KR20140004035A - Macromolecular compounds, antifouling coating composition, and product obtained by applying the same - Google Patents

Abstract

The present invention relates to an antifouling coating composition, particularly a chemically reformed perfluoropolyether macromolecular compound and an antifouling coating composition containing the same. The antifouling coating composition can provide a half-easy (finger print resistance) function or an easy cleaning function by being coated on the surface requiring the antifouling and the surface of a display with a touch screen such as cellular phones, and showing water repellency and oil repellency. [Reference numerals] (AA) Synthesis; (BB) Refining; (CC) Modified fluorinated silane nano-polymer compound

Description

TECHNICAL FIELD The present invention relates to an antifouling coating composition comprising a polymer compound and a polymer compound, and a product having an antifouling function using the same,

TECHNICAL FIELD The present invention relates to a polymer compound and an antifouling coating composition comprising the polymer compound and a product having an antifouling function using the same. More particularly, the present invention relates to a chemically modified perfluoropolyether polymer compound and an antifouling coating composition comprising the same, It is coated on a screen with a screen or on a surface requiring prevention of contamination, thereby exhibiting water repellency and oil repellency to give half-easy (easy to clean) or easy to clean (easy to clean) And an antifouling coating composition comprising the polymer compound and an article having an antifouling function using the same.

Some products used in everyday life may have fingerprints, sebum, sweat, cosmetics and other contaminants adhered to the surface depending on the user's use. Such contaminants are not easy to remove once they are adhered. Therefore, there is a problem that a product such as furniture or the like damages aesthetics of the appearance, or an electronic product such as a mobile phone affects a touch function and the like.

As a means for solving such a problem, there has been proposed a method of forming a layer having antifouling properties on a surface requiring antifouling property such that contaminants are difficult to adhere easily and can be easily removed even if adhered thereto.

However, a suitable antifouling coating composition has not yet been proposed.

Korean Patent Publication No. 10-2011-0104357

It is an object of the present invention to provide a novel material which can be applied to the surface of a product to produce a coating composition which can easily impart excellent half-edge and easy cleaning performance.

It is still another object of the present invention to provide a coating composition that can be applied to the product surface to easily impart excellent half-edge and easy cleaning performance.

It is still another object of the present invention to provide a method for producing a novel material capable of producing a coating composition which is applied to the surface of a product to easily impart excellent half-edge and easy cleaning performance.

It is another object of the present invention to provide a product having excellent half-edge and easy cleaning performance.

In order to accomplish the object of the present invention, the present invention provides a modified fluorine silane nano-polymer compound represented by the following formula (1)

[Formula 1]

_{AO - (- CF 2 -CF (} CF 3) -O-) x - (- CF 2 -CF2-O) y - (- CF 2 -O-) z -B

Wherein A and B are CF ₂ CH ₂ O - (- C ₂ H ₄ --O) n C ₃ H ₆ Si - (- OR) ₃ and 1≤x≤8, 1≤y≤6, 1≤z≤ 6, R is a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 8.

In order to accomplish still another object of the present invention, the present invention provides an antifouling coating composition comprising the modified fluorine silane nano-polymer compound of Formula 1.

In order to accomplish still another object of the present invention, the present invention provides a product coated with an antifouling coating agent according to the present invention.

When the coating layer is formed by the coating composition comprising the modified fluorine silane nano-polymer compound according to the present invention, the contamination source is not easily adhered to the surface and is easily removed even if it is adhered. Thus, the appearance of the product is not stained, It is possible to prevent a malfunction of a device sensitive to a pollution source.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram schematically illustrating a method for producing a modified perfluoropolyether according to an embodiment of the present invention. FIG.
FIG. 2 is a schematic view showing a method for producing a modified fluorine silane nanoparticle compound according to an embodiment of the present invention.

Hereinafter, the present invention will be described more specifically.

According to the present invention, there is provided a modified fluorine silane nano-polymer compound represented by the following formula (1).

