WO2018164339A1 - Anthracene-perfluoropolyether-based superhydrophobic surface treatment agent and method for superhydrophobic surface treatment of pet fiber using same - Google Patents

Abstract

The present invention relates to an anthracene-perfluoropolyether-based superhydrophobic surface treatment agent and a method for superhydrophobic surface treatment of a PET fiber using the same. More specifically, the present invention provides a method for superhydrophobic surface treatment of a PET fiber, the method comprising the steps of: feeding polyethylene terephthalate (hereinafter, "PET"), an anthracene-perfluoropolyether-based superhydrophobic surface treatment agent, and a fluorine-based solvent into a reactor (first step); heating the reactor to perform superhydrophobic surface treatment on a PET surface through a dyeing reaction of the superhydrophobic surface treatment agent (second step); and washing and drying the superhydrophobic surface-treated PET surface (third step). The treatment of the PET fiber surface with the bio-environmentally friendly anthracene-perfluoropolyether-based superhydrophobic surface treatment agent according to the present invention has advantages of excellent superhydrophobicity, regeneration in which initial superhydrophobicity is again restored, industrialization, and area enlargement, without damaging air permeability and physical characteristics of fabrics. Furthermore, the PET fiber treated with the superhydrophobic surface treatment agent can be applied to various industries, such as functional clothing, medical materials, and water and oil separators.

Description

Superhydrophobic surface treatment agent based on anthracene-perfluoropolyether and superhydrophobic surface treatment method of PET fiber using the same

The present invention is not only super water-repellent, but also super-water-repellent surface treatment agent based on an anthracene-perfluoropolyether (hereinafter referred to as 'Anthracene-PFPE') having a regeneration to recover the initial super water repellency and the super water repellency of the PPET fiber using the same It relates to a surface treatment method.

Superhydrophobicity surface refers to a surface having a water contact angle of 150 ° or more and a very small tilt angle. In such a super water-repellent surface, water does not penetrate, so the surface does not get wet well, but rather, the water is repelled or water droplets roll on the surface.

Super water-repellent, which is easily seen in nature such as lotus leaf and butterfly wings, also known as the lotus effect, is a special property exhibited by hydrophobic materials with microstructure of surface and low surface energy.

Increasing interest in the super water-repellent gradually, various researches using it are being conducted, specifically, water-repellent coating of electronic devices, microfiltration membranes for water treatment, medical materials, functional clothing with antifouling and protective properties, water ( It is applied to various industrial fields such as water separation membranes.

In particular, high-performance water-repellent clothing products such as gore-tex, which releases sweat to the outside and water-repellent water, and shirts that prevent contamination of external pollutants such as water and coffee, have recently been released. Are being developed and commercialized.

This smart and functional textile material has a stain release (SR) function that can be easily washed even if contaminants adhere while maintaining breathability and keeping clothing fit.It is suitable for various textile industries such as sports leisure and medical textile materials. It is used.

The most commonly used fiber material is polyethylene terephthalate (PET) fiber. PET fiber is a representative synthetic fiber and is widely used in various fields due to its low price and ease of production.

However, PET fibers are hydrophobic and have a very dense tissue structure, which makes dyeing and processing difficult. Therefore, PET fiber uses a special dyeing method such as dyeing method using a disperse dye or a method of increasing the ease of processing by using a pretreatment process such as plasma treatment, chemical etching.

In addition, in order to impart super water repellency to the surface of the fiber, the surface of the fiber is generally physicochemically treated and then subjected to sol-gel processing, chemical vapor deposition (CVD), self-assembly and layer-by-layer (LBL) methods. A method of introducing a fluorine material having low surface energy or coating inorganic particles modified with fluorine material on the surface of the fiber is used.

However, this approach inevitably leads to a loss of breathability and physical properties of the fabric itself by the hydrophobic layer formed on the fabric surface. In addition, there are limitations such as infrastructure and processing costs for large-scale use in the actual industry, and it is difficult to restore the effect again when super water repellency is degraded by wear. Therefore, there are still many problems to be solved before these findings can be applied to a variety of more industrial applications.

In addition, the toxicity of human and environment such as perfluorooctane sulfonates (PFOS) and perfluorooctanoic acid (PFOA) contained in surface-treated fluorine materials since 2000s As it emerged, governments in various countries, including the US Environmental Protection Agency (EPA), began regulating PFOS and PFOA.

Therefore, the current research on bio-friendly super water-repellent surface treatment agent to replace it is active.

An object of the present invention is to use an anthracene and a high fluorine-based perfluoropolyether polymer similar to the matrix of the disperse dye using a dyeing process of PET fibers through a disperse dye, super-water repellent based on anthracene-perfluoropolyether which is bio-friendly An anthracene-perfluoropolyether-based superwater-repellent surface treatment agent capable of synthesizing a surface treatment agent and treating the surface of the PET fiber by using the same, and having a regeneration to restore the superhydrophobic property, and the fabric itself It is to provide a surface treatment method of super water-repellent PET fiber that is easy to regenerate, industrialize, and large area of super water repellency without affecting the breathability and physical properties of.

