KR20210081900A - Resin composition for coating and coating film - Google Patents

Abstract

An embodiment of the present invention provides a resin composition for coating and a coating film including a coating layer formed by the resin composition for coating. The coating film according to an embodiment of the present invention has excellent anti-fouling properties and stain-removing properties, and has excellent hardness and scratch resistance.

Description

Coating resin composition and coating film {RESIN COMPOSITION FOR COATING AND COATING FILM}

The present invention relates to a coating film comprising a resin composition for coating and a coating layer formed by the resin composition for coating.

A transparent polymer film is a core material in the field of optical and flexible displays, and its importance is increasing recently. The transparent polymer film, in particular, is used as a material to replace glass in the display field because it has lightness, processability, and flexibility. However, since a general transparent polymer film has a lower surface hardness and abrasion resistance than glass, studies for improving the abrasion resistance of the polymer film are being conducted.

As a method for improving the abrasion resistance of the polymer film, there is a method of disposing a wear resistance coating layer on the polymer film. As a technology for forming a coating layer on a polymer film, for example, Korean Patent Publication No. 2010-0041992 discloses a high hardness hard coating film composition comprising an ultraviolet curable polyurethane acrylate-based oligomer, and Korean Patent Laid-Open No. 2011 -0013891 discloses a vinyl oligo siloxane hybrid composition containing a metal catalyst.

Recently, display devices for inputting information using a touch screen have been applied to electronic devices such as personal digital assistants. In addition, the transparent polymer film is disposed on the light emitting surface of such a display device, and is used as a window.

However, in the case of a display device that directly inputs information on a surface using a hand or a pen, such as a touch screen, the surface of the display device may be contaminated by contact with the hand or the pen. Accordingly, there is a demand for an optical film having excellent resistance to fingerprints or stains caused by the touch of a hand or pen, or excellent in removing fingerprints or stains.

An embodiment of the present invention is to provide a coating film having excellent slip characteristics and excellent resistance to fingerprints or stains caused by the touch of a hand or a pen.

An embodiment of the present invention is to provide a coating film having excellent abrasion resistance and excellent scratch resistance.

An embodiment of the present invention is to provide a resin composition for coating that can be used in the manufacture of a coating film having the above characteristics.

One embodiment of the present invention for solving the above problems is a reaction comprising a first silane compound represented by the following formula (1), a second silane compound represented by the following formula (2), and a third silane compound represented by the following formula (3) It provides a resin composition for coating, comprising a siloxane resin formed by a liquid.

<Formula 1>

R ¹ _n Si(OR ² ) _4-n

<Formula 2>

C _m F _2m+1 R ³ Si(OR ⁴ ) ₃

<Formula 3>

Si(OR ⁵ ) ₄

In Formula 1, R ¹ is a C1-C4 linear, branched or alicyclic alkyl group in which at least one hydrogen is substituted with an acryl group, R ² is a C1-C8 linear, branched or alicyclic alkyl group, n is 1 to an integer of 3.

In Formula 2, R ³ is a C1-C4 linear, branched or alicyclic alkylene group, R ⁴ is a C1-C8 linear, branched or alicyclic alkyl group, and m is an integer of 3 to 10.

In Formula 3, R ⁵ is a C1 to C4 linear or branched alkyl group.

The reaction solution may _{further include water (H 2} O).

The content ratio of the first silane compound to the second silane compound is 1:1 to 10:1 (first silane compound: second silane compound) based on a molar ratio.

The content ratio of the first silane compound to the second silane compound is 1:1 to 7:1 (first silane compound: second silane compound) based on a molar ratio.

The total mixing amount of the first silane compound and the second silane compound and the content ratio of the third silane compound are 3:1 to 5:1 (total mixing amount of the first silane compound and the second silane compound: content of the third silane compound).

The first silane compound is 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane and 3 -It may include at least one selected from acryloxypropyl tripropoxysilane.

The second silane compound is 1H.1H,2H,2H-perfluorooctyltriethoxysilane (1H.1H,2H,2H-Perfluoro-octyltriethoxysilan), 1H.1H,2H,2H-perfluorooctyltrimethoxysilane ( 1H.1H,2H,2H-Perfluoro-octyltrimethoxysilan), 1H.1H,2H,2H-Perfluorodecyltrimethoxysilane (1H,1H,2H,2H-Perfluoro-decyltrimethoxysilane) and 1H.1H,2H,2H- It may include at least one selected from perfluoro-decyltriethoxysilane (1H, 1H, 2H, 2H-Perfluoro-decyltriethoxysilane).

