KR20160083293A - Coating composition having improved slip and antifouling properties - Google Patents

Abstract

The present invention relates to a fluorocarbon polymer; At least one slip agent selected from the group consisting of a polyether-modified polydimethylsiloxane-based compound, a fluorine-modified polyacrylate-based compound and a perfluoropolyether (PFPE) -based compound; And a coating composition comprising a solvent. According to the present invention, it is possible to provide a coating composition having a slip property by lowering a friction coefficient by including a slip agent together with a fluorocarbon polymer, and the coating composition has a late contact angle measured after an initial contact angle and a wear resistance test Are all high, it is possible to form a coating film having excellent initial pollution prevention effect and durability.

Description

TECHNICAL FIELD [0001] The present invention relates to a coating composition excellent in slip properties and antifouling properties,

The present invention relates to a coating composition excellent in slip properties and antifouling properties, and more particularly, to a coating composition having excellent slip properties and antifouling properties by including a fluorocarbon polymer and a slip agent.

Fluorine forms a strong carbon-fluorine bond because it has a high electron density, a small atomic radius next to hydrogen atoms, and strong electronegativity. Due to the characteristics of fluorine, monomers containing perfluoroalkyl groups have a critical surface tension of about 6 ~ 8 dynes / cm and surface energy is very low, which repels both water and oil. As a result, the fluorine-based compound is superior in terms of chemical stability, heat resistance, weatherability, non-stickiness, low surface energy, water repellency and low refractive index.

At present, fluorocompounds have excellent performance that can not be realized by other materials due to stain resistance, weather resistance, heat resistance and optical characteristics. Therefore, fluorochemicals are used as core materials of next generation technology in optical communication, optoelectronics, semiconductor, . Especially, in relation to contamination resistance, it is applied to the household appliances, construction, shipbuilding and civil engineering fields requiring the conventional contamination surface property including the anti-toughening coating of the touch screen panel (TSP) With increasing interest in anti-fouling coatings in various paints and coatings, studies on fluorinated functional materials are actively under way.

The touch screen panel is expanded to include tablet PC, notebook, monitor, TV, and the like, including the display of a mobile phone, and the area to which the touch panel is applied is also widening. However, the touch screen panel is often exposed to the screen, and there is a disadvantage that a finger or a ball or the like is likely to come into direct contact with the touch screen panel, so that contaminants easily catch. Therefore, there is a growing demand for a technique for making fingerprints less likely to adhere to the surface of a display or a technique for preventing adhesion of contaminants to improve appearance and visibility.

Furthermore, the development of next-generation advanced displays and wearable devices will increase the need for anti-fouling coating materials. Particularly, wearable devices tend to easily adhere to their own parts, such as fingerprints, sebum, sweat, and cosmetics due to direct contact, and tend to be difficult to remove when they are attached.

 Conventionally, fluorine-based materials for imparting water repellency, oil repellency and anti-contamination properties include coating materials containing fluorine-silicon or fluorocarbon polymers. These compounds are composed of a fluorine-based compound exhibiting antifouling property, a network structure for facilitating adhesion with the substrate, or a functional group attached to the substrate. A so-called silane coupling method for bonding an inorganic material such as glass with an organic material as a representative fluorine-silicon based surface coating agent used for this purpose has been proposed.

The silane coupling method includes a chemical structure and a reactive alkoxysilane group that are highly compatible with an organic functional group or an organic material in one molecule. The reactive alkoxysilane group causes a self condensation reaction due to moisture in air or the like to become a siloxane, And forms a chemical bond with a surface of glass, a metal surface, or the like, thereby exhibiting strong adhesion. Due to these advantages, a silane coupling agent is widely used as a coating component and a primer on various substrate surfaces, and a great deal of research has been published.

