KR20120070858A - Recycled polyester fiber having uv blocking property and flame retardant, and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A recycled polyester fiber having a core part and a sheath part is provided to ensure excellent UV protection and flame retardant functions and to be used in wallpaper, blind, and curtain. CONSTITUTION: A recycled polyester fiber having a core part and a sheath part using recycled polyester resin is prepared by mixing waste polyester and ethylene glycol(EG) and generating bis-2-hydroxyethyl terephthalate(BHET) by depolymerization and complex-spinning polyester resin of the core part and sheath part by sheath-core. The core part is prepared by adding UV protection agent to BHET. The sheath part is prepared by adding phosphorus flame retardant to BHET and copolymerization.

Description

Recycled polyester fiber with excellent UV protection and flame retardant performance and manufacturing method thereof {RECYCLED POLYESTER FIBER HAVING UV BLOCKING PROPERTY AND FLAME RETARDANT, AND MANUFACTURING METHOD THEREOF}

The present invention relates to a regenerated polyester fiber and a method for manufacturing the same excellent in UV protection and flame retardant performance suitable for clothing and interior using excellent recycled polyester.

In general, polyester (POLYESTER) has excellent mechanical properties, heat resistance, moldability, chemical resistance is used for a wide range of applications in the field of fiber, film, bottle molded products and the like. These polyester (POLYESTER) products are disposed of after disposal, but incineration causes problems such as generation of harmful gases during combustion and damage to the incinerator due to high heat (corrosion). In addition, since it does not decay or disintegrate when it is disposed of without incineration, it remains permanently in the soil or in the water, which has been a problem in terms of environmental protection.

Therefore, in terms of environmental protection and recycling of resources, there is a growing interest in recycling waste plastics. In advanced countries, research on the recovery and recycling of useful resources from waste has been pursued in various fields under a long-term plan. . Public opinion on environmental pollution has begun to emerge in Korea, and a plan for economic recovery and recycling of waste resources has been established, and related research is being progressed.

In the process of recovering the waste polyester, terephthalic acid (TPA), dimethyl terephthalate (DMT) and ethylene glycol (ethlyene glycol: EG), which are used as raw materials through depolymerization of waste polyester using a catalyst or the like. And a process of preparing bis-2-hydroxyethyl terephthalate (BHET), which is an intermediate product.

The process of depolymerizing waste polyester to recover terephthalic acid, dimethyl terephthalate and ethylene glycol is complicated and takes a long time, and the process of producing recycled polyester using the recovered raw materials is an intermediate product, bis-2-hydroxy. Compared to the process of producing recycled polyester with ethyl terephthalate, the procedure is complicated and takes a long time to produce.

Therefore, a process for producing regenerated polyester recovering the intermediate bis-2-hydroxyethyl terephthalate has been developed, but regenerated polyester prepared from the recovered bis-2-hydroxyethyl terephthalate is recovered terephthalic acid and dimethyl. There was a problem that the physical properties or color is lower than the regenerated polyester made of terephthalate and ethylene glycol.

In addition, the demand for anti-glare properties is expanding to be used as uniforms and sports clothes, car covers, curtains, interior and industrial textiles.In particular, interior products are toxic gases generated from interior products in case of fire. As damage may occur, various regulations that require flame retardant performance are gradually increasing in interior products.

Generally, synthetic fibers that block ultraviolet rays include synthetic compounds such as organic compounds such as benzotriazole and benzophenone or inorganic compounds such as zinc oxide, titanium oxide, talc, and carolin, which impart the ability to absorb or shield ultraviolet rays to the synthetic fiber. To block ultraviolet rays.

Japanese Patent No. 3053248 "Polyester Composition with Ultraviolet Shielding Performance, Manufacturing Method and Fiber of the Polyester Composition" contains 1-10 wt% of zinc oxide and titanium oxide having an average particle size of 0.1-3.0 µm in polyester. To propose a polyester having a UV shielding performance. In the above patent, since the particles of titanium oxide and zinc oxide are uniformly dispersed in a fine state without agglomeration of particles by adding a specific compound during polymerization, filter clogging or trimming occurs when fibers are manufactured from polyester. It is proposed that the fiber having excellent UV shielding performance can be stably manufactured and that the same effect can be obtained in the production of the film in addition to the fiber. Problems such as guide abrasion due to high concentration of zinc oxide and titanium oxide, generation of pim yarn of yarn and poor workability have been pointed out when the guide passes in the weaving preparation process such as weaving and sizing.

In addition, UV protection synthetic fibers are widely used in interior applications such as curtains and blinds, or industrial covers such as automobile covers, so they should have flame retardant performance in case of emergency. However, conventional UV protection synthetic fibers have very limited use because they are not flame retardant. There was a problem.

In recent years, as consumers' living standards improve and pursue safer and more comfortable lives, not only the functionality of the product, but also environmental protection and preservation are increasing. However, at present, there is no recycled polyester product that satisfies such UV protection and flame retardant performance, and there is an urgent need for product development.

The present invention is to solve the above problems by using a bis-2-hydroxyethyl terephthalate produced by depolymerization by collecting the waste polyester discarded to provide a regenerated polyester fiber with high UV resistance and flame retardancy For the purpose of

In addition, an object of the present invention is to provide a method for producing recycled polyester fibers having excellent UV blocking rate and excellent flame retardancy, which are made of composite fibers of a core part and a sheath part.

