KR102230501B1 - Flame retardant fiber comprising microcapsulated inorganic flame retardant additive and method of manufacturing same - Google Patents

Abstract

Disclosed are a flame retardant fiber comprising a microencapsulated inorganic flame retardant additive, and a method for manufacturing the same. The microencapsulated inorganic flame retardant additive comprises: a core including an inorganic flame retardant additive; and a shell positioned on the core. The microencapsulated flame retardant additive of the present invention has an effect of improving dispersibility and compatibility with a polymer. In addition, the flame retardant fiber of the present invention uses zinc stannate as the inorganic flame retardant additive, thereby being less harmful to the environment and human body and having an excellent flame retardant effect.

Description

Flame-retardant fiber containing microencapsulated inorganic flame-retardant additives, and a manufacturing method thereof TECHNICAL FIELD [FLAME RETARDANT FIBER COMPRISING MICROCAPSULATED INORGANIC FLAME RETARDANT ADDITIVE AND METHOD OF MANUFACTURING SAME}

The present invention relates to a flame-retardant fiber and a method of manufacturing the same, and more particularly, to a flame-retardant fiber including a microencapsulated inorganic flame-retardant additive, and a method of manufacturing the same.

Recently, as the use of polymers has been widely expanded to construction, automobiles, electrical appliances, aircraft, ships, functional and safety textile products, etc., the need for flame retardancy in consideration of safety in the event of a fire continues to increase. Polymers are mostly organic substances composed of carbon, hydrogen, and oxygen, and are easily combustible, so a flame retardant additive is introduced to improve such properties physically and chemically to prevent burning. Flame retardant additives should have good compatibility with raw materials and additives, should not affect the mechanical properties of the final product, and should generate less smoke and toxic gases during combustion.

Flame retardant additive is an additive that slows ignition and prevents the expansion of combustion by adding substances with high non-combustible effects such as halogen, phosphorus, nitrogen-containing compounds, and metal hydroxide compounds to organic materials such as polymer materials and plastics that are easily combustible. Is defined as In addition to basic flame retardancy, properties such as environmental (low corrosion, low smoke, low harm) and compatibility with polymers are required.

Conventional flame-retardant additives are mainly halogen-based organic flame-retardant additives, and bromine-based or chlorine-based additives are mainly used. The use of these is restricted due to the rise of safety issues for the environment and human body due to the generation of harmful gases such as dioxin during injection.

In recent years, flame retardant additives are required to be environmentally friendly or environmentally safe in addition to flame retardancy, and thus, non-halogen-based flame retardants including phosphorus-based and inorganic flame retardants are emerging as alternatives. Among inorganic flame retardant additives, the main product is antimony oxide, which is the most commercially available because of its inexpensive price.

An object of the present invention is to solve the above problems and to provide a microencapsulated flame retardant additive capable of improving compatibility and dispersibility with a polymer.

In addition, an object of the present invention is to provide a flame-retardant fiber having less environmental and human hazards and excellent flame retardant effect by using zinc stannate as an inorganic flame retardant additive.

According to an aspect of the present invention, the core comprising an inorganic flame retardant additive; And a shell positioned on the core.

In addition, the inorganic flame retardant additive is 1 selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zinc stannate (ZnSnO ₃ ), zinc hydroxytinate (ZnSn(OH) ₆ ), zirconium, antimony oxide, zirconium compounds, zinc borate, and molybdenum oxide. It may contain more than one species.

In addition, the inorganic flame retardant additive may include at least one selected from the group consisting of _{zinc stannate (ZnSnO 3} ) and zinc hydroxy stannate (ZnSn(OH) _{6 ).}

In addition, the inorganic flame retardant additive may _{include zinc hydroxystannate (ZnSn(OH) 6} ).

In addition, the shell may include at least one selected from the group consisting of melamine, silicate, aluminum phosphate, polystyrene, and polyurethane.

