KR101985106B1 - Flameproof method of blended yarn goods having aramid fibers, and Blended yarn goods manufactured of the same - Google Patents

Abstract

The present invention relates to a method of flame-retarding a blended product comprising aramid fibers, and more specifically, a method of flame-proofing a blended product using aramid fibers without reducing the physical properties of the blended product, To provide a flame-retarded blended product.

Description

Flameproof method of blended yarn goods having aramid fibers, and blended yarn goods manufactured of the same}

The present invention relates to a flame-retarding process using a flame retarding processing technique of a blend product containing aramid fibers, and a flame-retarded blend product by this method.

Aromid and cellulose-based fibers such as cotton and rayon are one of flammable materials easily burned by flame or heat and have fire propagation ability in various applications such as clothing, bedding, and upholstery. Therefore, Various flame retarding regulations and laws have been enacted, and consumers are increasingly interested in and demanding flame retardant processing. In general, flame retarding treatment of fibers by post-processing imparts durable self-extinguishing properties by using organic phosphorus flame retardants or halogen flame retardants. However, in the case of halogen flame retardants, the toxicity of the flame retardant and the corrosive gas such as halogen acid during combustion may adversely affect the human body and the environment. Recently, studies on flame retardation using inorganic particles and organic phosphorus flame retardants have been actively carried out.

Organic phosphorus flame retardants do not generate a large amount of corrosive gas during the combustion process different from the halogen flame retardant because they function as a condensation phase mechanism that changes the pyrolysis mechanism to reduce the calorific value and increase the amount of residual carbide.

The THPC flame retardant does not react with cellulosic fibers alone and does not form a polymer. When treated with a substance having an active hydrogen such as amide or amine, the THPC flame retardant forms a water-insoluble polymer in the cellulosic fiber, It has the advantage of making aramid and cotton blend products which can give flame retardant effect. Studies have shown that sodium iodide monophosphate acts effectively as a catalyst when amide with an active hydrogen such as urea or cyanamide is treated with THPC flame retardant. Franklin et al. Have reported that THPC-Urea-sodium dihydrogenphosphate flame retardant Reported that the production of levoglucosan was significantly lower than that of aramid and cotton blend products treated with different flame retardants.

The process using THPC flame retardant is generally a method of imparting flame retardancy to aramid and cotton blend products by high temperature heat treatment of flame retardant and resin. However, in the high temperature heat treatment process, formaldehyde-based aramid and cotton blend product The crosslinking of the aramid and the cotton blend product, as well as the inherent properties of the aramid and the cotton blend product, causes problems such as the drop in strength and hardening of the tactile feeling. Thus, studies on the flame resistance treatment of aramid and cotton blend products using THPC flame retardant It is a difficult situation.

Korean Patent Publication No. 10-2013-0017757 (Feb. 20, 2013) Korean Patent Publication No. 10-2006-0002681 (2006.01.09)

The inventors of the present invention have found that, after a long period of research, the inventors of the present invention have found that a high-speed flame retarding treatment of blended knitted fabrics and / or fabrics produced by using aramid fibers significantly improves productivity, The treatment conditions, the optimum flame retardant concentration, and the like, thereby completing the present invention.

In order to solve the above problems, the present invention relates to a flame retarding process for an aramid fiber blend product, which comprises a first step of padding an aramid fiber blend product; A second step of drying the padded blended product; Curing the dried blend product using a high-speed ammonia curing device; A fourth step of oxidizing the cured mixed product; Washing the blended product with oxidation; And drying the washed washed blended product.

Another object of the present invention is to provide an aramid fiber-based blend product which is flame retarded by the above-mentioned method.

Unlike conventional aramid fiber blend products (knit and / or woven fabrics) which are repeatedly washed, the flame retardancy, strength and washing fastness are drastically lowered, the blended products produced by the flame retarding process of the present invention are excellent in flame retardancy, There is little or no deterioration in washing fastness.

1 is a side view showing an ammonia curing apparatus used in the present invention.
2 is a view showing an ammonia gas supply unit of the ammonia curing apparatus used in the present invention.
3 is a view showing a first ammonia gas injection unit of the ammonia curing apparatus used in the present invention.
4 is a view showing a second ammonia gas injection unit of the ammonia curing apparatus used in the present invention.
5 is a view showing a third ammonia gas injection unit of the ammonia curing apparatus used in the present invention.
6A and 6B are photographs of the inside of the ammonia curing apparatus used in the present invention.

The term " aramid fiber blend product " as used in the present invention means a fabric or fabric made by blending aramid fiber and other fibers.

Hereinafter, the present invention will be described in detail.

The flameproofing method of an aramid fiber blend product of the present invention comprises a first step of padding an aramid fiber blend product; A second step of drying the padded blended product; Curing the dried blend product using a high-speed ammonia curing device; A fourth step of oxidizing the cured mixed product; Washing the blended product with oxidation; And drying the washed washed blended product.

The aramid fiber blend product of step 1 includes a blend of aramid fiber and cellulose fiber, i.e., a knitted fabric or a fabric. The cellulose-based fibers may include at least one selected from cotton fibers, linen fibers, flax fibers, hemp fibers, and rayon fibers. In one preferred embodiment, the blend product is a blend fabric of recycled aramid and cotton, wherein the blend ratio of the material is from 65 to 75 wt%, the aramid fiber is from 25 to 35 wt%, the density is from 110 to 120 T, the weight is 180 A blend fabric of ~ 200 g / m 2 and number of slopes of 18 ~ 22 's / weft of 18 ~ 24' s can be used.