For example, Patent Document 1 is a fluorine ^{_{- C 8 F 17 C 2 H}} 4 Si (NH) 3/2, C 4 F 9 C 2 H 4 Si (NH) 3/2 or poly-siloxane as a surface coating of the silicon series Southern ( poly siloxazane) and the like. However, when these compounds are used singly, the crosslinking property with the inorganic oxide on the surface of the substrate is low, so that the durability against the friction is poor. When only the fluorine compound is used alone, the initial contamination prevention property is excellent, There is a durability problem apart. Further, there is a problem in application of a textile treatment agent for water repellency and IT equipment that requires elasticity, packing, or silp (silp) because of the unique elasticity of the fluorine compound and the soft feeling.

U.S. Patent No. 4,678,688

A problem to be solved by the present invention is to provide a coating composition capable of imparting slip properties and antifouling properties.

Another object of the present invention is to provide a coating composition having improved durability.

In order to solve the above-mentioned problems, the present invention relates to (i) a fluorocarbon polymer represented by the following formula (1); (Ii) at least one slip agent selected from the group consisting of a polyether-modified polydimethylsiloxane-based compound, a fluorine-modified polyacrylate-based compound and a perfluoropolyether (PFPE) -based compound; And (iii) a solvent.

[Chemical Formula 1]

In the above Chemical Formulas 1 to 4, n is 15 ~ 25, R is CH ₃ O ^-, or CH ₃ CH ₂ O ^-, and may be three OR bonded to Si are be the same or different from each other.

The content of the fluorocarbon polymer is preferably 0.05 to 1.0 wt% based on the total weight of the coating composition, and the fluorocarbon polymer preferably has a weight average molecular weight of 2,000 to 4,000.

The polyether-modified polydimethylsiloxane-based compound may be any one or two or more selected from the group consisting of a compound represented by the following formula (2) and a derivative thereof, and the perfluoropolyether compound is represented by the following formula , Compounds represented by the following formula (4) and derivatives thereof, and the content of the slip agent is 0.1 to 1.0% by weight, based on 100% by weight of the fluorocarbon polymer .

(2)

In the above formula (2), n is 1 to 25.

And,

(3)

[Chemical Formula 4]

In the above formulas (3) and (4), n is 8 to 45.

The solvent may be a fluorine-containing solvent selected from the group consisting of perfluoroether, perfluorohexane and mixed solvents thereof, 1,3-bis (trifluoromethyl) benzene, 1,3- 2,2,2-trifluoroethanol, and mixtures thereof. The second solvent may further include a second solvent selected from the group consisting of 2,2,2-trifluoroethanol and mixtures thereof. The content of the second solvent is preferably 1 to 5% by weight based on the total weight of the coating composition.

According to the present invention, by including a slip agent together with a fluorocarbon polymer, a coating composition having an excellent slip property can be provided by lowering the coefficient of friction. Therefore, in the case of the coating film prepared using the coating composition, it is easy to wipe off fingerprints or contaminants when adhered to the surface, and the touch sensitivity is improved.

In addition, the coating composition according to the present invention has a high initial contact angle and a late contact angle measured after the abrasion resistance test, so that a coating film having excellent initial contamination prevention effect and durability can be formed.

The present invention relates to (i) a fluorocarbon polymer represented by the following formula (1); (Ii) at least one slip agent selected from the group consisting of a polyether-modified polydimethylsiloxane-based compound, a fluorine-modified polyacrylate-based compound and a perfluoropolyether (PFPE) -based compound; And (iii) a solvent.

[Chemical Formula 1]

In the above Chemical Formulas 1 to 4, n is 15 ~ 25, R is CH ₃ O ^-, or CH ₃ CH ₂ O ^-, and may be three OR bonded to Si are be the same or different from each other.

In the fluorocarbon polymer, the fluorocarbon group is a functional group imparting water repellency, antifouling property and slip property, and the silicon functional group is bonded to the substrate surface and affects the durability.

Specifically, the fluorocarbon polymer hydrolyzes the? I-OR group during the drying process to produce a silanol group (-Si-OH) and forms siloxane bonds (-Si-O-Si-) between the silanol groups To form a coating layer having a transparency on a substrate. When the coating composition containing the perfluoroalkylsilane is coated on the hydrophilically modified substrate, the silanol group (-Si-OH) is bonded to the hydrophilic group (-OH) and the siloxane bond (-Si-O- Si-) is formed, so that a coating layer having excellent adhesion to a substrate can be formed.