In addition, the flame-retardant microcapsules may include 10 to 300 parts by weight of the shell based on 100 parts by weight of the core.

According to another aspect of the present invention, the flame retardant microcapsules; And flame-retardant copolymer; flame-retardant fiber comprising a is provided.

In addition, the flame-retardant copolymer may include at least one selected from modacrylic, acrylic, vinyl chloride, olefin, polyester and aramid copolymers.

In addition, the flame retardant copolymer may include a modacrylic copolymer.

In addition, the modacrylic copolymer is acrylonitrile (AN) 35 to 85 wt%; And, in the group consisting of vinyl chloride monomer (VCM) and vinylidene chloride monomer (VDCM) 15 to 65 wt% of at least one selected; may include a copolymer prepared by copolymerizing.

In addition, the flame-retardant fiber may be for use in any one selected from the group consisting of work clothes, protective clothes, automobile interior materials, interior interior materials, fire fighting clothes, and social safety clothes.

According to another aspect of the present invention, (a) preparing a dispersion containing an inorganic flame retardant additive; And (b) adding any one selected from the group consisting of a shell precursor and a shell material to the dispersion and stirring to prepare a flame-retardant microcapsule including a core containing the inorganic flame retardant additive and a shell positioned on the core. A method of manufacturing a flame-retardant microcapsule comprising; is provided.

In addition, the shell precursor is selected from the group consisting of _{aluminum hydroxide (Al(OH) 3} ), phosphoric acid (H ₃ PO ₄ ), ethyl silicate (Si(OC ₂ H ₅ ) ₄ ) and melamine (C ₃ H ₆ N _{6 ).} It may contain one or more.

In addition, the shell material may include one or more selected from the group consisting of polystyrene and polyurethane.

According to another aspect of the present invention, (a) dissolving a flame-retardant copolymer in a first solvent to prepare a solution containing the flame-retardant copolymer; (b) preparing a dispersion by dispersing the flame-retardant microcapsules prepared according to the preparation method in a second solvent; (c) preparing a spinning solution by mixing the solution containing the flame-retardant copolymer of step (a) and the dispersion of step (b); And (d) spinning the spinning solution to prepare flame-retardant fibers.

In addition, in step (b), the dispersion may be performed by a dispersion method including at least one selected from the group consisting of mechanical stirring, milling, and ultra sonication.

In addition, in step (b), the dispersion may be performed by a dispersion method of ultra sonication.

In addition, the flame-retardant microcapsules may be in powder form.

In addition, the first solvent may contain at least one selected from the group consisting of water, dimethyl sulfoxide (DMSO), acetone, and dimethylformamide (DMF).

In addition, the second solvent may contain at least one selected from the group consisting of dimethyl sulfoxide (DMSO), acetone, and dimethylformamide (DMF).

In addition, in the spinning solution, the concentration of the flame-retardant copolymer is 15 to 40 wt%, and the ratio (Wi/Wc) of the content (Wi) of the flame-retardant microcapsule to the content (Wc) of the flame-retardant copolymer is 0.1 to 15% Can be

In addition, in step (d), the spinning may be dry spinning or wet spinning.

The microencapsulated flame retardant additive of the present invention has an effect of improving compatibility and dispersibility with a polymer.

In addition, the flame-retardant fiber of the present invention uses zinc stannate as an inorganic flame-retardant additive, so that environmental and human hazards are small, and the flame retardant effect is excellent.

FIG. 1 is a SEM image of flame-retardant microcapsules and zinc hydroxystannate (ZHS) prepared according to Examples 1-1 to 1-3.
2 is a TGA (Thermogravimetric analysis) analysis results of flame-retardant microcapsules prepared according to Examples 1-1 to 1-3.
3 is a result of a flame retardant test after preparing the spinning solution of step (c) in the form of a film by a hot air drying method in Examples 2-1 to 2-3 and Comparative Examples 1 to 3;

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present invention.

However, the following description is not intended to limit the present invention to a specific embodiment, and in describing the present invention, when it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. .

