KR101167586B1 - Water And Oil Repellent Composition For Textiles And Process Of Repellent Treatment - Google Patents

Abstract

The present invention relates to a coating composition for water-repellent coating of a surface of a fiber polymer, a woven fabric or the like using a SiO ₂ nano-sol and a water-dispersible polymer. According to the present invention, It is possible to realize various functions such as water-repellent oil and the like simultaneously by implementing the surface.

Dual scale, nano sol, water dispersion polymer, surface, water repellent processing

Description

Technical Field [0001] The present invention relates to a water-repellent, water-repellent,

More particularly, the present invention relates to a coating composition for dispersing an SiO ₂ nano-sol in a water-dispersible polymer, thereby realizing a water-repellent surface on a fiber surface such as a fabric or a knitted fabric.

In recent years, with the development of measurement technology capable of observing nano-size, an attempt has been recently made to exhibit a water-repellent oil-repellent structure using a mechanism similar to that of a natural water-repellent mechanism. Among them, it is very interested in the implementation of lotus effect mimicking lotus leaf with microprojection. The factors that determine the hydrophobicity of the surface with the Lotus effect are the surface roughness and the surface energy. By changing these two conditions, the degree of hydrophobicity can be controlled and the superhydrophobic surface can be realized.

In order to realize superhydrophobic surface, various companies have developed a water-repellent emulsion to treat the fiber surface, but this method has a limitation in the durability of the fiber treatment or the implementation of the super-hydrophobic property. Therefore, a method of increasing the surface roughness using a plasma cutting method and the like has been searched to realize a superhydrophobic surface, but the plasma cutting method has a problem that the physical properties of the fiber are poor.

In addition to fiber products, water repellency is closely related to the contact angle, surface tension, and surface roughness of the product. For example, when the contact angle is more than 110 발, the water repellency is more than 100, and when the contact angle is about 140 에는, the water repellency and self-cleaning as well as water repellency and oiling are exhibited. In the case of a patent relating to water-repellent processing both domestically and externally, a method of using a silicone-based water repellent agent was disclosed in Japanese Patent Publication No. 51-2434 and Japanese Patent Laid-Open No. 53-3747, and Japanese Patent Publication No. 54-55697 A method of treating with an organic solvent solution of a fluorine-based water repellent agent, and a method of applying an organic solvent solution of an ethylenically unsaturated monomer containing a hydroxyl group or a carboxyl group and a cross-linking agent after treatment with a fluorine-based water repellent agent is disclosed in Japanese Patent Laid-Open No. 55-76167 However, most of them show a level of technology that achieves a contact angle of 110 ㅀ ~ 120 ㅀ and water repellency of 100. Domestic patents are no different. Korean Patent Application No. 1990-0021589 also discloses a technique of achieving a water repellency of 100 by using a fluorine-based water repellent agent and a three-dense high-density fabric. In Korean Patent Application No. 10-2001-0065617, the surface of a porous inorganic support And a polymer skin layer is formed by using a self-assembled initiator and a grafting surface polymerization to exhibit a water-repellent and water-repellent property. In addition, in order to provide a water-repellent coating, the conventional methods are firstly subjected to a process for forming a fractal surface structure, and then a water repellent material is coated thereon. However, the use of such a method requires a two-step process, and there is a problem in that the process of etching the surface of the coating material in order to form the fractal structure is expensive.

Accordingly, the present invention solves the problems of the prior arts and provides a coating composition capable of imparting a surface of initial and / or oily surface by increasing the surface roughness, the contact angle and the surface tension of the surface of the medium by imparting dual scale nano- To be a technical challenge.

Therefore, according to the present invention, a SiO ₂ sol (I) containing SiO ₂ nanoparticles having an average particle diameter of 5 to 100 nm and an SiO ₂ sol (II) containing SiO ₂ nanoparticles having an average particle diameter of 250 to 5,000 nm are mixed at a volume ratio of 1: 1 to 40: 1 mixed with SiO ₂ sol mixture can be provided with a fiber chobal caregiver oil coating compositions dispersed in the polymer dispersion.

Also, as a method of using the starting oil-and-water coating composition for fibers, the article to be treated is padded with a pickup ratio of 50 to 60% and cured at 170 to 175 ° C for 1 to 2 minutes Is provided.

Hereinafter, the present invention will be described in more detail.