The padding treatment is performed by immersing the aramid fiber-based blend product in a padding solution at 10 to 30 DEG C for 10 seconds to 1 minute, at a pressure of 2.5 to 3.5 kgf and at a rate of 1.5 to 2.5 m / A padding mangling treatment at a pressure of 2.8 to 3.2 kgf and a speed of 1.8 to 2.3 m / min, and then squeezing treatment.

The padding solution contains 30 to 45% by weight of a flame retardant containing THPC (Tetrakis Hydroxymethyl Phoshonium Chloride) -urea condensate, 3.0 to 4.5% by weight of a glyoxal resin, 0.05 to 0.5% by weight of a penetrant, Water, preferably 35 to 45% by weight of the flame retardant, 3.5 to 4.5% by weight of glyoxal resin, 0.05 to 0.35% by weight of a penetrant, and the balance water.

Among the padding liquid components, the flame retardant is a flame retardant containing a THPC-urea condensate, and may be a conventional flame retardant used in the art, preferably (HOCH ₂ ) ₃ PClCH ₂ NHCONHCH ₂ PCl (CH ₂ OH) ₃ . The flame retardant may be one having an equivalence ratio of THPC and urea of 1.8 to 2.2: 1, a specific gravity of 1. 28 to 1.30 (25 ° C) and a phosphorus content of 14 to 15 wt% per solid solid.

If the content of the flame retardant in the total weight of the padding liquid is less than 30% by weight, it may be difficult to secure long-term flame retardancy by repeated washing. Even if the flame retardant content exceeds 45% by weight, the flame retardant effect is not increased. It may be used within the above range.

Among the padding liquid components, the glyoxal resin functions as a crosslinking agent for cross-linking the flame retardant to the fiber fabric blended with the aramid fiber and the cotton fabric, and the THPC (Tetrakis Hydroxymethyl Phoshonium Chloride) -urea condensate If the total weight of the padding liquid is less than 3.0 weight% of the resin, crosslinking with the flame retardant does not occur well on the blend fabric composed of the aramid / cotton and the flame retardancy may not be ensured. If the blend fabric is used in excess of 4.5 weight% There is a problem that the tear strength is lowered due to the glyoxylation, the roughness of the blended product is increased, the flexibility is lowered, and the long time fastness due to repeated washing is rather lowered.

Among the padding liquid components, the penetrating agent serves to facilitate the swelling of the cellulosic water-based fiber, and may be a general one used in the art, preferably Triton X-100, 10Be At least one selected from the following caustic soda and monohydric alcohol may be used, and more preferably at least one selected from Triton X-100 and caustic soda having a concentration of 10Be or less may be used. If the content of the penetrating agent is less than 0.05% by weight of the total weight of the padding liquid, swelling may not occur easily and there may be a problem. If the content of the padding agent exceeds 0.5% by weight, swelling may occur. It is good.

When the pH of the padding liquid is less than 5.2, the cellulose fibers are mixed with the flame retardant, the penetrating agent and the water, and then the pH of the padding liquid is adjusted to 5.2 to 6, preferably to 5.4 to 5.8. There may be a problem of brittleness, and if the pH exceeds 6, there may be a problem that the flame retarding effect is lowered. As the alkali solution used for adjusting the pH, it is preferable to use one kind of alkali solution selected from an aqueous solution of sodium hydroxide and KOH.

Next, the drying in the second step may be performed by tentering at 130 to 150 ° C for 60 to 120 seconds, preferably at 132 to 148 ° C for 70 to 100 seconds. If the temperature is less than 140 ° C, the flame retardant may not be sufficiently dried to increase the moisture content, or the drying time may become too long. If the temperature exceeds 150 ° C, the flame retardant may completely dry, There may be a problem that it is too low, so it is preferable to carry out drying by tentering under the above temperature. The blended product obtained by performing the drying in the two steps may be 15 to 25%, preferably 22 to 25%, when the wet pick up (%) is measured according to the following formula (1).

[Equation 1]

(Wet pick up,%) = (Weight of blend before drying - Weight of blend after drying) Weight of blend after drying × 100 (%)

Next, in step 3, curing is performed by spraying ammonia gas onto the dried blend product, and the amount of the flame retardant is preferably 1.5 to 2.2 moles per mole of phosphorus (P) Is cured by adjusting the flow rate of the vaporized ammonia gas so that NH 3 can be crosslinked at a molar ratio of 1.95 to 2.05. To this end, liquid ammonia is vaporized by using an electric heating type forced vaporizer, and is passed through a flow meter capable of precisely controlling the discharge amount of the unit time gas, and then introduced again. In order to cause the crosslinking reaction of the flame retardant and NH3 in the chamber to take place within a short time of 1 to 2 seconds, the ammonia gas is injected into the blend product in one to three steps using a specific ammonia curing apparatus can do.

The ammonia curing apparatus used in the present invention will be described in detail as follows.

FIG. 1 is a side view showing an ammonia curing apparatus for knitting and fabric according to the present invention, FIG. 2 is a view showing an ammonia gas supplying unit of an ammonia curing apparatus for knitting and fabric according to the present invention, and FIG. FIG. 4 is a view showing a second ammonia gas jetting unit of the ammonia curing apparatus for knitted fabrics and fabrics according to the present invention, and FIG. 5 is a view showing the second ammonia gas jetting unit of the ammonia curing apparatus for knitted fabrics FIG. 2 is a view showing a second ammonia gas injection unit of an ammonia curing apparatus for knitted fabrics and fabrics according to the present invention.