Another embodiment of the present invention includes a base film and a coating layer on the base film, and the coating layer may be formed by the resin composition for coating.

The surface of the coating layer has a pencil hardness of 4H or more according to ASTM D3363 measurement.

The coating layer has a water contact angle of 105° to 125°.

The coating layer has a water contact angle after abrasion resistance of 100° to 120°.

The coating layer has a water contact angle of 98° to 118° after 1 hour of abrasion resistance.

Another embodiment of the present invention includes a base film and a coating layer on the base film, wherein the coating layer includes a siloxane resin, has a pencil hardness of 4H or more based on ASTM D3363 measurement, and a water contact angle of 105° to 125° It provides a coating film having a.

The coating film has a water contact angle after abrasion resistance of 100° to 120°.

The coating film has a water contact angle of 98° to 118° after 1 hour of abrasion resistance.

The resin composition for coating according to an embodiment of the present invention has a perfluoro group, and may provide excellent slip properties and excellent wear resistance. The coating layer according to an embodiment of the present invention prepared by the resin coating layer for coating having a perfluoro group has excellent sliding properties and excellent wear resistance.

The coating film according to an embodiment of the present invention including the coating layer as described above may have a large water contact adhesion, excellent "water contact angle after abrasion resistance" and excellent "water contact angle after 1 hour of wear resistance". Accordingly, the coating film according to an embodiment of the present invention may have excellent sliding properties, excellent antifouling properties, and excellent stain removal properties. In addition, according to an embodiment of the present invention, the contamination prevention durability of the coating film is excellent.

In addition, the resin composition for coating according to the present invention, including the polyfunctional silane compound, can be used for preparing a coating layer having excellent hardness and scratch resistance.

The coating film according to an embodiment of the present invention including such a coating layer may have excellent surface hardness, abrasion resistance and scratch resistance.

1 is a schematic cross-sectional view of a coating film according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail focusing on examples. The embodiments described below are presented for illustrative purposes only to help a clear understanding of the present invention, and do not limit the scope of the present invention.

When 'including', 'having', 'consisting', etc. mentioned in this specification are used, other parts may be added unless the expression 'only' is used. When a component is expressed in the singular, the plural is included unless specifically stated otherwise. In addition, in interpreting the components, it is interpreted as including an error range even if there is no separate explicit description.

In the case of a description of the positional relationship, for example, when the positional relationship of two parts is described as 'on', 'on', 'on', 'beside', etc., 'right' Alternatively, one or more other parts may be positioned between the two parts unless the expression 'directly' is used.

In the case of a description of a temporal relationship, for example, 'immediately' or 'directly' when a temporal relationship is described with 'after', 'following', 'after', 'before', etc. It may include cases that are not continuous unless the expression "

Although the first, second, etc. are used to describe various components, these components are not limited by these terms. These terms are only used to distinguish one component from another. Accordingly, the first component mentioned below may be the second component within the spirit of the present invention.

The term “at least one” should be understood to include all possible combinations from one or more related items. For example, the meaning of "at least one of the first, second, and third items" means 2 of the first, second, and third items as well as each of the first, second, or third items. It may mean a combination of all items that can be presented from more than one.

Each feature of the various embodiments of the present invention may be partially or wholly combined or combined with each other, technically various interlocking and driving are possible, and each of the embodiments may be implemented independently of each other or may be implemented together in a related relationship may be

In one embodiment of the present invention, a siloxane resin formed by a reaction solution including a first silane compound represented by the following Chemical Formula 1, a second silane compound represented by the following Chemical Formula 3, and a third silane compound represented by the following Chemical Formula 2 It provides a resin composition for coating comprising a.

<Formula 1>

R ¹ _n Si(OR ² ) _4-n

In Formula 1, R ¹ is a C1-C4 linear, branched or alicyclic alkyl group in which at least one hydrogen is substituted with an acryl group, R ² is a C1-C8 linear, branched or alicyclic alkyl group, and n is 1 to It is an integer of 3.

<Formula 2>

C _m F _2m+1 R ³ Si(OR ⁴ ) ₃

In Formula 2, R ³ is a C1-C4 linear, branched or alicyclic alkylene group, R ⁴ is a C1-C8 linear, branched or alicyclic alkyl group, and m is an integer of 3 to 10.

<Formula 3>

Si(OR ⁵ ) ₄

In Formula 3, R ⁵ is a C1 to C4 linear or branched alkyl group.