The present invention relates to a regenerated polyester fiber composed of a core part and a sheath part using a regenerated polyester resin, wherein bis-2-hydroxyethyl terephthalate (bis-) is mixed in a depolymerization process by mixing waste polyester and ethylene glycol (EG). 2-hydroxyethyl terephthalate (BHET) is produced, wherein the core portion is a recycled polyester resin prepared by adding a sunscreen agent to the bis-2-hydroxyethyl terephthalate (BHET), and the cis portion is the bis-2-hydrate. Phosphorus flame retardant is added to the oxyethyl terephthalate (BHET) is a regenerated polyester resin copolymerized, and the UV protection and flame retardant performance is characterized by being produced by complex spinning of the two-component polyester resin prepared by the sheath-core Provides excellent recycled polyester fibers.

In addition, the ultraviolet light blocking agent is one or two or more of the mixture of zinc oxide, titanium oxide having a particle size of 0.1 ~ 5.0㎛ particle size, 99 ~ 85% by weight of the recycled polyester resin and 1 ~ 15% by weight of the sunscreen mixed It provides a regenerated polyester fiber excellent in UV protection and flame retardant performance characterized in that.

In addition, the phosphorus-based flame retardant is a formula (2) below provides a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that the phosphorus atom (P) is contained in the regenerated polyester resin of the sheath portion 500ppm to 15,000ppm. .

 [Formula 2]

Provided that R ₁ and R ₂ are methyl, phenyl, halophenyl, alkyl, haloalkyl or haloaryl.

In addition, the regenerated polyester fiber provides a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that any one of the release cross-section of the rectangular, triangular, Y-type, flat, island-like, split type.

In addition, the sheath portion to the core portion of the regenerated polyester fiber provides a regenerated polyester fiber having excellent UV protection and flame retardant performance, characterized in that the ratio of 20:80 to 80:20 in the cross-sectional ratio.

In addition, the present invention is a method for producing a recycled polyester fiber comprising a core portion and a sheath portion, the recycled polyester resin is a bis-2-hydroxyethyl terephthalate (BHET) by mixing waste polyester and ethylene glycol (EG) Depolymerization process to produce; A core part recycled polyester resin manufacturing step of adding a copolymer with a sunscreen after the depolymerization process to produce a core part recycled polyester resin; Sheath portion recycled polyester resin manufacturing process for producing a cis portion recycled polyester resin by adding and copolymerizing a phosphorus flame retardant after the depolymerization process; A melting step of melting the core portion regenerated polyester resin at 260 to 330 ° C. and the sheath portion regenerated polyester resin at 250 to 320 ° C .; Spinning the composite of the two-component melt at a temperature of 250 to 320 ℃ to produce a regenerated polyester fiber; And it provides a method for producing a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that it is prepared, including heat-setting and stretching process to draw while heat-setting the spun regenerated polyester fiber.

In the depolymerization process, the waste polyester and ethylene glycol (EG) may be mixed in a molar ratio of 1.0: 0.1 to 2.0, pressurized to 1.5 to 2.5 kg / cm 2 using nitrogen (N ₂ ) gas, and then to 10 at 210 to 240 ° C. Melt mixed for 1 to 4 hours by stirring at -50 rpm, pressurized to 2.0 to 2.5 kg / cm 2 using nitrogen (N ₂ ) gas, depolymerized for 1.0 to 3.0 hours with stirring at 30 to 70 rpm at 245 to 260 ° C, and Bis-2. Provided is a method for producing recycled polyester fiber having excellent UV protection and flame retardant performance, characterized by producing hydroxyethyl terephthalate (BHET).

In addition, the depolymerization process is a primary depolymerization step of producing bis-2-hydroxyethyl terephthalate (BHET) by mixing waste polyester and ethylene glycol (EG); Bis-2-hydroxyethyl terephthalate (BHET) produced in the first depolymerization step is mixed with waste polyester and ethylene glycol (EG) bis-2-hydroxyethyl terephthalate (BHET) bis-2-hydroxyethyl terephthalate (BHET) The depolymerization process is performed, but the depolymerization process is repeated only in the second depolymerization step using a part of bis-2-hydroxyethyl terephthalate (BHET) generated in the second depolymerization step after the first depolymerization step. It provides a method for producing a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that proceeding.

In addition, the ultraviolet light blocking agent is one or two or more of the mixture of zinc oxide, titanium oxide having a particle size of 0.1 ~ 5.0㎛ particle size, 99 ~ 85% by weight of the recycled polyester resin and 1 ~ 15% by weight of the sunscreen mixed It provides a method for producing recycled polyester fiber excellent in UV protection and flame retardant performance.

In addition, the phosphorus-based flame retardant is represented by the formula (2) below the phosphorus atom (P) in the sheath portion of the regenerated polyester resin, characterized in that the production method of the regenerated polyester fiber excellent in UV protection and flame retardant, characterized in that containing 500ppm to 15,000ppm. To provide.

[Formula 2]

Provided that R ₁ and R ₂ are methyl, phenyl, halophenyl, alkyl, haloalkyl or haloaryl.

In addition, the regenerated polyester composite fiber is a release cross section selected from square, triangular, Y-type, flat, island-in-sea, split type, the sheath portion to the core portion is characterized in that the cross-sectional ratio of 20:80 to 80:20. Provided is a method for producing recycled polyester fiber having excellent UV protection and flame retardant performance.

In addition, the heat setting and stretching process is 600 to 2,000 mpm in the first gourd roller, the first heat set at 60 ~ 120 ℃, the second gourd roller at a speed of 3,000 to 5,000 mpm, the second temperature at 90 to 150 ℃ Provided is a method for producing recycled polyester fiber having excellent UV protection and flame retardant performance, characterized by stretching while heat setting.

In addition, the present invention provides a method for producing regenerated polyester fibers having excellent UV protection and flame retardant performance, characterized in that stretching at a draw ratio of 1.5 to 5.0 in the heat setting and stretching process.