In order to achieve the above object, the present invention provides an anthracene-perfluoropolyether complex represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

에서 선택되고,R is hydrogen or

Is selected from,

m is an integer from 0 to 50,

n is an integer from 0 to 88,

m + n is an integer from 7 to 88.

In another aspect, the present invention provides an anthracene-perfluoropolyether-based super water-repellent surface treatment agent comprising an anthracene-perfluoropolyether complex represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

에서 선택되고, R is hydrogen or

Is selected from,

m is an integer from 0 to 50,

n is an integer from 0 to 88,

m + n is an integer from 7 to 88.

In another aspect, the present invention is the step of introducing a polyethylene terephthalate (hereinafter referred to as 'PET'), the anthracene-perfluoropolyether-based super water-repellent surface treatment agent, and a fluorine-based solvent to the reactor (first step); Heating the reactor to perform a superhydrophobic surface treatment on the PET surface through a dyeing reaction of the superhydrophobic surface treatment agent (second step); And a step of washing and drying the superhydrophobic surface-treated PET surface (third step).

By treating the surface of PET fibers with an anthracene-perfluoropolyether based superhydrophobic surface treatment agent according to the present invention, the superhydrophobic and initial superwater repellency are recovered without damaging the breathability and physical properties of the fabric. It has the advantages of regeneration, industrialization and large surface area, and the PET fiber treated with the super water-repellent surface treatment agent can be applied to various industries such as functional clothing, medical material and oil / water separator.

1 is a diagram showing the synthesis process of an anthracene-perfluoropolyether (hereinafter 'Anthracene-PFPE') based super water-repellent surface treatment agent (hereinafter 'An-D4000');

2 is a view showing a comparison of fluorescence properties of An-D4000 and D4000 synthesized in Example 1;

Figure 3 shows the results of the ¹ H-NMR analysis of An-D4000 synthesized in Example 1;

4 is a view showing an FT-IR analysis result of An-D4000 synthesized in Example 1;

Figure 5 is a PET single fiber (plain) / fabric (a), PET single fiber (plain) / 0.1 g An-D4000 (b), PET single fiber (plain) / 0.5 g An-D4000 (c), PET fiber Polyester-nylon blend fiber (microfiber) / fabric (d), polyester-nylon blend fiber (microfiber) /0.1 g An-D4000 (e), including PET fiber, and polyester-nylon blend fiber, including PET fiber (Microfiber) / 0.5 g An-D4000 (f) shows the result of EDS analysis;

6 is a change in wettability of a polyester-nylon blended fiber (microfiber) including a PET fiber treated with a super water-repellent surface treatment agent (An-D4000), water splashing (b), and an air trap (c) Water-repellent properties for various liquids (d), treatment of various PET fibers (PET single fibers (typical, 100% polyester), polyester-nylon blended fibers including PET fibers (microfiber, 70% polyester and 30%) Blend of nylon) 1, polyester-nylon blended fiber including PET fiber (microfibre, blend of 70% polyester and 30% nylon) 2, and polyester-cotton blend fiber (T / C, 50% polyester and 50%) (E), a capture image (f) where water droplets do not adhere to the fiber surface, and a capture image (g) where water droplets are pushed out of the fiber surface;

7 is a tensile strength measurement results (a) of PET single fibers (general) and polyester-nylon blended fibers (microfiber) treated with a super water-repellent surface treatment agent (An-D4000), PET single fibers (general) SEM images before and after An-D4000 treatment (left: fabric, right: 0.1 g An-D4000 treatment) (b), and before and after An-D4000 treatment of polyester-nylon blended fibers (microfiber) including PET fibers ( Left: far-end, right: 0.1-g An-D4000 treatment) (c);

8 shows the results of EDS analysis of a PET single fiber (general) (a) and a polyester-nylon blend fiber (microfiber) (b) treated with a super water-repellent surface treatment agent (An-D4000);

9 shows a surface SEM image of a PET single fiber (general) (a) treated with a super water-repellent surface treatment agent (An-D4000) and a polyester-nylon blend fiber (microfiber) (b) including a PET fiber after 5000 cycles of wear. Drawing shown;

10 shows 5000 cycle wear (a), 10000 cycle wear (b), 15000 cycle wear (c), and reprocessing after 5000 cycle wear of PET single fiber treated with super water-repellent surface treatment agent (An-D4000) d), EDS analysis results after reprocessing after 10000 cycle wear (e), and after reprocessing after 15000 cycle wear (f);

11 shows 5000 cycle wear (a), 10000 cycle wear (b), 15000 cycle wear (c), of polyester-nylon blended fiber (microfiber) including PET fiber treated with super water-repellent surface treatment agent (An-D4000), Reprocessing after 5000 cycle wear (d), Reprocessing after 10000 cycle wear (e), and Reprocessing after 15000 cycle wear (f).