 The content of the fluorocarbon polymer is preferably 0.05 to 1.0 wt% based on the total weight of the coating composition. When the content is less than 0.1% by weight, the amount of the fluorocarbon polymer exhibiting antifouling property is very small, so that it is difficult to expect an effective antifouling effect from the coating film. On the other hand, when the content exceeds 1.0% by weight, And particularly abrasion resistance, water repellency, scratch resistance, hardness and the like may be lowered.

The weight average molecular weight of the fluorocarbon polymer is preferably 2,000 to 4,000. When the weight average molecular weight is less than 2,000, the fluorocarbon group may have a short length, resulting in insufficient antifouling performance. On the other hand, when the weight average molecular weight is more than 4,000, the proportion of silicon functional groups is decreased, have. In the present invention, the weight average molecular weight is a conversion value of standard polystyrene measured by GPC (Gel Permeation Chromatograph).

Examples of the fluorocarbon polymer include commercially available DC-2634 (trade name, Dow chemie), DC-24640 (trade name, Dow chemie), DC-2642 (trade name, Dow chemie), OPTOOL-DSX OPTOOL-DAC-HP (trade name, Daikin), and the like.

The slip agent provides a slip property to the surface of the substrate to prevent adhesion of the contaminants and to impart the property of effectively detaching the contaminants attached thereto.

As the slip agent, any one or two or more selected from the group consisting of a polyether-modified polydimethylsiloxane-based compound, a fluorine-modified polyacrylate-based compound and a perfluoropolyether-based compound is used. At this time, since the polyether-modified polydimethylsiloxane-based compound and the fluorine-modified polyacrylate-based compound contain a large amount of methyl groups in the structure, the methyl group contributes to the improvement of the slip feeling by lowering the surface tension of the base, The ether compound imparts surface slip properties through interaction in the coating composition in which the fluorocarbon polymer is dissolved.

The polyether-modified polydimethylsiloxane-based compound may be any one or two or more selected from the group consisting of compounds represented by the following general formula (2) and derivatives thereof, and currently commercially available examples include BYK-333 (trade name) BYK-342 (trade name), BYK-341 (trade name), BYK-344 (trade name), BYK-377 (trade name), BYK-322 (trade name) and BYK-340 (trade name).

(2)

In the above formula (2), n is 1 to 25.

Examples of the fluorine denatured polyacrylate compound include EFKA-3772N (trade name) available from BASF Corporation, which is commercially available.

The perfluoropolyether compound may be any one or more selected from the group consisting of a compound represented by the following general formula (3), a compound represented by the following general formula (4), and derivatives thereof. Solvay Krytox-105 (trade name) and krytox-107 (trade name) of Dupont Co., Ltd., and the like.

(3)

[Chemical Formula 4]

In the above formulas (3) and (4), n is 8 to 45.

The content of the slip agent is preferably 0.1 to 1.0% by weight based on 100% by weight of the fluorocarbon polymer. When the content is less than 0.1% by weight, the slip agent is insufficient in lowering the friction coefficient, On the other hand, if it exceeds 1.0% by weight, the coating property is affected. In addition, physical properties such as abrasion resistance, water repellency and scratch resistance may be deteriorated.

The solvent according to the present invention may be a fluorine-containing solvent selected from perfluoroether, perfluorohexane and mixed solvents thereof.

Examples of commercially available fluoroethers include HFE-7100 (trade name, 3M company) represented by the following chemical formula 5, HFE-7300 (trade name, 3M company) represented by the following chemical formula 6, HFE Commercially available products of perfluorohexane include FC-3283 (trade name, 3M company) represented by the formula 8, FC-40 (trade name, 3M) represented by the formula 9 , And FC-770 (trade name, 3M).

