KR100474798B1 - A process for producing polyester multifilament yarns having excellent adhesion to rubbers or polyvinyl chloride - Google Patents

Abstract

The present invention relates to an industrial polyester fiber having a high strength and low shrinkage property and excellent in adhesion to rubber or polyvinyl chloride (PVC) and a method for producing the same.

The process of the present invention imparts a spinning emulsion to the melt spun fibers, undergoes heat setting and relaxation during the continuous process of melt-stretching and winding to have high strength and low shrinkage properties, and then to rubber or polyvinyl chloride. The epoxy compound-containing functional emulsion is treated at 0.4 to 1.0% by weight, based on the weight of the fiber, immediately before the winding so that the adhesive force is improved.

    The high strength, low shrinkage polyester fiber produced by the method of the present invention has a strength of 7.4 g / d to 8.0 g / d, an elongation at break of 20% to 23%, and a dry heat shrinkage [190 ° C., 15 minutes, superload 0.01 g / d, measured using Testrite] is 3.5% or less, and when used as a reinforcement material for rubber or polyvinyl chloride, it is possible to reduce the shape deformation due to shrinkage of yarn during heat treatment, Since it has excellent adhesion with chloride, when used as a reinforcing material, it can exhibit high form stability, thereby improving the durability and stability of the product using the same can increase the added value of the product.

Description

A process for producing polyester multifilament yarns having excellent adhesion to rubbers or polyvinyl chloride}

The present invention relates to a method for producing industrial polyester fibers, and more particularly, to a high strength and low shrinkage industrial polyester fiber excellent in adhesion to rubber or polyvinyl chloride and a heat shrinkable adhesive and a method for producing the same.

In general, polyester fiber is excellent in physical properties such as excellent strength, elongation, dimensional stability, fatigue resistance, and the like, rubber reinforcement such as tire cords, conveyor belts, hoses or rubber structures, outdoor billboards, dome structures, various tents It is widely used as a coating of polyvinyl chloride (hereinafter referred to as PVC), such as a truck cover. However, in comparison with polyamide fibers such as nylon 6 and nylon 66 and rayon fibers, even when treated with resorcinol formalin rubber latex (hereinafter abbreviated as RFL), which is widely used for rubber and fiber adhesion, adhesion with rubber The properties are not good and the excellent properties of the polyester cannot be exhibited. This is because polyester fiber has poor affinity with RFL, its surface is inert, and its reactivity with rubber is insufficient, and the hydrogen bonding ability of ester bond of polyester fiber is lower than that of amide bond of nylon. to be. To improve this, a reactive group such as a hydroxyl group or the like is introduced on the surface of the polyester fiber to impart reactivity to RFL, or an adhesive using an epoxy compound, an isocyanate compound and a halogenated phenol compound as an adhesive matrix component A method of improving the adhesion to rubber or PVC by coating the surface of the fiber has been proposed in various ways.

Chakraravarti, US Patent No. 4,348,517 (October 07, 1982), European Patent Publication No. 0 175 587 B1 (1989. 08. 30), Shigemitsu US Patent No. 4,536, 526 (1985. 08. 20), Japanese Unexamined Patent Application Publication No. Hei 8-311,768 (Nov. 26, 1996), US Patent No. 4,438,178 (1984. 03. 20) by Powers, etc. For the unstretched yarn in the low-speed spin-draw two-stage process or spin-draw spin-draw one-stage process, a mixture of spinning emulsion and epoxy compound is used to give a mixed emulsion and a roller Stretching, heat setting, and relaxation of the phase are performed by hardening or deteriorating an epoxy compound on the roller to increase the generation of carbides, thereby increasing the contamination of the roller, thereby degrading workability or lowering the physical properties of the polyester fiber. The trend was shown.