The ammonia curing apparatus largely comprises a chamber 110; A blend product inlet 120; An ammonia gas supply unit 130; A first ammonia gas injecting unit 140; A mixed product transferring unit 150; A second ammonia gas injecting unit 160; A mixed product discharge unit 170; And a third ammonia gas injecting unit 180, and the chamber 110 is an enclosure.

The mixed product inlet 120 is provided at one side of the chamber 110 to allow the mixed product to flow into the mixed product inlet 120. The blend product introduced into the blend product inflow part 120 is a blend product obtained by padding and drying the flame retardant.

The ammonia gas supply unit 130 is provided outside the chamber 110 and supplies ammonia gas into the chamber 110.

2, the ammonia gas supply unit 130 includes a liquid ammonia supply tank 131, a vaporizer 132, and an ammonia gas storage tank 133 (not shown) to supply ammonia gas into the chamber 110. [ And an ammonia gas supply pipe 134.

The liquid ammonia supply tank 131 serves to supply liquid ammonia, which is accommodated in the liquid ammonia.

The vaporizer 132 serves to vaporize the liquid ammonia supplied from the liquid ammonia supply tank 131. The vaporizer 132 heats the liquid ammonia by a hot wire and forcibly vaporizes the liquid ammonia.

The present invention can increase the fixing force of the flame retardant by supplying the ammonia gas by using the forced vaporization method in which the amount of vaporization is increased as compared with the supply of ammonia gas by the natural vaporization method.

The ammonia gas storage tank 133 serves to store the ammonia gas vaporized by the vaporizer 132.

The ammonia gas supply pipe 134 serves to supply ammonia gas from the ammonia gas storage tank 133.

The first ammonia gas injecting unit 140 is provided at one side of the interior of the chamber 110 adjacent to the mixed product introducing unit 120 so that the lower part of the mixed product introduced by the mixed product introducing unit 120 And the ammonia gas supplied from the ammonia gas supply unit 130 is injected into the mixed gas so as to first cure the mixed product.

The first ammonia gas injecting unit 140 includes an ammonia gas inlet pipe 141 and an injection nozzle 142.

The ammonia gas inlet pipe 141 is connected to the ammonia gas inlet pipe 134 through the ammonia gas supply pipe 134 and supplies ammonia gas supplied from the ammonia gas supply pipe 134 to the interior of the chamber 110, Respectively.

The injection nozzle 142 is spaced apart from the ammonia gas inlet pipe 141 at a predetermined interval in the width direction of the mixed product and the ammonia gas introduced from the ammonia gas inlet pipe 141 flows into the lower portion of the mixed product And is made up of a plurality of nozzles.

As described above, the present invention is advantageous in that the ammonia gas is injected directly to the blend product to increase the fixing force of the ammonia adsorbed on the blend product, thereby improving the flame proofing property of the blend product.

The mixed product transferring unit 150 serves to transfer the first cured mixed product from the first ammonia gas injecting unit 140 by a plurality of upper and lower rollers 151 and 152 arranged in a zigzag fashion.

The second ammonia gas injecting unit 160 injects the ammonia gas supplied from the ammonia gas supplying unit 130 into the lower part of the mixed product located below the lower roller 152 of the mixed product conveying unit 150, Thereby curing the blend product secondarily.

The second ammonia gas injecting unit 160 has the same structure as the first ammonia gas injecting unit 140 and includes an ammonia gas inlet pipe 161 and an injection nozzle 162.

As described above, according to the present invention, ammonia is adsorbed on the mixed product by the second ammonia gas injecting unit 160 to increase the fixing force of the flame retardant to improve the flame resistance of the mixed product .

The mixed product discharging unit 170 discharges the secondarily cured mixed product from the second ammonia gas injecting unit 160 to the outside of the other side of the chamber 110.

The third ammonia gas injecting unit 180 is disposed below the mixed product discharging unit 170 and is supplied from the ammonia gas supplying unit 130 to the lower part of the mixed product discharged by the mixed product discharging unit 170 Ammonia gas is sprayed to perform the third-order curing of the blended product.

The third ammonia gas injecting unit 180 has the same structure as the first ammonia gas injecting unit 140 and the second ammonia gas injecting unit 160 and includes an ammonia gas inlet pipe 181, 182).

As described above, according to the present invention, the second cured mixed product is adsorbed by the third ammonia gas injecting unit 180 to the mixed product, thereby increasing the fixing force of the flame retardant to further improve the flame resistance of the mixed product .

In addition, it is preferable that the present invention is caused to precipitate in liquid ammonia in order to impart soft tactile feeling and shine resistance to the mixed product. At this time, it is preferable to provide the liquid ammonia bath 191 and the bass lifting unit 192 in order to give the mixed product a soft touch and a shine.

The liquid ammonia bath 191 is disposed between the first ammonia gas injecting unit 140 and the mixed product conveying unit 150 and is mixed with the first ammonia gas injected by the first ammonia gas injecting unit 140, To be immersed by liquid ammonia.

In the case of imparting a soft touch and a shine property to the blended product, the blended product is immersed in the liquid ammonia bath 191, and the liquid ammonia bath 191 is not passed in order to impart only flame resistance to the blended product.

To this end, the bass lifting portion 192 causes the primary cured product to be separated or immersed from the liquid ammonia contained in the liquid ammonia bath 191 by the first ammonia gas jetting portion 140.

