KR20160134894A - Fire retadant poly propylen fiber adding fire retardant of redction it - Google Patents

Abstract

The present invention relates to a fire-retardant polypropylene fiber obtained by making a polypropylene fiber be fire-retardant, and specifically, to a fire-retardant polypropylene fiber obtained by: adding an N-alkoxy stearic hindrance amine-based reactive fire-retardant to a polypropylene resin and a copolymer resin of propylene and ethylene, as an olefin-based resin, followed by blending and reaction at a first high-temperature, thereby obtaining a reaction product; adding, to the reaction product, a pigment, a dispersant, an antistatic agent, a foaming agent, and a UV absorbent, as functional additives, while the high temperature is maintained, thereby obtaining a pellet as a master batch; spinning the pellet to obtain a fiber, and then stretching the fiber to obtain a stretched yarn having a predetermined denier; and combining and stretching the stretched yarn, and then heating the stretched yarn.

Description

Fire retardant polypropylene fiber added with reactive flame retardant (Fire retardant of redion)

The present invention relates to a flame retardant polypropylene fiber yarn to which a reactive flame retardant having excellent adaptability to a polyolefin-based polymer is added. Specifically, the present invention relates to a flame retardant polypropylene fiber yarn comprising N-N'-ethane-1,2-diyl bis (1,3 propanediamine) 4-butylamino-2,2,6,6-tetramethylpiperidine and trichloro-1,2-5-1, 25-triazine in the presence of a base, Alkoxy-hindered amine-based reactive flame retardant represented by the following general formula (1)

………………구조식(1)

... ... ... ... ... ... The structural formula (1)

In particular, it has excellent adaptability to polyolefin-based polymers and has high extraction resistance, thereby ensuring washing resistance. Even when added at a low concentration to a polymer, it can exhibit a high level of heat resistance and flame retardancy. It does not affect the mechanical properties and physical properties of the polymer, and is an environmentally friendly flame retardant unlike flame retardants such as blends.

The flame retardant polypropylene fiber yarn obtained by the present invention is a polypropylene resin or a polyfluorene resin which is obtained by adding polyfluorene and ethenylene to a copolymerized resin copolymerized with poly The above-mentioned N-alkoxy steric hindered amine type reactive flame retardant is added, and the reaction product is reacted while blending while being melted at a high temperature. Secondly, a functional additive is added, and the temperature of the upper limit line is lowered by 20 캜 and maintained at 180 to 200 캜 , And is obtained by obtaining a masterbatch by blending in a state, and spinning and stretching the same to obtain a drawn yarn of a monofilament having a predetermined fineness, and subjecting the yarn to a heat treatment to obtain a flame-retardant polypropylene yarn.

The history of flame-retardant processing of fibers has been empirically known to have been made to treat flame retardant wood with acetic acid four centuries ago. The first flame-retarding process shown in the literature has been reported to have been treated with flame-retardant processing in 1735 by treating fibers with a mixture of alum, ferric sulfate and borax in the UK wide. By 1821, the famous Frenchman, Gay Lussac, found that the use of many kinds of salts in the flame retarding of flax and jute results in the application of a mixture of ammonium ammonium chloride and borax in it.

Verman and Oppenheim in the UK also reported that about 40 compounds were applied to the flame-retarding process of the fibers, resulting in a mixture of ammonium phosphate, ammonium phosphate, ammonium sulfate, sodium tungstate, and ammonium phosphate and ammonium chloride.

In France, Kling and Florentine announced that a mixture of borax and boric acid is effective, and this mixture is still in use.

In 1912, he succeeded in flame-retardant processing to withstand Perkin pretreatment. He studied how flame-resistant fibers survived the flame by forming a precipitate of stannic oxide inside the fiber.

Another method of excellent performance in permanent flame retarding, such as washing and immersion, is the treatment of mixed halogenated organic compounds and metal oxides, which appeared around 1930.

For example, chlorinated paraffin and antimony trioxide was used a lot (sb ₂ O ₃₎ as a method of fixing the fibers to the binder resin of the second of the US military tent during World War II the like.

This method has no problem in using as a military or industrial material because the treating agent has oil-based coating properties, but it is not suitable for processing into clothes fabric.

