KR20150039993A

KR20150039993A - Fluoride-containing anti-fingerprint agents

Info

Publication number: KR20150039993A
Application number: KR20130118465A
Authority: KR
Inventors: 최한영; 박대출; 박일우
Original assignee: 동우 화인켐 주식회사
Priority date: 2013-10-04
Filing date: 2013-10-04
Publication date: 2015-04-14

Abstract

The present invention relates to a fluorine based anti-fingerprint agent and, more specifically, to a fluorine based anti-fingerprint agent with a monofunctional silanol group represented by at least one compound selected from the group consisting of chemical formula 1, chemical formula 2 and chemical formula 3 which exhibits excellent abrasion resistance by forming a single coating layer on a surface of a substrate while having excellent anti-fingerprint properties as compared with existing fluorine. (In formula, X, R_1, R_2, R_3, y and n are identical with claim 1.)

Description

{FLUORIDE-CONTAINING ANTI-FINGERPRINT AGENTS}

FIELD OF THE INVENTION The present invention relates to a novel fluorine-based fingerprinting inhibitor excellent in fingerprint-preventing properties.

Since the display unit of various electronic devices such as a TV, a notebook, and a mobile phone is exposed to an external pollution environment, the display unit can be easily contaminated by contamination sources including oil, fingerprints and various foreign substances. It is likely to be distorted or deteriorate in the appearance quality of the electronic device.

In particular, in recent years, a touch screen for inputting various data and performing a specific command to a computer, such as a simple touch using an auxiliary input means such as a finger or a pen, or drawing a character or a picture, As a core component for various digital devices that transmit or exchange information to one or both of a computer, a camera, a certificate issuer, and industrial equipment, its importance is gradually increasing, and its use range is rapidly spreading.

Accordingly, various studies have been made on techniques for preventing contamination of the display unit due to foreign substances such as fingerprints.

With respect to the anti-fouling method in which contaminants are hardly adhered to the display unit and can be easily removed even if they are adhered to the display unit, techniques for preventing contamination of the display unit by coating a substance having antifouling property on the display unit are widely used.

Korean Patent Registration No. 607,716 discloses a fingerprint inhibitor prepared by subjecting a macromonomer formed by copolymerizing a perfluoroalkyl compound with a silane compound to silicon hydride.

Korean Patent No. 1,296,976 discloses a silicone resin obtained by hydrolyzing / condensing an organosilicon compound having a fluorine atom-containing organic group or a silane compound containing a hydrolyzate or a partial condensate thereof.

The anti-fingerprinting agent, silicone resin, and the like described above exhibit excellent fingerprint protection when coated with a single layer. However, there is a limit in that when the anti-fingerprinting agent layer is formed using the commonly used vapor deposition method and solution coating method, it is very difficult to quantify the anti-fingerprinting layer as a single layer.

Thus, the fingerprint preventing layer is formed by depositing and coating the layer in such a quantity that a plurality of layers can not be formed or a single layer can not be formed.

In addition, the fingerprint inhibitor and the silicone resin as described above are excellent in fingerprint-preventing property but have a disadvantage in that the abrasion resistance is insufficient and the water contact angle after the evaluation of abrasion resistance is reduced to 100 ° or less.

An object of the present invention is to provide a fluorine-based fingerprint-preventing agent excellent in abrasion resistance due to friction and at the same time preventing fingerprint.

In order to achieve the above object, the present invention provides one or more fluorine-based anti-fogging agents selected from the group consisting of the following formulas (1), (2) and (3)

(Wherein X represents a halogen group, a C ₁ -C ₈ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ represents a direct bond, a C ₁ -C ₈ aliphatic hydrocarbon group, N, O, Si, Or a C ₁ -C ₈ aliphatic hydrocarbon group or a C ₆ -C ₈ aromatic hydrocarbon group interrupted by SiO ₂ , R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group or a C ₆ -C 8 _And n is an integer of 1 to 20).

(Wherein X represents a halogen group, a C ₁ -C ₈ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ represents a direct bond, a C ₁ -C ₈ aliphatic hydrocarbon group, N, O, Si, Or a C ₁ -C ₈ aliphatic hydrocarbon group or a C ₆ -C ₈ aromatic hydrocarbon group interrupted by SiO ₂ , R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group or a C ₆ -C 8 ₈ aromatic hydrocarbon group).

(Wherein X is a halogen group, a C ₁ -C ₈ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ is a C ₁ -C ₈ aliphatic hydrocarbon group, C ₁ C ₈ aliphatic hydrocarbon group or C ₆ -C ₈ aromatic hydrocarbon group, R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group or a C ₆ -C ₈ aromatic hydrocarbon group, Y Is O or NH, and n is an integer of 1 to 20.)