In addition, the regenerated polyester fiber or the regenerated polyester fiber produced by the above production method is UV protection and flame retardant, characterized in that the strength of 2.0 ~ 7.0g / d, elongation 10 ~ 80%, specific value 3.0 ~ 20.0% Provided is a method for producing recycled polyester fibers with excellent performance.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. First of all, it should be noted that in the drawings, the same components or parts denote the same reference numerals as much as possible. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values as are indicative of the manufacturing and material tolerances inherent in the meanings mentioned, Absolute figures are used to prevent illegal unfair use of unscrupulous infringers.

The present invention is a regenerated polyester fiber having excellent UV protection and flame retardant performance, which is composed of a core part and a sheath part, and the core part is formed of a regenerated polyester resin containing a sunscreen that blocks ultraviolet rays, and the sheath part is taken over. It is formed of a regenerated polyester resin containing a flame retardant.

The recycled polyester resin is depolymerized by mixing waste polyester and ethylene glycol (EG) to produce bis-2-hydroxyethyl terephthalate (BHET), and removing foreign substances using a filter. After removing the foreign matter by the filtering process it can be polymerized again to prepare a regenerated polyester resin.

The sunscreen contained in the core portion may use zinc oxide or titanium oxide, which is an inorganic compound, or a mixture of zinc oxide and titanium oxide may be used.

The zinc oxide and titanium oxide has a high ultraviolet absorption and good infrared reflection, as well as ultraviolet rays and also infrared ray blocking effect. The zinc oxide and titanium oxide are contained in the polyester resin as a white pigment, thereby reducing the light transmittance of the polyester resin to enhance the anti-glare effect.

The particle size of the sunscreen is preferably used 0.1 ~ 5.0㎛, more preferably to use a sunscreen having a particle size of 0.3 ~ 3.0㎛.

It is preferable that the said core part contains 85 to 99 weight% of recycled polyester resin, and 1 to 15 weight% of an inorganic compound. If the content of the inorganic compound is less than 1.0% by weight, it does not have the effect of UV protection and anti-impregnation (impermeable). If the content is more than 15% by weight, it is difficult to control the process during polymerization and the excessive inorganic compounds are aggregated together. Blockage of spinnerets occurs, or trimming occurs, resulting in poor radioactivity.

The phosphorus flame retardant of the cis part may be a phosphorus flame retardant that is commonly sold, but it is to use a hydroxyphosphinylpropanoic acid derivative of the formula Would be preferred.

Provided that R ₁ and R ₂ are methyl, phenyl, halophenyl, alkyl, haloalkyl or haloaryl.

The phosphorus flame retardant is preferably 500 to 15,000 ppm of phosphorus atom (P) contained in the regenerated polyester resin, more preferably 3,000 to 10,000 ppm is contained.

If the content of the phosphorus-based flame retardant is less than 500ppm does not have a flame retardant performance, if more than 15,000ppm the yellowing phenomenon of the color change of the polymer chip produced after the polymerization is increased. In addition, since the main chain of the flame retardant is mostly composed of a single bond, when an excessive amount of the flame retardant is contained, the ratio of the amorphous region increases due to the flame retardant, which may cause a problem of strength deterioration.

An additive such as an antioxidant, an antibacterial agent, a deodorant, a fluorescent brightener, a polymerization stabilizer, or the like may be added to the sheath portion or the core portion.

In addition, the recycled polyester resin used in the sheath portion or the core portion should contain at least 80 mol% of the polyester constituent units, preferably at least 90 mol% using a polyester resin of polyethylene terephthalate unit The melting temperature is preferably 200 ° C. or higher for spinning stability.

Polyester fiber having excellent UV protection and flame retardant performance according to the present invention, as shown in Figures 2 to 7, depending on the use as a cross-section, such as circular, square, triangular, Y-type, flat, islands, split type It can manufacture.

The production method of the regenerated polyester fiber excellent in UV protection and flame retardant performance according to the present invention is depolymerization step, core part regenerated polyester resin manufacturing process, sheath part regenerated polyester resin manufacturing process, melting as shown in FIG. It is preferable that the manufacturing process includes a process, a spinning process, a heat setting, and a stretching process, wherein the core part recycled polyester resin manufacturing process and the sheath part recycled polyester resin manufacturing process are performed at the same time.

The depolymerization process is a process of recovering bis-2-hydroxyethyl terephthalate (BHET) by depolymerizing waste polyester by glycolysis using ethylene glycol.

In the depolymerization process of the present invention, after the waste polyester is melted, ethylene glycol (EG) is mixed to proceed with depolymerization.

The waste polyester may be used after removing metal components or synthetic resins of different components from the collected waste polyester, and then pulverizing them into flakes of 1 to 20 mm using a grinder or the like.

Melting so that the waste polyester can react and ethylene glycol (EG) is mixed with the waste polyester and ethylene glycol in a molar ratio of 1.0: 0.1 ~ 2.0 and to 1.5 ~ 2.5kg / ㎠ using nitrogen (N ₂ ) gas While pressurizing, the mixture is heated and melted continuously for 1 to 4 hours.

[Reaction Scheme 1]

~ COOCH ₂ CH ₂ OOC ~ + HOCH ₂ CH ₂ OH ↔ 2 (~ COOCH ₂ CH ₂ OH)

The ethylene glycol decomposes the polyester into bis-2-hydroxyethyl terephthalate by depolymerization by using a waste polyester and a transesterification reaction as in Scheme 1 above.

The molar ratio of the waste polyester may be calculated by a molar ratio of 192.17, which is a molecular weight of a polyester monomer made of terephthalic acid (TPA) or dimethyl terephthalate (DMT) and ethylene glycol (ethlyene glycol: EG). .