In addition, as a method for improving this, Japanese Patent Laid-Open No. 57-5974 (January 12, 1982), Japanese Patent Laid-Open No. 60-21970 (October 1985) and Japanese Patent Application Publication Publication No. 8-113877 (1996. 05. 07) and the like describe a method of imparting an epoxy compound between the final stretching roller and the relaxation roller, which also causes the physical properties of the yarn as tar is generated in the relaxation roller. It was not possible to remedy the disadvantages of lowering and worsening workability.

      On the other hand, Japanese Patent Application Laid-Open No. 2-154067 (June 13, 1990) and Japanese Patent Application Laid-Open No. 2-154068 (June 13, 1990), European Patent Publication No. 0 043 410 B1 (1985. 07. 24), Marshall, U.S. Patent No. 3,925,588 (Dec. 09, 1975), U.S. Patent No. 4,210,700 (July 01, 1980) and U.S. Patent No. 4,397,985 (1983.08.09) ), Etc., describes a method of imparting an adhesive compound between the final relaxation roller and the winder, but this method has a low dispersibility due to poor compatibility between the spinning emulsion and the adhesive compound, which makes it difficult to treat a uniform drug. Afterwards, it was found that there was a problem of separately performing heat aging treatment, and the measured adhesive strength of the yarn was also low.

      According to the conventional method, in order to produce a high strength, low shrinkage polyester fiber having good adhesion with rubber or PVC by the method of treating the adhesive component during or after spin-drawing, the physical properties of the polyester fiber are lowered or the adhesive strength is low. The problem was losing. In addition, such a two-step process is accompanied by a problem that the low production cost increases the manufacturing cost.

The object of the present invention is to use a spin-stretch one-step process without the problems of the prior art mentioned above, impart a conventional spinning emulsion in the unstretched stage via a spinning nozzle, undergo a stretching process and a relaxation process, and then immediately before winding By treating a functional emulsion containing an epoxy compound component, the polyester fiber maintains its high strength and low shrinkage properties, and has excellent adhesion to rubber or PVC even at high temperatures for a long time, and has low heat shrinkage and low form deformation at high temperatures. It is an object to provide a fiber.

The present invention is to produce a high-strength, low-shrinkage polyester fiber excellent in adhesion with rubber or PVC, melt-spun polyester chip, and cooled solidified polyester unstretched filament yarn as shown in Figure 1 The emulsion is previously applied using a conventional spinning emulsion, followed by stretching, relaxation and heat setting through six pairs of rollers, followed by treatment of the functional emulsion containing the epoxy compound component through the nozzle just before winding up. .

     The present invention simultaneously satisfies the properties of high strength and low shrinkage, which are physical properties of polyester yarns, in a one step spinning-stretching process, and the adhesion to rubber measured by the H-test method of JIS L 1017 is 7.0kg / cm to 9.0. kg / cm.

     In addition, according to the present invention, the compound of the epoxy component of the adhesive component functional emulsion used for PVC or rubber reinforcement contains at least two or more epoxy groups in the molecular chain, and contains 20 to 40% by weight of epoxy and 60 to Provided is a composition containing 80% by weight of polyethylene glycol compound, and a method for producing high strength and low shrinkage polyester fiber for reinforcing PVC or rubber that is adhered to 0.4 to 1.0% by weight with respect to the fiber weight.

According to the present invention, a polyester chip having a solid state polymerized intrinsic viscosity of 0.76 to 0.86 is melted and melt spun at a pulling speed of 3100 m / min or more through 192 nozzle holes, and the tensile strength is 7.4 g / d to 8.0 g as a directly drawn fiber. / d, elongation at break 20% to 23%, dry heat shrinkage [190 ° C., 15 minutes, ultrahigh load 0.01g / d, measured by Testrite] of 3.5% or less, birefringence of 205 or more, crystal orientation function 0.80 A method for producing a high strength, low shrinkage polyester fiber that satisfies the above and which is excellent in adhesion to rubber or PVC is provided.

Hereinafter, the present invention will be described in more detail.