At this time, when the liquid ammonia bath 191 is lifted up by the bass lifting part 192 to give the mixed product with soft touch and shine property, when the mixed product passes through the liquid ammonia bath 191, The ammonia is adsorbed to the mixed product by the second ammonia gas injecting unit 160 while being transferred by the mixed product transferring unit 150 in the wet state.

When ammonia is adsorbed to the mixed product by the second ammonia gas injecting unit 160 in a wet state, the mixed product may not maintain the flatness because the mixed product is not dried. In order to maintain the flatness of the blended product, it is preferable to provide the pressing portion 200 for pressing both surfaces of the blended product.

The pressing part 200 presses both surfaces of the secondarily cured mixed product from the second ammonia gas injecting part 160 to keep the mixed product in a flat state.

The pressing portion 200 for pressing both sides of the secondarily cured mixed product is provided with the pressing drum 201, the pressing drum rotating portion 204, the felt 202 and the felt rotating portion 203 do.

The pressing drum 201 is rotated once by one side of the second cured mixed product from the second ammonia gas injecting unit 160 so as to contact with the outer periphery of the second ammonia gas injecting unit 160 and the second ammonia gas injecting unit 160 to the mixed product discharging unit 170. The mixed product discharging unit 170 may be configured to transfer the mixed product to the mixed product discharge unit 170. [

The pressing drum rotating unit 204 serves to rotate the pressing drum 201.

The pressing drum rotating unit 204 includes a driving pulley 204a provided on a shaft of a driving motor and a driven pulley 204c provided on a rotating shaft 204b provided at the center of the pressing drum 201, And a transmission belt 204d that connects the drive pulley 204a and the driven pulley 204c to transmit power.

The felt 202 is installed so as to be in contact with the outer circumference of the pressure drum 201 and is provided with the other side of the secondarily cured mixed product from the second ammonia gas spraying unit 160 with the pressing drum 201 Pressurized and made into an infinite orbit.

The felt rotation unit 203 serves to rotate the felt 202 in an endless track. The felt rotating unit 203 is provided with a felt rotating drum 203a which rotates the felt 202 while rotating the pressing drum 201 so that the felt 202 is rotated.

In addition, it is preferable to pressurize the mixed product while heating the mixed product to improve the flatness of the mixed product while the mixed product passes through the pressing part 200.

To this end, it is preferable that steam is supplied into the pressure drum 201 to pressurize the secondarily cured mixed product from the second ammonia gas jetting unit 160 by the pressing drum 201 .

An ammonia gas recovery pipe connected to the chamber 110 to recover ammonia gas to recover the ammonia gas supplied to the inside of the chamber 110; And a liquid ammonia recovery unit comprising a condenser and a condenser for condensing and recovering the liquid ammonia to be stored in the liquid ammonia supply tank 131.

When the ammonia gas is supplied from the ammonia gas supply part to the first ammonia gas injection part, the second ammonia gas injection part and the third ammonia gas injection part, the supply pressure may be 0.90 to 1.20 MPa, preferably 0.95 to 1.10 MPa. If the supply pressure is not appropriate, there may be a problem that THPC-UREA does not cross-link with NH ₃ , and if it exceeds 1.20 MPa, excessive ammonia gas may cause a problem in processing safety.

When the ammonia is injected from the first ammonia gas injecting part, the second ammonia gas injecting part and the third ammonia gas injecting part to the mixed product, the injection pressure is preferably 0.5 to 1.0 MPa, preferably 0.65 To 0.75 MPa. At this time, if the injection pressure is less than 0.65 Mpa, ammonia gas is not appropriately injected into the interior of the mixed product, and crosslinking between THPC-UREA and NH ₃ does not occur, There is a problem that the injection pressure is unnecessarily high.

Next, the oxidation treatment in four steps can be carried out by immersing the cured mixture in an aqueous H ₂ O ₂ solution having a concentration of 5 vol% or less, preferably 2 to 4 vol%, for 30 to 40 seconds . At this time, if the concentration of H ₂ O ₂ H ₂ O ₂ aqueous solution exceeds 5% by volume up excessively the oxidation may be an issue, such as the brittleness of the fabric takes place.

Next, in the step (5), the oxidation-treated mixed product is subjected to primary washing with hot water at 85 to 95 ° C for 1 to 2 minutes, followed by sufficient secondary washing with cold water to remove unreacted THPC-Urea p) and impurities such as formaldehyde and hexamethylene tetramine produced by the addition reaction are completely removed.

Next, in the step 6, the washed mixed product was heated at 160-170 ° C under hot air at 1,500 to 2,000 rpm and 1 to 30 m / min in a tenter machine (Tenter, Iseong Machinery Industry Co., Ltd.) Min, and drying can be carried out such that the over feed of the dried blended product is 11.5 to 12.5%.

According to the aramid fiber blend product of the present invention produced by the above-described flame-retarding process, the tensile strength can be increased by 8 to 70% as compared with the aramid fiber blend product not subjected to curing under tensile strength measurement according to the KS K 0521 standard , The tensile strength may be increased by 20 to 70%, more preferably by 25 to 68.5%, as compared with the aramid fiber-based blended product which is not cured.

Also, the aramid fiber blend product may have a limiting oxygen index (LOI) of 24 to 30, preferably LOI of 25.5 to 29 when measured according to ASTM D2863-91.

The aramid fiber blend product may have a wash fastness of 4 to 5 when measured according to the KS K ISO 1005-C06 standard.

Hereinafter, the present invention will be described in more detail based on examples. However, the scope of the present invention should not be construed as being limited by the following examples.

