KR20200114398A - High Strength Flame Retardant Composite Yarn - Google Patents

Abstract

The present invention relates to a high-strength flame-retardant composite yarn manufactured by an interlace yarn device using a polyester fiber manufactured by mixing a master batch chip containing a polyester base resin having an intrinsic viscosity (IV) of 1.0 to 1.4 dl/g and a flame retardant with a polyester resin having an intrinsic viscosity of 0.9 to 1.0 dl/g and melt spinning the mixture through a spinneret; and a low-melting-point polyester composite fiber in which a polyester resin for a binder comprising terephthalic acid or an ester-forming derivative thereof as an acidic component and 2-methyl-1,3-propanediol, 2-methyl-1,3-pentanediol, and ethylene glycol as a diol component is composed as a sheath part or a low-melting-point polyester fiber composed of only a polyester resin for a binder. Accordingly, the present invention can provide a polyester composite yarn which is environmentally friendly, capable of expressing strength suitable for industrial and leisure sports application, and having excellent flame retardant properties.

Description

High Strength Flame Retardant Composite Yarn

The present invention relates to a high-strength flame-retardant composite yarn, and more particularly, to a high-strength flame-retardant composite yarn having a high-strength flame-retardant composite yarn having excellent bonding strength between materials by using the fusion behavior of the low-melting-point yarn as a high-strength composite yarn having flame retardant properties.

Recently, fiber materials with flame retardant properties have been used in various fields, from living materials such as curtains and flooring, to poor industrial environments such as safety nets and protection nets at construction sites, large ship ropes, automobile hoses, sewing threads, and seat belts. Has become. When used in various industrial environments as above, heat-resistant properties that can be used at a certain temperature or higher are required, and in particular, flame-retardant performance is basically required to prevent the fire from spreading and spreading into a large fire when a fire occurs.

Accordingly, high-functional flame-retardant raw-bonded high-strength polyester fibers have been developed and used in the material market requiring various high-functional properties, as in the preceding patent'Method of manufacturing polyester fibers (patent registration 10-1865394)'.

However, if the high-functional flame-retardant high-strength polyester fiber itself does not have a connective tissue during commercial application, its application is limited and there is difficulty in use.

Therefore, the present invention uses the fusion behavior of the low-melting-point yarn by combining and applying low-melting-point yarn to high-functional flame-retardant high-strength polyester fiber in order to facilitate the bonding of the product. It is expected to be applicable in various fields.

The technical problem to be achieved by the present invention is to solve the above problems, the manufacturing process is eco-friendly, it is possible to develop strength suitable for industrial, leisure and sports use, has excellent flame retardant properties, and can be commercialized and applied in various fields only by thermal fusion. It is to provide a high-strength flame-retardant composite yarn in which possible low melting point yarns are mixed.

In order to solve the above problems, the present invention provides a master batch chip including a polyester base resin having an intrinsic viscosity (IV) of 1.0 to 1.4 dl/g and a flame retardant to a polyester resin having an intrinsic viscosity of 0.9 to 1.0 dl/g. It is mixed, and it contains a polyester fiber prepared by melt spinning through a spinneret and terephthalic acid or an ester-forming derivative thereof as an acid component, and as a diol component, 2-methyl-1,3-propanediol, 2-methyl-1 ,3-pentanediol, and a polyester resin for a binder, characterized in that it comprises a sheath, a low-melting-point polyester composite fiber composed of a sheath portion or a low-melting-point polyester fiber composed of only the polyester resin for the binder as an entanglement generator. It provides the manufactured high-strength flame-retardant composite yarn.

In addition, the present invention provides a high-strength flame-retardant composite yarn, characterized in that the content of the master batch chip is 1 to 30 parts by weight based on 100 parts by weight of the polyester resin.

In addition, in the present invention, the flame retardant included in the master batch chip is a phosphoric acid ester compound, a pyrophosphate flame retardant, a phosphonate flame retardant, a phosphinate flame retardant, a non-halogen condensed phosphorus flame retardant, and a frost-based flame retardant. It provides a high-strength flame-retardant composite yarn, characterized in that at least one selected from.

In addition, the present invention provides a high-strength flame-retardant composite yarn, characterized in that the diol component of 2-methyl-1,3-pentanediol contains 0.01 to 5 mol% of the diol component.

In addition, the present invention provides a high-strength flame-retardant composite yarn, characterized in that the difference between the melt viscosity of 220°C and the melt viscosity of 260°C is 600 poise or less.

In addition, the present invention provides a high-strength flame-retardant composite yarn, characterized in that the polyester resin for the binder has a melt viscosity of 600 to 1,500 poise at 260°C.

In addition, the present invention provides a fabric, knitted fabric, and non-woven fabric having excellent shape safety, composed of a high-strength flame-retardant composite yarn.