Melting polyester chips having an intrinsic viscosity of 0.76 to 0.86, preferably polyester chips having an intrinsic viscosity of 0.84, according to the method of the present invention, using a pair of high-pressure rollers through 192 nozzle holes, a pulling rate of 3100 m / Melt spinning at min or more, and wind up after stretching and relaxation. Polyester chips having an intrinsic viscosity of 0.76 or less are difficult to produce yarn having a low molecular weight and a high degree of orientation, and thus are not sufficient to express high strength, and polyester chips having an intrinsic viscosity of 0.86 or more are determined upon increase in molecular weight and spinning. Increasing the size makes it impossible to express shrinkage below 3.5%. In order to show the characteristic of low shrinkage in accordance with the objective of this invention, it is preferable to maintain the temperature of the high roller 4 which is an extending roller in the range of 230-240 degreeC. When the temperature of the roller 4 is lower than 230 ° C, an increase in shrinkage is accompanied, whereas when the temperature of the roller 4 exceeds 240 ° C, a decrease in strength is accompanied. Before passing through the first roller, the roller oiler or jet oil guide is used to impart a conventional spinning emulsion, and then the thermal roller is hot drawn with the stretching ratio of the roller 1 and the roller 4 from 5.0 to 6.0. And the loosening ratio of the high roller 5 or high roller 6 is 7.0% to 10.0%, past the last high roller 5 or high roller 6, and the epoxy-containing functional emulsion is treated with a jet guide immediately before winding. Here, each of the intrinsic viscosity of 0.76 or 0.84 by using a polyester chip melt spinning, and by changing the draw ratio and relaxation rate to produce a yarn that can maintain high strength while maintaining the properties of low shrinkage.

As the spinning emulsion, an aqueous emulsion emulsion may be used, or a knitted emulsion or a straight emulsion diluted with a low viscosity mineral oil may be used, and the adhesion amount to the fiber is preferably 0.6 to 1.2% by weight. The higher the supply amount of the spinning emulsion, the better the stretching, but in terms of workability, due to the increased generation of tar or carbide, workability is lowered. The epoxy compound added to the functional emulsion contains at least two epoxy groups in the molecular chain, and contains 20 to 40% by weight of epoxy and 60 to 80% by weight of polyethylene glycol compound.

The oil supply method of a functional oil agent is given so that it may become 0.4 to 1.0 weight% based on the weight of a fiber just before winding-up by the nozzle type oil supply method. When the supply amount of the epoxy component compound is 0.4% or less, the epoxy content ratio in the functional oil is low, and there are few reactive groups that can be adhered to the rubber when adhering to rubber, so that the adhesion strength is small, and the supply amount of the epoxy component compound is 1.0%. In this way, the ratio of epoxy content in the functional emulsion is considerably high, which is advantageous for improving the adhesion, but there is no significant difference with the adhesion in the above range, but rather due to the excessive amount, the contamination increases during the operation and the operation due to the excessive supply Degradation may occur. This manufacturing method is a continuous process of high strength, low shrinkage polyester fiber with excellent adhesion to rubber or PVC with strength of 7.4g / d to 8.0g / d, elongation at break of 20% to 23% and dry heat shrinkage of 3.5% or less. It can be prepared by.

Hereinafter, the present invention will be described in more detail with reference to Examples.

In the measurement of yarns evaluated in Examples and Comparative Examples, the birefringence (n) was measured using a polarization microscope, and the degree of crystallinity (Xc) was calculated according to the following Equation 1 by volume fraction from the value by density measurement.

Crystal orientation (f _c ) was calculated | required from the value by X-ray diffraction measurement method.

The dry heat shrinkage was measured as a change in the contracted length by standing at a measurement temperature of 190 ° C. for 15 minutes at an initial load of 0.01 g / d using a Testrite machine.

The adhesive force between the yarn and the rubber was measured according to the H-test method of JIS L 1017 A method.

Hereinafter, a more specific example of the present invention will be described, but it is not intended to limit the scope or scope of the present invention.