The reaction rate of the depolymerization of the present invention depends on the temperature, catalyst, feedstock granularity and the amount of glycol. The final monomer composition is also determined by the decomposition reaction time and the duration after depolymerization. Lower amounts of glycol require higher temperatures and longer reaction times, resulting in higher molecular weight oligomers.

Therefore, when less than 0.1 mole of ethylene glycol is mixed with respect to 1 mole of the waste polyester, the reaction time becomes too long, and when it is mixed with 2.0 moles or more, the shortening effect of the reaction time is not large. Most preferably, the ethylene glycol is mixed with the waste polyester in a molar ratio of 1.0: 0.3.

In addition, by using bis-2-hydroxyethyl terephthalate as a catalyst in the melt mixing, the reaction time of the transesterification reaction can be shortened and the molecular weight of bis-2-hydroxyethyl terephthalate produced by the depolymerization process can be made uniform. have.

When using the bis-2-hydroxyethyl terephthalate as a catalyst, it will be preferable to further mix 0.05 to 1.0 mole with respect to 1 mole of waste polyester.

In the melt mixing, the waste polyester starts melting at about 210 ° C. by continuous heating, and the temperature is continuously raised, and when the temperature rises to about 230 ° C. to 240 ° C., melting is actively performed while the temperature rise is slowed down.

In the melt mixing, the stirring should be carried out to 10 ~ 50rpm after the melting to some extent to prevent the concentration of thermal energy in one place.

When melting is completed in the melt mixing, when the temperature of the mixture of the waste polyester and ethylene glycol is gradually increased, the depolymerization process is performed.

When the depolymerization process proceeds, pressurized to 2.0 ~ 2.5㎏ / ㎠ using nitrogen (N ₂ ) gas, the stirring speed is increased to 20 ~ 60rpm and the temperature is raised to 245 ~ 260 ℃ waste polyester by ethylene glycol The transesterification reaction is promoted to produce bis-2-hydroxyethyl terephthalate.

In the depolymerization process, after about 1 to 3 hours, the transesterification reaction is completed, so that the waste polyester disappears and only bis-2-hydroxyethyl terephthalate remains. The depolymerization process will most preferably proceed for 2.0 hours at 56 rpm at 255 ℃.

When the depolymerization process is carried out in the same manner as described above, a lot of time is required for the melt mixing process. Therefore, in order to shorten the time required for the melt mixing process, a depolymerization process is performed by mixing waste polyester and ethylene glycol (EG) to produce bis-2-hydroxyethyl terephthalate (BHET), and the first depolymerization. By using all or part of the bis-2-hydroxyethyl terephthalate (BHET) generated in the step to proceed to the secondary depolymerization step of depolymerization can reduce the time required for the melt mixing process.

When the depolymerization process is carried out in the first and second depolymerization steps as described above, the depolymerization process after the production of bis-2-hydroxyethyl terephthalate (BHET) in the first depolymerization step is performed only in the second depolymerization step. It would be desirable to.

The first depolymerization step is carried out in the same manner as the depolymerization process described above to mix the waste polyester and ethylene glycol (EG) in a molar ratio of 1.0: 0.1 ~ 2.0 and using nitrogen (N ₂ ) 1.5 ~ 2.5㎏ / After pressurizing to 2 cm 2 and stirring for 3 to 4 hours by stirring at 10 to 50 rpm at 210 to 240 ° C., the molten mixture was pressurized to 2.0 to 2.5 kg / cm 2 using nitrogen (N ₂ ) gas and then at 245 to 260 ° C. It is a step of depolymerization for 1.0-3.0 hours with 30-70 rpm stirring.

In the second depolymerization step, all or part of the bis-2-hydroxyethyl terephthalate (BHET) produced in the first depolymerization step is mixed with waste polyester and ethylene glycol (EG) to form bis-2-hydroxyethyl tere. In the step of producing phthalate (BHET), the second depolymerization step is a waste polyester, ethylene glycol (EG), bis-2-hydroxyethyl terephthalate is mixed in a molar ratio 1.0: 0.1 ~ 2.0: 0.5 ~ 2.0 and nitrogen Pressurized to 1.5 ~ 2.5㎏ / ㎠ by using (N ₂ ) gas and stirred for 30 to 50 minutes by stirring 10 ~ 50rpm at 210 ~ 240 ℃, the molten mixture 2.0 using nitrogen (N ₂ ) gas Pressurized to ˜2.5 kg / cm 2 and depolymerized for 1 to 3 hours while stirring at 245 to 260 ° C. for 30 to 70 rpm, and the polymerization conditions proceed in the same manner as in the first depolymerization process.

In the second depolymerization step, the melting time of the waste polyester is much shorter than that of the first depolymerization step, and bis-2-hydroxyethyl terephthalate catalyzes to shorten the reaction time of the transesterification reaction, thereby reducing the overall time required for the depolymerization process. Significantly shortens the molecular weight of the resulting bis-2-hydroxyethyl terephthalate.

30 to 60% by weight of the bis-2-hydroxyethyl terephthalate produced in the first and second depolymerization steps is used in the next second depolymerization step, and the remaining bis-2-hydroxyethyl terephthalate is polymerized into a regenerated polyester resin. It can be transferred to a reaction tank to proceed to the recycled polyester resin manufacturing process.

When transferring to the polymerization reactor, a bis-2-hydroxyethyl terephthalate is passed through a filter to carry out a filtering process to remove foreign substances and solids generated during the depolymerization reaction when the waste polyester is selected. It would be desirable to reduce the productivity of the recycled polyester and to prevent factors that inhibit physical properties.