The first silane compound represented by Formula 1 is, for example, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryl It may include at least one selected from oxypropyltriethoxysilane and 3-acryloxypropyl tripropoxysilane.

The first silane compound represented by Formula 1 forms a dense network cross-linking upon curing, so that the coating layer has excellent surface hardness, abrasion resistance and scratch resistance.

In addition, the first silane compound represented by Formula 1 includes an acryl group. The acrylic group improves the adhesion of the resin composition for coating, and can form a crosslinked structure by photocuring. The curing of the resin composition for coating may be smoothly performed by the first silane compound.

The first silane compound may be used in an amount of 5 mol% to 20 mol% based on the total moles of the reaction solution used for preparing the resin composition for coating.

The first silane compound may include, for example, a compound represented by Chemical Formula 4 below.

<Formula 4>

In order to impart a slip property and improve the anti-contamination property and scratch resistance of the coating layer, the reaction solution used in the preparation of the resin composition for coating according to an embodiment of the present invention is the agent represented by Formula 2 2 contains a silane compound.

The second silane compound represented by Formula 2 is 1H.1H,2H,2H-perfluorooctyltriethoxysilane (1H.1H,2H,2H-Perfluoro-octyltriethoxysilan), 1H.1H,2H,2H-perfluorooctyltriethoxysilan Remethoxysilane (1H.1H,2H,2H-Perfluoro-octyltrimethoxysilan), 1H.1H,2H,2H-Perfluorodecyltrimethoxysilane (1H,1H,2H,2H-Perfluoro-decyltrimethoxysilane) and 1H.1H, It may include at least one selected from 2H, 2H-perfluorodecyltriethoxysilane (1H, 1H, 2H, 2H-Perfluoro-decyltriethoxysilane).

The coating layer formed by the coating composition prepared by the reaction solution containing the second silane compound represented by Formula 2 may have a water contact angle of 105° or more, and may have a water contact angle after abrasion resistance of 100° or more, 98 It can have a contact angle after 1 hour of wear resistance of more than °. A coating layer having such a water contact angle may have excellent sliding properties. As a result, anti-contamination properties and scratch resistance of the coating layer may be improved. In addition, the wear resistance of the coating layer may be improved by the fluorine (F) contained in the second silane compound.

In addition, since the coating layer prepared by the coating composition according to an embodiment of the present invention has a water contact angle after abrasion resistance of 100° or more, even after the surface of the coating layer is exposed to an abrasion environment, it can have excellent sliding properties. Accordingly, even if the coating layer is worn, the anti-contamination properties and scratch resistance of the coating layer can be maintained.

In addition, since the coating layer prepared by the coating composition according to an embodiment of the present invention has a water contact angle of 98° or more after 1 hour of abrasion resistance, the surface of the coating layer is exposed to an abrasive environment, and then left in a high humidity condition However, it can have excellent sliding properties. Therefore, even if the coating layer is worn and a bad condition such as a high humidity condition is treated, the stain-preventing property and scratch resistance of the coating layer can be maintained.

The second silane compound may be used in an amount of 1 mol% to 20 mol% based on the total moles of the reaction solution used for preparing the resin composition for coating.

Examples of the second silane compound include a compound represented by the following formula (5) and a compound represented by the following formula (6).

<Formula 5>

<Formula 6>

The perfluoro group included in the second silane compound lowers the surface tension of the coating layer, so that the contact angle after abrasion resistance of the coating layer can be maintained excellently.

The resin composition for coating according to an embodiment of the present invention may further include a third silane compound represented by Chemical Formula 3 in order to form a coating layer having more excellent hardness. The third silane compound represented by Formula 3 has four alkoxy groups. A silane compound having four alkoxy groups as represented by Formula 3 is also referred to as a silane compound having a Q structure.

When the resin composition for coating according to an embodiment of the present invention includes the third silane compound, siloxane having a Q structure is formed in the polymer chain of the siloxane resin, so that the coating layer formed by the resin composition for coating has high hardness like glass. and scratch resistance.

The third silane compound may include, for example, at least one of tetraethyl orthosilicate (TEOS) and tetramethyl orthosilicate (TMOS).

The third silane compound may be used in an amount of 2 mol% to 10 mol% based on the total moles of the reaction solution used for preparing the resin composition for coating.

Examples of the third silane compound include a compound represented by the following formula (7).

<Formula 7>

According to an embodiment of the present invention, the reaction solution used for preparing the resin composition for coating may include water (H ₂ O). Water (H ₂ O) may be used as a linker between monomers for forming a siloxane resin, and is involved in a dehydration condensation reaction.