[Formula 1]

_{AO - (- CF 2 -CF (} CF 3) -O-) x - (- CF 2 -CF2-O) y - (- CF 2 -O-) z -B

Wherein A and B are CF ₂ CH ₂ O - (- C ₂ H ₄ --O) n C ₃ H ₆ Si - (- OR) ₃ and 1≤x≤8, 1≤y≤6, 1≤z≤ 6, R is a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 8.

PFPE (perfluorinated ether group) polymers are incompatible with common organic solvents. Therefore, a hydrosilylation interfacial reaction should be performed in a very diluted state using only a fluorine solvent.

The present invention provides a method for synthesizing and purifying a perfluoropolyether-modified silane-based fluorine polymer compound having a basic structure of PFPE but containing a polyalkylene oxide functional group between a PFPE structure and a silane structure in order to improve adhesion.

The denatured fluorine silane nano-macromolecule compound of the above formula (1) is modified with trialkoxysilane at both ends using PFPE characterized by hydroxy functional groups at both ends to prepare a highly concentrated PFPE-based modified silane-based macromolecule compound, And suitable additives are selected to produce a coating composition having excellent antifouling properties such as a fingerprint-preventing property.

≪ Modification of Chemical Formula 1 Fluorine silane  Preparation of nanoporous polymer compound >

According to one embodiment of the present invention, the modified fluorine silane nano-polymer compound of Formula 1 is prepared by the following steps:

Reacting perfluoropolyether and polyalkylene oxide in the presence of a catalyst under a pressure of 3 to 7 bar at 35 to 65 ° C for 10 to 20 hours to prepare a modified perfluoropolyether;

Cooling the modified perfluoropolyether to room temperature, introducing an organic solvent to phase-separate the polymerized perfluoropolyether; And

Collecting the lower layer in the phase-separated solution and reacting it with alkoxysilane or alkylsilane in the presence of a catalyst.

- degeneration Perfluoropolyether  Produce

The original perfluoropolyether compounds can be synthesized according to known methods [JAMES T. HILL, J. Macromol. Sci. Chem. , A8, (3), p499 (1974)]. Can be obtained by reacting hexafluoropropylene oxide (HFPO) with cesium fluoride in an appropriate solvent, for example, tetraglyme. The degree of polymerization (molecular weight) of the obtained perfluoropolyether can be controlled by the introduction rate of HFPO and the reaction temperature, and the degree of polymerization is confirmed by gel permeation chromatography (GPC) as a polymerized ester polymerized by reacting terminal functional groups with methanol The synthesis of the polymer having the optimum length (molecular weight) was possible.

According to an embodiment of the present invention, the catalyst may be platinum (Pt), zeolite, or ruthenium (Ru), preferably a platinum catalyst.

According to one embodiment of the present invention, the polyalkylene oxide preferably has a weight average molecular weight of 300 to 800, and may be prepared by using an organic halide such as allyl bromide according to a method known in the art .

According to one embodiment of the present invention, the perfluoropolyether and the polyalkylene oxide are reacted at 35 to 65 ° C for 10 to 20 hours under a pressure of 3 to 7 bar to prepare a modified perfluoropolyether.

At this time, the reaction may be carried out in an organic solvent. For example, THF (tetrahydrofuran), MEK (methyl ethyl ketone) and the like may be used as the organic solvent.

The organic solvent such as THF is preferably used as a catalyst recovery solvent.

Thereafter, water is added to terminate the reaction, and a phase separation catalyst and an organic solvent for phase separation are added to induce phase separation.

As the phase separation catalyst, tetra-n-butylammonium bromide (TBAB) and the like may be used.

As the phase separation solvent, a fluorine-based solvent may be used, and for example, perfluoroether-based, perfluorocarbon-based, perfluoroalkane-based, hydrofluorocarbon-based, etc. may be used. Specific examples thereof include octafluorobutane, decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,2,2-tetrafluoro-1 - (2,2,2-trifluoroethoxy) ethane or the like is preferably used.