The present invention is environmentally friendly, capable of expressing strength suitable for industrial and leisure sports, and can provide a polyester composite yarn having excellent flame retardant properties.

In addition, when manufacturing industrial polyester fibers requiring flame retardancy, the production process can be flexibly applied because the production process can be shortened and the phosphorus content required according to product characteristics can be freely adjusted without going through separate copolymerization and solid phase polymerization processes. have.

In addition, the present invention has a feature that can be commercialized and applied to various fields only by thermal fusion using a high-strength flame-retardant composite yarn mixed with a low melting point yarn.

In addition, the constituent resin of the high-strength flame-retardant composite yarn of the present invention is polyester and has the same kind, which is advantageous for recycling.

Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention.

The terms'about','substantially', etc. of the degree used in the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and are used in the sense of the present invention. To assist, accurate or absolute figures are used to prevent unfair use of the stated disclosure by unscrupulous infringers.

The present invention relates to a high-strength flame-retardant composite yarn manufactured by using a flame-retardant high-strength polyester fiber and a low-melting-point polyester fiber with an entanglement generator.

The type of interlacing device that is applied to the present invention is PolyJet-SP type for spinning process, SlideJet-DT type for interlacing nozzle for stretching process, SlideJet-HFP type for interlace nozzle for manufacturing composite covering yarn, and SlideJet- interlace nozzle for combustible texturing process. Although it is possible to apply the FT type, the SlideJet-DT type, which is the most general-purpose nozzle, was used in the present invention, and the firing speed was set to 100 to 500 m/min when the air pressure was 0.5 to 10 kgf/cm 2.

First, the polyester fiber is mixed with a polyester resin master batch chip including a polyester base resin and a flame retardant having an intrinsic viscosity (IV) of 1.0 dl/g or more, and melt-spinned through a spinneret.

The polyester base resin and the polyester resin may each independently use at least one selected from the group consisting of polyethylene terephthalate resin, polytrimethylene terephthalate resin, and polybutylene terephthalate resin, but is not limited thereto. . Preferably, a polyethylene terephthalate resin is used which is excellent in heat resistance, mechanical strength and molding processability and is advantageous in terms of economy.

The polyester resin may be prepared by condensation polymerization of at least one dicarboxylic acid compound and at least one glycol compound. Preferably, the dicarboxylic acid compound may be an aromatic, aliphatic or alicyclic dicarboxylic acid, and the glycol compound may be an aliphatic or alicyclic glycol. More preferably, the aromatic dicarboxylic acid is an aromatic dicarboxylic acid having 6 to 20 carbon atoms, the aliphatic or alicyclic dicarboxylic acid is an aliphatic or alicyclic dicarboxylic acid having 3 to 20 carbon atoms, and the aliphatic or alicyclic The group glycol is an aliphatic or alicyclic glycol having 2 to 20 carbon atoms.

More specifically, the dicarboxylic acid compound includes terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, seba Acid, (1,4-, 1,5-, 2,3-, 2,6- or 2,7-) naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4' -Dibenzyldicarboxylic acid may be used, but is not limited thereto. Preferably, terephthalic acid, isophthalic acid or mixtures thereof are used. Examples of the glycol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, (1,2-, 1,3- or 1,4-)cyclohexanedimethanol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, etc. may be used, but limited thereto. It does not become. Preferably, ethylene glycol, cyclohexanedimethanol or a mixture thereof is used.

The polyester resin can be synthesized using the above-described dicarboxylic acid compound and glycol compound. Preparation of a polyester resin using a dicarboxylic acid compound and a glycol compound is usually carried out in two steps of an ester reaction and a polycondensation reaction, and the manufacturing process is already well known in the art.

At this time, the polyester base resin has an intrinsic viscosity (IV) of 1.0 dl/g or more, preferably 1.0 to 2.0 dl/g, more preferably, in order to minimize the viscosity drop phenomenon due to thermal decomposition and shear stress during the manufacturing process. What is 1.0 to 1.4 dl/g is used.

The flame retardant may be applied as long as it is a non-halogen flame retardant, but preferably may be a phosphorus-based flame retardant.

The phosphorus-based flame retardant is eco-friendly because it does not generate a halogen-based gas during processing or molding and combustion of the resin composition, and is used in combination with a nitrogen-based flame retardant to be described later, thereby minimizing deterioration of mechanical and thermal properties of the composition.

As a phosphorus-based flame retardant that can be used, preferably one or a mixture of two or more of them selected from a phosphoric acid ester compound, a pyrophosphate-based flame retardant, a phosphonate-based flame retardant, a phosphinate-based flame retardant, a non-halogen condensed phosphorus-based flame retardant, and an enemy-based flame retardant. You can use

Examples of the phosphoric acid ester compound include, but are not limited to, a monomer compound having one aromatic group, such as triphenyl phosphate (TPP), tricxylenyl phosphate (TXP), or tricresyl phosphate. (Tricresyl phosphate, TCP); Monomer compounds having two or more aromatic groups, such as resorcinyl diphenyl phosphate (RDP), phenyl diresorcinyl phosphate, Cresyl diphenyl phosphate, xylenyl Diphenyl phosphate (Xylenyl diphenyl phosphate) or phenyl di(isopropylphenyl) phosphate (Phenyl di(isopropylphenyl) phosphate); And oligomers or polyphosphates of dimer or more.