In the filtering process, it is preferable to use a filter of about 300 to 1500 Mesh, and can be pressurized to 1.5 ~ 3.0 kg / ㎠ to shorten the filtering process time.

The core portion regenerated polyester resin manufacturing process is a process for producing a regenerated polyester resin having a UV blocking function by adding a sunscreen to the bis-2-hydroxyethyl terephthalate (BHET) produced by the depolymerization process to polymerize As described above, zinc oxide and titanium oxide may be used, or zinc oxide and titanium oxide may be mixed and used, and particle sizes of 0.1 to 5.0 μm are preferably used.

In addition, the sunscreen and the regenerated polyester resin is preferably used by mixing 99 to 85% by weight of the regenerated polyester resin and 1 to 15% by weight of the sunscreen.

The cis part regenerated polyester resin manufacturing process is a process of producing a regenerated polyester resin having a flame retardant function by adding a phosphorous flame retardant to the bis-2-hydroxyethyl terephthalate (BHET) produced by the depolymerization process to polymerize. As described in the above Formula 2, using a phosphorus-based flame retardant to prepare a recycled polyester resin containing 500ppm to 15,000ppm phosphorus atom (P) in the recycled polyester resin of the sheath portion.

The core portion and the sheath portion regenerated polyester resin manufacturing process is to be produced by a general polyester polymerization reaction can be produced a regenerated polyester resin by polymerization for 60 to 300 minutes while stirring at 30 ~ 90rpm at 240 ~ 290 ℃ in a vacuum state have.

The produced regenerated polyester resin may be prepared in the form of a chip for convenience of use.

In addition, it is possible to further increase the radioactivity by adding a drying step to remove moisture in the resin.

The drying process may be carried out in the pre-drying and the main drying step, the pre-drying may be carried out for 2 to 6 hours at 100 to 140 ℃, the main drying may be dried for 4 to 8 hours at 140 ℃ to 170 ℃. .

The melting step is a step of melting the two-component regenerated polyester resin in a melt extruder to melt a regenerated polyester resin containing a sunscreen to block ultraviolet rays at 260 to 330 ℃, a regenerated polyester resin containing a phosphorus-based flame retardant Is melted at 250 to 320 ° C.

The melt after the melting process should have a residence time of 20 minutes or less in order to prevent spin operation and viscosity decrease. If the residence time of the two regenerated polyester resins of the core part and the sheath part is increased due to the complex spinning, there is a concern that a drop in viscosity due to thermal decomposition (IV drop) may occur.

The spinning step is a step of producing a regenerated polyester fiber by complex spinning a two-component melt of the core part regenerated polyester resin and the sheath part regenerated polyester resin at a temperature of 250 to 320 ℃.

The composite spinning can be produced by a general composite spinning method, as shown in the composite spinning as shown in Figure 2 to Figure 7 to fit a variety of purposes, such as square, triangular, Y-type, flat, islands, split type, etc. It will be possible to manufacture a composite fiber having a heteromorphic cross-sectional shape.

As described above, the composite fiber of the core part-sheath part may not efficiently exhibit the ultraviolet ray blocking and anti-reflective performance to be implemented in the present invention when the fiber cross-sectional area ratio of the core part is less than 20%. There is a possibility that the spinning work may cause yarn defects, problems such as poor workability and yarn bursting due to metal parts and guide contact in the weaving and weaving preparation process, so that the cross-sectional ratio of the sheath portion to the core portion is 20:80 to 80. It would be desirable to be: 20.

The heat setting and stretching process is 600 to 2,000 mpm in the first gouging roller (Godet Roller), the first heat setting at 60 ~ 120 ℃, the second gouging roller at a speed of 3,000 to 5,000 mpm, temperature 90 to 150 ℃ 2 If the speed of the primary high-speed roller is less than 600mpm by the process of heat-setting while the car is fixed, there is a possibility that the physical properties of the yarn may change with time, and there is a fear that stable operation is difficult due to the lack of force entering the primary high-speed roller. If it exceeds 2,000mpm, there is a possibility of raising or cutting off.

In addition, if the primary heat setting temperature is less than 60 ℃, the heat setting temperature is too low, there is a fear that the sufficient orientation of the molecular chain by stretching does not occur, while if the primary heat setting temperature exceeds 120 ℃, There is a risk of trimming when stretching due to increased tremor.

The second high-speed roller speed is preferably 3,000 to 5,000, but more preferably 3500 to 4500mpm is most stable considering the spinning operation. When the secondary high-speed roller speed is less than 3,000mpm, the properties of the spun yarn, in particular, the elongation is lowered and the productivity is lowered. In order to increase the speed difference between the second roller roller and the take-up machine, there is a possibility that trimming occurs and the stability of the yarn cake form deteriorates.

In addition, when the secondary heat setting temperature is less than 90 ° C., there is a possibility that a change in physical properties such as elongation with time may occur. If the temperature exceeds 150 ° C., noise may increase on a high-speed roller and stable operation may be difficult.

In the drawing process, the drawing ratio is preferably 1.5 to 5.0. When the drawing ratio is less than 1.5, the elongation of the fiber may be lowered. When the drawing ratio is greater than 5.0, trimming may occur during spinning or defects may occur in the final yarn. have.

The stretched recycled polyester fiber will preferably be wound at 3,000 to 5,000 mpm.

In addition, by controlling the tension before spinning, stretching and winding uniformly to manage the fiber elongation deviation to the minimum, the fiber is managed stably through the elongation deviation, and then in the post-process such as weaving, weakness of the pharmacist or yarn The same problem is less likely to occur.