* When phase separation occurs, the lower layer is collected and reacted with the silane-based compound. The silane compound may be any compound capable of producing a silane-based modified polymer compound such as alkoxysilane or alkylsilane. For example, tetramethoxysilane (TMS), trimethoxysilane and the like can be preferably used.

According to the above method, the modified fluorine silane nano-polymer compound of formula (1) according to the present invention is obtained.

≪ Preparation of antifouling coating composition >

The antifouling coating composition according to the present invention comprises the modified fluorosilane nano-macromolecular compound of formula (1) prepared according to the present invention, preferably a modified fluorosilane nano-polymer compound of formula (1), a fluorinated solvent and an additive.

The fluorine-based solvent is the same as the above-mentioned solvent, and as the additive, a curing agent or other functional additives may be preferably included.

Examples of the curing agent include R- (NCO) 3 (wherein R is an alkyl group having 1 to 10 carbon atoms) and can be easily selected by those skilled in the art.

Or two or more of the following curing agents may be mixed and used.

Among these, preferred curing agents are polycarboxylic acid anhydrides such as nadic anhydride (NA), methylnadic anhydride (available from MNA-Aldrich), 1,4-cyclohexane-bis (methylamine) Bis (3-aminopropyl) tetramethyldisiloxane, hexamethylenediamine, triethylenetetramine, N-aminoethylpiperazine (available from AEP-Aldrich), 1,3-diaminobenzene, Benzene, 4,4'-diaminodiphenylmethane and polyaminosulfone, and also polyols such as ethylene glycol (purchased from EG-Aldrich), poly (propylene glycol), and poly (vinyl alcohol).

According to an embodiment of the present invention, the modified fluorine silane nano-polymer compound of Formula 1 is contained in an amount of 0.1 to 10% by weight based on the total weight of the antifouling coating composition. If it is contained in an amount less than the above-mentioned content, it is difficult to exhibit an antifouling function, and if it is contained in a large amount, the coating strength of the coating layer may be lowered.

According to an embodiment of the present invention, the organic solvent may be contained in an amount of 90 to 99.5% by weight of the antifouling coating composition, and the additive may be included in an amount of 0.3 to 3% by weight.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by the following examples.

Degeneration Fluorine silane  Preparation of nanoporous polymer compound >

Synthetic example  One

2000 g of perfluoropolyether (Dupont Krytox 157 FSM), 6000 g of tetrahydrofuran, 360 g of water and 112.2 g of KOH were added in this order to a stainless steel high-pressure reactor equipped with a stirrer, a cooling jacket, a thermometer and a pressure gauge and stirred at 50 DEG C for 1 hour .

2 g of tetra-n-butylammonium bromide was added to the stirring solution, and 30 minutes later, 1-bromoprop-2-ene was added.

Further, 112.20 g of KOH was further added.

Thereafter, water was added for 72 hours or longer to terminate the reaction [amount of water (180 g x 2 times)]

Thereafter, the mixture was phase-separated using perfluoropolyether (Dupont Krytox 157 FSM), and phase-separated once with dilute sulfuric acid and once with water.

It was then washed twice with tetrahydrofuran.

After dehydration and adsorption with magnesium sulfate anhydride (MgSO ₄ anh.) And silica mixture, it was filtered and concentrated under vacuum to solid content to obtain 70% modified perfluoropolyether.

The modified perfluoropolyether was diluted with perfluoropolyether (Solvay's Galden HT-170.) At a concentration of 50%. To 200 g of the diluted modified perfluoropolyether 2082.00 g of perfluoropolyether (Dupont Krytox 157 FSM), 2082.00 g of ethoxy-nonafluorobutane (HFE-7200, 3M Novec) of 0.2 mol%, 6 g of platinum catalyst and 6 g of hexa-methyl-disilazane were added in this order and the temperature was adjusted to 50 ° C. 10% MeOH was added dropwise.

After reacting for 17 hours, the reaction mixture was cooled to room temperature, and 4164 g of tetrahydrofuran was added thereto for phase separation.

The lower layer was collected and the upper layer was washed with perfluoropolyether to induce phase separation again. The lower layer was collected again and the upper layer was washed with perfluoropolyether.