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the existence of features, numbers, steps, actions, elements, or combinations thereof described in the specification, but one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, actions, elements, or combinations thereof is not preliminarily excluded.

Hereinafter, the flame-retardant microcapsules of the present invention will be described.

The present invention includes a core containing an inorganic flame retardant additive; And a shell positioned on the core.

core

The flame-retardant microcapsules of the present invention include a core, and the core may contain an inorganic flame-retardant additive.

The inorganic flame retardant additive is one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zinc stannate (ZnSnO ₃ ), zinc hydroxytinate (ZnSn(OH) ₆ ), zirconium, antimony oxide, zirconium compounds, zinc borate, and molybdenum oxide. It may include the above, preferably at _{least one selected from the group consisting of zinc stannate (ZnSnO 3} ) and zinc hydroxy stannate (ZnSn (OH) ₆ ), more preferably zinc hydroxy stannate (ZnSn (OH) ₆ ) may be included.

Compared with other inorganic materials, zinc stannate and zinc hydroxy stannate have excellent flame retardant effects, and are less toxic and less gaseous during combustion, so they are less harmful to the environment and human body.

Shell

The flame-retardant microcapsule of the present invention includes a shell, and the shell may be located on the core.

The shell may include at least one selected from the group consisting of melamine, silicate, aluminum phosphate, polystyrene, and polyurethane, and preferably aluminum phosphate.

The flame-retardant microcapsules may include 10 to 300 parts by weight of the shell based on 100 parts by weight of the core. If the shell is less than 10 parts by weight, it is not preferable to completely enclose the core material to form a capsule, and if it exceeds 300 parts by weight, it is preferable because it does not help the flame-retardant mechanism by delaying the time for the flame retardancy of the core material to be expressed during combustion. I don't.

Microencapsulation of flame retardant additives improves thermal stability, prevents toxic gas emission, increases compatibility with polymers, and reduces water solubility. Since the core material, which is the core, can be protected from the external environment or the user can control the sustained release according to the purpose, it is compatible with matrix polymers with improved heat resistance to the processing temperature and sustained release characteristics by controlling core material release during polymer compounding processing. It is possible to prevent desorption due to plasticization from the resin because organic substances with high properties are used as the shell, that is, the wall material. The advantage is that it maintains the flame retardant effect by the primary combustion of the wall material even during the combustion of the polymer.

Hereinafter, the flame-retardant fiber of the present invention will be described.

The present invention is the flame retardant microcapsules; It provides a flame-retardant fiber comprising; and flame-retardant copolymer.

Flame-retardant microcapsules

Since the flame-retardant microcapsules are the same as those described in the flame-retardant microcapsules of the present invention described above, the detailed information will be referred to that part.

Flame retardant copolymer

The flame retardant fiber of the present invention may include a flame retardant copolymer.

The flame-retardant copolymer may include at least one selected from modacrylic, acrylic, vinyl chloride, olefin, polyester, and aramid copolymers, and preferably modacrylic copolymers. .

The modacrylic copolymer is acrylonitrile (AN) 35 to 85 wt%; And, 15 to 65 wt% of at least one selected from the group consisting of vinyl chloride monomer (VCM) and vinylidene chloride monomer (VDCM). .

The flame-retardant fiber may be for use in any one selected from the group consisting of work clothes, protective clothes, automobile interior materials, interior interior materials, fire fighting clothes, and social safety clothes.

Hereinafter, a method of manufacturing a flame-retardant microcapsule of the present invention will be described.

first, Weapon system A dispersion containing a flame retardant additive is prepared (step a).

Next, any one selected from the group consisting of a shell precursor and a shell material is added to the dispersion, and By stirring remind Weapon system A core comprising a flame retardant additive and positioned on the core Shell To prepare a flame-retardant microcapsule containing (step b).