The starting oil-and-water coating composition for fibers according to the present invention is prepared by mixing two types of SiO ₂ sols containing SiO ₂ nanoparticles having different average particle diameters and dispersing them in an aqueous dispersion polymer. When applied to fibers, The surface of the fiber can be increased by increasing the surface roughness, the contact angle, and the surface tension of the fiber, thereby providing a super water repellent surface.

Of the groups containing a SiO ₂ nano-particles with a mean particle size of different of the present invention, SiO ₂ sol is an SiO ₂ SiO ₂ sol (Ⅰ) and average particle diameter of 250 to 5,000nm containing SiO ₂ nano-particles is 5 to 100nm mean particle size may be separated by a SiO ₂ sol (ⅱ) containing nano-particles, in the present invention, SiO ₂ sol (ⅰ) and SiO ₂ sol (ⅱ) the volume ratio of 1: the combined SiO ₂ sol mixed at a 1: 1 to 40 If it is outside the above range, the contact area between the water droplet and the surface of the fiber, which is the treatment medium, becomes large, and the hydrophobic group may be lowered.

When the nanoparticles having different particle diameters are mixed, the nanostructures of the dual scale are formed well and the hydrophobicity is increased. When the water drops are dropped on the dual-scale nanostructure, the water drops come into contact with the vertices of the dual scale nanostructures And water droplets can not penetrate into the structure under the vertex. In other words, the contact area between the water droplet and the solid surface is reduced to a very small level, which is very low. The microstructure of the lotus leaf in the natural world is also very small due to this principle. This principle is called the lotus effect. The factors that determine the hydrophobicity of the surface with the Lotus effect are the surface roughness and the surface energy. By changing these two conditions, the degree of hydrophobicity can be controlled and the superhydrophobic surface can be realized.

SiO ₂ sol containing nano-SiO ₂ particles having a Si content of SiO ₂ sol (I) is 3200 ~ 6400ppm, and the average particle size of 250 to 5,000nm containing SiO ₂ nano-particles is 5 to 100nm and the average particle diameter in the present invention ( II) preferably has an Si content of 3600 to 7200 ppm. In particular, since the fibers are in a converging state of many filaments, the surface is not flat, such as a film or a glass surface, It is good for scale expression.

The SiO ₂ sol (I) used in the present invention is prepared by reacting a mixed solution composed of 1 to 30% by weight of tetraethyl orthosilicate, 3 to 4% by weight of nitric acid and 1 to 25% by weight of methanol and ultrapure water as the remainder by the mixed solution of pure water as a reaction product is obtained, it said SiO ₂ sol (ⅱ) is tetraethylorthosilicate (tetraethyl orthosilicate) 1 ~ 30% by weight, ammonia 3-4% by weight, methanol 1-25% by weight and the balance It is preferable to use a reaction product obtained by the reaction because it can be durably bonded directly with the fiber as the treatment medium. By selectively using nitric acid or ammonia as the catalyst, the size of the SiO ₂ sol can be appropriately controlled.

The water-dispersible polymer is preferably a water-soluble fluorine-based polymer and a water-soluble fluorosilane-based polymer in view of dual-scale development on the surface of the fiber and improvement in fastness. And the water-soluble fluorosilane-based polymer is preferably the same as the chemical formula (5). The water-soluble fluorine-based polymer and the water-soluble fluorosilane-based polymer may be a known water-soluble fluorine-based water-repellent agent and a water-soluble fluorosilane-based water-repellent agent.

[Chemical Formula 1]

CF ₃ (CF ₂ ) ₃ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OH

(2)

CF ₃ (CF ₂ ) ₃ SO ₂ N (CH ₃ ) CH (CH ₃ ) CH ₂ OH

(3)

CF ₃ (CF ₂ ) ₃ SO ₂ N (CH ₃ ) CH ₂ CH (CH ₃ ) OH

[Chemical Formula 4]

CF ₃ (CF ₂ ) ₃ SO ₂ N (CH ₂ CH ₃ ) CH ₂ CH ₂ OH

[Chemical Formula 5]

The present invention provides a method for fiber water-repellent processing wherein a to-be-processed material is padded at a pick-up rate of 50 to 60% and cured at 170 to 175 ° C for 1 to 2 minutes. This is to create a dual scale surface protrusion on the fiber surface to create a superhydrophobic surface on the fiber surface.

According to the present invention, nanoparticles of different sizes are mixed and mixed with a water-dispersible polymer in order to maximize the contact angle between the water droplet and the surface of the fiber, thereby imparting a low water solubility to the fiber without changing the physical properties of the fiber itself Which can provide a foot-and-mouth workout.