12 shows cytotoxicity test results for anthracene-9-carboxylic acid, An-D4000 synthesized by Example 1, and D4000;

FIG. 13 shows self-cleaning ability (a) by water droplets of super water-repellent surface treated PET single fibers (general) and polyester-nylon blended fibers (microfiber) including PET fibers (a), antifouling ability (left: Before and after washing: after washing) (b), and in accordance with Example 2, showing the anti-pollution ability of the actual shirt treated with super water-repellent surface (made of 30% polyester and 70% cotton blend fibers, bag-only treatment) drawing;

FIG. 14 shows the cytotoxicity test results of polyester water-repellent surface treated PET single fiber (general) and polyester-nylon blended fiber (microfiber) according to Example 2; FIG. And

FIG. 15 is a water-oil separation experiment (blue: water, transparent: CHCl ₃ ) of a superhydrophobic surface-treated PET single fiber (general) and a polyester-nylon blend fiber (microfiber) including PET fiber according to Example 2. FIG. The figure which shows.

Hereinafter, the superhydrophobic surface treatment agent based on the anthracene-perfluoropolyether of the present invention, and the superhydrophobic surface treatment method of PET fiber using the same will be described in more detail.

The inventors of the present invention focus on the molecular structural characteristics of the disperse dyes used for dyeing PET fibers, and synthesize an anthracene-perfluoropoly compound that is synthesized using anthracene and a high fluorine-based perfluoropolyether polymer similar to the matrix of the disperse dyes. When superhydrophobic surface treatment of ether-based superhydrophobic surface treatment agent is applied to PET fibers, it has excellent regeneration of the superhydrophobic and initial superhydrophobic properties without loss of breathability and physical properties of the fabric, and also industrialization and large area The present invention was completed by finding that the PET fiber treated with the super water-repellent surface treatment agent can be easily applied to various industries such as functional clothing, medical materials and oil / water separators.

The present invention provides an anthracene-perfluoropolyether complex represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

에서 선택되고,R is hydrogen or

Is selected from,

m is an integer from 0 to 50,

n is an integer from 0 to 88,

m + n is an integer from 7 to 88.

The anthracene-perfluoropolyether complex may be a compound represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

In Chemical Formula 2,

o is an integer from 0 to 33,

p is an integer from 0 to 58,

o + p is an integer from 15 to 58.

In another aspect, the present invention provides an anthracene-perfluoropolyether-based super water-repellent surface treatment agent comprising an anthracene-perfluoropolyether complex represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

에서 선택되고,R is hydrogen or

Is selected from,

m is an integer from 0 to 50,

n is an integer from 0 to 88,

m + n is an integer from 7 to 88.

The anthracene-perfluoropolyether complex may be a compound represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

In Chemical Formula 2,

o is an integer from 0 to 33,

p is an integer from 0 to 58,

o + p is an integer from 15 to 58.

In another aspect, the present invention is the step of introducing a polyethylene terephthalate (hereinafter referred to as 'PET'), the anthracene-perfluoropolyether-based super water-repellent surface treatment agent, and a fluorine-based solvent to the reactor (first step); Heating the reactor to perform a superhydrophobic surface treatment on the PET surface through a dyeing reaction of the superhydrophobic surface treatment agent (second step); And a step of washing and drying the superhydrophobic surface-treated PET surface (third step).

The second step may be to react the reactor for 2 to 4 hours by heating the reactor to 110 to 150 ℃, but is not limited thereto.

Hereinafter, the superhydrophobic surface treatment agent based on the anthracene-perfluoropolyether and the superhydrophobic surface treatment method of PET fiber using the same according to the present invention will be described in detail by the following examples. However, the present invention is not limited by these examples.

Example 1 Synthesis of Super Water-Repellent Surface Treatment Agent Based on PFPE (An-D4000)

Referring to Figure 1, in order to synthesize a super water-repellent surface treatment agent based on anthracene-perfluoropolyether (hereinafter 'Anthracene-PFPE') was carried out as follows. 1 g of anthracene-9-carboxylic acid, 0.59 g of trimethylamine, and 21 cm ³ of anhydrous dichloromethane were added to a 100 cm ³ round bottom flask, followed by 25 ° C. The reaction solution was prepared by stirring for 10 minutes at.

Thereafter, 1.36 g of diphenylphosphoryl azide was slowly added to the reaction solution, followed by reaction at 25 ° C. for 30 minutes to concentrate the reaction solution.

Anhydrous tetrahydrofuran 9 cm ³ was added to the concentrated reaction solution, and then 1.76 g of compound 1 (FLUOROLINK D4000, manufactured by Solvay's 'D4000') was dissolved in asacycline AK225G 21 cm ³ and dibutyl. 0.11 g of dibutyltin dilaurate was added. After reaction at 55 ℃ for 16 hours.

[Compound 1]

HO-CH ₂ -CF ₂ O (CF ₂ O) _o (CF ₂ CF ₂ O) _p -CF ₂ CH ₂ -OH

After the reaction was completed, the product was extracted with fluorine-based FC-770 (3M), washed several times with 10% Na ₂ CO ₃ aqueous solution and dichloromethane (dichloromethane).