[Example]

Preparation Example 1: Preparation of padding liquid

30% by weight of a flame retardant containing THPC-urea condensate having the specifications shown in Table 1, 3.0% by weight of glyoxal resin, 0.1% by weight of a penetrating agent (Triton X-100) Solution.

Next, an aqueous sodium hydroxide solution was added to the mixed solution to adjust the pH to 5.5, thereby preparing a padding solution.

Flame retardant specification - Tetrakis Hydroxymethyl Phosphonium Chloride-Urea Precondensate (THPC: urea = 2: 1 molar ratio)
- Molecular structure: (HOCH2) 3PClCH2NHCONHCH2PCl (CH2OH) 3
- Specific Gravity: 1.28 ~ 1.30 (25 ℃)
- Active Ingredients: 68%
- Phosphorous Values: 10% P
- Net solid content per minute: 14.7% (10.0% x 100/68)

Preparation Example  2 to 4 and Comparative Manufacturing Example  1 to 8: Padded  Produce

A padding solution was prepared in the same manner as in Preparation Example 1, except that the content of the flame retardant was varied as shown in Table 2 below.

division Flame retardant content Glyoxal resin Penetration agent pH pH Preparation Example 1 30 wt% 3.0 wt% 0.1 wt% Remaining balance 5.5 Preparation Example 2 35 wt% 3.5 wt% 0.1 wt% Remaining balance 5.5 Preparation Example 3 40 wt% 4.0 wt% 0.1 wt% Remaining balance 5.5 Preparation Example 4 45 wt% 4.5 wt% 0.1 wt% Remaining balance 5.5 Comparative Preparation Example 1 27 wt% 2.7 wt% 0.1 wt% Remaining balance 5.5 Comparative Preparation Example 2 48 wt% 3.5 wt% 0.1 wt% Remaining balance 5.5 Comparative Preparation Example 3 35 wt% 3.5 wt% 0.1 wt% Remaining balance 6.2 Comparative Preparation Example 4 35 wt% 3.5 wt% 0.1 wt% Remaining balance 5.0 Comparative Preparation Example 5 35 wt% 3.5 wt% - Remaining balance 5.5 Comparative Preparation Example 6 35 wt% 3.5 wt% 0.8 wt% Remaining balance 5.5 Comparative Preparation Example 7 35 wt% 2.5 wt% 0.1 wt% Remaining balance 5.5 Comparative Preparation Example 8 35 wt% 5.0 wt% 0.1 wt% Remaining balance 5.5

Example 1: Manufacture of Flame Retarded Aramid Fiber Blended Fabrics

A blend fabric of 70% by weight of mixed cotton, 30% by weight of aramid fiber, density of 115T, weight of 190 g / m 2, number of warp 20s / weft 20 'was prepared as a recycled aramid and cotton blend fabric.

Next, the blend fabric was immersed for one minute in a padding solution at 22 to 23 DEG C prepared in Preparation Example 1, and then passed through a padding mangle at a pressure of 3 kgf and a speed of 2 m / min to constantly squeeze (Squeezing).

Next, the THPC-urea having different concentrations penetrated into the outer portion of the micelle filler is migrated by heat and can be hardened at the surface of the blend fabric. Therefore, the blended fabric having padding treatment can be heat- And dried at 145 ° C. for 90 seconds with a Tenter (Iseong Machinery Industry Co., Korea). At this time, the wet pick up contents measured according to the formula (1) of the dried blend fabric using the moisture meter were 15%.

[Equation 1]

(Wet pick up,%) = (Weight of blend before drying - Weight of blend after drying) Weight of blend after drying × 100 (%)

Next, curing was performed by spraying primary, secondary and tertiary ammonia gases onto the blend fabric using a high-speed ammonia curing device as shown in the schematic side view in Fig. At this time, when the ammonia gas was supplied from the ammonia gas supply part to the first ammonia gas injection part, the second ammonia gas injection part and the third ammonia gas injection part, the supply pressure was 0.97 MPa. When the ammonia was injected from the first ammonia gas injecting portion, the second ammonia gas injecting portion and the third ammonia gas injecting portion into the mixed product, the injection pressure was 1 MPa.

2 schematically shows the ammonia gas supply portion of the high-speed ammonia curing device. A schematic diagram of the first ammonia gas injection portion, the second ammonia gas injection portion and the third ammonia gas injection portion of the curing device is shown in FIGS. 5, respectively. 6A and 6B show a photograph of the gas injection portion in which the actual ammonia gas is injected and a photograph of the inside of the curing device.

Next, the high-speed cured mixed product was immersed in an aqueous 3% H ₂ O ₂ solution for 34 to 35 seconds to carry out the oxidation process.

Next, the oxidation-treated blend fabric was put in a hot water of 90 for 1 minute and 30 seconds, washed thoroughly with cold water to remove unreacted THPC-urea (p) remaining on the surface and formaldehyde And impurities such as hexamethylene tetramine were completely removed.

Next, the washed blend fabric was dried at 167 to 168 with a hot air of 1,800 rpm and 14 to 15 m / min in a tenter machine (Tenter, Iseong Machinery Co., Korea) in which heat could be released, over feed of 12% to obtain a final flame retarded blended fabric.

Examples 2 to 3 and Comparative Examples 1 to 2

The flame-retarded blended fabric was produced in the same manner as in Example 1 except that the moisture content of the blend fabrics was dried to a wet pick-up rate as shown in Table 3 below after the padding treatment and the drying process, A high-speed curing process, an oxidation process, a washing process and a drying process were carried out in the same manner as in Example 1.