According to an embodiment of the present invention, water may be used in an amount of 20 mol% to 50 mol% based on the total moles of the reaction solution used for preparing the resin composition for coating.

According to an embodiment of the present invention, an organic solvent may be used to dilute the solid content. As the organic solvent, for example, butanone can be used. The organic solvent may be used in an amount of 30 mol% to 70 mol% based on the total moles of the reaction solution.

According to an embodiment of the present invention, in order to improve pencil hardness, abrasion resistance, scratch resistance, and water contact angle of the coating layer formed by the resin composition for coating, the content of the first silane compound, the second silane compound and the third silane compound this is regulated

For example, if the content of the first silane compound included in the resin composition for coating is not sufficient, the coatability and curability of the resin composition for coating may be reduced, and the heat curing process time may dramatically increase. In addition, when the content of the first silane compound is insufficient, scratch resistance of the coating layer may be deteriorated.

When the content of the second silane compound in the resin composition for coating is insufficient, the water contact angle of the coating layer formed by the resin composition for coating is reduced and sliding properties are deteriorated. On the other hand, when the content of the second silane compound is too large, workability may be deteriorated and coating properties may be deteriorated.

In consideration of these characteristics, according to an embodiment of the present invention, the content ratio of the first silane compound to the second silane compound is 1:1 to 10:1 (first silane compound: second silane compound) based on a molar ratio. can be adjusted within the range of

More specifically, the content ratio of the first silane compound to the second silane compound may be adjusted in the range of 1:1 to 7:1 (first silane compound:second silane compound) based on the molar ratio.

In addition, when the third silane compound is included in the resin composition for coating in excess, the flexibility of the coating layer formed by the resin composition for coating may be reduced. On the other hand, when the content of the third silane compound is insufficient, the silane Q structure is not sufficiently formed in the polymer chain of the siloxane resin, and thus the pencil hardness and scratch resistance of the coating layer formed by the resin composition for coating may be reduced.

Accordingly, the total mixing amount of the first silane compound and the second silane compound and the content ratio of the third silane compound are 3:1 to 5:1 based on a molar ratio (total mixing amount of the first silane compound and the second silane compound: 1 3 content of the silane compound).

According to an embodiment of the present invention, a siloxane resin is formed by a reaction solution including a first silane compound, a second silane compound, and a third silane compound, and as a result, a resin composition for coating is prepared. As already described, the reaction solution may include water (H ₂ O).

In one embodiment of the present invention, the siloxane resin may be formed through an alkoxy diol substitution reaction and condensation polymerization. This reaction may be carried out at room temperature, but in order to promote the reaction, it may be carried out with stirring at 50° C. to 120° C. for 1 hour to 120 hours.

According to an embodiment of the present invention, one of the formation processes of the siloxane resin may be represented by the following Reaction Scheme 1.

<Scheme 1>

In the reaction for forming the siloxane resin, alkoxy undergoes a substitution reaction (or hydrolysis) with water, and also condensation polymerization proceeds. As the catalyst, acid catalysts such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, sulfuric iodic acid, etc., base catalysts such as ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide, imidazole, etc., and ion exchange resins such as amberite can be used. have. These catalysts may be used alone, or two or more of them may be used in combination. The catalyst may be added in an amount of 0.0001 to about 10 parts by weight based on 100 parts by weight of the total silox compound, but the content of the catalyst is not limited thereto.

When the substitution reaction and the condensation polymerization proceed, water or alcohol is generated as a by-product, and by removing this, the reverse reaction can be reduced and the forward reaction can proceed faster, and the reaction rate can be controlled through this. By-products may be removed by pressure reduction and heating after completion of the reaction.

The resin composition for coating according to an embodiment of the present invention may further include one or more additives selected from the group consisting of an organic solvent, a polymerization initiator, an antioxidant, a leveling agent, and a coating aid in addition to the siloxane resin. By controlling the type and content of additives, it is possible to provide a resin composition for coating suitable for various uses. According to an embodiment of the present invention, there may be provided a resin composition for coating capable of increasing hardness, abrasion resistance, flexibility, and anti-curling properties of a film or sheet.