The phosphonate-based flame retardant preferably has a reactive crosslinked polyphosphonate structure by introducing a phosphate ester bond in the molecule, and a flame retardant copolymerized with polycarbonate may be used.

As the phosphinate-based flame retardant, preferably a metal-substituted monophosphinate or diphosphinate flame retardant may be used alone or in combination.

The content of phosphorus in the flame retardant may be 10,000 to 100,000 ppm, preferably 40,000 to 80,000 ppm, more preferably 60,000 to 80,000 ppm, based on 100% by weight of the master batch chip. When the phosphorus content satisfies this range, there is an advantage of reducing the amount of addition when the master batch chip is introduced, and flame retardancy can be effectively imparted without deterioration of mechanical properties such as thermal deformation temperature and tensile strength.

The master batch chip may further include one or more types of ultraviolet stabilizers, antioxidants, antistatic agents, organic colorants, inorganic colorants, etc. in addition to flame retardants, depending on required physical properties.

In order to manufacture industrial polyester fibers having better flame retardant performance than conventional commercial products, a hole diameter of 0.4 mm or more, preferably 0.2 to 1.2 mm, more preferably 0.4 to 0.8 mm, 40 to 400, preferably A nozzle having 144 to 192 holes can be assembled into a pack and applied as a spin-block.

In addition, the polyester resin may have an intrinsic viscosity (IV) of 0.9 to 1.0 dl/g in order to manufacture high-strength fibers.

The polyester resin having such an intrinsic viscosity can be easily prepared by a method of solid-phase polymerization of a conventional polyester chip having an intrinsic viscosity of about 0.6 according to a known method.

The content of the master batch chip may be 1 to 30 parts by weight, preferably 3 to 15 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the polyester resin. When the content of the master batch chip satisfies this range, flame retardancy can be effectively imparted without deterioration of mechanical properties such as heat deflection temperature and tensile strength, and there is no problem of deterioration of workability in injection and molding during extrusion, It can be produced in fibrous form.

The temperature for melt spinning is, for example, 300°C, preferably 290 to 310°C, and the spinning temperature may be appropriately determined in consideration of the melt index of the polyester resin. The melt-spun fibers are cooled to form undrawn yarn.

The melt-spun undrawn yarn single fiber fineness (D.P.F., denier per filament) may be adjusted to 5 to 120 denier, preferably 30 to 60 denier.

At this time, the number of holes of the spinneret may be 40 to 400, preferably 144 to 192.

The size of the hole of the spinneret is 0.2 to 1.2 mm, more preferably 0.4 to 0.8 mm, and the depth of the hole of the spinneret is 0.8 to 4.8 mm, more preferably 1.6 to 3.2 mm.

Thereafter, the undrawn yarn released through the spinneret undergoes a cooling process through a quenching zone, and the cooling temperature may be adjusted to a temperature of 15 to 30°C, more preferably 20 to 25°C.

In addition, the wind speed during cooling may be adjusted to 1.0 to 2.0 m/sec, more preferably 0.8 to 1.5 m/sec.

Then, a spinning oil is supplied and attached to the undrawn yarn.

In this step, the linear speed and the spinning oil during running of the undrawn polyester yarn can be applied according to a conventional method.

The polyester undrawn yarn may be driven at a linear speed of 200 to 600 m/min, and a spinning oil containing a lubricant having a viscosity of 90 to 1000 cps may be supplied to the undrawn yarn to be attached.

As described above, by controlling the running speed of the undrawn polyester yarn in the range of 200 to 600 m/min, scattering of the oil agent can be suppressed. In addition, if the viscosity of the lubricant contained in the emulsion satisfies the range of 90 to 1000 cps, when the lubricant is mixed with the spinning oil, it can be controlled to a low viscosity through temperature control, has excellent heat resistance, and is a high temperature godet in the subsequent drawing process. It is possible to prevent scum on the roller surface when passing through the roller.

As an example of such a high viscosity lubricant, a paraffinic wax having 24 to 40 carbon atoms, a silicone wax having a weight average molecular weight of 1,000 to 8,000, or a mixture thereof may be used.

As a specific example of the paraffin wax, a polymethylene-based, polyethylene-based, polypropylene-based wax, or a mixture thereof may be used.