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In addition, the solvent is preferably selected from the group consisting of 1,3-bis (trifluoromethyl) benzene, 2,2,2-trifluoroethanol ( 2,2,2-trifluoroethanol), and mixtures thereof. When the second solvent is contained in the range of 1 to 5% by weight based on the total weight of the coating composition, it is preferable from the viewpoint of improving the dissolution ability.

The coating composition according to the present invention can be coated on a substrate by conventional methods. For example, the coating method using the coating composition may include spin coating, dip coating, spray coating, flow coating, roll coating, and the like. The coated substrate is thermally cured at a temperature of 120 to 130 ° C. for 10 to 30 minutes Followed by drying.

In the thermosetting process, the coating composition is cured to form a coating layer having slipperiness and antifouling property on the substrate.

Examples of the substrate include glass or polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), poly A polymer composed of at least one of polycarbonate (PC), polyimide (PI), polyether sulfone (PES), polyarylite, and cyclic olefin copolymer (COC) And it can be used without restriction as long as slip property and antifouling property are required such as textile, household appliance, architecture, shipbuilding, and civil engineering field.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.

Example 1

First, 0.1 wt% of a fluorocarbon polymer (trade name: OPTOOL DSX, Daikin) and 0.01 wt% of a slipping agent (trade name: BYK-333, BYK) are mixed. The above mixture is added to 96.89 wt% based on 100 parts by weight of perfluoro ether (trade name: FC-3283, 3M) as a solvent and dissolved. In order to improve the solubility of the slip agent and the solvent, 3 wt% of 1,3-bis (trifluoromethyl) benzene solvent was further diluted by 3 wt%, and the mixture was dissolved at 200 rpm for 30 minutes to prepare a coating composition.

Example 2

A coating composition was prepared in the same manner as in Example 1, except that BYK-306 (trade name) manufactured by BYK was used instead of BYK-333 as the slip agent.

Example 3

A coating composition was prepared in the same manner as in Example 1, except that LRFAFLOW100 (trade name) of BASF was used instead of BYK-333 as the slip agent.

Example 4

A coating composition was prepared in the same manner as in Example 1, except that Z-15 (trade name) of Solvay was used instead of BYK-333 as the slip agent.

Example 5

A coating composition was prepared in the same manner as in Example 1, except that Krytox-103 (trade name) manufactured by DuPont was used instead of BYK-333 as the slip agent.

Comparative Example 1

0.1 wt% of a fluorocarbon polymer (trade name: OPTOOL DSX, Daikin) was added to 99.9 wt% wt% of perfluoroether (trade name: HFE-7100, 3M) as a solvent and dissolved at 200 rpm for 30 minutes to prepare a coating composition .

Comparative Example 2

A coating composition was prepared in the same manner as in Example 1, except that BYK-3500 (trade name), BYK Co., which is a fluorine-modified polymer compound, which is an acrylic siloxane compound, was used instead of BYK-333 as the slip agent.

Comparative Example 3

A coating composition was prepared in the same manner as in Example 1, except that EFKA-3772N (trade name), a fluorine-modified polymer compound, was used instead of BYK-333 as the slip agent.

<Evaluation method>

2 g of the coating compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were coated on soda lime glass treated for 3 seconds with Ar plasma and spin-coated (3000 rpm, 20 seconds). The coated soradedium was heat-treated at 100 ° C for 20 minutes in a hot-air dryer (OF-02G-4C, JEO-Tech) without any waiting time.

One. Initial contact angle

The contact angle of water was measured using Phoenix300, a contact angle of SEO. The amount of liquid drop at room temperature was 3 ?. In this case, the higher the contact angle, the lower the surface energy, and when the contact angle of water is 100 deg. Or more, the contact angle acceptance criterion is selected.

2. Late contact angle

Measurements were made with CORETECH's LT-RB instrument. The surface of the coating was rubbed with 500 g of an eraser for abrasion resistance test and 1500 g, and contact angle was measured. At this time, when the contact angle of water is 100 deg. Or more, it was selected as the acceptance criteria for wear resistance.