Preferably, X in the formula (1) is a halogen group, a C ₁ -C ₄ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ is a C ₁ -C ₈ aliphatic hydrocarbon group, R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group, and n is an integer of 1 to 10; Wherein X is a halogen group, a C ₁ -C ₄ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ is a direct bond, a C ₁ -C ₈ aliphatic hydrocarbon group, R ₂ and R ₃ Are each independently a C ₁ -C ₄ aliphatic hydrocarbon group; Wherein X is a halogen group, a C ₁ -C ₄ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ is a C ₁ -C ₈ aliphatic hydrocarbon group, R ₁ is a C ₁ -C ₈ Or an aliphatic hydrocarbon group of C ₁ -C ₈ , or an aliphatic hydrocarbon group of C ₁ -C ₈ terminated by N or O, R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group, Y is O or NH , and n may be an integer of 1 to 20.

More preferably, the fluorine-based fingerprinting inhibitor may be at least one selected from the group consisting of the following formulas (4) to (13).

The present invention provides a coating material on which the fluorine-based anti-fingerprinting agent is applied.

The substrate may be glass, metal, ceramic or plastic.

The covering material may have a water contact angle of 110 to 120 °.

The anti-fingerprint layer coated with the fluorine-based anti-fingerprinting agent according to the present invention has a water contact angle in the range of 110 to 120 °, which is superior to the conventional fluorine-based anti-fingerprinting and has excellent wear resistance.

Such fluorine-based anti-fingerprinting agents can be used for various purposes in various industries such as fine chemical products, biological / biochemical industries, and particularly useful for preventing oily pollution such as fingerprints of automobiles, residential glass and displays.

Hereinafter, the present invention will be described in detail.

The fluorine-based fingerprinting inhibitor of the present invention is represented by at least one selected from the group consisting of the following formulas (1), (2) and (3)

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

At least one selected from the group consisting of the formulas (1), (2) and (3) according to the present invention is a fluorinated fingerprint inhibitor having a monofunctional silanol group. Since the monofunctional silanol group is capable of forming a monolayer structure on the glass surface since the three-dimensional bonding between the anti-fingerprinting agent is suppressed and only the bonding with the glass is proceeded, the fingerprint- great.

Further, the present invention is characterized in that the fluorine-based anti-fingerprinting agent is applied onto a substrate.

The fluorine-based fingerprint-preventing agent may be dispersed and dissolved in an organic solvent and used as a fluorine-based fingerprint-preventing composition. Examples of the organic solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol and diacetone alcohol, ethylene glycol monomethyl ether, Glycol ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone, ethyl acetate, butyl acetate and ethyl acetoacetate Xylene, toluene, and the like.

Such an organic solvent is preferably maintained such that the concentration of the fluorine-based anti-fingerprint agent composition is 0.1 to 10% by weight, particularly 0.5 to 8% by weight.

In addition, the fluorine-based anti-fingerprint composition of the present invention can be used as an organic or inorganic ultraviolet absorber, a leveling agent, a buffer for controlling the pH in the system to pH 2 to 7 at which silanol groups are easily present, Disodium hydrogenphosphate-citric acid, and the like.

The substrate is preferably glass, metal, ceramic or plastic, and if the substrate is transparent, it can be applied to optical applications.

The plastic is specifically a polycarbonate resin; Polyalkylene terephthalate resins such as polyethylene terephthalate (PET); Cellulose resins such as diacetyl cellulose, acetate butyrate cellulose and triacetyl cellulose; Acrylic resin; Polystyrene type resin; Polyimide resin; Polyester resin; Polyethersulfone resin; Liquid crystalline resins such as polyarylate; Polyurethane resin; Polysulfone resin; Polyetherketone resins; A polyolefin resin such as trimethylpentene and polyvinylnorbornene, and a high-refractive-index resin containing sulfur. It is preferably applied to a transparent substrate which is required to have antifouling properties such as polycarbonate resin, polyalkylene terephthalate resin such as PET, triacetyl cellulose resin and the like.

The coating film formed on the substrate by the fluorine-based anti-fingerprint agent composition of the present invention preferably has a thickness of 0.1 nm to 100 nm, preferably 0.1 nm to 10 nm.

Further, the method of coating the fluorine-based anti-fogging agent composition on the substrate is generally used in the art and includes, for example, a dipping method, a spin coating method, a flow coating method, a roll coating method, a spray coating method, Can be used. Among them, dipping method, spray coating method and roll coating method are preferable considering easiness of controlling the thickness of the coating film.

The water contact angle of the fluorine-based fingerprint-preventing agent in the formation on the substrate is 110 to 120 °, preferably 115 to 120 °.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example One

(Gelest) was dissolved in toluene (100 g), and the glass was dip coated for 10 seconds. The glass was dried in a hot air drier at 80 占 폚 for 1 minute and left at 50 占 폚 and 50% RH for 1 day to obtain a coating material .