MgSO 4 anh. Was added to the lower layer, and the mixture was stirred for 3 hours or more, and filtered using a 1 μm porous filter (Grade 1, Wattman, USA).

The mixture was rotated at a rotation speed of 30 times / minute for 30 minutes at 50 DEG C and left under vacuum at room temperature for 30 minutes to obtain a solid fluorinated silane nano-polymer compound (yield: 35%).

The obtained modified fluorine silane nano-macromolecule compound was subjected to ¹ H-NMR measurement to obtain the following spectral data.

_{- 0.7ppm t, 2H CF 2 CH} 2 O - (- CH 2 -CH 2 -O) 2 -CH 2 -CH 2 - CH 2 Si - (- OCH 3) 3

- 1.7 ppm m, 2H CF ₂ CH ₂ O - (- CH ₂ --CH ₂ --O) ₂ --CH ₂ --CH ₂ --CH ₂ Si - (- OCH ₃ ) ₃

- 3.5 ppm t, 2H CF ₂ CH ₂ O - (- CH ₂ --CH ₂ --O) ₂ --CH ₂ --CH ₂ --CH ₂ Si - (- OCH ₃ ) ₃

- 3.8 ppm s, 2H CF ₂ CH ₂ O - (- CH ₂ --CH ₂ --O) ₂ --CH ₂ --CH ₂ --CH ₂ Si - (- OCH ₃ ) ₃

_{- 3.6ppm s, 9H CF 2 CH} 2 O - (- CH 2 -CH 2 -O) 2 -CH 2 -CH 2 -CH 2 Si - (- O CH 3) 3

- 3.8 ppm s, 4H CF ₂ CH ₂ O - (- CH ₂ - CH ₂ --O) ₂ --CH ₂ --CH ₂ --CH ₂ Si - (- OCH ₃ ) ₃

- 3.8 ppm d, 4H CF ₂ CH ₂ O - (- CH ₂ --CH ₂ --O) ₂ --CH ₂ --CH ₂ --CH ₂ Si - (- OCH ₃ ) ₃

≪ Preparation of antifouling coating composition >

Example  1 to 5

An antifouling coating composition was prepared using the modified fluorine silane nano-macromolecular compound obtained in Synthesis Example 1, isocyanic acid as a curing agent, and ethoxy-nonafluorobutane as a fluorinated solvent at the blending ratios shown in Table 1 below.

(Unit weight%) Modified fluorine silane
Nano-polymer compound Hardener Fluoric solvent Example 1 0.1 2 97.9 Example 2 One One 98 Example 3 5 0.5 94.5 Example 4 10 0.3 89.7 Example 5 15 0.3 84.7

Experimental Example  1: coating

Piece: Corning (USA) Gorilla Glass 4 inches was used. Coater ACE-200 was used as a coater and 0.8 mm (orifice) FA110 (P) of Meiji (Japan) was used as a spray gun. A Korean Trade 150L hot air oven was used as the curing oven.

The coating conditions were a spin-coater speed of 1000 rpm, spraying conditions of 5 ml / min, 10 sec and 0.8 kg / cm 2 (injection pressure), and curing and drying conditions were set at 120 ° C for 1 hour in a hot air oven.

The coating procedure is to pre-treat the specimen with a plasma or cleaning agent to keep the surface clean, place the specimen (gorilla glass) on a spin-coat chuck, press a vacuum button to specimenize, hold the spin coater at 0-1000 rpm , And at an air pressure of 0.8 kg / cm < 2 > for 5 seconds at a rate of 5 ml per minute.

The injection pattern was a full cone type, and the specimen was allowed to stand at room temperature for 20 to 30 seconds after the spin coater vacuum was released after injection.

The specimen was cured and dried in a hot air oven at 120 DEG C for about 1 hour.

The cured specimens were allowed to stand at room temperature (23 ° C, 60% RH) for 24 hours and then subjected to reliability evaluation.