Examples 1 to 3

Using a polyester chip with an inherent viscosity of 0.84, spin through a spinneret with 192 holes in a spin-draw continuous process at a discharge temperature of 350 g / min at a spinning temperature of 295 ° C, and oil ring before passing through the roller 1 Conventional emulsions are imparted by roller or nozzle lubrication to 0.65%, 0.66% and 0.82% by weight, based on the weight of the fibers, in Examples 1, 2 and 3 respectively, A polyester filament yarn of 1000 denier / 192 filaments (1000d / 192f) is produced through a two-step drawing, heat setting, and relaxation process using a drawing machine composed of a pair of rollers.

As shown in Table 1, the draw ratios from the high roller 1 to the high roller 4 were drawn to 5.4, 5.5 and 5.4 in Examples 1, 2 and 3, respectively, wherein the speed of the high roller 4 was 3100 m. / min. The relaxation rate from the high roller 4 to the high roller 6 is relaxed to 9.0%, 9.0% and 8.0% in Examples 1, 2 and 3, respectively. At this time, the temperature of the roller 4 is 235 ℃, 235 ℃ and 230 ℃ in Example 1, Example 2 and Example 3, respectively, the temperature of the roller 5 is 160 ℃, after the roller 6 by the nozzle method The functional emulsion containing epoxy was treated at 0.4%, 0.65% and 0.55% by weight in Examples 1, 2 and 3, respectively, based on the weight of the fibers, followed by polyester filament yarns. Wind up.

Example 4

Using a polyester chip having an inherent viscosity of 0.79, it was spun by the method of Example 1 as described in Table 1, but the draw ratio was 5.3, and the relaxation rate was 8.0%. The spinning emulsion is fed and the epoxy component compound-containing functional emulsion is treated 0.6% by weight, based on the weight of the fiber, before winding up.

Example 5

     Using a polyester chip having an inherent viscosity of 0.79, it was spun by the method of Example 1 as described in Table 1, with a draw ratio of 5.7 and a relaxation rate of 8.0%. The spinning emulsion is fed and the epoxy component compound-containing functional emulsion is treated 0.7% by weight, based on the weight of the fiber, before winding up.

Comparative Example 1

      Using a polyester chip having an intrinsic viscosity of 1.0, spinning was carried out as in Example 1, but with a draw ratio of 5.4 and a relaxation rate of 10%, 0.6 wt% of a spinning emulsion was fed before passing through the roller 1 and wound up. The epoxy component compound-containing functional emulsion was previously treated with 0.7% by weight, based on the weight of the fiber.

Comparative Example 2

Spinning was carried out as in Example 1 using a polyester chip having an intrinsic viscosity of 0.84, but with a draw ratio of 5.5 and a relaxation rate of 9.0%, 0.65% by weight of a spinning emulsion was supplied before winding the roller 1 and wound up. No previous treatment with epoxy component compounds containing functional emulsions.

Comparative Example 3

     Spinning was carried out as in Example 1 using a polyester chip having an inherent viscosity of 0.84, while the draw ratio was 5.6, the relaxation rate was 9.0%, and 0.83% by weight of a spinning emulsion was supplied before winding the roller 1 while winding up. The functional emulsion containing the epoxy component compound was previously treated with 0.18% by weight, based on the weight of the fiber.

Comparative Example 4

     Spinning was carried out as in Example 1 using a polyester chip having an inherent viscosity of 0.84, but with a draw ratio of 5.6 and a relaxation rate of 9.0%, 0.66% by weight of a spinning emulsion was supplied before passing through Goch roller 1. The temperature of the roller 4 is set to 225 degreeC, and 0.5 weight% of epoxy component compound containing functional oils are processed before winding up based on the weight of a fiber.