Since these lubricants have a high viscosity, the viscosity of the whole mixed spinning oil is increased. If the viscosity of the mixed spinning oil is too high, the uniform adhesion of the oil to the fibers may be lowered, and thus the spinning oil may be heated and supplied to the fibers so that the viscosity is maintained at 10 cps or less.

The spinning oil may contain 50 to 80% by weight of a high viscosity lubricant, and when the content of the high viscosity lubricant satisfies this range, uniform adhesion of the spinning oil may be improved.

In addition, in addition to high-viscosity lubricants, conventional oil additive components such as mineral oil, antistatic agent, and surfactant may be additionally used in the spinning oil, and known components that impart various properties to polyester fibers such as rubber adhesion and water repellency. Of course, more can be added.

The undrawn yarn to which the spinning oil is attached is supplied to a stretching process according to a conventional polyester fiber manufacturing process and is drawn, and the OPU of the polyester fiber produced here may be 0.7 to 2.0%. If the OPU value of the fiber satisfies the above range, the abrasion resistance effect is improved, and the problem of increasing the contamination source in the drawing and winding process due to the high OPU can be prevented.

Next, the undrawn yarn to which the emulsion is attached is drawn.

The heat treatment conditions and draw ratio of the drawing process can be easily adjusted by a person skilled in the art according to the intrinsic viscosity of the raw material resin, the use and strength of the desired polyester fiber, and the like.

In the previous process, the undrawn yarn may be supplied with an initial feed rate of 400 to 700 m/min using a feed roller, and a stretched hot roller controlled at a temperature of 80 to 250°C. At this time, the draw ratio may be extended by about 4 to 7 times according to the speed of the feed roller.

Further, if necessary, the stretched polyester fiber may be additionally subjected to relaxation treatment.

Subsequently, the drawn yarn is wound, and the interlace pressure used to entangle the existing filaments in the winding step can be focused at a pressure of 5.0 to 9.0 bar, more preferably 6.0 to 8.0 bar. .

The single yarn fineness of the polyester fiber may be 4 to 10 denier, preferably 5 to 7 denier.

The strength of the polyester fiber may be 7.0 g/d or more, preferably 7.5 to 8.5 g/d, and the elongation may be 10 to 30%, preferably 15 to 25%.

The content of phosphorus in the flame retardant with respect to 100% by weight of the polyester fiber may be 2,000 ppm or more, preferably 3,000 to 90,000 ppm, more preferably 3,000 to 7,000 ppm. When the phosphorus content satisfies this range, flame retardancy may be effectively imparted without deteriorating mechanical properties such as heat distortion temperature and tensile strength of the polyester fiber.

Next, look at the low melting point polyester fiber.

A binder comprising terephthalic acid or an ester-forming derivative thereof as an acidic component, and 2-methyl-1,3-propanediol, 2-methyl-1,3-pentanediol, and ethylene glycol as a diol component The polyester resin may be a low-melting-point polyester composite fiber composed of a sheath portion or a simple low-melting-point polyester fiber composed of only the polyester resin for the binder.

Polyester resin for a binder containing terephthalic acid or its ester-forming derivative as an acidic component, and 2-methyl-1,3-propanediol, 2-methyl-1,3-pentanediol, and ethylene glycol as a diol component It is about.

2-methyl-1,3-propanediol, which is one of the diol components, facilitates rotation of the polymer main chain by bonding a methyl group to the second carbon, and acts as if it is an end part of the polymer to widen the free space between the main chains, Increase the liquidity of This makes the polymer amorphous and has the same thermal properties as isophthalic acid. Due to the flexible molecular chains present in the polymer main chain, it improves the elasticity and thus improves the tear property when binding the nonwoven fabric.

That is, 2-methyl-1,3-propanediol contains a methyl group (-CH ₃ ) in the ethylene chain bonded to terephthalate as a side chain, thereby securing a space so that the main chain of the polymerized resin can rotate. It is possible to adjust the softening point (Ts) and/or the glass transition temperature (Tg) by inducing an increase and a decrease in crystallinity of the resin. This may exhibit the same effect as in the case of using isophthalic acid (IPA) containing an asymmetric aromatic ring in order to lower the crystallinity of the conventional crystalline polyester resin.

Another one of the diol components, 2-methyl-1,3-pentanediol, like the 2-methyl-1,3-propanediol, has a methyl group bonded to the second carbon to facilitate rotation of the main chain of the polymer. It has the property of imparting low melting point characteristics to the polyester resin, and increases the melt viscosity of the polyester resin with a longer molecular chain than 2-methyl-1,3-propanediol, while preventing the melt viscosity from rapidly decreasing at high temperatures.

The polyester resin for a binder formed of the diol component as described above contains 20 to 50 mol% of 2-methyl-1,3-propanediol in the polyester resin for the binder to improve low melting point properties and adhesion. Would be desirable.