The shell precursor is aluminum hydroxide (Al (OH) ₃ ), phosphoric acid (H ₃ PO ₄ ), ethyl silicate (Si (OC ₂ H ₅ ) ₄ ) and melamine (C ₃ H ₆ N ₆ ) 1 selected from the group consisting of It may include more than one species, preferably aluminum hydroxide (Al (OH) ₃ ) and phosphoric acid (H ₃ PO ₄ ) It may include one or more selected from the group consisting of. Aluminum hydroxide and phosphoric acid may be used to prepare an aluminum phosphate shell, ethyl silicate may be used to prepare a silica shell, and melamine and formaldehyde may be used to prepare a melamine shell.

The shell material may include one or more selected from the group consisting of polystyrene and polyurethane.

Hereinafter, a method of manufacturing the flame-retardant fiber of the present invention will be described.

First, a flame-retardant copolymer in a first solvent Dissolve To prepare a solution containing the flame-retardant copolymer (step a).

The first solvent may contain at least one selected from the group consisting of water, dimethyl sulfoxide (DMSO), acetone, and dimethylformamide (DMF).

Next, a dispersion is prepared by dispersing the flame-retardant microcapsules prepared according to the method for preparing the flame-retardant microcapsules in a second solvent (step b).

The dispersion may be performed by a dispersion method including at least one selected from the group consisting of mechanical stirring, milling, and ultrasonic treatment, and preferably, ultra sonication. It can be carried out in a dispersion method.

The flame-retardant microcapsules may be in powder form.

The second solvent may contain at least one selected from the group consisting of dimethyl sulfoxide (DMSO), acetone, and dimethylformamide (DMF).

Next, a spinning solution is prepared by mixing the solution containing the flame-retardant copolymer of step (a) and the dispersion of step (b) (step c).

In the spinning solution, the concentration of the flame-retardant copolymer is 15 to 40 wt%, and the ratio (Wi/Wc) of the content (Wi) of the flame-retardant microcapsule to the content (Wc) of the flame-retardant copolymer is 0.1 to 15% I can.

Finally, the spinning solution is spun to prepare flame-retardant fibers (step d).

The spinning may be dry spinning or wet spinning.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

Example 1: Preparation of flame retardant microcapsules ( AlP /ZHS)

Example 1-1: AlP (20wt%) / ZHS

100 ml of distilled water was dispersed by _{ultrasonic treatment with 10 g of zinc hydroxytinate (ZnSn(OH) 6} ), 0.01 g of sodium lauryl sulfate (SDS), and 0.1 g of cetrimonium bromide (CTAB) as a dispersion medium. After adding 1 g of aluminum hydroxide (Al(OH) ₃ ) and 1 g of phosphoric acid (H ₃ PO ₄ ) to the dispersion, the mixture was stirred at 80° C. for 1.5 hours (mechanical stirring). After completion of the reaction, it was centrifuged and dried to prepare flame-retardant microcapsules (AlP (20wt%)/ZHS) powder.

Example 1-2: AlP (100wt%) / ZHS

Instead of using 1 g of aluminum hydroxide (Al(OH) ₃ ) and 1 g of phosphoric acid (H ₃ PO ₄ ) in Example 1-1, 5 g of aluminum hydroxide (Al(OH) ₃ ) and 5 g of phosphoric acid (H ₃ PO ₄ ) were used. Except for using, a flame-retardant microcapsule (AlP (100wt%)/ZHS) powder was prepared in the same manner as in Example 1-1.

Example 1-3: AlP (200wt%) / ZHS

Instead of using 1 g of aluminum hydroxide (Al(OH) ₃ ) and 1 g of phosphoric acid (H ₃ PO ₄ ) in Example 1-1, 10 g of aluminum hydroxide (Al(OH) ₃ ) and 10 g of phosphoric acid (H ₃ PO ₄ ) were used. Except for using, flame-retardant microcapsules (AlP (200wt%)/ZHS) powder was prepared in the same manner as in Example 1-1.