Experimental Example 1: Measurement of the limit oxygen index

The limiting oxygen index of each flame retarded fabric prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was measured and the results are shown in Table 3 below.

At this time, the limiting oxygen index was measured according to ASTM D2863-91 using a limiting oxygen index tester (SUGA Co., Japan).

division % (Wet pick up contents) Limit Oxygen Index (LOI) Example 1 15% 26.1 Example 2 20% 26.7 Example 3 25% 26.8 Comparative Example 1 12% 21.1 Comparative Example 2 27% 27.0

As for the limit oxygen index of Table 3, there was a problem that the LOI value was significantly lowered in Comparative Example 1, compared with Example 1, and in Comparative Example 2, there was no significant difference as compared with Example 3 . Therefore, it was confirmed that the moisture content was about 15 to 25%.

Examples 4 to 8 and Comparative Examples 3 to 11

The padding process was carried out by varying the padding solution as shown in Table 4, and then the padded blend fabric was dried at a water content of 25% as in Example 3, Using this, a high-speed curing process, an oxidation process, a washing process and a drying process were carried out in the same manner as in Example 1 to prepare flame retarded blended fabrics.

division Padding liquid Example 1 Preparation Example 1 Example 4 Preparation Example 2 Example 5 Preparation Example 3 Example 6 Preparation Example 4 Comparative Example 3 not used Comparative Example 4 Comparative Preparation Example 1 Comparative Example 5 Comparative Preparation Example 2 Comparative Example 6 Comparative Preparation Example 3 Comparative Example 7 Comparative Preparation Example 4 Comparative Example 8 Comparative Preparation Example 5 Comparative Example 9 Comparative Preparation Example 6 Comparative Example 10 Comparative Preparation Example 7 Comparative Example 11 Comparative Preparation Example 8

Experimental Example 2: Wash fastness measurement

The washing fastness of the blend fabric of each of Examples and Comparative Examples in Table 4 was measured and the results are shown in Table 5 below.

At this time, the washing fastness was measured in accordance with the KS K ISO 105-C06 standard using a washing tester (Launder Ometer Co., Korea).

division Flame retardant in padding solution
content(%) 10 times washing
(washing cycles) 20 times washing 50 times washing Comparative Example 3 0 4-5 4-5 4-5 Example 1 30 4-5 4-5 4-5 Example 4 35 4-5 4-5 4-5 Example 5 40 4-5 4-5 4-5 Example 6 45 4-5 4-5 4-5 Comparative Example 4 27 4-5 4-5 4-5 Comparative Example 5 48 4-5 4-5 4-5 Comparative Example 6 35 4 4 4 Comparative Example 7 35 4 4 4 Comparative Example 8 35 3-4 3-4 3-4 Comparative Example 9 35 3-4 3-4 3-4 Comparative Example 10 35 4-5 4-5 4-5 Comparative Example 11 35 4-5 4-5 3-4

The washing fastness of the padding solution of Comparative Example 3, Example 1, Examples 4 to 6, and Comparative Examples 3 to 5 was excellent regardless of the flame retardant content in the padding solution, There was no phenomenon. This is because the blend fabrics treated with the THPC-urea flame retardant have no deformation even after the water is absorbed and no shrinkage occurs even after washing, because the inherent characteristics of the aramid and cotton blend fabrics are preserved even when the ammonia gas curing process is performed. The THPC-urea flame retarded blend fabrics treated with ammonia gas curing process were crosslinked using ammonia gas as a catalyst to form an inactive polymer, while the insoluble polymer in the blend fabric was formed inside the blend fabric. It is believed that the durability was formed.

In the case of Comparative Example 6 using a padding solution having a pH of more than 6, in Comparative Example 7 using a padding solution having a lowered fastness and a pH of less than 5.2, the cellulose fibers in the blend fabric were embrittled to lower the fastness Results. In the case of Comparative Example 8 using a padding liquid not containing a penetrating agent, the result showed low fastness. In Comparative Example 9 using a padding liquid having a penetrating agent content exceeding 0.5% by weight, the fastness was low . Also, in Comparative Example 11 using 4.5% by weight or more of the glyoxal resin, there was a problem in that the washing fastness was poor after washing 50 times.

Experimental Example 3: Measurement of flame retardancy and long term flame retardance for washing

The long-term flame retardancy was measured according to the number of washes of the blend fabrics of Examples 1, 4 to 6 and Comparative Examples 4 to 6 and Comparative Examples 8 to 11, and the results are shown in Tables 6 to 7 below. Table 6 shows the results of 10 times of washing, Table 7 shows 20 times of washing, and Table 8 shows results of 50 times of washing.

In this case, the flammability of the flame retardant was measured by a flame resistance tester (United State Testing Co., USA) according to the KS K 0585 standard.