The following examples illustrate non-limiting examples of a water-miscible coating composition for fibers of the present invention.

[Synthesis Examples 1 to 4]

1. Preparation of SiO ₂ sol.

To prepare the SiO ₂ sol, 330 ml of a mixed solution of ammonia, methanol and distilled water was preliminarily packed in a reactor, and a precursor, tetraethyl orthosilicate and methanol were added at the same volume ratio as in Table 1 to prepare a SiO ₂ sol (II).

In addition, 330 ml of a mixed solution of nitric acid, methanol and distilled water was prepared in the reactor, tetraethyl orthosilicate and methanol were added in various volume ratios according to the conditions of Table 2 to prepare SiO ₂ sol (I) Lt; RTI ID = 0.0 > rpm < / RTI > for 2 hours. After completion of the reaction, quench at 30 ° C and filter. The particle size distribution and size of the SiO ₂ sol of the _two groups were analyzed with a particle size analyzer (ELS-8000, OTSUKA).

division TEOS dosage Amount of methanol input SiO ₂ nanoparticle particle size Synthetic Example 1 10ml 90ml 295.4 nm Synthetic Example 2 30ml 70ml 313.7 nm Synthetic Example 3 50ml 50ml 558.7 nm Synthetic Example 4 70ml 30ml 628.5 nm Synthetic Example 5 90ml 10ml 965.4 nm

division TEOS dosage Amount of methanol input SiO ₂ nanoparticle particle size Synthetic Example 6 10ml 90ml 44.4 nm Synthetic Example 7 30ml 70ml 50.6 nm Synthetic Example 8 50ml 50ml 70.1 nm Synthesis Example 9 70ml 30ml 89.1 nm Synthetic Example 10 90ml 10ml 100.2 nm

[Examples 1 to 15]

1. Preparation of SiO ₂ sol / water repellent

The SiO ₂ nano sol prepared in each of Synthesis Examples 1 to 10 was mixed according to the conditions shown in Table 3 below and then mixed with the fluorosilane polymer of Formula 5 to prepare a fiber weevil water and oil coating composition.

The coating composition was padded to a polyester fabric surface at a pick-up rate of 60% and cured at 170 占 폚 for 2 minutes.

[Chemical Formula 5]

division SiO ₂ particle size type Mixing ratio Example 1 100.2: 558.7 1: 1 Example 2 100.2: 558.7 20: 1 Example 3 100.2: 558.7 40: 1 Example 4 100.2: 965.4 1: 1 Example 5 100.2: 965.4 20: 1 Example 6 100.2: 965.4 40: 1 Example 7 313.7: 558.7 1: 1 Example 8 313.7: 558.7 20: 1 Example 9 313.7: 558.7 40: 1 Example 10 313.7: 965.4 1: 1 Example 11 313.7: 965.4 20: 1 Example 12 313.7: 965.4 40: 1 Example 13 558.7: 965.4 1: 1 Example 14 558.7: 965.4 20: 1 Example 15 558.7: 965.4 40: 1

2. Measurement of physical properties

1) Contact angle measurement

 The changes in the surface properties and physical properties of the water-repellent polyester fabric can be confirmed by measuring the contact angle, which is the change in the surface free energy, that is, the change in the surface tension, using a contact angle meter (DSA100, Kruss, Germany) Respectively. In each measurement, the solution was dropped by an amount of 10 μl, and the measurement was repeated three times to obtain an average value and a deviation. At this time, distilled water was used and the hydrophobicity was evaluated by photographing with a digital camera. FIG. 2 is a schematic diagram for explaining the contact angle according to the particle size. FIG. Figs. 3 to 7 show the result of measuring the contact angle.