Therefore, the lower the elongation deviation is possible to produce a yarn having a stable physical properties, the less than 1.0% of the elongation deviation is the result of the ideal spinning, if it exceeds 20.0% is a factor of the trimming in the spinning process, It may also be a factor that reduces trimming and operation rate in post-processing such as weaving, twisting yarn, canon, and weaving.

In addition, the non-numerical value is to give the appropriate shrinkage by controlling the shrinkage due to dyeing, processing, etc. in advance, the fiber yarn produced through the present spinning process in advance, the level is preferably 3% to 20%. When the non-numerical value is less than 3%, there is a concern that the axis does not enter the fabric during processing after weaving, and if the ratio exceeds 20%, the axis may be excessively entered.

Therefore, it is preferable that the strength of the regenerated polyester fiber excellent in UV protection and flame retardant performance of the present invention is in the range of 2.0 to 7.0 g / d, elongation of 10 to 80% and specific value of 3.0 to 20.0%.

Fabrics, such as woven fabrics, knitted fabrics, etc., prepared using the regenerated polyester fibers according to the present invention may be widely used in various industrial fields because of excellent flame retardancy and UV blocking effect.

The present invention is a regenerated polyester fiber composed of a sheath portion and a core portion, the sheath portion exposed on the surface is formed of a regenerated polyester resin containing a phosphorus-based flame retardant and the core portion of the fiber, such as zinc oxide, titanium oxide, etc. It is formed of a regenerated polyester resin containing an inorganic compound, and has an effect of providing a regenerated polyester fiber having excellent UV blocking and flame retardant performance.

In addition, it can be used for a variety of applications such as interior products, such as wallpaper, blinds, curtains, furniture, building materials, automotive interior materials that are environmentally friendly and require UV protection and flame retardancy by being made of recycled polyester fibers.

1 is a process chart for the production of recycled polyester fiber excellent in UV protection and flame retardant performance according to an embodiment of the present invention,
2 to 7 is a view showing a variety of cross-section of the regenerated polyester fiber excellent in UV protection and flame retardant performance according to the present invention.

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

The following examples are merely illustrative of the present invention, but the scope of the present invention is not limited to the following examples.

◎ Depolymerization and Core, Sisbu  Regenerated Polyester Resin Manufacture

The collected waste polyester is sorted and pulverized into flakes having a size of 2-3 mm, and the waste polyester and ethylene glycol (EG) are mixed in a molar ratio of 1.0: 0.5 by a first depolymerization process, and nitrogen (N ₂ ) gas is used. After pressurizing to 2.0kg / ㎠ and fully melted by stirring 25rpm at 210 ~ 240 ℃, the molten mixture was pressurized to 2.0kg / ㎠ using nitrogen (N ₂ ) gas and stirred 55rpm at 245 ~ 260 ℃ Depolymerized to prepare bis-2-hydroxyethyl terephthalate.

In the second depolymerization process, waste polyester, ethylene glycol (EG), and bis-2-hydroxyethyl terephthalate prepared in the first depolymerization process were mixed in a molar ratio of 1.0: 0.5: 1.2 and nitrogen (N ₂ ) gas was used. After pressurizing at 2.0 kg / cm 2 and completely melting by stirring 20 rpm at 210 to 240 ° C., the molten mixture was depressurized to 2.0 kg / cm 2 using nitrogen (N ₂ ) gas and stirred at 245 to 260 ° C. at 58 rpm. Bis-2-hydroxyethyl terephthalate was prepared.

The core part recycled polyester resin was added to titanium bis-2-hydroxyethyl terephthalate (BHET) prepared above using a sunscreen and polymerized for 180 minutes while stirring at 75 rpm at 265 ° C. in a vacuum to obtain recycled poly An ester resin was prepared and formed in chip form.

The cis part regenerated polyester resin was added to the bis-2-hydroxyethyl terephthalate (BHET) prepared in the above-mentioned phosphorus flame retardant (BHET) and polymerized for 180 minutes while stirring at 75 rpm at 265 ° C. under vacuum. Resin was prepared and formed in chip form.

1. Examples and Comparative Examples

Example 1

The area ratio of the sheath portion occupies 60% using a conventional spin draw composite spinning apparatus having two rollers. The core part was a recycled polyester resin containing 7% by weight of titanium oxide having an average particle diameter of 0.3 μm, and the sheath part was copolymerized by adding 6,000 ppm of phosphorus flame retardant of formula (2) based on phosphorus atoms during regenerated polyester polymerization. Ester resin was used. Spinnerets were used to form a circular cross section of the fiber, and after spinning at a spinning temperature of 280 ° C, an oil roller was used to attach the emulsion.In the heat setting and stretching process, the first high-speed roller speed was 1200mpm and 91 ° C The first heat setting was performed, and the second heat setting was performed at a speed of 4,000mpm at a second gourd roller at a temperature of 125 ° C, and stretched at a drawing ratio of 3.33, followed by a winding at 3,930mpm. Thus, a polyester composite fiber of 40 denier / 24 filaments was obtained.

Example 2

The area ratio of the core part was 80%, and the core part was made of a polyester resin containing 5% by weight of titanium oxide having an average particle diameter of 0.3 μm. A polyester resin copolymerized by adding 10,000 ppm was used. A polyester composite fiber of 40 denier / 24 filaments was obtained in the same manner as in Example 1 except this.

Example 3

Spinnerets were used to form a triangular fiber cross section, except that this was prepared in the same manner as in Example 1 to obtain a polyester composite fiber of 40 denier / 24 filaments.

Example 4

After cooling, the stretching process is performed by the first heat setting at speed 1300mpm and 89 ℃ on the first high speed roller, and the second heat setting at speed 4,000mpm and temperature 123 ℃ on the second high speed roller, stretching to 3.08 and stretching ratio 3,910 Winding process in mpm. A polyester composite fiber of 75 denier / 24 filaments was obtained in the same manner as in Example 1 except this.

