KR101339753B1 - Fluoro type water and Oil repellent Composition with Hyper Hydrophobic performance - Google Patents

Abstract

상기 화학식 1에서, n = 0 ~ 19, m = 5 ~ 20,
[화학식 2]

상기 화학식 2에서, n = 0 ~ 19, m = 5 ~ 20이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine water repellent composition having super water-repellent oil repellency. In the fluorine water repellent composition for fibers, a reactive surfactant having a structure of the following formula (1) or (2) is mixed with a fluorine water repellent monomer.
[Chemical Formula 1]

In Formula 1, n = 0 ~ 19, m = 5 ~ 20,
(2)

In Formula 2, n = 0 to 19 and m = 5 to 20.

Description

Fluoro type water and Oil repellent Composition with Hyper Hydrophobic performance}

The present invention relates to a fluorine water repellent composition having super water-repellent oil repellency, and more particularly, super water repellent for the purpose of improving both initial water repellency and washing durability by replacing a hydrophilic surfactant component with a fluorine-type reactive surfactant. A fluorine water repellent composition for fibers having oil repellency.

Water repellents generally used for textiles include wax-based, higher alcohol-based, silicone-based and fluorine-based water repellents. Among these, fluorine-based water repellents are most usefully used because of their excellent water repellency and oil repellency due to the basic physical properties of fluorine.

However, due to the characteristics applied to the fiber, it is exposed to various contaminants during use, and deterioration of water repellency is inevitable through repeated washing processes. Usually, after 10 times of washing process, only water repellency of less than 50% of the initial water repellency is shown. This is because the fluorine-based water repellent is the best hydrophobic material and does not have any water dissolving power, so there should be no deterioration in water repellency even during washing. Because it has to go through a forced emulsification using a component called a surfactant is subjected to a process of processing to the fabric. At this time, since the surfactant component remaining in the fluorine-based resin or the fabric has a very hydrophilic property, it accelerates the dropping of the fluorine water-repellent component during washing, resulting in a decrease in water repellency during several washing processes. .

In order to improve the water repellency lowering after the normal washing, a method of adding and processing a crosslinking agent which increases the degree of crosslinking of the fluororesin and delays dropping is preferred. Blocking isocyanate is used as the most commonly used type of crosslinking agent. When the blocked isocyanate dissociates at high temperature (mainly 150 ° C. or higher), the isocyanate acts as a crosslinking agent for the fluororesin, thereby improving the binding force between the fluorine water repellent and the fiber. It is reported to improve the durability by forming a three-dimensional network.

However, the conventional blocked isocyanate is also a hydrophobic material, so it cannot be used in combination with a fluorine water repellent used in water because it is not soluble in water. Therefore, this kind of crosslinking agent is inevitably prepared in liquid form using a hydrophilic surfactant through a forced emulsification process. In this case, since the compatibility with the fluorine water repellent does not come out, it has a disadvantage in that each of the two water repellents and block crosslinking agent to be prepared separately after treatment to the fabric. In addition, blocked isocyanate has no effect on improving oil repellency, although it imparts water repellency improving effect.

The surfactant used for the fluorine-repellent agent is used by mixing a fluorine-based and emulsion dispersibility suitable nonionic surfactant and a cationic surfactant for controlling the adsorption performance to the fiber. Some can be used alone, but mixed use yields better performance.

HLB (Hydrophilic Lipophilic Balance) is very important for the emulsifying nonionic surfactant, and typical surfactants used in this field include polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, and polyoxyethylene. Mono (substituted phenyl) ethers, polyol fatty acid esters, polyoxyalkylene polyoxypropylene copolymers (Co-Polymer) and the like. At this time, the alkyl group of the nonionic surfactant for emulsification may include an octyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a hexadecyl group, an oleyl group, and the like.

The cationic surfactants should be considered more carefully than non ions because they affect the zeta potential. As a representative cationic surfactant used in this field, a substituted ammonium salt type surfactant is used. , Dialkyl dimethyl ammonium chloride, dimethyl monolauryl amine acetate, and the like.

Since the choice of surfactant influences the size of the emulsified particles of the fluororesin, it affects the change of the emulsion stability over time, the stability of the dye or PH regulator, and the water repellency after heat treatment.