When the 2-methyl-1,3-pentanediol is contained in an amount of less than 0.01 mol% of the diol component, the effect of improving the melt viscosity is insignificant, and when it exceeds 5 mol%, the melt viscosity rapidly increases, thereby deteriorating the spinning processability. It will be preferable that 2-methyl-1,3-pentanediol contains 0.01 to 5 mol% of the diol component.

Most preferably, the 2-methyl-1,3-pentanediol contains 0.05-2 mol%.

The polyester resin for a binder containing 2-methyl-1,3-pentanediol as described above has a melt viscosity of less than 600 poise at 220°C and 260°C. Has a specificity that does not degrade.

The lower the difference between the melt viscosity of 220°C and the melt viscosity of 260°C of the polyester resin for a binder, the lower it is, the more preferable it is, and it will be more preferably 500 poise or less.

In addition, when the melt viscosity is high at high temperature, it is possible to prevent the adhesiveness from deteriorating due to the lowering of the melting point at high temperature. Therefore, the polyester resin for the binder preferably has a melt viscosity of 600 to 1,500 poise at 260°C, and a melting point of 260°C. It would be more preferable to have a degree of 700 poise or higher.

As described above, the polyester resin for a binder with improved adhesive strength contains 2-methyl-1,3-propanediol and 2-methyl-1,3-pentanediol as described above, and has a softening temperature of 100°C to 150°C. , The glass transition temperature is 50 ℃ to 90 ℃, the intrinsic viscosity of 0.50 ㎗ / g or more to have excellent physical properties.

As described above, it may be formed into fibers by using a polyester resin for a binder having improved adhesive strength.

Fibers containing polyester resin for binder can be made into fibers by spinning a polyester resin for binder alone, and a polyester resin for binder is used in the sheath part, and a general polyester resin is used in the core part through composite spinning. It may be a sheath-core composite fiber.

If the melt viscosity of the general polyester resin of the core portion is too high, the spinning processability may be deteriorated, resulting in a thread trimming phenomenon, and if the melt viscosity of the core portion is lower than that of the polyester resin of the sheath portion, the shape stability of the composite fiber may be reduced. In other words, it is preferable that the fiber cross section of the cis-core type may not be formed, and the general polyester resin of the core portion has a melt viscosity of 2,000 to 4,000 poise at 280°C.

The difference between the melt viscosity of the general polyester resin forming the core part and the melt viscosity of the polyester resin for the binder forming the sheath part within a certain range is advantageous for improving the shape stability and spinning processability of the composite fiber. The difference between the melt viscosity of the polyester resin at 280°C and the melt viscosity at 260°C of the polyester resin forming the sheath is preferably 700 to 2500 poise, and more preferably 1,000 to 2,000 poise.

The polyester fiber for a binder containing the polyester resin for a binder as described above can be thermally bonded at a low temperature in a range similar to the temperature applied to the existing binder fiber, and adhesion is improved.

In addition, when using a polyester resin for a binder to produce a composite fiber, the difference in melting point between the sheath portion and the core portion is not large, so that the processability is improved, so that the physical properties of the fiber are uniform and the adhesive strength is improved.

<Manufacture of binder polyester resin>

Experimental example 1 to 6

Terephthalic acid (TPA) and ethylene glycol (EG) were added to the ester reaction tank, and a conventional polymerization reaction was performed at 258° C. to prepare a polyethylene terephthalate polymer (PET oligomer) having a reaction rate of about 96%.

In the prepared polyethylene terephthalate (PET), 2-methyl-1,3-propanediol contained about 42 mol% of the diol component, and the content ratio of 2-methyl-1,3-pentanediol was shown in Table 1 below. The mixture was mixed with, and a transesterification catalyst was added to perform a transesterification reaction at 250±2°C. Thereafter, a condensation polymerization reaction catalyst was added to the obtained reaction mixture, and a polycondensation reaction was performed while controlling the final temperature and pressure in the reaction tank to be 280±2° C. and 0.1 mmHg, respectively, to prepare a polyester resin for a binder with improved adhesion. .

compare Experimental example One

Terephthalic acid (66.5 mol%) and isophthalic acid (33.5 mol%) were used as acid components, and diethylene glycol (10.5 mol%) and ethylene glycol (89.5 mol%) were used as diol components to prepare polyester resin for binder I did.

.

