sulfide sea-island false-twisted yarn, characterized in that in the shrinking step, the sea-island yarn is contracted at an over feed rate of 0.75 to 0.95. According to claim 1,
The non-contact heat treatment temperature in the shrinkage step is a polyphenylene sulfide sea-island false twisted yarn manufacturing method, characterized in that 250 ~ 360 ℃. A polyphenylene sulfide sea-island false-twisted yarn, characterized in that produced by the method of any one of claims 1 to 4. 6. The method of claim 5,
Polyphenylene sulfide sea-island false-twisted yarn, characterized in that the sea-island yarn has a dry heat shrinkage of 1 to 5%. 6. The method of claim 5,
Polyphenylene sulfide sea-island false twist yarn, characterized in that the creep rate of the sea-island yarn is 20% or more.

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