Example 2

The procedure of Example 1 was repeated,

Instead of

To prepare a coating material.

Example 3

The procedure of Example 1 was repeated,

Instead of

To prepare a coating material.

Example 4

The procedure of Example 1 was repeated,

Instead of

To prepare a coating material.

Example 5

The procedure of Example 1 was repeated,

Instead of

To prepare a coating material.

Example 6

The procedure of Example 1 was repeated,

Instead of

To prepare a coating material.

Example 7

The procedure of Example 1 was repeated,

Instead of

To prepare a coating material.

Example 8

The procedure of Example 1 was repeated,

Instead of

To prepare a coating material.

Comparative Example One

The glass was dip-coated for 10 seconds in a solution of 1 g of tetraethoxysilane (TCI) in CF ₃ CHFCHFCF ₂ CF ₃ (100 g), dried at 80 ° C in a hot-air drier for 1 minute, And allowed to stand for one day to prepare a covering material.

Comparative Example 2

(Gelest Co.) was dissolved in CF ₃ CHFCHFCF ₂ CF ₃ (100 g), the glass was dip-coated for 10 seconds, then dried in a hot air drier at 80 ° C for 1 minute, And allowed to stand for one day to prepare a covering material.

Test Example

The physical properties of the coating materials prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

One. Fingerprint Prevention evaluation ( Water contact angle )

The water contact angle of the surface of the above-prepared coating material treated with the anti-fingerprint coating was measured.

2. Coating uniformity

The water contact angles at 10 positions were measured on the treated surface of the 10cm × 10cm cover of the coating material to calculate the difference between the maximum value and the minimum value.

3. Reliability (Fingerprint prevention Maintainability )

The treated surface of the coating material was rubbed 10 times at a constant pressure, and then the contact angle of the friction surface was measured.

division Water contact angle (°) Coating uniformity responsibility Example 1 116 2 112 Example 2 116 2 111 Example 3 116 2 111 Example 4 116 2 112 Example 5 115 2 111 Example 6 115 2 111 Example 7 118 2 114 Example 8 117 2 113 Comparative Example 1 112 4 110 Comparative Example 2 111 3 108

As shown in Table 1, the anti-fingerprinting layers of Examples 1 to 8 containing the fluorine-based fingerprinting inhibitor according to the present invention had better water contact angles and coating uniformity than those of Comparative Examples 1 and 2, And the water contact angle was maintained.

Claims

(1), (2) and (3): < EMI ID =
[Chemical Formula 1]

(Wherein X represents a halogen group, a C ₁ -C ₈ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ represents a direct bond, a C ₁ -C ₈ aliphatic hydrocarbon group, N, O, Si, Or a C ₁ -C ₈ aliphatic hydrocarbon group or a C ₆ -C ₈ aromatic hydrocarbon group interrupted by SiO ₂ , R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group or a C ₆ -C 8 _And n is an integer of 1 to 20).
(2)

(Wherein X represents a halogen group, a C ₁ -C ₈ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ represents a direct bond, a C ₁ -C ₈ aliphatic hydrocarbon group, N, O, Si, Or a C ₁ -C ₈ aliphatic hydrocarbon group or a C ₆ -C ₈ aromatic hydrocarbon group interrupted by SiO ₂ , R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group or a C ₆ -C 8 ₈ aromatic hydrocarbon group).
(3)

The method according to claim 1, X of Formula 1 is a halogen group, an alkoxy group, a dialkyl amine group, a C ₁ -C _4, or an acetoxy group, and, R ₁ is an aliphatic hydrocarbon group of C ₁ -C _8, R _2, and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group, n is an integer of 1 to 10;
Wherein X is a halogen group, a C ₁ -C ₄ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ is a direct bond, a C ₁ -C ₈ aliphatic hydrocarbon group, R ₂ and R ₃ Are each independently a C ₁ -C ₄ aliphatic hydrocarbon group;
Wherein X is a halogen group, a C ₁ -C ₄ alkoxy group, a dialkylamine group or an acetoxy group, R ₁ is a C ₁ -C ₈ aliphatic hydrocarbon group, R ₁ is a C ₁ -C ₈ Or an aliphatic hydrocarbon group of C ₁ -C ₈ , or an aliphatic hydrocarbon group of C ₁ -C ₈ terminated by N or O, R ₂ and R ₃ are each independently a C ₁ -C ₄ aliphatic hydrocarbon group, Y is O or NH , and n is an integer of 1 to 20.

The fluorine-based fingerprint sealer according to claim 2, wherein the fluorine-containing fingerprint sealer is at least one selected from the group consisting of the following formulas (4) to (13)
[Chemical Formula 4]