Interestingly since 1930, there have been studies dealing with the reaction of flame retardants with fibrin. For example, there has been a method of producing flour-resistant cellulose cellulose by reaction with urea-phosphate systems and fibers, It is disadvantageous that it is decomposed to cause a decrease in tensile strength.

The reaction of cellulose with a mixture of titanium oxide and antimony oxide appeared in a completely different form.

The permanent flame retarding process based on the reaction of fibrin was performed before and after the World War II by G. L. L. of the SRRL Institute in New Orleans, Louisiana, USA. Excellent flame retarding agents such as THPC (Tetrakis hydroxy methyl phosphonium chloride) and APO (tri (1-aziridinyl) phosphine oxide) developed by researchers such as Drake and JD Guther have emerged. Pyrobatex cp (hardoxymethylated phosphonocarboxyamide), recently manufactured by Ciba SA, Switzerland, and unlike this, it does not react with the fiber but is an interesting flame retarding process as described in the aforementioned SRRL Brominated organic compounds which become dibromoarylphosphonitrile or 2.3 dibromopropylphosphonitrile are polymerized on a fiber and are fixed with resin to fix them, and a method of using a flame-retardant organic compound is also reported, and in particular, bromine Containing organic compounds have been used as flame retardant plasticizers for plastics Will.

In addition, many inorganic flame retardants such as phosphate ester, halohane phosphate ester, non-halogen condensate phosphorus, polyphosphate, and many other inorganic flame retardants, including aluminum hydroxide, magnesium hydroxide, zinc borate, olivine trioxide, antimony trioxide and antimony pentoxide And has developed many flame-retardant additives as well as additive flame retardants, and application areas such as plastic, rubber, and wood are expanding widely in the fields of fiber, cellulosic, chemical fiber as well as insulation paper, kraft paper, wallpaper.

However, there are many problems to be solved by over-exploiting only the effect of the flame retardant.

As a requirement, the applicability with polymer should be good in mixing property, miscibility or reactivity. Do not decrease the mechanical properties and physical properties by adding a large amount of flame retardant.

In consideration of environmental and human stability, development of a product having low-harmful gasification low-softening, low corrosion resistance and recycling is required. In particular, in 1994, Germany regulated the use of brominated flame retardants that generate dioxins. The Netherlands also announced the ban on the use of PBOPE based flame retardants, and regulations on harmful flammable substances are expected to expand in the future.

In the above, the development process of the flame retardant and recent trends have been mentioned. However, the more detailed prior art regarding the application of the flame retardant is disclosed in Korean Patent Publication No. 1070649. The method is related to a method of manufacturing a stretchable flame- 5 to 15% by weight of a polyurethane constituent, and 85 to 95% of a polyester fire retardant are blended to produce a stretchable flame retardant fiber fabric, which is excellent in flame retardancy due to a bromine-based flame retardant as a flame retardant. As a flame retardant that can generate harmful dioxins in the human body, it is particularly troublesome to use in a fabric having frequent contact with the human body. There is a step of immersing polyurethane yarn having no flame retardancy in the solution to obtain flame retardancy, It can be helpful, but I can hardly expect it to be salty.

As another conventional technology, a flame-proofing method of cellulosic system is described in domestic patent publication (registration number: 28991), and another flame-proofing method of polyester fiber is disclosed in another registered patent publication (registration number: 866477) .

In both the former and the latter, the fabrics are woven with cerulose-based fibers and polyester-based yarns by a flame-proofing method, dyed in a dyeing process and simultaneously dyed in a solution containing a drug, The method is not dispersed in the texture of the fiber but is coated only on the surface, so that the flame retardant function is easily deteriorated, so that the flame retardant durability can not be expected.

In order to solve the problems caused by flame retardation of conventional synthetic fiber yarns, the present invention relates to a process for producing an N-alkoxy-steric hindered amine reactive flame retardant represented by the above-mentioned structural formula (1) at an initial high temperature and adding the olefinic polypropylene resin The polypropylene fiber yarn is provided with a high level of flame retardancy and semi-permanent washing resistance by adding a functional additive to ensure the physical properties and functionality required by the synthetic fiber yarn, It is an object to obtain a polypropylene fiber yarn.