After washing, the fluorine solvent layer containing the product was dried using magnesium sulfate (MgSO ₄ ), filtered using Asacycline AK225G and concentrated by anthracene-PFPE based super water-repellent surface treatment agent (hereinafter 'An-D4000'). ') Was obtained (solid, light yellow, obtained: 1.56 g).

Example 2 Super Water Repellent Surface Treatment of PET Fiber Using An-D4000

In order to introduce a super water-repellent surface treatment agent to the surface of the PET fibers, the following process was carried out. PET fabric, 0.1 g of An-D4000, and fluorinated solvent FC-40 10 cm ³ were added to a 100 cm ³ round bottom flask.

After heating to 130 ℃ through the dyeing reaction of An-D4000 for 3 hours PET fabric (PET single fiber (general, 100% polyester), polyester-nylon blend fiber including PET fiber (microfiber, 70% polyester and Super water-repellent surfaces of 30% nylon blends), polyester-cotton blend fibers (P / C, 50% polyester and 50% cotton blends, and 30% polyester and 70% cotton blends) including PET fibers The treatment reaction proceeded. After the reaction time, the PET fabric treated with An-D4000 was washed with FC-770 (3M) and acetone and dried at room temperature to treat the surface of PET fiber with An-D4000.

Example 3 Super Water Repellent Surface Treatment of PET Fiber Using An-D4000

Except that 0.05 g of An-D4000 was used, the surface of the polyester single-nylon blend fiber (microfiber) including PET single fiber (general) and PET fiber was treated under the same conditions as in Example 2.

<Example 4> Super water-repellent surface treatment of PET fibers using An-D4000

Except that 0.3 g of An-D4000 was used, the surface of the polyester-nylon blend fiber (microfiber) including the PET single fiber (general) and the PET fiber was treated under the same conditions as in Example 2.

Example 5 Super Water Repellent Surface Treatment of PET Fiber Using An-D4000

Except for using 0.5 g of An-D4000, the surface of the polyester-nylon blend fiber (microfiber) including PET single fiber (general) and PET fiber was treated under the same conditions as in Example 2.

Comparative Example 1 Super Water Repellent Surface Treatment of PET Fiber Using D4000

Except for using 0.1 g of D4000, the surface of the polyester single-nylon blend fiber (microfiber) including PET single fiber (general) and PET fiber was treated under the same conditions as in Example 2.

Experimental Example 1 Synthesis of An-D4000

Synthesis of An-D4000, a super water-repellent surface treatment agent, was performed using anthracene-9-carboxylic acid and D4000, a high fluorine-based PFPE having a hydroxyl group at both ends. .

For more effective synthesis, functional groups of anthracene-9-carboxylic acid were converted to isocyanate, and the reaction was performed with the hydroxyl group of D4000 under catalytic conditions. Synthesis was confirmed using the fluorescence properties of the material, ¹ H-NMR and FT-IR results.

Anthracene included in the An-D4000 is well known as a material exhibiting unique fluorescence properties by UV. When the An-D4000 synthesized in Example 1 was dissolved in Asacycline AK225G, a fluorine solvent, and confirmed the fluorescence characteristics, it was confirmed that the anthracene-specific fluorescence appeared differently from D4000 (see FIG. 2).

In addition, proton peaks of anthracene and D4000 were identified by ¹ H-NMR (400Mhz, a mixed solution of CDCl ₃ and 1,1,2-trichloro-1,2,2-trifluoroethane). It was confirmed that the NH peak of the urethane bond generated by the reaction between the hydroxyl groups appeared (see FIG. 3).

The results of FT-IR (KBr pellet) also revealed that urethane bonds were formed through stretching absorption peaks of N-H bonds and C═O bonds (see FIG. 4).

The fluorescence characteristics, ¹ H-NMR and FT-IR results confirmed that the An-D4000 was successfully synthesized.

<Experiment 2> Confirmation of the introduction of a super water-repellent surface treatment agent (An-D4000) to the polyester single-polyester fiber (general) and polyester-nylon blended fiber (microfiber) including PET fiber

Super water-repellent surface treatment of PET fibers was performed by applying a dyeing method using a dispersion dye of PET fibers already used in the industry.

Simply put synthetic An-D4000 and PET single fiber (general) or polyester-nylon blended fiber (microfiber) including PET fiber into fluorine solvent, and water repellent treatment is possible simply by heating for 3 hours at 130 ℃ high temperature. .

Super water-repellent surface treatment of PET fibers was carried out by varying the amount of An-D4000 (0.05 g, 0.1 g, 0.3 g, 0.5 g) according to Examples 2 to 5, wherein the fiber fabric (PET single fiber) (General), polyester-nylon blended fibers (microfibers) including PET fibers) were all used in the same size as 3 cm x 3 cm.

TABLE 1

Table 1 shows the amount of An-D4000 used for super water-repellent surface treatment of PET single fiber (general) and polyester-nylon blend fiber (microfiber) including PET fiber, and the mass increase rate of the fiber before and after treatment (treatment time: 3 Time, treatment temperature: 130 ℃), after treating the surface of the PET fiber with An-D4000, it was confirmed that the mass of the fiber increases as the An-D4000 is introduced to the surface of the PET fiber. In addition, the mass increase rate tended to increase as the amount of An-D4000 used for the super water-repellent surface treatment increased.