In addition, since the hydrophilic component is contained in the surfactant component, it affects the water repellency, oil repellency and fastness after washing, depending on the size and structural orientation of the hydrophilic component.

Existing fluorine water repellent composition includes a hydrophilic surfactant in order to be sprayed on water, the water repellency and oil repellency is poor as having a hydrophilic function, in particular, there is a disadvantage that the water repellency / oil repellency after washing is very low. Since water repellency and oil repellency in the water repellent for textiles require the most essential superiority, it is necessary to develop a water repellent capable of maintaining high water / oil repellency even after washing.

The present invention for solving the problems as described above has a hydrophilic surfactant component to disperse the water in the conventional fluorine water repellent composition for the hydrophilic surfactant to compensate for the disadvantages of both the initial water repellency and water repellency and oil repellency after washing It is an object of the present invention to provide a fluorine water repellent composition having a super water- and oil-repellent property capable of improving both initial water repellency and laundry durability by replacing a component with a fluorine-type reactive surfactant.

To this end, an object of the present invention is to prepare a reactive emulsifier having an HLB value (Hydrophile-Lipophile Balance) that can replace the hydrophilic surfactant component and to use it as an emulsifier for fluorine water repellents.

The present invention for achieving the above object is characterized in that in the fluorine water repellent composition for fibers, a mixture of a reactive surfactant having a structure of the formula (1) or (2) and a fluorine water repellent monomer.

[Formula 1]

In Formula 1, n = 0 ~ 19, m = 5 ~ 20,

(2)

In Formula 2, n = 0 to 19 and m = 5 to 20.

In addition, the fluorine water repellent monomer,

(A)

Fluoroacrylate

R = -H or -CH ₃

l, m = 1 ~ 20

[Formula b]

Special reactive acrylates

R = -H or -CH ₃

q = 1-20

(C)

Alkyl acrylate

R = -H or -CH ₃

q = 1 to 22

[Chemical formula d]

Vinyl halogen compounds

R = -H or -CH ₃

 X = Halogen compound (ex. -F, -Br, -Cl)

It is characterized by having any one of formula.

In addition, Formula 1 and Formula 2 are characterized in that it corresponds to a complex composition having a double bond group, a fluorine group, and a polyoxyethylene group.

The present invention constructed and operated as described above replaces the fluorine-type reactive surfactant with a hydrophilic surfactant to maintain the degree of hydrophilicity, while improving the water repellency and oil repellency while maintaining the overall emulsifying power in addition to the lipophilic property. There is an advantage to maximize.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the superhydrophobic oil repellent composition having a water- and oil-repellent according to the present invention.

The fluorine water repellent composition having a super water- and oil-repellent property according to the present invention is characterized in that the fluorine water repellent composition for fibers is formed by mixing a reactive surfactant having a structure of the following formula (1) or (2) with a fluorine water repellent monomer.

Where n = 0 to 19, m = 5 to 20,

Where n = 0 to 19 and m = 5 to 20.

The superhydrophobic water repellent may be synthesized by forcibly emulsifying the emulsifier having the structure of Formula 1 or Formula 2 and the monomer for fluorine water repellent.

HLB, the most distinctive feature of surfactant, meets the needs of searching for a surfactant that is suitable for the purpose of use because there are many kinds of surfactants.The concept of HLB (Hydrophile-Lipophile Balance) Is a value indicating the degree of affinity for water and oil. The HLB values are from 0 to 20, and the closer to 0, the better the lipophilicity, and the closer to 20, the better the hydrophilicity. Conventional surfactants used for fluorine water repellents have a high HLB of about 15 to 20 surfactants and have high hydrophilicity.

The reactive emulsifier to be synthesized by the present invention aims to improve the water repellency and oil repellency while maintaining the degree of hydrophilicity while introducing a fluorine group to the lipophilic portion while maintaining the emulsifying force as a whole.

In particular, since the reactive emulsifier has a reactor such as a double bond in its molecular structure, it also reacts with the fluorine water-repellent resin to be covalently bonded to the resin, so that the water resistance can be improved unlike the conventionally added emulsifier. . In addition, the contained fluorine component is thought to further improve oil repellency due to the molecular structure oriented next to the hydrophilic portion with the addition effect.