Reacted flame retardant with an alkoxy steric hindrance amine is added to a polyolefin-based polypropylene resin or a copolymer resin obtained by copolymerizing a certain amount of ethylene with furopyrene, and the reaction product is reacted while being maintained at a temperature of 180 ° C to 220 ° C for 20 to 30 minutes , A dispersant, a UV absorber, and a defoaming agent as a functional additive, and then kneading the mixture at a high temperature for 15 to 20 minutes to obtain a masterbatch, which is then spun to obtain a monofilament, which is stretched to increase the tensile strength, 6 ~ 8de Total length of filament yarn is combined with multifilament with a total fineness of 1000 ~ 1300deg at 250 ~ 300TM and heat treated at 170 ~ 180 ℃ for 30 ~ 40 seconds to provide high level of flame retardancy, semi-permanent washability and environment friendliness The object of the present invention can be achieved by obtaining the flame-retardant polyfluorene.

The flame retardant polypropylene fiber yarn obtained by the present invention has a reactive flame retardant which is reactive with the olefin resin and is dispersed in the polypropylene melt and thus has excellent durability due to excellent washing resistance, It is a pigment of metal oxide which is not easily changed. It is dispersed in the texture of fiber yarn. It can keep color for a long time. It is environment-friendly and can be called polyfluoprene fiber with excellent tensile strength, have.

Hereinafter, the flame retardant polyfuran fiber yarn of the present invention will be described in more detail.

The base polymer of the flame-retardant polypropylene fiber yarn of the present invention is a polyolefin-based polymer in which the polypropylene resin is used as a base resin and the olefin-based polymer Based copolymer resin added with 5 to 15% of ethylene as a base resin, and the flame retardant added to the base polymer is an N-alkoxy-steric hindered amine-based reactive flame retardant represented by the following structural formula (1)

…………………구조식(1)

... ... ... ... ... ... ... The structural formula (1)

The reactive flame retardant can obtain a good flame retardant effect on fibers, nonwoven fabrics and woven fabric even if only 1 part by weight is added to 100 parts by weight of the polyolefin base resin. When 2 parts by weight is added, the flame retardancy can be raised to M1 level. The use of a large amount of a flame retardant for a base resin for producing a conventional synthetic fiber deteriorates physical properties such as tensile strength and coloring property of the fiber and raises the stainability of the fiber, In addition, when the fibers are immersed in an aqueous solution such as ammonium sulfate or ammonium chloride, which is conventionally added type flame retardant, or when the fiber is coated on the surface of the fiber, the crystals may precipitate as the water evaporates and is dried, Unlike flame retardants that are immersed or coated by immersing or coating with additive type flame retardant or metal oxide flame retardant solution, which has a sublimation property and deteriorates easily as time elapses, it is a flame retardant having reactivity with the base resin of polyolefin type. It can keep the flame retardant effect for a long time. And is excellent in washing resistance to ensure flame retardant durability.

It is also a flame retardant that provides ultraviolet and thermal stability to olefinic polymers and exhibits low interactions with acidic systems derived from pesticide residues or other halogenated products.

The amount of the N-alcoholic disoriented amine-based reactive flame retardant to be added to 100 parts by weight of the base resin with the polypropylene resin or the copolymer resin copolymerized with 95 to 85% of fluorine and 5 to 15% 0.5 to 2.5 parts by weight of the base polymer is added to 100 parts by weight of the base polymer, and the functional additive is added to the reaction product which is reacted for 20 to 30 minutes while blending while maintaining the temperature at 180 to 220 °.

The amount of the functional additive to be added is 2 to 3 parts by weight of the pigment, 1 to 2 parts by weight of the dispersant, 1 to 1.5 parts by weight of the antistatic agent and 0.5 to 1 part by weight of the antifoaming agent to 0.1 to 0.5 parts by weight of the UV absorber And the mixture is blended at a temperature of 180 to 200 ° C for 10 to 15 minutes to obtain a pellet.

The process of adding the functional additive to the reaction product proceeds in a continuous process of the reaction process while keeping the upper limit temperature at 20 占 폚 and maintained at 180 to 200 占 폚.