According to an embodiment of the present invention, as the polymerization initiator, for example, a photopolymerization initiator such as an organometallic salt and a thermal polymerization initiator such as an amine or imidazole may be used. The polymerization initiator may be used in an amount of about 0.5 to 5 parts by weight based on 100 parts by weight of the siloxane resin. When the content of the polymerization initiator is less than 0.5 parts by weight based on 100 parts by weight of the siloxane resin, the curing time of the coating layer to obtain sufficient hardness increases and the efficiency decreases, and when the content of the polymerization initiator exceeds 5 parts by weight, the yellowness of the coating layer increases to form a transparent coating layer can be difficult to obtain.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; cellosolves such as methyl cellosolve and butyl cellosolve; ethers such as ethyl ether and dioxane; alcohols such as isobutyl alcohol, isopropyl alcohol, butanol, and methanol; halogenated hydrocarbons such as dichloromethane, chloroform and trichloroethylene; and hydrocarbons such as normal hexane, benzene, and toluene; at least one selected from the group consisting of may be used. By controlling the amount of the organic solvent added, the viscosity of the siloxane resin can be controlled, and the processability or the thickness of the coating layer can be adjusted.

According to another embodiment of the present invention, the resin composition for coating according to an embodiment of the present invention is molded by a method such as coating, casting, molding, etc., and then photopolymerized and thermally polymerized to form a high hardness coating layer. .

According to the present invention, when the resin composition for coating is polymerized, the light quantity conditions suitable for photopolymerization are 50 mJ/cm 2 or more and 20000 mJ/cm 2 or less, and heat treatment at a temperature of 40° C. or more and about 300° C. or less to obtain a uniform surface before light irradiation. can In addition, a temperature suitable for thermal polymerization is 40° C. or more and 300° C. or less, and the temperature is not limited thereto.

1 is a schematic cross-sectional view of a coating film 100 according to an embodiment of the present invention.

Referring to FIG. 1 , the coating film 100 according to an embodiment of the present invention includes a base film 110 and a coating layer 120 on the base film 110 .

A polyimide (PI) film may be used as the base film 110 . However, one embodiment of the present invention is not limited thereto, and a polycarbonate film (PC), a polyacrylic film, a polyethylene terephthalate film, a cellulose film, etc. may be used as the base film 110 .

The coating layer 120 includes a siloxane resin. The siloxane resin may include a perfluoro group.

According to an embodiment of the present invention, the coating layer 120 may be formed by the above-described resin composition for coating. In the process of forming the coating layer 120 , a perfluoro group included in the second silane compound may be mainly located on the coating layer. As a result, a perfluoro group may affect the physical properties of the surface of the coating layer 120 .

According to an embodiment of the present invention, the coating film 100 may have a pencil hardness of 4H or more according to ASTM D3363 measurement. More specifically, the surface of the coating layer 120 formed on the coating film 100 may have a pencil hardness of 4H or more according to ASTM D3363 measurement.

According to an embodiment of the present invention, the coating film 100 has a water contact angle of 105° to 125°, a water contact angle after abrasion resistance of 100° to 120°, and abrasion resistance 1 of 98° to 118° It can have a water contact angle after time.

More specifically, the coating layer 120 of the coating film 100 according to an embodiment of the present invention has a water contact angle of 105 ° to 125 °.

Using KRUSS's DSA100 model, after dropping 5 uL of water droplet (H ₂ O) on the coating layer 120, by measuring the angle between the surface of the coating layer 120 and the boundary between the water droplet, the water contact angle can be obtained. . Specifically, the water contact angle is measured by a contact angle measuring device (DSA100 manufactured by KRUSS Co., Ltd.) 1 minute after dripping water droplets on the surface of the coating layer 120 at room temperature (25° C.). The left and right contact angles of the water droplet are measured 5 times using the same sample, and the average value is called the contact angle.

The coating film 100 according to an embodiment of the present invention has a water contact angle after abrasion resistance of 100° to 120°.

After abrasion resistance, the water contact angle was fixed to the substrate plane using an adhesive tape (3M) so that the coating film 100 sample cut into 20 cm X 5 cm was made with the coating layer 120 facing upward, and then #0000 (LIBERON Corporation). ) This is the water contact angle measured after reciprocating the surface for 3,000 times at a load of 0.5 kgf and a speed of 45 RPM with a rod wound on a nonwoven fabric. At this time, using KRUSS's DSA100 model, 5uL of water droplet (H ₂ O) is dropped on the coating layer 120, and then the angle of the boundary between the surface of the coating layer 120 and the water droplet is measured. The contact angle is obtained.

The coating film 100 according to an embodiment of the present invention has a water contact angle after 1 hour of abrasion resistance of 98° to 118°.