Example 2: Preparation of flame retardant fiber

Example 2-1: AN- VDC / AlP ( 20wt% ) / ZHS

Step (a): Preparation of flame retardant copolymer solution

A copolymer containing 50:50 (wt%) of acrylonitrile (AN) and vinylidene chloride (VDC) was prepared by a suspension polymerization method and dissolved in dimethyl sulfoxide (DMSO) to be flame retardant. A copolymer solution was prepared.

Step (b): Preparation of flame retardant microcapsule dispersion by stirring

A dispersion was prepared by dispersing the AlP (20wt%)/ZHS powder prepared according to Example 1-1 in dimethyl sulfoxide (DMSO) as a solvent by an ultra sonication method.

The ultrasonic treatment (Ultra sonication) was performed for a total of 60 minutes at a frequency of 20 KHz and an intensity of 1500 watt, 6 times each for 10 minutes using a Sonics device.

Step (c): Preparation of spinning solution

A spinning solution was prepared by mixing the flame-retardant copolymer solution of step (a) and the flame-retardant microcapsule dispersion of step (b) at 0K (-273.15°C). The spinning solution had a flame-retardant copolymer concentration of 30 wt%, and the flame-retardant microcapsules were prepared with 15% of the flame-retardant copolymer.

Step (d): spinning the spinning solution to prepare flame-retardant fibers

Flame-retardant fibers were prepared by wet spinning the spinning solution prepared in step (c). Wet spinning was performed in the order of primary coagulation, secondary coagulation, water washing, hot water stretching, emulsion treatment, heat drying, and winding. At this time, a solution of water and dimethyl sulfoxide (DMSO) was used as the solvent in the coagulation bath.

Example 2-2: AN-VDC/ AlP (100wt%)/ZHS

In Example 2-1, instead of using the AlP (20 wt%) / ZHS powder prepared according to Example 1-1, except for the use of the AlP (100 wt%) / ZHS powder prepared according to Example 1-2 Then, a flame-retardant fiber was prepared in the same manner as in Example 2-1.

Example 2-3: AN-VDC/ AlP (200wt%)/ZHS

In Example 2-1, instead of using the AlP (20 wt%) / ZHS powder prepared according to Example 1-1, except for the use of the AlP (200 wt%) / ZHS powder prepared according to Example 1-3 Then, a flame-retardant fiber was prepared in the same manner as in Example 2-1.

Comparative Example 1: Preparation of flame retardant fiber (AN-VDC)

Instead of performing steps (b) and (c) of Example 1, and using the flame-retardant copolymer solution of step (a') below instead of using the spinning solution of step (c) in step (d) Except for, a flame-retardant fiber was prepared in the same manner as in Example 2-1.

Step (a'): Preparation of flame retardant copolymer solution

A copolymer containing 50:50 (wt%) of acrylonitrile (AN) and vinylidene chloride (VDC) was prepared by a suspension polymerization method and dissolved in dimethyl sulfoxide (DMSO) to be flame retardant. A flame-retardant copolymer solution having a copolymer concentration of 30 wt% was prepared.

Comparative Example 2: Flame-retardant fiber containing antimony trioxide (AN-VDC/Sb ₂ O ₃ ) Of the manufacture

Instead of using AlP (20wt%)/ZHS powder prepared according to Example 1-1 in Example 2-1, antimony trioxide (Sb ₂ O ₃ ) powder (powder size 1.0 μm or less, purity 99.5%) was used. Except for that, a flame-retardant fiber was prepared in the same manner as in Example 2-1.

Comparative example 3: Zinc hydroxytinate (ZHS) Flame-retardant fiber containing (AN- VDC / ZHS ) Of the manufacture

Instead of using the AlP (20wt%)/ZHS powder prepared according to Example 1-1 in Example 2-1, zinc hydroxytinate (ZnSn(OH) ₆ ) powder (powder size 1.0 μm or less, purity 99.5% A flame-retardant fiber was prepared in the same manner as in Example 2-1, except that) was used.