The polypropylene resin can be said to be the melting point of the polypropylene resin which is in the range of 180 to 220 ° C. in which the flame retardant is added to the polypropylene resin and subjected to the reaction treatment while blending. The temperature range higher than the melting point is high to improve the workability and shorten the reaction time And the homogeneity of the masterbatch can be ensured.

However, if the temperature is raised to 220 ° C or higher, the polypropylene resin may deteriorate to deteriorate physical properties.

The suitable use temperature of the reactive flame retardant is 250 DEG C or lower, and the flame retarding function is lowered as the temperature rises to 250 DEG C or higher. Therefore, the blending and reaction temperature can be defined as the temperature and time set so as to obtain a quality masterbatch.

The amount of the flame retardant and the functional additive to be added to the base resin in the above production method is preferably 0.5 to 2.5 parts by weight of a flame retardant based on 100 parts by weight of a polypropylene resin or a polypropylene resin obtained by adding polyetylene to a polypropylene resin, 1 to 2 parts by weight of a dispersing agent, 1 to 1.5 parts by weight of an antistatic agent, 0.5 to 1 part by weight of an antifoaming agent and 0.1 to 0.5 part by weight of an ultraviolet absorber are added to the first base resin, And a two-step process in which additives are added.

It reacts first with a flame retardant which has good adaptability to the polyolefin resin, so that it does not get disturbed in the reaction process, and it improves the reaction rate and the quality of the reactant. The remaining compositions are generally thermally unstable materials compared to the flame retardant, and the temperature is set to be 20 占 폚 lower than the upper limit temperature of the first flame retardant addition process. This is evident as a result of measuring the physical properties of the produced propylene fiber yarn.

In order to accelerate the reaction, 0.5 to 2.5 parts by weight of a flame retardant containing 5 to 10% of triethanolamine and N, N-methylamine as an accelerator is added to the N-alkoxy steric hindered amine flame retardant to increase the reactivity And can shorten the working time.

In addition, as the additive, the dispersant uniformly disperses the solid fine particles of the additive in the melt of the polypropylene, so that homogeneous masterbeds can be obtained, so that homogeneous polyfuran filament yarns can be obtained. As the dispersing agent, An alkyl benzene sulfonate salt, and a higher alcohol sulfate ester salt.

As the coloring agent, the use of the pigment of the metal oxide makes it possible to maintain the color even under severe conditions. In the case of synthetic fiber yarn, it is mainly dyed with synthetic dye with azo dye reactive dye. However, organic dyestuffs are more vulnerable to heat, light and moisture than pigments, The pigment of the metal oxide of the present invention is safe for heat, ultraviolet ray, moisture and solvent, thus ensuring durability of color. In the case of heat treatment at high temperature as in the process of the present invention, a pigment is suitable.

Further, the polypropylene fiber yarn obtained in the present invention is used in harsh conditions such as horizontal and vertical safety net geosynthetics and belts used for construction work, belt tent papers for moving and transporting heavy loads, and automobile covers, and therefore color durability is required .

As an additive, an antistatic agent is added to prevent the fiber from being cut by adsorbing dust by generating static electricity by friction, such as polypropylene fiber yarn or synthetic fiber yarn. Especially when it is required to be a safety net made of polypropylene yarn By adsorbing a lot of dust, the workers are hurting the heat by blocking the vertical ventilation holes in the vertical safety net in the summer, and when the impact or wind blows, the adsorbed dust is blown up and the working conditions are deteriorated.

As the antistatic agent, there is a great advantage to use a polyoxyethyl alkylamine having good compatibility with a base resin and a miscibility with an antistatic agent that is soluble in water, such as a dialkyl phosphate salt or a quaternary ammonium salt.

The ultraviolet absorbent absorbs harmful ultraviolet rays of 290 to 400 占 퐉 and converts into harmless energy to prevent generation of free radicals and generation of peroxides. As described above, the use of the flame retardant polypropylene fiber yarn according to the present invention It is used in outdoor fabrics, so that it takes much time to be exposed to sunlight, so that the deterioration of the physical properties of the product can be prevented by the antistatic function.