The superhydrophobic oil and water repellent composition according to the present invention is to replace the hydrophilic surfactant component with a fluorine-type reactive surfactant to synthesize both fluorine alcohol and acrylic monomer to improve both initial water repellency and washing durability. The main technical point of the present invention is to provide a fluorine water repellent composition which is prepared, and mixed during the synthesis of the fluorine water repellent agent to introduce a reactive fluorine group into the resin molecular structure, thereby improving both water repellency and oil repellency.

Formula 1 and Formula 2 are both complex performance materials having a double bond group (polymerization with acrylic resin), a fluorine group (water repellency impartment), and a polyoxyethylene group (emulsification impartment) in the molecular chain. The longer the length of the carbon chain in the fluorine group is, the more water-repellent effect is provided, but if it is too long, it may be a factor to lower the emulsifying power.

Existing fluorine-based water-repellent monomer may have a structure of formula 3 to formula 6 below.

R = -H or -CH ₃

 l, m = 1 ~ 20

Fluoroacrylate

R = -H or -CH ₃

 q = 1-20

Special reactive acrylates

R = -H or -CH ₃

 q = 1 to 22

Alkyl acrylate

R = -H or -CH ₃

 X = Halogen compound (ex. -F, -Br, -Cl)

Vinyl halide compounds

Therefore, the fluorine water repellent composition according to the present invention synthesizes fluorine alcohol with an acrylic monomer to produce a fluorine-based reactive emulsifier, and the prepared reactive emulsifier is mixed during synthesis of the fluorine water repellent to introduce a reactive fluorine group into the resin molecular structure to prepare a water repellent composition. do. The reaction scheme of the reactive emulsifier according to the present invention is as follows.

[Reaction Scheme 1]

Where n = 0-19, m = 5-20.

[Reaction Scheme 2]

Where n = 0-19, m = 5-20.

Examples 1 to 3 and Example 4 for the water repellent mixed test are carried out.

Example 1

Prepare a reactor equipped with an air inlet tube, reflux condenser, thermometer, agitator, and vacuum pump, and after completely dehydration, into the reactor, 130 parts of Itaconic Acid, 80 parts of Toluene, 5 parts of p-TolueneSulfonic Acid, fluorine alcohol ( 500 parts of Fluowet EA 812, Clariant), 600 parts of polyoxyethylene glycol (PEG-600, KPX), and 1 part of MEHQ were added, and the temperature was raised to 110 degrees while stirring to proceed with the reaction for about 10 hours. The end point of the reaction is neutralized with acid and confirmed by GC based on unreacted fluorine alcohol to terminate the reaction at 0.5% or less.

(GC Condition: SE-30 10% 1m, INJ temperature: 280 ° C, column temperature: 320 ° C, carrier gas: N ₂ (30ml / min), detector: FID 300 ° C, sample injection rate: 0.6μl)

The finished reaction solution was washed three times with caustic soda solution (10% diluent) and ion-exchanged water solution, and then filtered using a fine filter cloth. It can be confirmed that the final compound is synthesized with an efficiency of over 99% (based on GC quantitative analysis).

[Example 2]

Prepare a reactor equipped with an air inlet tube, reflux condenser, thermometer, agitator, and vacuum pump, and after completely removing water, 58 parts of aryl alcohol, 80 parts of Hexane, 5 parts of sodium hydroxide, and fluorine alcohol (Fluowet EA) 812, Clariant) 500 parts, Epichlorohydrin 93 parts, TriethanolAmine 150 parts, MEHQ 1 part was added, the temperature was raised to 80 degrees while stirring to proceed the reaction for about 10 hours. The end point of the reaction is to neutralize the reaction solution with an acid and terminate the reaction at 0.5% or less by checking GC on the basis of fluorine alcohol.

(GC Condition: ： SE-30 10% 1m, INJ temperature: 280 ° C, column temperature: 320 ° C, carrier gas: N ₂ (30ml / min), detector: FID 300 ° C, sample injection rate: 0.6μl)

The finished reaction solution was washed three times with caustic soda solution (10% diluent) and ion-exchanged water solution, and then filtered using a fine filter cloth. It can be confirmed that the final compound is synthesized with an efficiency of over 99% (based on GC quantitative analysis).

The composite product was put into a separate high-pressure reactor and connected with an ethylene oxide (molar ratio based on about 10 to 15 mol) gas pipe to undergo an ethoxylated reaction at high pressure for 120 ° C and a reaction time of 5 hours. Synthesize The final composite is identified by GC, FT-IR (1120 cm ^-1 -ethylene glycol group).