division Chip Intrinsic Viscosity Speed of high roller 4 (m / min) Extension ratio (times) % Relaxation Temperature of high roller 4 (℃) Spinning emulsion supply (%) Functional emulsion supply ^* (%) Example 1 0.84 3100 5.4 9.0 235 0.65 0.4 Example 2 0.84 3100 5.5 9.0 235 0.66 0.65 Example 3 0.84 3100 5.4 8.0 230 0.82 0.55 Example 4 0.79 3100 5.3 8.0 230 0.84 0.6 Example 5 0.79 3100 5.6 8.0 230 0.65 1.0 Comparative Example 1 1.0 3100 5.4 10 238 0.64 0.7 Comparative Example 2 0.84 3100 5.5 9.0 235 0.65 0 Comparative Example 3 0.84 3100 5.6 9.0 235 0.83 0.18 Comparative Example 4 0.84 3100 5.6 9.0 225 0.66 0.5

(*% By weight based on weight of yarn)

division Island Strong (kg) Strength (g / d) Elongation at Break (%) Shrinkage (%) Birefringence (n) Crystal orientation (f _c ) Crystallinity (%) Adhesive force (kg) Example 1 1010 7.84 7.76 23.0 2.8 0.207 0.895 49 7.0 Example 2 1007 7.92 7.86 22.5 3.0 0.210 0.901 51 9.0 Example 3 1012 8.05 7.95 20.3 3.5 0.215 0.905 50 7.8 Example 4 1011 7.51 7.43 23.8 2.8 0.205 0.890 45 7.9 Example 5 1009 7.91 7.84 22.6 2.8 0.214 0.903 47.5 8.9 Comparative Example 1 1010 8.43 8.35 22.5 4.8 0.200 0.911 50 7.9 Comparative Example 2 1005 7.78 7.74 20 2.8 0.205 0.906 48 3.6 Comparative Example 3 1007 7.93 7.87 22.2 2.9 0.206 0.904 49 5.3 Comparative Example 4 1004 7.95 7.92 21.8 4.5 0.208 0.906 49 7.8

The present invention relates to roller contamination when the polyester multifilament undrawn yarn produced by melt spinning and cooling solidified using a polyester solid polymerized chip having an intrinsic viscosity of 0.76 to 0.86 is mixed with a conventional emulsion and an epoxy component. There was a problem of workability, and as a result of the embodiment of the present invention, after giving a conventional emulsion to the undrawn yarn and using a pair of high-pressure rollers, the functionalities of the epoxy components immediately before winding after the stretching process, heat setting process, and relaxation process By applying an emulsion, it has high strength and low shrinkage properties, and has excellent adhesion to rubber or PVC, and when used as a reinforcing material of rubber or PVC, it is possible to minimize yarn deformation and to produce yarn having stability. Could.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows roughly the spinning process and the winding-up process of a polyethylene naphthalate fiber.

Claims (3)

A high strength, low shrinkage polyester fiber having excellent adhesion to rubber or PVC, characterized by an intrinsic viscosity (I.V) of 0.76 to 0.86 and satisfying the following physical properties of (a) to (d): (a) 45-50% crystallinity, crystal orientation (fc) ≥ 0.890 (b) strength> 7.4 g / d, elongation at break> 20% (c) dry heat shrinkage ≤ 3.5% (d) Content ratio (weight%) of the epoxy component to the weight of yarn: 0.4 to 1.0 weight%. The high strength and low shrinkage polyester fiber excellent in the adhesive force with respect to rubber | gum or PVC of Claim 1 whose adhesive force measured by the H-test method of JISL1017A method is 7 kg / cm or more. Melt-spun polyester chips having an intrinsic viscosity of 0.76 to 0.86, impart a conventional spinning emulsion to the undrawn yarn, and then continuously stretched at a draw temperature of 238 ° C. or lower so that the total draw ratio is 5.0 to 5.6 times. At a temperature of 230 to 238 ° C. at 4 and a relaxation roller 5 and 6 at a temperature of 120 to 160 ° C., the heat setting was carried out so that the relaxation ratios of the rollers 5 and 6 were 8.0 to 10%, and then the epoxy components immediately before winding. A method for producing the high strength and low shrinkage polyester fiber according to claim 1, wherein the functional oil is imparted.