Comparative Example 1

The area ratio of the core portion was 20%, except that this was prepared in the same manner as in Example 1 to obtain a polyester composite fiber of 40 denier / 24 filaments.

Comparative Example 2

A polyester polymer containing 1.0% by weight of titanium oxide having an average particle diameter of 0.3 μm was used in the core portion, except that this was prepared in the same manner as in Example 1 to obtain a polyester composite fiber having 40 denier / 24 filaments.

Comparative Example 3

A polyester polymer copolymerized by adding 500 ppm of phosphorus-based flame retardant of formula (2) to the cis part in the case of polyester polymerization was used. Except this, it manufactured similarly to Example 1 and obtained the polyester composite fiber of 40 denier / 24 filament.

Comparative Example 4

The heat setting and stretching steps are carried out with the first heat fixing at the speed 600mpm and 89 ℃ on the first high speed roller, the second heat setting at the speed 4,000mpm and the temperature 123 ℃ on the second high speed roller, and stretching to 6.67. It proceeded to a winding process at 3,900mpm, except that this was prepared in the same manner as in Example 1 to obtain a polyester composite fiber of 40 denier / 24 filaments. However, the number of trimming due to problems such as fracture in the drawing process in spinning increased rapidly, so that the spinning work was poor and smooth spinning was not possible.

2. Experiment and Evaluation Method.

(1) fineness measurement

A coil of 1 m was wound 90 m in one rotation, and the weight was measured and converted into 9000 m.

(2) Measurement of strength and elongation

The strength and elongation of the fibers were measured by applying a 50 cm / m speed and a 50 cm gripping distance using an automatic tensile tester (Textechno).

Strength and elongation is the value obtained by dividing the load (g / de) divided by the denier (denier) until the fiber is stretched until it is cut with a constant force on the fiber (strength, the initial length as a percentage of the elongated length) %) Is defined as Shinto.

(3) non-number measurement

The evaluation sample was heat set at 30 ° C. for 30 minutes in water, and then the difference between the measured length and the original length was calculated.

Ratio (%) = (First sample length-sample length after heat setting) / First sample length × 100

(4) spinning workability (%)

Yarn workability = (total number of yarns produced-number of yarns trimmed) / total number of yarns produced * 100

(5) drape

Sensory evaluation by 10 experts showed that 8 or more were judged to be draped, and 5 to 7 were draped.

(6) anti-impregnation

It is excellent when 10 or more experts can't judge the number by 10 experts by writing the number 10cm below the fabric made of weaving and knitting. 5 ~ 7 people usually can't judge the number. When less than a person was classified as bad.

(7) UV blocking rate (%) measurement

UV shielding rate (%): 100-transmittance of the measured sample

Measurement of transmittance of wavelength 320 ~ 390 nm using spectrophotometer

When the ultraviolet ray shielding rate is 10% or less, it can be judged that the ultraviolet ray blocking property is excellent.

(8) Limiting Oxygen Index

In order to evaluate a flame retardance, it measured based on KS-M ISO 4589-1-3 or JIS K7201 A-1. In general, if the LOI index is 27 or more, it can be determined that the flame retardancy is excellent.

The average values for the above experiments are shown in Tables 1 and 2 for the comparative examples.

division unit Example 1 Example 2 Example 3 Example 4 Sunscreen content weight% 7 5 7 7 Area ratio of core part % 60 80 60 60 Phosphorus Flame Retardant Content ppm 6,000 10,000 6,000 6,000 Area ratio of the sheath % 40 20 40 40 Fiber cross section - circle circle triangle circle Elongation ratio - 3.33 3.33 3.33 3.08 Fineness d 40.3 39.0 40.0 74.5 burglar g / d 4.05 4.00 4.35 4.43 Shinto % 32.7 34.8 34.0 33.5 Dagger % 8.4 8.0 8.5 8.2 Radiation workability % 95 94.0 94.0 94.0 Drape Castle - Great Great Great Great Anti-spill resistance - Great Great Great Great UV protection rate % 7.9 6.0 8.2 8.0  LOI Index - 32 30 28 30

division unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Inorganic Compound Content weight% 7 7 One 7 Area ratio of core part % 20 60 60 60 Phosphorus Flame Retardant Content ppm 6,000 6,000 500 6,000 Area ratio of the sheath % 80 40 40 40 Fiber cross section - circle circle circle circle Elongation ratio - 3.33 3.33 3.33 6.67 Fineness d 39.2 39.5 39.8 39.0 burglar g / d 4.20 4.10 4.25 5.20 Shinto % 34.8 34.4 32.9 8.5 Dagger % 8.7 9.0 8.4 4.8 Radiation workability % 90.5 96.0 95.0 20 (non-irradiable) Drape Castle - usually Bad Great Great Anti-spill resistance - Bad Bad Great Great UV shielding rate % 20.0 25.0 7.8 10.5  LOI Index - 33.0 29.0 22.0 26.5

As can be seen from the above embodiments, the regenerated polyester fiber having excellent UV blocking and flame retardant performance according to the present invention has excellent radiation workability and excellent UV blocking rate, good flame retardancy, and excellent anti-reflective property compared to the comparative examples. The strength of the fiber is 2.0-7.0 g / d, the elongation is 10-80%, and the specific value is 3.0-20.0%.