The water contact angle after 1 hour of abrasion resistance is the water contact angle measured after measuring the water contact angle after abrasion resistance and leaving the coating film 100 sample in an environment where water droplets are sprayed for 1 hour. At this time, using KRUSS's DSA100 model, 5 uL of water (H ₂ O) was dropped on the coating layer 120, and then the angle of the boundary between the surface of the coating layer 120 and the water was measured. The water contact angle is obtained.

Hereinafter, the present invention will be described in more detail through specific examples and comparative examples. These Examples and Comparative Examples are only for illustrating the present invention in more detail, and the present invention is not limited thereto.

<Example 1>

3-methacryloxypropyl trimethoxysilane (KBM-503, Shinetsu Corporation) 1.75 mol, 1H,1H,2H,2H-Perfluoro-octyltriethoxysilane (Sigma Aldrich Corporation) 0.25 mol, TEOS (Evonik Corporation) 0.5 mol was added to the reactor and stirred at 100 rpm for 30 minutes using a Mechanical Stirrer. Thereafter, 0.003 mol of NaOH _{is dissolved in 4 mol of water (H 2} O) and put into a stirred reactor. The reactor was stirred for 5 hours while maintaining the internal temperature at 60°C. Thereafter, 7 mol (504.77 g) of 2-butanone was added and diluted, and the resultant was filtered using a 0.45 μm Teflon filter to obtain a siloxane resin.

Then, 3 parts by weight of IRGACURE250 (BASF) as a photoinitiator was added to the siloxane resin diluted in a solvent based on 100 parts by weight of the siloxane resin to finally obtain a resin composition for coating. This composition was coated on the surface of a polyimide film (KOLON, CPI) using a bar, dried at 80° C. for 20 minutes, and then exposed to an ultraviolet lamp of 315 nm wavelength for 30 seconds to form a 10 μm thick coating layer. A film was prepared.

<Example 2>

1.5 mol of 3-methacryloxypropyl trimethoxysilane (KBM-503, Shinetsu Corporation) was used, and 0.5 mol of 1H,1H,2H,2H-Perfluoro-octyltriethoxysilane (Sigma Aldrich) was used, except that 0.5 mol was used. In the same manner as in 1, a resin composition for coating and a coating film were prepared.

<Example 3>

Except that 1.0 mol of 3-methacryloxypropyl trimethoxysilane (KBM-503, Shinetsu Corporation) was used, and 1.0 mol of 1H,1H,2H,2H-Perfluoro-octyltriethoxysilane (Sigma Aldrich) was used, Example In the same manner as in 1, a resin composition for coating and a coating film were prepared.

<Comparative Example 1>

Example, except that 2.0 mol of 3-methacryloxypropyl trimethoxysilane (KBM-503, Shinetsu Corporation) was used, and 1H, 1H, 2H, 2H-Perfluoro-octyltriethoxysilane (Sigma Aldrich Corporation) was not used. In the same manner as in 1, a resin composition for coating and a coating film were prepared.

<Comparative Example 2>

Example except that 0.75 mol of 3-methacryloxypropyl trimethoxysilane (KBM-503, Shinetsu Corporation) was used, and 1.25 mol of 1H,1H,2H,2H-Perfluoro-octyltriethoxysilane (Sigma Aldrich) was used. In the same manner as in 1, a resin composition for coating and a coating film were prepared.

<Comparative Example 3>

Except that 1.88 mol of 3-methacryloxypropyl trimethoxysilane (KBM-503, Shinetsu Corporation) was used, and 0.13 mol of 1H,1H,2H,2H-Perfluoro-octyltriethoxysilane (Sigma Aldrich) was used, Example In the same manner as 1, a resin composition for coating and a coating film were prepared.

<Comparative Example 4>

Use 1.75 mol of 3-methacryloxypropyl trimethoxysilane (KBM-503, Shinetsu Corporation), 0.25 mol of 1H,1H,2H,2H-Perfluoro-octyltriethoxysilane (Sigma Aldrich), and do not use TEOS Except that, in the same manner as in Example 1, a resin composition for coating and a coating film were prepared.

<Example of measurement>

For the coating films prepared in Examples 1 to 3 and Comparative Examples 1 to 4, physical properties were evaluated according to the following method, and the results are shown in Table 1 below.

(1) Surface hardness: Using a pencil hardness measuring instrument manufactured by IMOTO of Japan, ASTM D3363, at a speed of 180 mm/min, under a load of 750 gf, the pencil hardness was measured.