The photo-oxidation mechanism is caused by ultraviolet light. It absorbs ultraviolet light of several microns on the surface of polymer materials such as polypropylene fiber and synthetic resin and asphalt which are exposed to the outside. Over time, an oxide film is formed and this film is easily dissolved in rainwater This phenomenon is repeated due to the phenomenon of disappearance, which is an indispensable additive for polymer products which are exposed to the outside, because the durability is lowered.

As the ultraviolet additive, dozens of ultraviolet absorbers such as phenyl salicylate, benzotriazole and the like are available, but hexaethylphosphoryl triamide is used which has thermal stability and good compatibility with polypropylene resin.

In addition, since the defoaming agent as an additive has a function of destroying bubbles caused by the gases generated during the heat treatment of bubbles by the air introduced during the processing and preventing the generation of bubbles, when the bubbles are mixed in the synthetic fiber yarn, The fibers are broken or the workability is not good at the time of post-processing, the strength of recognition of the fiber yarn is lowered, and the fibers may be easily broken, resulting in various problems.

There are many antifoaming agents such as silicone, higher alcohol type, and fatty acid ester type. However, as in the present invention, when pigment is colored in the polypropylene resin as a pigment, silicon can prevent staining phenomenon by preventing coloring It is preferable to use a silicone antifoaming agent.

The flame-retardant polypropylene fiber yarn obtained by spinning with the masterbeddle produced above was stretched to obtain a single fineness of 6 to 8 denier, and a total fineness of 1000 to 1300 denier was obtained. The twist yarn obtained by twisting the twin yarn at 250 to 300 TW (Twistperm) Heat treatment at 180 ° C for 30 to 40 minutes to stabilize the fiber yarn, thus completing the post-processing of the flame retardant polypropylene fiber yarn.

The flame retardant polypropylene fiber yarn according to the present invention can be applied to products requiring high tensile strength, such as horizontal and vertical stabilization nets, high strength bands for container applications, geotextiles and belts, ropes, tent papers, Stretching process is indispensable because tensile strength can be further increased by orienting the crystal arrangement in the longitudinal direction through the stretching process of the polypropylene fiber yarn having excellent strength. The monodenier is a synthetic fiber for garments requiring a warmth There is no necessity of fine finishing and there is an advantage of increasing the tensile strength by increasing the single fineness, facilitating the difficult spinning processing for obtaining the fine fineness, reducing the cost of spinning processing, and increasing the tensile strength. It is the reason to increase the fineness.

In addition, heat treatment in the range of the melting point induces thermal adhesion between the surface and the surface of the single yarn to reduce the walking volume of the fiber yarn and prevent the occurrence of lint of the fiber, thereby preventing the problems occurring at the time of weaving.

The polypropylene filament yarn according to the present invention is excellent in adaptability to a polyolefin-based synthetic resin and has a high flame retardancy with high extraction resistance as a masterbette, so that semi-permanent washing resistance can be ensured and excellent flame retardancy have. In addition, it is possible to prevent deterioration of physical properties of fiber yarn by adding a remarkably small amount compared to the addition amount of flame retardant used in general flame retarding processing of synthetic fiber yarn, and unlike brominated flame retardant and other harmful flame retardant, It can be said to be eco-friendly by using a flame retardant which is non-flammable and can be said to be a flame retardant polyfuropylene fiber yarn having a high tensile strength by satisfying the function of a fiber yarn required by a synthetic fiber yarn by adding a functional material and appropriately post-

The properties and functions of the flame retardant polypropylene fiber yarn obtained by the above method will be described.

Example (1)

2 parts by weight of an N-alkoxy steric hindrance amine-based reactive flame retardant was added to 100 parts by weight of a polypropylene resin, blending was carried out for 25 minutes while maintaining the temperature at 210 DEG C, 3 parts by weight of pigment, 1.5 parts by weight of dispersant, 0.5 part by weight of an anti-foaming agent and 0.5 part by weight of an ultraviolet absorber were added and blended for 10 minutes to obtain a pellet. The obtained flame retardant polypropylene filament yarn was stretched to a length of 2 times to obtain a single fineness 8 denier fiber yarn, And twisted yarn with 300 TW (Twistperm) was thermally treated at a temperature of 180 DEG C for 30 seconds to obtain a flame retardant polypropylene yarn.