To determine whether this mass increase is a result of the introduction of a superhydrophobic surface treatment agent, analyze the elements of the treated PET fiber surface using energy-dispersive X-ray spectroscopy (EDS) analysis. It was.

As a result, it was found that the F element of An-D4000 was detected on the surface of PET fiber into which An-D4000 was introduced. In particular, as the amount of An-D4000 increased, the amount of F element detected increased. It could be done (see Figure 5).

The mass increase of the treated PET fibers and the results of EDS analysis confirmed that the super water-repellent surface treatment agent An-D4000 was effectively introduced onto the PET fiber surface according to Examples 2 to 5.

The introduction of An-D4000, a high fluorine-based super water-repellent surface treatment agent, on the surface of PET fibers reduces the surface energy of the fiber surface, and an air trap between the water and the PET fiber surface due to the rough surface generated by weaving. ) Forms a more powerful water repellent effect.

This superhydrophobic effect could be confirmed through various surface property experiments. In particular, the super water-repellent surface treatment of PET fibers using the An-D4000 of Examples 2 to 5 was carried out using polyester-nylon blend fibers (microfiber, 70% poly) in addition to PET single fibers (general, 100% polyester). Blends of polyester and 30% nylon), polyester-cotton blend fibers (T / C, 50% polyester and 50% cotton blends, and 30% polyester and 70% cotton blends) Irrespective of this, it can be widely applied to various blend fibers, so that the application range of the treatment is very wide (see FIGS. 6 and 13 (c)).

Experimental Example 3 Measurement of Water Contact Angle of Water on PET Single Fiber (Normal) and Polyester-Nylon Blend Fiber (Microfiber) Treated with Super Water Repellent Surface Treatment Agent (An-D4000)

In order to confirm the water repellent effect of the super water-repellent surface treated PET fibers according to Examples 2 to 5 and Comparative Example 1, the contact angle to water was measured.

For measurement, Phoenix 300 (SEO, Surface Electro Optics) was used, and the contact angle was measured using 3 μL of water at room temperature. The measured image was analyzed using Image J. Five contact angles per sample were measured and the average of the measurements was taken as the final contact angle.

In order to evaluate the superhydrophobic performance of the super-water-repellent PET fiber treated with An-D4000 according to Examples 2 to 5, the contact angle with respect to water was measured. For comparison, according to Comparative Example 1, the water contact angle of the PET fiber treated with the super water-repellent surface treated with D4000 was also measured, and the results are shown in Table 2 below.

TABLE 2

Table 2 shows the results of measuring the water contact angle according to the amount of treatment of An-D4000 of the PET single fiber (general) and polyester-nylon blend fiber (microfiber) including the PET fiber.

In the case of PET fabric that was not treated in the actual measurement process, water was soaked in and it was impossible to measure. In the case of the PET fiber subjected to the super water-repellent surface treatment using the An-D4000 according to Examples 2 to 5, it is seen that the water-repellent effect of pushing the water occurs as the super water-repellent surface treatment agent is introduced to the surface of the PET fiber. Could.

Specifically, the contact angle of the super-water-repellent PET single fiber (general) and the polyester-nylon blended fiber (microfiber) including PET fiber with An-D4000 synthesized according to Example 1 exhibited a high contact angle of 150 ° or more overall. After the measurement, the water did not penetrate the fiber and the water repellency was maintained.

In addition, as the amount of An-D4000 used for the super water-repellent surface treatment, the contact angle tended to be slightly higher, but the change in contact angle with the amount did not appear substantially. In particular, we see that higher contact angles are measured in polyester-nylon blended fibers (microfiber), including PET fibers with thinner fibers than PET single fibers (normal), which have surfaces that are finer and can form more air traps. Could.

In the case of PET fibers treated with D4000 0.1 g according to Comparative Example 1, the contact angle was also measured. However, during the measurement of the contact angle, water gradually penetrated into the fiber, resulting in a wet phenomenon.

That is, the surface energy is lower than the PET fabric before the treatment due to the very small amount of D4000 remaining in the washing process after treating the surface of PET fiber according to Comparative Example 1, and it is regarded as the contact angle caused by the delay of water penetration. There was a slight difference in the water repellent effect seen in one fiber.

Experimental Example 4 Measurement of Water shedding angle of water of PET single fiber (general) and polyester-nylon blended fiber (microfiber) treated with super water-repellent surface treatment agent (An-D4000)

The water shedding angle for water was measured to confirm the water repellent properties of the PET single fiber (general) and the polyester-nylon blend fiber (microfiber) including the super water-repellent surface treatment. The measurement is described in 'Zimmermann et al, Text. Res. J. 2009, 79, 1565 '.