division
(10 times washing) In padding solution
Flame retardant content (%) Brine Time
(Afterflame time, sec) Time remaining
(Afterglow time, sec) Carbonization distance
(Char Length, cm) Comparative Example 3 0 36 45 30 Example 1 30 16 3 26 Example 4 35 6 0 18 Example 5 40 5 0 12 Example 6 45 0 0 9 Comparative Example 4 27 20 4 28 Comparative Example 5 48 5 0 12 Comparative Example 6 35 10 3 25 Comparative Example 8 35 27 36 25 Comparative Example 9 35 5 0 18 Comparative Example 10 35 22 31 26 Comparative Example 11 35 6 0 17

division
(20 times washing) In padding solution
Flame retardant content (%) Brine Time
(Afterflame time, sec) Time remaining
(Afterglow time, sec) Carbonization distance
(Char Length, cm) Comparative Example 3 0 35 28 30 Example 1 30 17 0 27 Example 4 35 One 0 10 Example 5 40 One 0 8 Example 6 45 45 0 7 Comparative Example 4 27 20 4 28 Comparative Example 5 48 5 0 12 Comparative Example 6 35 13 5 26 Comparative Example 8 35 29 39 27 Comparative Example 9 35 12 3 26 Comparative Example 10 35 24 32 26 Comparative Example 11 35 7 2 16

division
(50 times washing) In padding solution
Flame retardant content (%) Brine Time
(Afterflame time, sec) Time remaining
(Afterglow time, sec) Carbonization distance
(Char Length, cm) Comparative Example 3 0 35 35 30 Example 1 30 21 0 30 Example 4 35 5 0 15 Example 5 40 2 0 10 Example 6 45 0 0 8 Comparative Example 4 27 20 4 28 Comparative Example 5 48 5 0 12 Comparative Example 6 35 15 8 28 Comparative Example 8 35 32 41 28 Comparative Example 9 35 4 0 15 Comparative Example 10 35 26 34 28 Comparative Example 11 35 16 7 19

As shown in Tables 6 to 8, in Examples 1 and 4 to 8, overall excellent flame retardancy and long term flame retardancy were secured. In particular, when Example 1 and Examples 4 to 6 are compared with each other, the flame retardancy and long term flame retardancy are greatly improved when the flame retardant content in the padding solution is 35% by weight or more. This is because the aramid and cotton blend fabrics treated with THPC-urea flame retardant by ammonia gas curing process are crosslinked with ammonia gas catalyst to form an inactive polymer while the active polymer forms an inactive polymer, and the aramid and cotton blend fabric has high durability The flame retardancy of the aramid and cotton blend fabrics treated with THPC-urea flame retardant after 10, 20, and 50 repetitions of washing, and the burning time such as residual time, carbonization distance, etc., greatly affect the blend fabrics It is judged that it is not insufficient.

However, in Comparative Example 4, the flame retardancy was greatly reduced compared with Example 1, and in Comparative Example 5, the flame retardancy improvement effect was not substantially different from Example 5.

In the case of Comparative Example 6 using the padding solution having a pH exceeding 6, the padding treatment was not performed well, and the flame retardancy was deteriorated as the number of times of washing increased. Comparative Example 8 using a padding liquid containing no penetrating agent showed very low flame retardancy and long term flame retardancy as in Comparative Example 3. In Comparative Example 9 using a padding liquid having a penetrating agent content exceeding 0.5 wt% The results are shown to be similar to those of the fourth embodiment.

In Comparative Example 10 using less than 3.0% by weight of glyoxal resin, the flame retardancy was not good. Comparative Example 11, in which glyoxal resin was used in an amount exceeding 4.5% by weight, There has been a problem that the long-term flame-retarding stability sharply decreases with an increase in the number of times.

Experimental Example 4: Measurement of limit oxygen index and color difference measurement

(1) Measurement of limit oxygen index

The marginal oxygen index of the flame-retarded blend fabrics washed repeatedly 50 times in the same manner as in Example 2 was measured, and the results are shown in Table 9 below.

At this time, the limiting oxygen index was measured according to ASTM D2863-91 using a limiting oxygen index tester (SUGA Co., Japan).

(2) Color difference measurement

The color difference of the flame-retarded blended fabrics washed repeatedly 50 times in the same manner as in Example 2 was measured, and the results are shown in Table 9 below. The color difference was measured on the basis of Comparative Example 3.

The color difference (ΔE) of each flame retardant treatment concentration was measured using a color difference meter (Macbeth Co., USA) based on the D65 light source and 10 field of view conditions.

division
(50 times washing) Flame retardant in padding solution
content(%) Marginal oxygen index
(LOI) Color difference
(E) Comparative Example 3 0 18.4 - Example 1 30 24.3 0.93 Example 4 35 26.0 0.97 Example 5 40 26.6 0.97 Example 6 45 28.1 0.93 Comparative Example 4 27 19.7 0.94 Comparative Example 5 48 28.2 1.03 Comparative Example 10 35 21.8 0.92 Comparative Example 11 35 26.3 1.08

In the measurement results of Table 9, in the case of Examples 1 and 4 to 6, the LOI value was 24 or more and the color difference value was lower than 1.0.

On the other hand, in the case of Comparative Example 4, the LOI value was less than 20, and in the case of Comparative Example 10, the LOI value was significantly low as compared with Example 4. In the case of Comparative Example 5 and Comparative Example 11, there was no difference in LOI value as compared with Example 6, but the color difference value exceeded 1.0.

Experimental Example 5: Measurement of tensile strength

The tensile strength of the flame-retarded blended fabric was measured 50 times in the same manner as in Example 2, and the results are shown in Table 10 below.

At this time, the tensile strength was measured in accordance with the KS K 0521 standard.

division
(50 times washing) Flame retardant in padding solution
content(%) The tensile strength
(Mpa) The tensile strength
Growth rate (%) ¹⁾ Comparative Example 3 0 473.5 0% Example 1 30 512.8 8.29% Example 4 35 593.5 25.33% Example 5 40 675.8 42.72% Example 6 45 796.6 68.22% Comparative Example 4 27 495.7 4.68% Comparative Example 5 48 797.5 68.41% 1) Tensile Strength Growth Rate (%) The increase rate was calculated based on the tensile strength value of Comparative Example 3.