Comparative example Experimental example 2

Terephthalic acid was used as the acidic component, and 2-methyl-1,3-propanediol (42.5 mol%) and ethylene glycol (57.5 mol%) were used as the diol component to prepare a polyester resin for a binder.

division Softening point
(℃) Tg
(℃) IV
(dl/g) 2-methyl-1,3-pentanediol (mol%) Melt viscosity 220℃ 240℃ 260℃ Experimental Example 1 122 60.9 0.561 0.1 1254 1019 783 Experimental Example 2 119 61.8 0.562 0.5 1314 1078 864 Experimental Example 3 120 61.9 0.562 1.0 1528 1387 1196 Experimental Example 4 123 63.5 0.562 2.0 2271 1739 1444 Experimental Example 5 123 64.8 0.563 3.5 2833 2571 2213 Experimental Example 6 126 67.3 0.561 5.0 3341 3041 2733 compare
Experimental Example 1 113 56.8 0.563 0 1011 739 467 compare
Experimental Example 2 121 61.5 0.561 0 1197 992 664

As shown in Table 1, it can be seen that the melt viscosity increases as the content of 2-methyl-1,3-pentanediol increases, and in Experimental Examples 1 to 6, the melt viscosity at 260° C. is all 700 poise or more, which is high at high temperature. It can be seen that the melt viscosity is maintained.

In addition, in Experimental Examples 2 to 4 in which 2-methyl-1,3-pentanediol was contained in 0.5 to 2 mol% of the diol component, the difference between the melt viscosity at 220°C and the melt viscosity at 260°C was 300 to 500 poise. It can be seen that the difference is lower than that of Comparative Examples 1 and 2 of 684 and 674 poise.

In addition, it can be seen that, as in Experimental Examples 5 and 6, when 2-methyl-1,3-pentanediol is contained in an amount of 3 mol% or more in the diol component, the melt viscosity at 260°C is 2,000 poise or more, and the melt viscosity is rapidly increased. .

◈ Experimental Example and Comparative Experimental Example Physical Property Measurement

The following physical properties of the polyester resin for the binder and the polyester fiber for the binder prepared in the Experimental Examples and Comparative Experimental Examples were measured, and the results are shown in Tables 1 and 2.

(1) Softening point (or melting point) and glass transition temperature (Tg) measurement

The glass transition temperature (Tg) of the copolymerized polyester resin was measured using a differential scanning calorimeter (Perkin Elmer, DSC-7), and the softening behavior was measured in TMA mode using a dynamic mechanical analyzer (DMA-7, Perkin Elmer). I did.

(2) Intrinsic viscosity (IV) measurement

The polyester resin was dissolved in a solution in which phenol and tetrachloroethane were mixed at a ratio of 1:1 by weight at a concentration of 0.5% by weight, and the intrinsic viscosity (I.V) was measured at 35°C using an Uberod viscometer.

(3) Melt viscosity measurement

After melting the polyester resin at the measurement temperature, the melt viscosity was measured using RDA-III of Rheometric Scientific. Specifically, when measured by setting from Initial Frequency = 1.0 rad/s to Final Frequency = 500.0 rad/s under Frequency Sweep condition at the set temperature, the value at 100 rad/s was calculated as the melt viscosity.

(4) Measurement of compression hardness

5 g of polyester fibers were opened, stacked at a height of 5 cm in a circular mold having a diameter of 10 cm, and then thermally bonded at a set temperature for 90 seconds to prepare a cylindrical molded article. The manufactured molded article was compressed by 75% through Instron, and the compressive hardness was measured by measuring the load applied to the compression. In this experiment, the compression hardness was measured by thermal bonding at 140°C, 150°C, and 160°C, respectively.

(5) Measurement of spinning yield (%, 24hr)

The spinning yield was calculated by the following equation by measuring the amount of the polyester resin used for 24 hours and the amount of spun fibers.

Spinning yield (%) = (Amount of spun fiber (kg) / Amount of PET resin used (kg)) * 100

(6) Room temperature and high temperature adhesion measurement

The polyester fibers of the Experimental Examples and Comparative Experimental Examples were thermally fused to prepare a nonwoven fabric having a density of 2g/100cm2, and the prepared nonwoven fabric was prepared at 25±0.5°C (room temperature) and 100±0.5°C (high temperature) according to ASTM D1424. The adhesion of the was measured.

(7) High temperature shrinkage

After the polyester fiber for the binder is prepared as short fiber, it is carded to form a cylindrical shape. After applying heat at 170° C. for 3 minutes, the reduced volume is measured. The existing volume is 330 cm3, which can be evaluated as poor shape stability as the volume decreases. Usually, if it is 250 cm 3 or less, the shape stability is inferior, and if it is 280 cm 3 or more, it can be evaluated as excellent.

division Compression hardness (kgf) Spinning yield Adhesion Shape stability 140℃ 150℃ 160℃ (%, 24hr) Room temperature adhesion
[kgf] High temperature adhesion
[kgf] High temperature shrinkage
[Cm3] Experimental Example 1 0.55 0.72 0.98 98.5 56.2 4.1 268 Experimental Example 2 0.57 0.79 1.07 99.2 57.4 4.3 271 Experimental Example 3 0.62 0.88 1.21 99.3 57.3 4.7 275 Experimental Example 4 0.61 1.24 1.36 99.5 58.1 4.9 281 Experimental Example 5 0.73 1.39 1.55 95.6 58.3 5.1 274 Experimental Example 6 0.76 1.54 1.86 91.3 57.2 5.2 271 compare
Experimental Example 1 0.41 0.57 0.74 97.8 55.3 3.2 254 compare
Experimental Example 2 0.52 0.73 0.91 98.1 55.7 3.9 260

As shown in Table 2, the polyester resins for binders of Experimental Examples 1 to 6 and Comparative Examples were both excellently measured at room temperature adhesiveness of 55 kfg or more, but it can be seen that Experimental Examples 1 to 6 had better adhesive strength than Comparative Experimental Examples 1,2. have.