[Test Example]

Test Example 1: Analysis of the shape and components of flame retardant microcapsules

SEM images of the flame-retardant microcapsules prepared according to Examples 1-1 to 1-3 and zinc hydroxytartrate (ZHS) are shown in FIG. 1.

Referring to FIG. 1, after microencapsulation, the shape of the surface particles of zinc hydroxytinate changed from square to spherical, and the diameter of zinc hydroxytinate was changed from about 103 nm to 124 nm in AlP (20 wt%)/ZHS. Increased. In addition, it was confirmed that as the content of aluminum phosphate (AlP), which is a shell material, increased from 20 wt% to 200 wt%, the particle diameter of the microcapsules increased and a circular capsule shape was formed.

2 shows the results of thermogravimetric analysis (TGA) analysis of the flame-retardant microcapsules prepared according to Examples 1-1 to 1-3. Referring to FIG. 2, the weight of zinc hydroxytinate (ZHS) not microencapsulated was observed to decrease in weight by about 23% at around 200°C, but the weight of zinc hydroxytinate (AlP/ZHS) microencapsulated in the same temperature range The reduction was found to be less than 15%. In particular, AlP (200wt%)/ZHS microcapsules showed a 5% weight reduction, and the decomposition temperature tended to increase as the amount of aluminum phosphate (AlP), which is a shell material, increased.

Test Example 2: Viscosity Analysis of Polymer Fiber Solution According to Flame Retardant Additive

Viscosity was measured using a plate-plate type rotary viscometer, and the viscosity increase rate was based on a polymer solution without microencapsulated zinc hydroxytinate. By calculating the viscosity increase as a percentage, the viscosity and viscosity increase rate due to the injection of the flame retardant additive in the polymer fiber spinning process were measured to analyze the effect of the microencapsulation method of the flame retardant additive on the viscosity.

In Table 1 below, the viscosity and viscosity increase rates of Examples 2-1 to 2-3 and Comparative Examples 1 and 3 are shown.

Sample Viscosity (cP) Viscosity increase rate (%) Comparative Example 1 (AN-VDC) 14,489 - Comparative Example 3 (AN-VDC/ZHS) 25,254 74% Example 2-1 (AN-VDC/AlP (20wt%)/ZHS) 16,277 12% Example 2-2 (AN-VDC/AlP (100wt%)/ZHS) 15,243 5% Example 2-3 (AN-VDC/AlP (200wt%)/ZHS) 15,181 5%

Referring to Table 1, in Comparative Example 3 in which zinc hydroxytinate (ZHS) was added, the viscosity of the spinning solution was 25,254 cP, which greatly increased the viscosity increase rate to 74%, but decreased to 5% after microencapsulation. This indicates that the effect of the flame retardant additive on the viscosity of the polymer fiber spinning solution is reduced by microencapsulation of zinc hydroxytinate. When manufacturing microcapsules, the viscosity increase rate can be adjusted according to the ratio of the core material (core) and the wall material (shell). It was confirmed that it was possible.

Test Example 3: Analysis of flame retardancy according to flame retardant additives

In Examples 2-1 to 2-3 and Comparative Examples 1 to 3, the spinning solution of step (c) was prepared in a film shape by a hot air drying method, and then a flame retardant test was performed. The results are shown in Table 2 and FIG. 3 below.

The flame retardancy test was determined by burning time after exposure to a flame source two times by the method of UL94 the Standard for Safety of Flammability of Plastic Materials for Parts in Devices and Appliances testing.

sample Combustion time(s) 1 ^st(a) 2nd ^(b) Total Comparative Example 1 (AN-VDC) 5.93 - ^(c) 5.93 Comparative Example 2 (AN-VDC/Sb ₂ O ₃ ) 4.63 - ^(c) 4.63 Comparative Example 3 (AN-VDC/ZHS) 0 0 0 Example 2-1 (AN-VDC/AlP (20 wt%)/ZHS) 0 0 0 Example 2-2 (AN-VDC/AlP (100 wt%)/ZHS) 0 0 0 Example 2-3 (AN-VDC/AlP (200 wt%)/ZHS) 0.2 0 0.2