[Example 3]

After preparing a reactor equipped with an addition funnel, reflux condenser, thermometer, and stirring device, pre-injected ion-exchanged water into the reactor, 20 parts of the synthetic product synthesized in Example 1, 100 parts of fluoroacrylate (FLUOWET AC812, Clariant), 100 parts of bihenyl acrylate, 150 parts of lauryl acrylate, 50 parts of vinyl chloride, 5 parts of polyoxyalkylene polyoxypropylene copolymer (PE-74, KPX) and 10 parts of dialkyldimethylammonium chloride were added to raise the temperature to 80 degrees. Complete emulsification. The emulsion is separated when stirring stops. The emulsion is prepared through a forced emulsification process three times at a pressure of 600Bar using a high pressure homogenizer to prepare a stable emulsion.

The synthesis is carried out at 80 ° C. for about 3 hours using an organic catalyst (AIBN) diluted in a hydrophilic solvent in a separate catalyst input tube.

Dipropylene glycol is added in about 5% of solids for emulsion stability. Dilute 5 parts of glacial acetic acid, add to mature for 1 hour, and then add water to obtain about 1,000 parts of a pale yellow-light yellow semi-transparent dispersion having a solid content of 30%.

Example 4

It carried out by the same method as Example 3 except having used the synthetic product of Example 2 instead of the synthetic product of Example 1 in the said Example 3.

Comparative Example 1

Except for the synthesis of Example 1 in Example 3, it was carried out in the same manner as in Example 3.

The liquid synthesized in Examples and Comparative Examples was prepared to compare stability, durability, water repellency, and oil repellency.

No
division
stability
(40 ℃ * 1 month)
Durable water repellency ¹⁾

Oil repellent ²⁾
HL = 0
HL = 5
One

Comparative Example 1
An Jung
100
50
Grade 4
2

Example 3
An Jung
100
70
6th grade
3

Example 4
An Jung
100
80
6th grade

1) The fabric was immersed in 30g / l liquid based on water repellent using 40'S of 100% polyester fabric, and then padded by pick-up 80% by passing through mangle, and dried and cured (170 ℃ * 1min). After that, the water repellency was measured according to the AATCC 22 method (spray method). The washing method of the fabric was tested according to KS K 0432 method.

2) The oil repellency test measured oil repellency according to AATCC 18 method. Since the oil repellency improvement effect is proportional to the fluorine content, it indirectly suggests that the fluorine-based reactive emulsifier is distributed in the water repellent agent.

The present invention configured as described above can maximize the water repellency and oil repellency by replacing the fluorine-type reactive surfactant with a hydrophilic surfactant to add hydrophilicity while maintaining hydrophilicity as it is to maintain the emulsifying power as a whole There is an advantage.

While the invention has been described and illustrated in connection with a preferred embodiment for illustrating the principles of the invention, the invention is not limited to the construction and operation as shown and described. Rather, those skilled in the art will appreciate that many modifications and variations of the present invention are possible without departing from the spirit and scope of the appended claims. And all such modifications and changes as fall within the scope of the present invention are therefore to be regarded as being within the scope of the present invention.

Claims (3)

In the fluorine water repellent composition for fibers,
It is made by mixing a reactive surfactant having a structure of Formula 1 or Formula 2 and a fluorine water repellent monomer,
The fluorine water repellent monomer,
(A)
Fluoroacrylate

R = -H or -CH ₃
l, m = 1 ~ 20

[Formula b]
Special reactive acrylates

R = -H or -CH ₃
q = 1-20

(C)
Alkyl acrylate

R = -H or -CH ₃
q = 1 to 22

[Chemical formula d]
Vinyl halide compounds

R = -H or -CH ₃
X = Halogen compound (ex. -F, -Br, -Cl)
Super water- and oil-repellent fluorine water repellent composition, characterized in that it has any one of the formula.
[Chemical Formula 1]

In Chemical Formula 1, n = 1 to 19, m = 5 to 20,

(2)

In Formula 2, n = 1 to 19, m = 5 to 20. delete According to claim 1, Formula 1 and Formula 2,
A fluorine water repellent composition having super water / oil repellency having a double bond group, a fluorine group, and a polyoxyethylene group.