The results of the tensile strength measurement of Table 10 show that the tensile strength of Examples 1 and 4 to 6 is greatly improved as compared with Comparative Example 3 in which no flame retardant is used. However, in Comparative Example 4, the tensile strength increase rate was very low as compared with Example 1. In Comparative Example 5, the tensile strength increase rate was very low as compared with Example 6.

In general, when flame-retarding fabrics are flame-retarded, conventional flame retardant treatment methods cause a decrease in the strength of the blend fabrics. On the contrary, when the blend fabrics are flame retarded by the method proposed by the present invention, THPC-urea flame retardants Uniform penetration to the center, and high durability and flame retardancy are uniformly formed in the fibril layer in the aramid and cotton blend fabric, the tensile strength of the aramid and cotton blend fabric does not decrease due to the THPC-urea flame retardant treatment, . In addition, the tensile strength of the blend fabrics was improved with each increase of THPC-urea flame retardant, so that aramid and cotton blend fabrics treated with THPC-urea flame retardant were crosslinked with ammonia gas catalyst, It is considered that the tensile strength increases when the content of the flame retardant increases as the insoluble polymer of the film is formed in the blend fabric.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

110: chamber 120: mixing product inlet
130: ammonia gas supply unit 131: liquid ammonia supply tank
132: vaporizer 133: ammonia gas storage tank
134: ammonia gas supply pipe 140: first ammonia gas discharge part
141, 161, 181: Ammonia gas inlet pipe
142, 162, 182: Injection nozzle 150: Mixed product conveyance part
151, 152: Upper and lower roller 160: Second ammonia gas injection part
170: Mixed-product discharging part 180: Third ammonia gas discharging part
191: liquid ammonia bass 192:
200: pressing portion 201: pressing drum
202: felt 203: felt rotating part

Claims (11)

delete delete delete delete delete delete delete delete A padding method in which a blended product of an aramid fiber and a cellulose-based fiber is dipped in a padding solution and is saddled by padding mangling at a speed of 2.8 to 3.2 kgf and a speed of 1.8 to 2.3 m / One step to process;
A second step of tentering the padded mixed product at 132 to 148 DEG C for 70 to 100 seconds to perform drying;
Curing the dry blended product having a wet pick up content of 15 to 25% by using a high-speed ammonia curing apparatus;
A fourth step of immersing the cured mixture in an aqueous solution of H ₂ O _{2 at a} concentration of 5 vol% or less for 30 to 40 seconds to oxidize the mixture;
A fifth step of subjecting the mixed product obtained by oxidizing the blended product subjected to the oxidation treatment to primary washing with hot water at 85 to 95 캜 for 1 to 2 minutes and then secondary washing with cold water; And
The washed blended product is dried at 165-180 ° C at a speed of 1,500-2,000 rpm and at a rate of 1 to 30 m / min, and dried so that the over feed of the dried blended product is 11.5 to 12.5% Comprising:
The blended product is a knitted or woven fabric,
The padding solution comprises 35 to 45% by weight of a flame retardant comprising THPC (Tetrakis Hydroxymethyl Phoshonium Chloride) -urea condensate, 3.5 to 4.5% by weight of glyoxal resin, 0.05 to 0.35% by weight of a penetrant, , The padding solution was adjusted to have a pH of 5.2 to 6,
Wherein the flame retardant has a THPC and urea equivalent ratio of 1.8 to 2.2: 1, a specific gravity of 1.28 to 1.30 (25 ° C), a phosphorus content (P) of 14 to 15%
The curing process may include curing by spraying ammonia gas onto a dried blend product using an ammonia curing device,
The ammonia curing apparatus comprises a chamber;
A blend product inflow portion for allowing the blended product to flow into the chamber;
An ammonia gas supply unit for supplying ammonia gas;
And a first curing unit for curing the mixed product by spraying the ammonia gas supplied from the ammonia gas supply unit to a lower portion of the mixed product introduced by the mixed product inflow unit, which is provided at one side of the chamber adjacent to the mixed product inflow unit A first ammonia gas injection part;
A mixed product conveying unit for conveying the first cured mixed product from the first ammonia gas spraying unit by a plurality of upper and lower rollers arranged vertically and zigzag;
A second ammonia gas spraying unit positioned below the lower roller of the mixed product conveyance unit for spraying ammonia gas supplied from the ammonia gas supply unit to the lower part of the mixed product to be conveyed to cure the mixed product;
A mixed product discharge unit for discharging the second cured mixed product from the second ammonia gas spraying unit to the outside of the other side of the chamber; And
A third ammonia gas spraying unit disposed below the discharge unit of the mixed product discharge unit for spraying the ammonia gas supplied from the ammonia gas supply unit to the lower part of the mixed product discharge unit, Lt; / RTI >
When the ammonia gas is supplied from the ammonia gas supply part to the first ammonia gas injection part, the second ammonia gas injection part and the third ammonia gas injection part, the supply pressure is 0.90 to 1.20 MPa, and the first ammonia gas injection part, When ammonia is injected into the blend product from the third part and the third ammonia gas injection part, the injection pressure is performed at 0.5 to 1.0 MPa,
According to KS K 0521, the flame-retarded blended product manufactured by carrying out Step 6 has a tensile strength of 8 to 70% higher than that of the aramid fiber blend without curing,
The flame retarded blended product has a limiting oxygen index of 24 to 30 when measured according to ASTM D2863-91, and a washing fastness of 4 to 5 when measured according to KS K ISO 1005-C06 By weight based on the total weight of the aramid fiber blend.
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