Polyester-nylon blend containing PET single fiber (general) and PET fiber (microfiber) with treated PET single fiber (general) and PET fiber in a hand-made tilting apparatus A syringe was installed to drop droplets 1 cm above the fibers (microfiber). The angle of the tilting device was measured by decreasing the angle from 20 ° to 1 °, and the minimum angle was measured by dropping the water droplets onto the PET fiber at every angle and dropping more than 2 cm from the point where the water droplets dropped.

At this time, two types of needles were used and the volume was 5.4 ± 0.06 μL (26 G, inner diameter: 241 μm, Kovax-Needle, Korea Vaccine) and 8.2 ± 0.10 μL (23 G, inner diameter: 318 μm, Kovax-Needle , Korea vaccine) water droplets were measured, and the results are shown in Table 3 below.

TABLE 3

Table 3 shows the flow angle measurement results according to the treatment amount of An-D4000 of PET single fiber (general) and polyester-nylon blend fiber (microfiber) including PET fiber. Measurements vary with the amount of material used in the treatment, the type of fiber and the volume of water used.

Specifically, in the PET single fiber (general) treated according to Comparative Example 1 and the polyester-nylon blended fiber (microfiber) including PET fibers, the water droplets did not roll off, but the PET single treated according to Examples 2 to 5 Polyester-nylon blended fibers (microfibers), including fibers (general) and PET fibers, had a flow angle of 15 ° or less.

In addition, as the amount of material used for the super water-repellent surface treatment increased, the flow angle tended to decrease gradually. Especially, in the polyester-nylon blended fiber (microfiber) including PET fiber, a low flow angle of 10 ° or less was observed. I could see having

Experimental Example 5 Measurement of Tensile Strength of PET Single Fiber (Normal) and Polyester-Nylon Blend Fiber (Microfiber) Treated with Super Water Repellent Surface Treatment Agent (An-D4000)

Tensile strength was measured to determine the change in physical strength of PET single fiber (general) and polyester-nylon blended fiber (microfiber) under high temperature superhydrophobic surface treatment conditions. The tensile strength was measured by using a universal testing machine (Universal Testing Machine, AG-X, Shimadzu Corp., Kyoto, Japan), and proceeded by a modified grab test in accordance with ASTM D 5034.

Samples were prepared by longitudinally cutting both parts of the central portion of a polyester single-nylon blend fiber (microfiber) including 90 mm × 150 mm in size and a polyester-nylon blend fiber (microfiber) including PET fiber. Thereafter, the experiment was conducted until the fracture completely occurred at a tensile speed of 300 mm / min, and the maximum stress (N) was calculated using the measured maximum force (N). The measurement was performed five times, and the results thus obtained were averaged and used as final results.

Tensile strength measurement experiments were conducted to determine the effect of very harsh superhydrophobic surface treatment conditions at 130 ° C on the physical strength of PET single fibers (typical) and polyester-nylon blended fibers (microfiber) including PET fibers ( See FIG. 7).

As a result of tensile strength measurement, PET single fiber (normal) increased the strength of the fiber after treatment, and polyester-nylon blended fiber (microfiber) including PET fiber showed little change in strength.

In other words, the results were somewhat different depending on the type of fiber, but it was found that problems such as damage to the fiber and a decrease in physical strength did not occur under severe superhydrophobic surface treatment conditions at a very high temperature (FIG. 7 (a). ) Reference).

Also referring to SEM images before and after the treatment of An-D4000 according to Examples 2 to 5, PET single fibers (general) before and after the treatment increased the strength of the fibers rather than after the treatment, and polyester-nylon containing PET fibers. It can be seen that the super water-repellent surface treatment method of An-D4000 of the present invention does not have a physical effect on the PET fiber through no significant difference in the state of the blend fiber (microfiber) (FIG. 7 (b), and FIG. 7). (c)).

Experimental Example 6 Reproducibility Analysis of Water Repellent Effect of PET Single Fiber (Normal) and Polyester-Nylon Blend Fiber (Microfiber) Treated with Super Water Repellent Surface Treatment Agent (An-D4000)

In order to evaluate the regeneration of the water repellent effect after physical damage such as abrasion, the contact angle and shedding angle with respect to water were measured for the retreated fibers after wear.

Abrasion was conducted to the specifications of ASTM D 4966-2012 using a Martindale abrasion tester (James H. Heal & Co. Ltd.). PET single fiber treated with 0.1 g of An-D4000 (poly) and polyester-nylon blended fiber (microfiber) containing PET fiber were treated with 5000, 10000, and 15000 cycles at 9 kpa load. The surfaces were artificially worn and retreated under the same superhydrophobic surface treatment conditions after wear. The contact angle and the flow angle were measured in the same manner as in Experimental Example 3 and Experimental Example 4, and the results are shown in Tables 4 and 5 below.

TABLE 4

TABLE 5

Table 4 shows the change in contact angle according to wear and reprocessing, Table 5 shows the change in flow angle according to wear and reprocessing.