(2) Water contact angle: Using a KRUSS DSA100 model, 5uL of water droplet (H ₂ O) was dropped on the coating layer 120, and then the angle between the surface of the coating layer 120 and the boundary between the water droplet was measured. The left and right contact angles of the water droplets were measured five times, and the average value was used.

(3) Scratch resistance: After fixing the coating film 100 sample cut into 20cm X 5cm with adhesive tape (3M) on a plane so that the coating layer 120 faces upward, #0000 (LIBERON Corporation) non-woven fabric is wound. It was measured whether scratches occurred when the surface was reciprocated with a rod at a load of 1.5 kgf and a speed of 45 RPM for 10 times. If scratch did not occur, it was indicated as "good" and if scratch occurred, it was indicated as "N.G".

(4) Water contact angle after abrasion resistance: The water contact angle is measured for the coating film 100 sample after evaluation of scratch resistance. Specifically, after fixing the sample of the coating film 100 cut to 20cm X 5cm on a plane with an adhesive tape (3M) so that the coating layer 120 faces upward, it is 1.5kgf with a rod wound with #0000 (LIBERON) nonwoven fabric. The water contact angle was measured after reciprocating the surface for 10 times at a load of 45 RPM. At this time, using KRUSS's DSA100 model, 5uL of water droplet (H ₂ O) is dropped on the coating layer 120, and then the angle of the boundary between the surface of the coating layer 120 and the water droplet is measured. The contact angle is obtained.

(5) water contact angle after 1 hour of wear resistance; After measuring the water contact angle after abrasion resistance, the coating film 100 sample is left in an environment where water droplets are sprayed for 1 hour, and then the water contact angle is measured. At this time, using KRUSS's DSA100 model, 5 uL of water (H ₂ O) was dropped on the coating layer 120, and then the angle of the boundary between the surface of the coating layer 120 and the water was measured. The water contact angle is obtained.

(6) Transmittance and haze: The coating film 100 prepared according to Examples and Comparative Examples was cut into 50 mm × 50 mm and transmittance according to ASTM D1003 using MURAKAMI’s haze meter (model name: HM-150) equipment. And haze was measured 5 times to confirm the average value.

pencil hardness scratch resistant water contact angle Water contact angle after wear resistance Water contact angle after 1 hour of abrasion resistance permeability Haze Example 1 4H Good 110° 102° 100° 91.5% 1.0% Example 2 4H Good 112° 105° 102° 91.5% 1.0% Example 3 4H Good 112° 105° 103° 91.5% 1.0% Comparative Example 1 4H Good 80° 60° 50° 91.5% 1.0% Comparative Example 2 4H N.G. 112° 105° 103° 91.5% 1.0% Comparative Example 3 4H Good 95° 70° 62° 91.5% 1.0% Comparative Example 4 2H N.G. 110° 100° 96° 91.5% 1.0%

Referring to Table 1, the coating films according to Examples 1 to 3 have excellent pencil hardness and scratch resistance, and have excellent water contact angle characteristics.

Referring to Comparative Example 1, when the coating composition is prepared by using the coating solution that does not contain the second silane compound, the water contact angle characteristics of the coating layer and the coating film are deteriorated. In particular, the water contact angle and abrasion resistance after abrasion resistance for 1 hour After that, it can be seen that the water contact angle is significantly reduced.

Referring to Comparative Example 2, when the content of the first silane compound is decreased and the content of the second silane compound is increased, so that the second silane compound is used more than the first silane compound, scratch resistance of the coating layer and the coating film It can be seen that this decreases.

Referring to Comparative Example 3, when the amount of the second silane compound is reduced, and the amount of the second silane compound is less than 10 mol% compared to the amount of the first silane compound, the water contact angle of the coating layer and the coating film is not 100°, , it can be seen that the water contact angle after abrasion resistance and the water contact angle after 1 hour of wear resistance are significantly reduced.

Referring to Comparative Example 4, when the third silane compound is not used, it can be seen that the scratch resistance and pencil hardness of the coating layer and the coating film are reduced.

When referring to the above examples and comparative examples, when the content of the second silane compound containing a perfluorinated group is insufficient (Comparative Examples 1 and 3), it was confirmed that the reduction ratio of the water contact angle after abrasion resistance to the water contact angle was 20% or more. . On the other hand, in the case of an embodiment in which the content of the second silane compound is sufficient, it can be seen that the reduction ratio of the water contact angle after abrasion resistance to the water contact angle is 10% or less, and the reduction rate of the water contact angle after 1 hour of wear resistance is 3% or less.