3. Friction coefficient (slip property)

Measurements were made with PARAM FPT-F1 equipment. The friction coefficient of the coated surface was measured by using polyurethane (PU) as the friction agent, artificial sebum as the friction agent, and attaching the friction material to the load cell of 250 g

Slip agent Exterior Initial contact angle (˚) Late contact angle (˚) Coefficient of friction Example 1 BYK-333 clear 110 ± 3 106 ± 3 0.13 + 0.02 Example 2 BYK-306 Clear 110 ± 3 107 ± 3 0.13 + 0.02 Example 3 LRFAFLOW100 Clear 110 ± 3 106 ± 3 0.13 + 0.02 Example 4 Z-15 Clear 111 ± 2 108 ± 2 0.11 + 0.02 Example 5 Krytox-103 Clear 110 ± 3 108 ± 2 0.10 0.02 Comparative Example 1 - Clear 111 ± 2 107 ± 2 0.14 + 0.02 Comparative Example 2 BYK-3500 Haze 107 ± 2 104 ± 3 0.20 ± 0.03 Comparative Example 3 EFKA3772N Layer separation

 As shown in Table 1, in Examples 1 to 5 using the coating composition according to the present invention, the appearance was clear when observed with the naked eye, and both the initial contact angle and the latter contact angle were high, indicating excellent durability. On the other hand, Comparative Example 2 using an acrylic siloxane-based compound as a slip agent exhibited a non-transparent appearance, and it was confirmed that the acrylic siloxane-based compound was inferior to the initial and latter contact angle embodiments. In the case of Comparative Example 3 in which the fluorine denatured polymer compound was used as a slip agent, the coating layer was separated from the substrate and thus could not be used as a coating composition.

Further, when coated with the coating compositions of Examples 1 to 5, the friction coefficient was smaller than Comparative Example 1 in which the slip agent was not contained and Comparative Example 2 in which the acryl siloxane compound was used as the slip agent, and the slip property was improved I can confirm

 While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the present invention is not limited to the disclosed exemplary embodiments but is to be construed as being limited only by the appended claims. Should be construed as being included in the scope of the present invention.

Claims (9)

(I) a fluorocarbon polymer represented by the following formula (1);
(Ii) at least one slip agent selected from the group consisting of a polyether-modified polydimethylsiloxane-based compound, a fluorine-modified polyacrylate-based compound and a perfluoropolyether (PFPE) -based compound; And
(Iii) a coating composition comprising a solvent:
[Chemical Formula 1]

In the above Chemical Formulas 1 to 4, n is 15 ~ 25, R is CH ₃ O ^-, or CH ₃ CH ₂ O ^-, and may be three OR bonded to Si are be the same or different from each other. The method according to claim 1,
Wherein the content of the fluorocarbon polymer is 0.05 to 1.0 wt% based on the total weight of the coating composition. The method according to claim 1,
Wherein the fluorocarbon polymer has a weight average molecular weight of from 2,000 to 4,000. The method according to claim 1,
Wherein the polyether-modified polydimethylsiloxane-based compound is any one or two or more selected from the group consisting of a compound represented by the following formula (2) and a derivative thereof:
(2)

In the above formula (2), n is 1 to 25. The method according to claim 1,
Wherein the perfluoropolyether compound is one or more selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a derivative thereof:
(3)

[Chemical Formula 4]

In the above formulas (3) and (4), n is 8 to 45. The method according to claim 1,
Wherein the content of the slip agent is 0.1 to 1.0 wt% based on 100 wt% of the fluorocarbon polymer. The method according to claim 1,
Wherein the solvent is a fluorine-based solvent selected from the group consisting of perfluoroether, perfluorohexane and mixed solvents thereof. 8. The method of claim 7,
The solvent is preferably selected from the group consisting of 1,3-bis (trifluoromethyl) benzene, 2,2,2-trifluoroethanol, &Lt; / RTI &gt; further comprising a second solvent selected from the mixture. 9. The method of claim 8,
Wherein the content of the second solvent is 1 to 5 wt% based on the total weight of the coating composition.