The tensile strength, flame retardancy, heavy metal content and PBBS (polyvrominated diphenylethers) content test results were obtained from the FITI test institute (498, Worryong Road, Daegu, Korea)

Tensile strength test result table Item Test result Remarks Tensile load (KN) 1.65 KS F 8081: 2011
CRE strip method Tensile load (KN x elongated length) 169.3

Flammability test result table Item Test result Remarks Residual salt time (S) 0
KsF 8081: 2011
Xchel Burner method The remaining period (S) 5 Carbonization length (cm) 5.1 Determination pass

Heavy metal content test result table ingredient Test result Detection limit Remarks Cart (cd) Not detected 1.0 mg / kg IEC 62321
(111/116 / FDIS)
Test Methods Lead (Pb) 〃 10.0 mg / kg Mercury (Hg) 〃 0.1 mg / kg Chrome (cr) 〃 0.1 mg / kg

PBBs (POLYBROMINATED BIPHENYLS) Content test results ingredient content Test Methods Detection limit BROMOBIPHENYL Not detected



IEC 62321
(111/116 / FDIS)







1 mg / kg




DIBROMOBIPHENYL Not detected TRIBROMOBIPHENYL Not detected TETRABROMOBIPHENYL Not detected PENTABROMOBIPHENYL Not detected HEXABROMOBIPHENYL Not detected HEPTABROMOBIPHENYL Not detected OCTABROMOBIPHENYL Not detected NONABROMOBIPHENYL Not detected DECABROMOBIPHENYL Not detected

PBBs (POLYBROMINATED DIPHENYL ETHERS) Content test results ingredient content Test Methods Detection limit BROMOBIPHENYL ETHERS Not detected



IEC 62321
(111/116 / FDIS)







1 mg / kg




DIBROMOBIPHENYL ETHERS Not detected TRIBROMOBIPHENYL ETHERS Not detected TETRABROMOBIPHENYL ETHERS Not detected PENTABROMOBIPHENYL ETHERS Not detected HEXABROMOBIPHENYL ETHERS Not detected HEPTABROMOBIPHENYL ETHERS Not detected OCTABROMOBIPHENYL ETHERS Not detected NONABROMOBIPHENYL ETHERS Not detected DECABROMOBIPHENYL ETHERS Not detected

Claims (8)

Reacting flame retardant of the n-alkoxy steric hindrance amine type represented by the following structural formula (1) to the polyfuropylene resin at a temperature of 180 to 220 DEG C and reacting the reaction product with the blend in a temperature range of 180 to 220 DEG C as a secondary functional additive The pellet is obtained by blending with a pigment, a dispersant, an antistatic agent, a defoaming agent, and an ultraviolet absorber while maintaining the temperature at 180 to 200 ° C for 10 to 15 minutes. The fiber yarn obtained by spinning is stretched, The stretched yarn was heat-treated at a temperature of 170 to 180 ° C for 30 to 40 seconds to obtain a flame-retardant polypropylene yarn

The flame-retardant polypropylene fiber yarn according to claim 1, wherein the polypropylene resin is a copolymer resin obtained by copolymerizing 85 to 95% of furopyrene and 5 to 15% of ethylene The flame-retardant polypropylene fiber yarn according to claim 1, wherein 0.5 to 2.5 parts by weight of the N-alkoxy steric hindrance amine-based reactive additive amount is added to 100 parts by weight of the polypropylene resin The filament according to claim 1, wherein the drawn yarn has a single fineness of 6 to 8 de, The method according to claim 1, wherein the twist yarn is a twist yarn twisted at 250 to 300 (TW) meters. The functional additive is added in an amount of 2 to 3 parts by weight, 1 to 2 parts by weight of a dispersant, 1 to 1.5 parts by weight of an antistatic agent, 0.5 to 1 part by weight of a defoamer, 0.5 to 1 part by weight of an antifoamer, And 0.1 to 0.5 parts by weight of an absorbent is added to the flame-retardant polypropylene fiber yarn The flame retardant polypropylene fiber yarn according to claim 4, wherein the antistatic agent is polyoxyethylene alkylamine The flame-retardant polypropylene fiber yarn according to claim 4, wherein the ultraviolet absorber is a hexaethylphosphoryl triamide ultraviolet absorber.