Specifically, the wear caused loss of the super water-repellent surface treatment agent on the surface of the PET single fiber (Normal) treated with the super water-repellent surface treatment agent An-D4000 and the polyester-nylon blend fiber (microfiber) including the PET fiber ( 8, 10, and 11), as the spacing between the fibers widened (see FIG. 9), the superhydrophobic effect decreased.

Therefore, the contact angle with respect to water was reduced than before wear, and water droplets did not occur on the surface of the fiber. After retreatment under the same conditions it was confirmed that the super water-repellent properties are restored as the super-water-repellent surface treatment agent is introduced back to the surface (see FIGS. 10 and 11). Although the contact angle decreased than before wear, it was confirmed that the contact angle increased again on the surface through reprocessing under the same conditions (see Table 4).

In particular, in the measurement of the flow angle, PET single fiber (general) and polyester-nylon blended fiber (microfiber) including PET fiber, which could not be measured because water droplets did not roll down after abrasion, regained effect after reprocessing. I could see it rolling down.

Through the above results, it can be seen that when the water repellent property of the PET fiber is degraded due to physical damage, it is possible to easily reproduce the water repellent effect by simply reprocessing.

Experimental Example 7 Cytotoxicity Test of PET Single Fiber (Normal) and Polyester-Nylon Blend Fiber (Microfiber) Treated with Super Water Repellent Surface Treatment Agent (An-D4000)

Poly-containing PET single fiber (General) and PET fibers treated with An-D4000, a super water-repellent surface treatment agent synthesized in Example 1, and An-D4000, a super water-repellent surface treatment agent according to Examples 2 to 5 Cytotoxicity tests were performed on the ester-nylon blend fibers (microfiber).

Toxic elution was carried out for 72 hours under 37 ° C in accordance with ISO 10993-12 standard, and cytotoxicity test for 24 hours under 37 ° C with WST-1 assay method according to ISO 10993-5 standard using the eluted eluate. Was carried out.

For cytotoxicity, the sample was evaluated as non-cytotoxic if the relative cell viability against the highest concentration of the sample eluate was 70% or more of the control group.

Referring to FIG. 12, the cytotoxicity test result showed that anthracene-9-carboxylic acid showed cytotoxicity, whereas An-D4000 synthesized according to Example 1 had a cell viability of 70. Higher than%. In particular, it showed a higher cell viability than D4000, it was confirmed that there is no harmful to the living body of the An-D4000.

Experimental Example 8 Confirmation of Functional Clothing, Medical Material, and Oil Separation Membrane

A water repellency measurement was conducted to evaluate the water repellency of the PET single fiber (general) and the polyester-nylon blend fiber (microfiber) treated with the super water-repellent surface treatment agent (An-D4000). The measurement was carried out in accordance with AATCC 22-2014 (spray method). A total of three measurements were taken and the results were graded.

A moisture permeability measurement experiment was conducted to confirm the moisture permeability of the PET single fiber treated with the super water-repellent surface treatment agent (An-D4000) and the polyester-nylon blend fiber (microfiber) including the PET fiber. The measurement was performed using ASTM E 96 / E96M-2015, B (water method). The experiment was carried out in a chamber with a temperature of 23 ± 1 ° C. and a humidity of 50 ± 2% R.H. and a total of three experiments were conducted to average the results.

It was confirmed that a strong water repellent effect was introduced as the An-D4000 synthesized according to Example 1 was introduced on the surface of the PET single fiber (general) and the polyester-nylon blend fiber (microfiber) including the PET fiber.

Specifically, in the actual water repellency evaluation, the fabric was absorbed by the water, the rating was 0, but according to Example 2 super water-repellent surface treated PET single fiber (typical) grade 60, polyester-nylon including PET fiber Blended fibers (microfibers) were found to show water repellency of grades 70-75 (see Table 6).

In the case of moisture permeability, although the water repellency of water repelling was generated by the super water repellent surface treatment, the PET single fiber (general) which was super water repellent surface treated according to Example 2 compared to the fabric was 60 grade, polyester-nylon including PET fiber. The moisture permeability of the blended fibers (microfiber) did not change significantly (see Table 6).

Unlike the general water-repellent surface treatment method of coating the surface with a water-repellent material, it is a super water-repellent surface treatment method using a dyeing process. Therefore, a high fluorine-based super water-repellent surface treatment agent is adsorbed onto the fiber surface and diffused into the fiber to be directly introduced into the PET fiber. This is because it does not affect the pores of polyester-nylon blended fibers (microfibers) including fibers (general) and PET fibers.

TABLE 6

In addition, the self-cleaning of various contaminants while reducing the surface energy of the super-water-repellent surface treated PET single fiber (general) and polyester-nylon blended fiber (microfiber) including PET fibers according to Example 2 It was seen that the function and stain release ability appeared (see Figs. 13 (a) and 13 (b)). The actual shirt (made of 30% polyester and 70% cotton blended fibers) was treated in accordance with Example 2 and the same stain release capability was observed for common contaminants such as coffee and ink. (See FIG. 13 (c)).

In addition, the cytotoxicity test for the superhydrophobic surface treated PET single fiber (general) and the polyester-nylon blended fiber (microfiber) including the PET fiber was conducted in the same manner as the cytotoxicity test for the superhydrophobic surface treatment agent An-D4000. It became.