In particular, Experimental Examples 1 to 6 were superior to the comparative example in high-temperature adhesion, and the high-temperature adhesion was 4.1 to 5.2kgf, but the comparative experimental examples were 3.2 and 3.9, so that the high-temperature adhesion of the experimental examples was very excellent.

In addition, it can be seen that both Experimental Examples 1 to 6 and Comparative Experimental Examples have a good level of high-temperature shrinkage of 260 cm 3 or more, but Experimental Examples 1 to 6 are superior to Comparative Experimental Examples 1,2.

In particular, Experimental Examples 2 to 4 containing 0.5 to 2.0 mol% of the diol component had a spinning yield of 99% or more, excellent both at room temperature and at high temperature, and very excellent in high temperature shrinkage. The 2-methyl-1,3- It will be preferable that the pentanediol is contained in an amount of 0.5 to 2.0 mol% in the diol component.

<Manufacture of high-strength flame-retardant composite yarn>

Example And Comparative example

A polyethylene terephthalate master batch chip having an intrinsic viscosity of 1.0 containing 15,000 ppm of phosphorus is mixed in a ratio of 20 parts by weight to 100 parts by weight of a polyester resin having an intrinsic viscosity of 0.9 to 1.0 using a dosing machine. Was put in. The phosphorus-based flame retardant used at this time was a phosphinate-based exolit op-950 manufactured by Clariant. The spinning temperature is 300℃, and the molten polymer is extruded through a nozzle with a diameter of 0.4mm in the spinneret with a discharge rate of 333g per minute using a polymer gear pump, and the number of holes is 192. Polyester fiber (first fiber) Was prepared.

Terephthalic acid (TPA) and ethylene glycol (EG) were added to the ester reaction tank, and a conventional polymerization reaction was performed at 258°C to prepare a polyethylene terephthalate polymer (PET oligomer) having a reaction rate of about 96%, and the prepared polyethylene terephthalate In phthalate (PET), 2-methyl-1,3-propanediol contained about 42 mol% of the diol component, mixed with 0.5 mol of 2-methyl-1,3-pentanediol, and a transesterification catalyst was added. The transesterification reaction was carried out at 250±2°C. Thereafter, a polycondensation reaction catalyst was added to the obtained reaction mixture, and a polycondensation reaction was carried out while controlling the final temperature and pressure in the reaction tank to be 280±2°C and 0.1 mmHg, respectively, using a polyester resin for a binder with improved adhesion. A low melting point polyester fiber (second fiber) composed of a polyester fiber for a binder was prepared.

The prepared polyester fiber and the low-melting polyester fiber were prepared by using a entanglement device in the composition ratio and entanglement conditions as shown in Table 3.

division Example 1 Example 2 Comparative Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 4 Comparative Example 5 1st fiber: 2nd fiber
Ratio (% by weight) 90:10 85:15 95:5 100:0
(Useful) 80:20 90:10 90:10 Bridge strength (kgf) 5 3 One - 5 10 5 Interlocking speed (m/min) 300 300 300 - 300 300 500 Number of bridges (n/m) 25 18 3 - 15 36 11 Yarn
Strong utilization rate (%) 97 98 99 98 98 92 98 Flame retardant
(KSF 8081) pass pass pass pass fail pass Pass Shape stability
(O, △, X) O O X O O O △ flexibility
(mm) 30 35 29 25 57 31 33 Warp fabric strength
(kgf/5cm) 203 208 164 205 210 180 183

The polyester fiber (first fiber) that determines the physical properties of the fabric used in the Examples and Comparative Examples was a 1000 denier product, which is most commonly used for industrial purposes, and at this time, the ratio of the fused yarn was 5 (50d), 10 (100d), Four types were combined at 15 (150d) and 20 (200d)%. Using this composite yarn, the shape stability, strength, and flame retardancy were compared with a 15X15/inch low-density plain fabric and a warp knitted fabric tied with a warp tie yarn.

As a result, the result according to the ratio of the low-melting-point polyester fiber (second fiber) is 168kgf compared to 203kgf of Example 1 due to the eccentricity of the fabric because of the low morphological stability of the fabric when it is compounded at a ratio of 5% or less as in Comparative Example 1. It was confirmed that the drop was about 15 to 20%, and when more than 20% was added as in Comparative Example 3, the shape stability was excellent, but the flexibility of the fabric was 57, resulting in a result that the flexibility fell to a level of 1/2 compared to the existing product, Comparative Example.