As such, the coating film according to an embodiment of the present invention has a high water contact angle and thus has excellent sliding properties, and thus has excellent anti-pollution properties and stain-removing properties, and hardness. It can be confirmed that the film can be appropriately used as a protective film for a flexible display device due to its excellent scratch resistance and abrasion resistance.

100: coating film
110: base film
120: coating layer

Claims (15)

a first silane compound represented by the following formula (1);
a second silane compound represented by the following formula (2); and
a third silane compound represented by the following formula (3);
A resin composition for coating comprising a siloxane resin formed by a reaction solution comprising:
<Formula 1>
R ¹ _n Si(OR ² ) _4-n
<Formula 2>
C _m F _2m+1 R ³ Si(OR ⁴ ) ₃
<Formula 3>
Si(OR ⁵ ) ₄
In Formula 1, R ¹ is a C1-C4 linear, branched or alicyclic alkyl group in which at least one hydrogen is substituted with an acryl group, R ² is a C1-C8 linear, branched or alicyclic alkyl group, n is 1 an integer of to 3;
In Formula 2, R ³ is a C1-C4 linear, branched or alicyclic alkylene group, R ⁴ is a C1-C8 linear, branched or alicyclic alkyl group, and m is an integer of 3 to 10.
In Formula 3, R ⁵ is a C1 to C4 linear or branched alkyl group. According to claim 1, wherein the reaction solution further comprises water (H ₂ O), the resin composition for coating. The resin composition for coating according to claim 1, wherein the content ratio of the first silane compound and the second silane compound is 1:1 to 10:1 (first silane compound: second silane compound) based on a molar ratio. The resin composition for coating according to claim 1, wherein the content ratio of the first silane compound and the second silane compound is 1:1 to 7:1 (first silane compound: second silane compound) based on a molar ratio. The molar ratio of claim 1 , wherein the total mixing amount of the first silane compound and the second silane compound and the content ratio of the third silane compound is 3:1 to 5:1 (the first silane compound and the second silane compound). The total mixing amount of the silane compound: the content of the third silane compound), the resin composition for coating. According to claim 1, wherein the first silane compound, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl A resin composition for coating comprising at least one selected from triethoxysilane and 3-acryloxypropyl tripropoxysilane. The method of claim 1, wherein the second silane compound is 1H.1H,2H,2H-perfluorinated octyltriethoxysilane (1H.1H,2H,2H-Perfluoro-octyltriethoxysilan), 1H.1H,2H,2H-perfluorinated Octyltrimethoxysilane (1H.1H,2H,2H-Perfluoro-octyltrimethoxysilan), 1H.1H,2H,2H-Perfluoro-decyltrimethoxysilane (1H,1H,2H,2H-Perfluoro-decyltrimethoxysilane) and 1H. 1H,2H,2H-Perfluorodecyltriethoxysilane (1H,1H,2H,2H-Perfluoro-decyltriethoxysilane) comprising at least one selected from, the resin composition for coating. base film; and
a coating layer on the base film;
The coating layer is formed by the resin composition for coating of any one of claims 1 to 7, a coating film. According to claim 8, The surface of the coating layer, ASTM D3363 measurement standard, having a pencil hardness of 4H or more, the coating film. The coating film according to claim 8, wherein the coating layer has a water contact angle of 105° to 125°. The coating film according to claim 8, wherein the coating layer has a water contact angle after abrasion resistance of 100° to 120°:
Here, the water contact angle after abrasion resistance is 0.5 with a rod wound with #0000 (LIBERON) nonwoven fabric after fixing the coating film sample cut to 20 cm X 5 cm on a flat surface using an adhesive tape so that the coating layer faces upward. It is the water contact angle measured after reciprocating the surface for 3,000 times at a load of kgf and a speed of 45 RPM. According to claim 11, wherein the coating layer, 98 ° to 118 ° abrasion resistance after 1 hour having a water contact angle, the coating film;
Here, the water contact angle after 1 hour of the abrasion resistance is the water contact angle measured after the coating film sample is left in an environment where water droplets are sprayed for 1 hour after the measurement of the water contact angle after the abrasion resistance. base film; and
a coating layer on the base film;
The coating layer comprises a siloxane resin,
Has a pencil hardness of 4H or higher according to ASTM D3363 measurement,
A coating film having a water contact angle of 105° to 125°. The coating film according to claim 13, having a water contact angle after abrasion resistance of 100° to 120°. The coating film according to claim 13, having a water contact angle after 1 hour of abrasion resistance of 98° to 118°.

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