According to Example 2, the cytotoxicity test results of the superhydrophobic surface-treated PET single fiber (general) and the polyester-nylon blended fiber (microfiber) including the PET fiber showed a cell viability of 70% or more, similar to that of the An-D4000. It was confirmed, rather than the case of the fabric was confirmed that the result of increasing the number of cells (see Figure 14).

Based on the above results, the superhydrophobic surface treatment method using the high fluorine-based superhydrophobic surface treatment agent of the present invention can be applied regardless of the type and ratio of blended fibers, and various industries such as superficial water treatment of functional clothing, medical gowns and medical materials. It seems to be widely applicable to

In recent years, studies on oil and water separation membranes that separate water and oil to purify water contaminated by mixing oil such as industrial water and oil spills using super water-repellent fibers have been actively conducted.

Specifically, in order to confirm the applicability as a water / oil separator for a polyester-nylon blend fiber (microfiber) including a super water-repellent surface treated PET single fiber (general) and a PET fiber according to Example 2, water and CHCl ₃ Separation experiment was carried out for the mixed solution of.

As a result, water is not allowed to pass through water-repellent PET single fibers (plain) and polyester-nylon blended fibers (microfiber) including PET fibers, while CHCl ₃ is a polyester containing PET single fibers (plain) and PET fibers. It was confirmed that water and CHCl ₃ were separated from each other through the nylon blend fiber (microfiber) (see FIG. 15).

Based on the results, it can be seen that the superhydrophobic surface-treated PET single fiber (general) and polyester-nylon blended fiber (microfiber) including PET fiber according to Example 2 can also be utilized as an oil / water separator.

Through various experimental results above, An-D4000, a high water-insoluble superhydrophobic surface treatment agent synthesized according to Example 1, was effectively introduced to the surface of PET fibers under superhydrophobic surface treatment conditions, and PET single fibers (normal) and PET fibers were used. It was confirmed that the water-repellent property appeared on the surface of the polyester-nylon blend fiber (microfiber) included.

PET fiber super water-repellent surface treatment method of the present invention is a super water-repellent surface treatment method devised in the dyeing method of PET fiber can be easily applied to the dyeing process of the fiber already equipped with the industrial base, it is said that the large area and industrial application is very easy. Can be.

Non-hazardous biotoxicity test was conducted on the superhydrophobic surface treatment agent synthesized according to Example 1 and the superhydrophobic surface treated PET single fiber (general) and the polyester-nylon blend fiber (microfiber) including the PET fiber. It can be seen that it is a bio-friendly treatment.

In particular, the An-D4000 synthesized according to Example 1 can easily recover the water repellent effect by simple reprocessing, even if the water repellent properties are degraded by physical damage after the water repellent treatment, it is said that the durability and reproducibility of the effect is also excellent super water repellent surface treatment method can do.

As mentioned above, although this invention was demonstrated by the limited embodiment and drawing, this invention is not limited by this, The person of ordinary skill in the art to which this invention belongs, Of course, various modifications and variations are possible within the scope of equivalents of the claims to be described.

Claims (6)

Anthracene-perfluoropolyether complex represented by Formula 1 below: [Formula 1]

In Chemical Formula 1, R is hydrogen or

Is selected from, m is an integer from 0 to 50, n is an integer from 0 to 88, m + n is an integer from 7 to 88. The method according to claim 1, The anthracene-perfluoropolyether complex, Anthracene-perfluoropolyether complex, characterized in that the compound represented by the formula (2): [Formula 2]

In Chemical Formula 2, o is an integer from 0 to 33, p is an integer from 0 to 58, o + p is an integer from 15 to 58. An anthracene-perfluoropolyether-based super water-repellent surface treatment agent comprising an anthracene-perfluoropolyether complex represented by Formula 1 below: [Formula 1]

In Chemical Formula 1, R is hydrogen or

Is selected from, m is an integer from 0 to 50, n is an integer from 0 to 88, m + n is an integer from 7 to 88. The method according to claim 3, The anthracene-perfluoropolyether complex, An anthracene-perfluoropolyether-based superhydrophobic surface treatment agent, characterized in that the compound represented by the formula (2): [Formula 2]

In Chemical Formula 2, o is an integer from 0 to 33, p is an integer from 0 to 58, o + p is an integer from 15 to 58. Injecting polyethylene terephthalate (hereinafter referred to as 'PET'), an anthracene-perfluoropolyether based superhydrophobic surface treatment agent, and a fluorine-based solvent into the reactor (first step); Heating the reactor to perform a superhydrophobic surface treatment on the PET surface through a dyeing reaction of the superhydrophobic surface treatment agent (second step); And Washing and drying the superhydrophobic surface-treated PET surface (third step); A super water-repellent surface treatment method of PET fibers, including. The method according to claim 5, The second step, The reactor is heated to 110 to 150 ℃ to react for 2 to 4 hours, super water-repellent surface treatment method of PET fibers.

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