When the entanglement strength is different, as in Comparative Example 4, if the entanglement is too high, as in Comparative Example 4, if it is too high, it causes damage to the yarn, which adversely affects the final fabric strength at the level of 180kgf, and even if it is too low, the number of entanglements is reduced as in Comparative Example 1. Decreases stability. Accordingly, the strength of the air pressure during interlocking is optimal between 3kgf and 5kgf, and the speed during processing should be 500m/min or less as in Comparative Example 5.

Therefore, the characteristic of this product is that it is a product that is easy to apply to low-density products in any organization, and its applications are diverse.

◈ Example and comparative example evaluation method

1. Method of measuring the strength of yarn

The yarn was left in a constant temperature and humidity room at a standard condition, that is, a temperature of 25°C and a relative humidity of 65% for 24 hours, and then measured through a tensile tester by the method of ASTM D885.

2. Method of measuring the strength of fabric

The fabric was allowed to stand for 24 hours in a constant temperature and humidity room in a standard condition, that is, a temperature of 25°C and a relative humidity of 65%, and then measured by a tensile tester using the KSK 0521 Strip method.

3. How to measure fabric flexibility

The fabric was left in a constant temperature and humidity room in a standard condition, that is, a temperature of 25°C and a relative humidity of 65% for 24 hours, and then measured by the method of KSM ISO 5979.

3. Strong utilization rate

It is calculated by measuring the strength of the fiber before and after initial braiding with the value of the rate of change of strength before and after processing of the yarn. The calculation formula is as follows.

Strong utilization rate = (Strong after consolidation ÷ Strong in consolidation) X 10

The physical properties of the low melting point polyester fiber are not considered. During subsequent processing, the fused yarn is melted and only the adhesive properties are expressed.

4. Flame retardancy evaluation (KS F 8081)

As a standard for evaluating flame retardancy for thin fabrics, salt was burned using a micro burner in the middle of a sample located on an inclined surface of 45 degrees, and non-conformity was determined by measuring residual dust, residual salt, and carbonization distance.

Measurements were made three times per sample, and if the criteria of a residual salt time of less than 3 seconds, a residual time of less than 5 seconds, and a carbonization distance of less than 20cm were satisfied, it was judged as pass.

The high-strength flame-retardant composite yarn of the present invention can be used for fabrics, knitted fabrics, and non-woven fabrics, and has strength in shape stability by using binder fibers of flame-retardant polyester fibers and low-melting-point polyester fibers having high strength characteristics, and the resin of the constituent fibers is poly It is the same as ester, so it has excellent recycling characteristics.

The present invention described above is not limited by the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope of the technical spirit of the present invention. It will be obvious to those with knowledge

Claims (7)

A master batch chip containing a polyester base resin having an intrinsic viscosity (IV) of 1.0 to 1.4 dl/g and a flame retardant is mixed with a polyester resin having an intrinsic viscosity of 0.9 to 1.0 dl/g, and the melt spinning furnace Manufactured polyester fiber and
A binder comprising terephthalic acid or an ester-forming derivative thereof as an acidic component, and 2-methyl-1,3-propanediol, 2-methyl-1,3-pentanediol, and ethylene glycol as a diol component A high-strength flame-retardant composite yarn made of a low-melting-point polyester fiber composed of only the polyester resin for the binder or a low-melting-point polyester fiber composed of only the polyester resin for the binder with a entanglement generator.
The method of claim 1,
High-strength flame-retardant composite yarn, characterized in that the content of the master batch chip is 1 to 30 parts by weight based on 100 parts by weight of the polyester resin.
The method of claim 1,
The flame retardant included in the master batch chip is one selected from the group consisting of a phosphoric acid ester compound, a pyrophosphate flame retardant, a phosphonate flame retardant, a phosphinate flame retardant, a non-halogen condensed phosphorus flame retardant, and a frost-based flame retardant. High-strength flame-retardant composite yarn, characterized in that the above.
The method of claim 1,
Of the diol component, 2-methyl-1,3-pentanediol is a high-strength flame-retardant composite yarn, characterized in that it contains 0.01-5 mol% of the diol component.
The method of claim 1,
The polyester resin for the binder is a high-strength flame-retardant composite yarn, characterized in that the difference between the melt viscosity of 220 ℃ and the melt viscosity of 260 ℃ 600 poise (poise) or less.
The method of claim 1,
The polyester resin for the binder is a high-strength flame-retardant composite yarn, characterized in that the melt viscosity of 260 ℃ 600 ~ 1,500 poise (poise).
A woven, knitted or non-woven fabric having excellent shape safety, composed of the high-strength flame-retardant composite yarn of any one of claims 1 to 6.