When the nanoparticles of 100.2 nm / 558.7 nm of Example 1 were mixed at a volume ratio of 1: 1, when the contact angle was 138 ° and the nanoparticles of 100.2 nm / 558.7 nm of Example 2 were mixed at a volume ratio of 20: 1, The contact angle was 142 ° (FIG. 3), and the 100.2 nm / 965.4 nm nanoparticles of Example 4 were mixed in a volume ratio of 1: 1, the contact angle was 135 °, the contact angle was 142 ° when 100.2 nm / 965.4 nm nanoparticles of Example 5 were mixed at a volume ratio of 20: 1, and 100.2 nm / 965.4 nm nanometer of Example 6 When the particles were mixed at a volume ratio of 40: 1, the contact angle was 138 ° (FIG. 4). When the nanoparticles of Example 7 were mixed at a volume ratio of 1: 1, the contact angle was 138 °, Of the nanoparticles of 313.7 nm / 558.7 nm were mixed at a volume ratio of 20: 1, the contact angle was 141 °. When the nanoparticles of Example 9 were mixed at a volume ratio of 40: 1, the contact angle was 140 ° (Fig. 5), Example 10 of 313.7 nm / 965.4 nm were mixed at a volume ratio of 1: 1, the contact angle was 142 °. When the nanoparticles of 313.7 nm / 965.4 nm of Example 11 were mixed at a volume ratio of 20: 1, the contact angle was 144 °, the contact angle was 147 ° (FIG. 6) when 313.7 nm / 965.4 nm nanoparticles of Example 12 were mixed at a volume ratio of 40: 1, the ratio of 313.7 nm / 965.4 nm nanoparticles of Example 13 was 1: 1 When the nanoparticles were mixed at a volume ratio of 136 °, the contact angle was 151 ° and the nanoparticles of 313.7 nm / 965.4 nm of Example 15 were mixed when the contact angle was 136 ° and the nanoparticles of 313.7 nm / 965.4 nm of Example 14 were mixed at a volume ratio of 20: When mixed at a volume ratio of 40: 1, the contact angle was 158 ° (FIG. This indicates that the contact area between the water droplet and the fiber surface is the smallest, and that the dual scale structure having the nanoscale structure simultaneously increases the hydrophobicity.

2) Surface condition measurement

The surface state of the treatment medium was measured by using a field emission scanning electron microscope (FE-SEM, JSM-7500A, JEOL) capable of observing the surface microstructure change to the nano level and measuring the acceleration voltage 1 kV and the current 9A. We also investigated the surface morphology using atomic force microscopy (AFM, Digital instruments, NanoScope MulSimode).

FIG. 8 shows a form obtained by mixing particles of 313.7 nm with a water-soluble fluorine-based and fluorine-containing water repellent on the surface of the film, and FIG. 9 shows a dual scale shape of a leaflet-like shape obtained by mixing particles of 100.2 nm / 558.7 nm, .

In Fig. 10, nano-dots confirmed by FE-SEM were observed as the AFM shape of Example 3 in which SiO ₂ sol, water-soluble fluorine-based, and fluorine-water repellent were mixed.

FIG. 1 is a flow chart showing a process for producing a SiO ₂ sol,

FIG. 2 is a schematic view for explaining the contact angle according to the particle size,

Figs. 3 to 7 are the results of measuring the contact angles of Examples 3, 6, 9, 12 and 15,

8 is a field-emission scanning electron microscope image obtained by measuring the surface state of a fabric treated with a mixture of a particle of 313.7 nm and a water repellent agent on the fabric surface,

9 is a field emission scanning electron microscope photograph of the surface of the fabric of Example 3,

10 is an AFM shape photograph of Example 3. Fig.

Claims (5)

SiO ₂ sol (I) containing SiO ₂ nanoparticles having an average particle diameter of 5 to 100 nm and SiO ₂ sol (II) containing SiO ₂ nanoparticles having an average particle diameter of 250 to 5,000 nm have a volume ratio of 1: 1 to 40: 1 the mixed mixture SiO ₂ sol dispersed in the dispersion of polymer fibers chobal caregiver oil coating composition. The method according to claim 1, wherein the SiO ₂ sol (1) containing SiO ₂ nanoparticles having an average particle diameter of 5 to 100 nm has an Si content of 3200 to 6400 ppm, SiO ₂ nanoparticles having an average particle diameter of 250 to 5,000 nm _{2 < /} RTI > sol (II) has a Si content of 3600 to 7200 ppm. The composition of claim 1, wherein the water dispersible polymer is any one of a water-soluble fluoropolymer and a water-soluble fluorosilane-based polymer. The method according to claim 1, wherein the SiO ₂ sol (I) is a mixture of 1 to 30 wt% of tetraethyl orthosilicate, 3 to 4 wt% of nitric acid, 1 to 25 wt% of methanol, Wherein the SiO ₂ sol (II) is a mixed solution of 1 to 30% by weight of tetraethyl orthosilicate, 3 to 4% by weight of ammonia, 1 to 25% by weight of methanol and ultrapure water as the remainder Of the total weight of the composition. A process for producing a fiber-initiated water-repellent coating composition for fiber according to any one of claims 1 to 4, characterized in that the object to be processed is padded at a pickup ratio of 50 to 60% and cured at 170 to 175 ° C for 1 to 2 minutes Fiber water repellent processing method.

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