Experimental Example  2: Reliability evaluation

The evaluation device was a contact angle meter (Surface Tech, Korea) GSX-300 (condition: 3rd order (water)), an abrasion tester [Daesung precision rubber eraser tester (test condition: 45 rpm, 1500 times)], [Core Tech CT-ST60 (Condition: 30 ° C, 5% aqueous solution of NaCl solution for 72 hours)] was used.

The initial contact angle of the coated specimen was measured, and the contact angle of the coated specimen was measured using a rubber eraser with an abrasion tester at a speed of 45 rpm for 1500 times.

The coated specimens were maintained in a salt sprayer maintained at 30 캜 for 72 hours in an atmosphere in which an aqueous solution of 5% NaCl was continuously sprayed, and contact angle was measured.

The initial contact angle and the deviation of the contact angle after evaluation were evaluated.

Sensitivity evaluation (slip evaluation = blind evaluation) was performed to at least 5 persons to touch the surface of each coated specimen with a finger, and sensory evaluation of the degree of slip was carried out. The evaluation score of 1 to 5 (lowest: 1 point, Best: 5 points).

The results are shown in Table 2 below.

Performance Example
Easy Cleaner
(Korea) Bertrale K
(United States of America) Nanos rain)
Japan) One 2 3 4 5 Coating method Wet Wet Wet Wet Wet Wet Wet Wet Early
Contact angle 114 ° 115 ° 115 ° 114 ° 113 ° 108 ° 112 ° 110 ° Abrasion resistance (1500 times) 113 ° 111 ° 111 ° 111 ° 112 ° 95 ° 110 ° 103 ° Salt spray (72 hours) 106 °
(OK) 108 °
(OK) 110 °
(OK) 107 °
(OK) 106 °
(OK) 100 °
(OK) 105 °
(OK) 96 °
(NG) Sensitivity touch (sensory) 4 5 5 4 4 2 4 3

As can be seen from the above Table 2, the coating composition comprising the modified fluorine silane nano-polymer compound according to the present invention shows excellent antifouling properties as compared with the conventional coating composition.

Claims (11)

A modified fluorine silane nano-polymer compound represented by the following formula (1)
[Chemical Formula 1]
_{AO - (- CF 2 -CF (} CF 3) -O-) x - (- CF 2 -CF2-O) y - (- CF 2 -O-) z -B
Wherein A and B are CF ₂ CH ₂ O - (- C ₂ H ₄ --O) n C ₃ H ₆ Si - (- OR) ₃ and 1≤x≤8, 1≤y≤6, 1≤z≤ 6, R is a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 8. An antifouling coating composition comprising the modified fluorine silane nano-polymer compound of claim 1. 3. The method of claim 2,
Wherein the modified fluorine silane nano-polymer compound is contained in an amount of 0.1 to 10% by weight of the antifouling coating composition. 3. The method of claim 2,
Wherein the antifouling coating composition further comprises an organic solvent and a curing agent. 5. The method of claim 4,
Wherein the organic solvent comprises 90 to 99.5% by weight of the antifouling coating composition,
Wherein the curing agent is contained in an amount of 0.3 to 3% by weight of the antifouling coating composition. 5. The method of claim 4,
Wherein the modified fluorine silane nano-polymer compound is contained in an amount of 0.1 to 5 wt%, the organic solvent is 93 to 99.5 wt%, and the curing agent is contained in an amount of 0.40 to 2 wt%. 5. The method of claim 4,
Wherein the organic solvent is at least one fluorinated solvent selected from the group consisting of perfluoroplyether, perfluorocarbon, perfluoroalkane and hydrofluorocarbon, By weight of the antifouling coating composition. 5. The method of claim 4,
Wherein the curing agent is a compound of R- (NCO) 3, wherein R is an alkyl group having 1 to 10 carbon atoms. Characterized in that the surface is coated with the coating composition of any one of claims 2 to 8. 10. The method of claim 9,
Characterized in that the product is an electronic product or furniture. 10. The method of claim 9,
Wherein the product is an electronic product having a display surface with a touch screen.

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