Claims (14)

In the regenerated polyester fiber composed of a core part and a sheath part using a regenerated polyester resin,
By mixing waste polyester and ethylene glycol (EG) to produce bis-2-hydroxyethyl terephthalate (BHET) by depolymerization process,
The core part is a recycled polyester resin prepared by adding a sunscreen agent to the bis-2-hydroxyethyl terephthalate (BHET),
The cis part is a recycled polyester resin copolymerized by adding a phosphorus flame retardant to the bis-2-hydroxyethyl terephthalate (BHET),
Regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that produced by the composite spinning of the two-component polyester resin prepared in the sheath-core. The method of claim 1,
The UV sunscreen is one or a mixture of two or more of zinc oxide, titanium oxide having a particle size of 0.1 ~ 5.0㎛, characterized in that 99 to 85% by weight of the recycled polyester resin and 1 to 15% by weight of the sunscreen is mixed. Recycled polyester fiber with excellent UV protection and flame retardant performance. The method of claim 1,
The phosphorus-based flame retardant is represented by the following formula (2) is a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that the phosphorus atom (P) is contained in the regenerated polyester resin of the sheath portion 500ppm to 15,000ppm.
(2)

Provided that R ₁ and R ₂ are methyl, phenyl, halophenyl, alkyl, haloalkyl or haloaryl. The method of claim 1,
The regenerated polyester fiber is a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that any one of the release cross-section selected from square, triangular, Y-type, flat, island-shaped, split type. The method of claim 1,
The sheath portion to the core portion of the recycled polyester fiber is 20:80 to 80:20 in the cross-sectional ratio ratio of the regenerated polyester fiber excellent in UV protection and flame retardant performance. In the manufacturing method of the regenerated polyester fiber which consists of a core part and a sheath part,
A depolymerization process of mixing waste polyester and ethylene glycol (EG) to produce bis-2-hydroxyethyl terephthalate (BHET);
A core portion recycled polyester resin manufacturing step of preparing a core portion recycled polyester resin by adding a sunscreen agent after the depolymerization process;
Sheath portion recycled polyester resin manufacturing process for producing a cis portion recycled polyester resin by adding and copolymerizing a phosphorus flame retardant after the depolymerization process;
A melting step of melting the core portion regenerated polyester resin at 260 to 330 ° C. and the sheath portion regenerated polyester resin at 250 to 320 ° C .;
Spinning the composite of the two-component melt at a temperature of 250 to 320 ℃ to produce a regenerated polyester fiber; And,
Method for producing a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that it is prepared, including the heat-setting and stretching step of stretching while heat-setting the spun regenerated polyester fiber. The method of claim 6,
In the depolymerization process, the waste polyester and ethylene glycol (EG) are mixed at a molar ratio of 1.0: 0.1 to 2.0, pressurized to 1.5 to 2.5 kg / cm 2 using nitrogen (N ₂ ) gas, and 10 to 50 rpm at 210 to 240 ° C. 1-4 hours by melt mixing, pressurized to 2.0-2.5 kg / cm 2 using nitrogen (N ₂ ) gas and depolymerized for 1.0-3.0 hours with stirring at 30-70 rpm at 245-260 ° C. A process for producing recycled polyester fibers with excellent UV protection and flame retardancy, characterized by producing oxyethyl terephthalate (BHET). The method of claim 6,
The depolymerization process includes a first depolymerization step of producing bis-2-hydroxyethyl terephthalate (BHET) by mixing waste polyester and ethylene glycol (EG); Bis-2-hydroxyethyl terephthalate (BHET) produced in the first depolymerization step is mixed with waste polyester and ethylene glycol (EG) bis-2-hydroxyethyl terephthalate (BHET) bis-2-hydroxyethyl terephthalate (BHET) The depolymerization process is performed, but the depolymerization process is repeated only in the second depolymerization step using a part of bis-2-hydroxyethyl terephthalate (BHET) generated in the second depolymerization step after the first depolymerization step. Method for producing a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that the progress. The method of claim 6,
The UV sunscreen is one or a mixture of two or more of zinc oxide, titanium oxide having a particle size of 0.1 ~ 5.0㎛, characterized in that 99 to 85% by weight of the recycled polyester resin and 1 to 15% by weight of the sunscreen is mixed. Process for producing recycled polyester fiber with excellent UV protection and flame retardant performance. The method of claim 6,
The phosphorus-based flame retardant is a formula (2) of the phosphorus atom (P) in the regenerated polyester resin of the sheath portion, characterized in that the production method of the regenerated polyester fiber excellent in UV protection and flame retardant, characterized in that it comprises 500ppm to 15,000ppm.
(2)

Provided that R ₁ and R ₂ are methyl, phenyl, halophenyl, alkyl, haloalkyl or haloaryl. The method of claim 6,
The regenerated polyester composite fiber is a release cross section selected from square, triangular, Y-shaped, flat, island-in-the-sea, and split type, and the sheath-to-core portion is 20:80 to 80:20 in cross-sectional ratio. And a method for producing recycled polyester fiber having excellent flame retardant performance. The method of claim 6,
The heat setting and stretching process is the first heat setting at 600 to 2,000mpm, 60 to 120 ℃ in the first high speed roller, the second heat setting at a speed of 3,000 to 5,000 mpm, temperature 90 to 150 ℃ in the second high speed roller Method for producing a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that while stretching. The method of claim 6,
Method for producing a regenerated polyester fiber excellent in UV protection and flame retardant performance, characterized in that the stretching in the heat-setting and stretching process at a draw ratio of 1.5 to 5.0. The regenerated polyester fiber according to any one of claims 1 to 5 or the regenerated polyester fiber prepared by the method according to any one of claims 6 to 13 has a strength of 2.0 to 7.0 g / d, elongation 10 to 80% , Non-aqueous value 3.0 ~ 20.0%, characterized in that the production method of recycled polyester fibers excellent in UV protection and flame retardant performance.

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