^(a) Combustion time in the first ignition, ^(b) Combustion time in the second ignition, ^(c) Complete combustion in the first ignition

Referring to Table 2, when antimony trioxide was added to the modacrylic copolymer, the combustion time did not show a significant difference compared to when not added. On the other hand, when zinc hydroxytinate and microencapsulated zinc hydroxytinate are added to the modacrylic copolymer, self-extinguishing properties are expressed immediately after ignition without burning, so that the flame retardant effect is much greater than when antimony trioxide is added. In addition, it was confirmed that the flame retardancy of the core material itself was sufficiently expressed even after microencapsulation of zinc hydroxytinate.

3, the AN-VDC polymer fiber of Comparative Example 1 was burned at the same time as the fire was ignited, and the embers were not extinguished for about 6 seconds and the embers remained. Comparative Example 2 in which antimony trioxide was added to the polymer fiber was also burned for about 5 seconds and black smoke was generated. On the other hand, Comparative Example 3, a polymer fiber to which zinc hydroxytinate was added, was immediately extinguished after fire ignition, and smoke generation was insufficient. Polymer fibers of Examples 2-1 to 2-3 to which zinc hydroxytinate microcapsules prepared using aluminum phosphate (AlP) as a wall material were introduced also had a short self-extinguishing time and insufficient smoke generation.

Test Example 4: Analysis of flame retardant properties of flame retardant fibers through heat release

In order to check the flame-retardant properties of the flame-retardant fibers prepared through wet spinning in Examples 2-1 to 2-3 and Comparative Examples 1 to 3, the amount of heat release was measured using a microcalorimeter and shown in Table 3 below.

Referring to Table 3 below, it was confirmed that the heat release capacities (HRC) of the flame-retardant fiber to which the microencapsulated zinc hydroxy tartarate was added was lower than that of the flame-retardant fiber to which antimony trioxide and zinc hydroxy tartarate were added. HRC represents the amount of heat released, and refers to the heat released by the material when it is burned. The combustion risk of the flame-retardant fiber to which AlP (200wt%)/ZHS, a microencapsulated zinc hydroxytinate, was added was relatively low.

Sample HRC(J/g·K) Comparative Example 1 (AN-VDC) 172 Comparative Example 2 (AN-VDC/Sb ₂ O ₃ ) 132 Comparative Example 3 (AN-VDC/ZHS) 149 Example 2-1 (AN-VDC/AlP (20 wt%)/ZHS) 125 Example 2-2 (AN-VDC/AlP (100 wt%)/ZHS) 114 Example 2-3 (AN-VDC/AlP (200 wt%)/ZHS) 106

Test example 5: Analysis of tensile strength of flame retardant fiber

In Examples 2-1 to 2-3 and Comparative Examples 1 and 3, the results of measuring the tensile strength and elongation of short fibers after making flame-retardant fibers through wet spinning are shown in Table 4 below. Referring to Table 4 below, compared to the physical properties of the modacrylic polymer without the addition of additives (Comparative Example 1), there was a slight decrease in physical properties when ZHS and AlP/ZHS were added. It is believed that the decrease in physical properties by 2~3% after microencapsulation is due to the increase in particle size due to microencapsulation. However, it seems to be sufficiently overcome by increasing the dispersibility and reducing the amount added through the application of a microencapsulated flame retardant afterwards.

Tensile strength (g/d) Elongation (%) Comparative Example 1 (AN-VDC) 3.21 27.50 Comparative Example 3 (AN-VDC/ZHS) 3.04 26.45 Example 2-1 (AN-VDC/AlP (20 wt%)/ZHS) 2.97 26.21 Example 2-2 (AN-VDC/AlP (100 wt%)/ZHS) 2.92 26.23 Example 2-3 (AN-VDC/AlP (200 wt%)/ZHS) 2.95 26.14

The scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention. do.

Claims (20)

A core containing an inorganic flame retardant additive; And
Including; a shell positioned on the core,
The inorganic flame retardant additive includes at least one selected from the group consisting of _{zinc stannate (ZnSnO 3} ) and zinc hydroxy stannate (ZnSn(OH) _{6 ),}
Flame-retardant microcapsules wherein the shell contains aluminum phosphate. delete delete delete delete The method of claim 1,
Flame-retardant microcapsules, characterized in that the flame-retardant microcapsule comprises 10 to 300 parts by weight of the shell based on 100 parts by weight of the core. Flame-retardant microcapsules of claim 1; And
Flame retardant copolymer;
Flame retardant fiber containing. The method of claim 7,
Flame-retardant fiber, characterized in that the flame-retardant copolymer comprises at least one selected from modacrylic-based, acrylic-based, vinyl chloride-based, olefin-based, polyester-based and aramid-based copolymers. The method of claim 8,
Flame-retardant fiber, characterized in that the flame-retardant copolymer comprises a modacrylic copolymer. The method of claim 9,
The modacrylic copolymer is selected from the group consisting of acrylonitrile (AN) 35 to 85 wt%; and vinyl chloride monomer (VCM) and vinylidene chloride monomer (VDCM) Flame-retardant fiber comprising a copolymer prepared by copolymerizing one or more 15 to 65 wt%. The method of claim 7,
The flame-retardant fiber is a flame-retardant fiber, characterized in that for use in any one selected from the group consisting of work clothes, protective clothes, automobile interior materials, interior interior materials, fire fighting clothes and social safety clothes. (a) preparing a dispersion containing an inorganic flame retardant additive; And
(b) adding and stirring a shell precursor to the dispersion to prepare a flame-retardant microcapsule including a core including the inorganic flame retardant additive and a shell positioned on the core; including,
The inorganic flame retardant additive includes at least one selected from the group consisting of _{zinc stannate (ZnSnO 3} ) and zinc hydroxy stannate (ZnSn(OH) _{6 ),}
The method for producing flame-retardant microcapsules wherein the shell precursor comprises aluminum hydroxide (Al(OH) ₃ ) and phosphoric acid (H ₃ PO _{4 ).} delete delete (a) dissolving the flame-retardant copolymer in a first solvent to prepare a solution containing the flame-retardant copolymer;
(b) preparing a dispersion by dispersing the flame-retardant microcapsules prepared according to the manufacturing method of claim 12 in a second solvent;
(c) preparing a spinning solution by mixing the solution containing the flame-retardant copolymer of step (a) and the dispersion of step (b); And
(D) spinning the spinning solution to prepare a flame-retardant fiber;
Method for producing a flame-retardant fiber containing. The method of claim 15,
In step (b),
The method of manufacturing a flame-retardant fiber, characterized in that the dispersion is carried out by a dispersion method comprising at least one selected from the group consisting of mechanical stirring, milling, and ultra sonication. The method of claim 15,
The method of manufacturing a flame-retardant fiber, characterized in that the flame-retardant microcapsules are in powder form. The method of claim 15,
The method of manufacturing a flame-retardant fiber, wherein the first solvent contains at least one selected from the group consisting of water, dimethyl sulfoxide (DMSO), acetone, and dimethylformamide (DMF). The method of claim 15,
The second solvent is a method of producing a flame-retardant fiber, characterized in that it contains at least one selected from the group consisting of dimethyl sulfoxide (DMSO), acetone, and dimethylformamide (DMF). The method of claim 15,
In the spinning solution, the concentration of the flame-retardant copolymer is 15 to 40 wt%, and the ratio (Wi/Wc) of the content (Wi) of the flame-retardant microcapsule to the content (Wc) of the flame-retardant copolymer is 0.1 to 15%. Method for producing a flame retardant fiber, characterized in that.

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