KR20170026939A - Antifouling coating composition, and antifouling sheet using the same - Google Patents

Antifouling coating composition, and antifouling sheet using the same Download PDF

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KR20170026939A
KR20170026939A KR1020150123063A KR20150123063A KR20170026939A KR 20170026939 A KR20170026939 A KR 20170026939A KR 1020150123063 A KR1020150123063 A KR 1020150123063A KR 20150123063 A KR20150123063 A KR 20150123063A KR 20170026939 A KR20170026939 A KR 20170026939A
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antifouling
acrylate
group
coating composition
hard coat
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KR101772275B1 (en
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김운기
예창준
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희성전자 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

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Abstract

The present invention provides an antifouling coating composition and an antifouling sheet using the same. The antifouling coating composition is characterized by containing an acrylate-based compound, a fluorine-containing acrylate-based compound and a silicone-based compound represented by the formula (1). The antifouling resin composition according to various embodiments of the present invention has an effect of providing a hard coat layer having not only antifouling property but also excellent abrasion resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to an antifouling coating composition and an antifouling sheet using the antifouling coating composition.

The present invention relates to an antifouling coating composition and an antifouling sheet using the antifouling coating composition, and more particularly, to an antifouling coating composition capable of imparting antifouling property to various surfaces and improving abrasion resistance.

In general, the antifouling coating composition is used for a coating for protecting the surface of a plastic material used for portable electronic devices, optical materials, household appliances, etc., which are frequently physically contacted by people, from various contaminants and scratches. Particularly, in recent years, in various displays such as TVs, monitors, mobile phone liquid crystals, and various types of polarizers, the use of displays for inputting information using touch screens has been increasing. Therefore, such displays are characterized by resistance to various pollutants The necessity of having antifouling property has emerged.

In order to impart such antifouling properties, a protective film or sheet having a hard coat layer having antifouling property is formed on the outermost layer of the surface.

More specifically, as a method of forming a hard coat layer having antifouling properties, a doped metal oxide, for example, antimony doped tin oxide (ATO), antimony doped zinc oxide AZO), or a method using a surfactant was used. However, the doped metal oxide and the surfactants have been detached to the coating surface over time, so that the antifouling effect can not be maintained for a long time. When the coating is applied to the transparent substrate, sufficient transparency can not be ensured.

Also, a method of using a coating composition containing a fluorine-containing compound such as a fluorine-containing acrylate monomer or a fluorine-containing olefin copolymer was used as a method of forming a hard coat layer having antifouling property. Fluorine has a high electron density, small atomic radius, and strong electronegativity, thus forming a solid carbon-fluorine bond. Due to the nature of fluorine, fluorine-based compounds exhibit very low water solubility and very low surface energy, and are highly resistant to water and oil. Therefore, the fluorine-based compound can impart water repellency, oil repellency and antifouling property to the hard coat layer.

However, the antifouling coating composition using the conventional fluorine-based compound often has insufficient antifouling properties, and even if it has antifouling properties, there is a problem that the hardness is insufficient or the antifouling property is extinguished with time. Accordingly, there is a demand for development of a coating composition capable of sustaining antifouling property regardless of the passage of time and physical damage, and an antifouling sheet prepared using the coating composition.

 [Related Technical Literature]

1. A plastic sheet having a hard coat layer having antifouling properties and a hard coating composition and a coating method of the plastic sheet using the same (Patent Application No. 10-2005-0135310)

Accordingly, an object of the present invention is to provide a coating composition excellent in antifouling property, and to provide an antifouling sheet capable of preventing adhesion of various contaminants such as fingerprint traces by coating it on a substrate sheet.

Another object to be solved by the present invention is to provide an antifouling sheet excellent in antifouling performance as well as excellent abrasion resistance and thus excellent in antifouling performance irrespective of the physical damage of the surface or the passage of time.

The problems of the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

In order to solve the above-mentioned problems, an antifouling coating composition according to an embodiment of the present invention comprises an acrylate compound, a fluorine-containing acrylate compound and a silicone compound represented by the following formula (1) .

 [Chemical Formula 1]

Figure pat00001

Wherein R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a (meth) acrylate group, or an alkyl (meth) acrylate group having 1 to 10 carbon atoms. Acrylate group, R 2 is hydrogen or a methyl group, and n is an integer of 2 to 20.

According to another aspect of the present invention, the silicone compound represented by Formula 1 is contained in an amount of 5 wt% to 90 wt% based on the total solid content.

According to another aspect of the present invention, there is provided an antifouling sheet comprising a substrate sheet and a hard coat layer formed on at least one side of the substrate sheet, wherein the hard coat layer comprises an acrylate- A fluorine-containing acrylate compound and a silicone compound represented by the formula (1) is cured to form a hard coat layer having a thickness of 0.5 to 40 μm.

According to another aspect of the present invention, the hard coating layer is characterized in that the water contact angle is at least 110 ° at 25 ° C, and the water contact angle change rate after the abrasion resistance evaluation is 10% or less.

The details of other embodiments are included in the detailed description and drawings.

The present invention provides a coating composition excellent in antifouling property, and has an effect of providing an antifouling sheet capable of preventing adhesion of various contaminants such as fingerprint traces by coating it on a substrate sheet.

The present invention has an effect of providing an antifouling sheet capable of sustaining antifouling properties for a long time irrespective of the physical damage of the surface or the elapse of time, as well as antifouling property and abrasion resistance.

The effects according to the present invention are not limited by the contents exemplified above, and more various effects are included in the specification.

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

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. In addition, the size and thickness of each component shown in the drawings are shown for convenience of explanation, and the present invention is not necessarily limited to the size and thickness of the components shown in the drawings.

The term "(meth) acrylate group" is defined to mean "acrylate group" or "methacrylate group", and "alkyl (meth) acrylate group" Quot; alkyl acrylate group "or" alkyl methacrylate group ".

Hereinafter, various embodiments of the present invention will be described in detail.

The antifouling coating composition according to an embodiment of the present invention is characterized by containing (A) an acrylate compound having two or more functional groups, (B) a fluorine-containing acrylate compound, and (C) .

The type of the acrylate compound having two or more functional groups (A) of the present invention is not particularly limited as long as it is a UV curable compound containing at least two acrylate groups or methacrylate groups. More specifically, the acrylate compound may be at least one selected from the group consisting of bifunctional or higher acrylate monomers and bifunctional or higher acrylate oligomers. At this time, each compound may contain 2 to 6 (meth) acrylate groups as functional groups.

The bifunctional or higher acrylate monomer may be at least one selected from the group consisting of dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, ethylene glycol diacrylate, hexanediol diacrylate, trimethylol Propane triacrylate, triacrylate of trimethylol propane, triacrylate of 3 mol propylene oxide adduct of trimethylol propane, triacrylate of trimethylol propane of 6 mol ethylene oxide adduct, glycerin propoxytriacrylate, hexaacrylate of caprolactone adduct of dipentaerythritol Selected from the group consisting of trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, 1,2,3-cyclohexanetetramethacrylate ethylene glycol dimethacrylate, and butanediol dimethacrylate, It may include one or more, but is not limited thereto.

The bifunctional or higher acrylate oligomer may be obtained by reacting an organic polyisocyanate with hydroxy methacrylate or a urethane-modified acrylate oligomer obtained by reaction of a polyol, an organic polyisocyanate and a hydroxy (meth) acrylate, An epoxy acrylate oligomer obtained by the reaction of a bisphenol-type epoxy resin with (meth) acrylic acid, and a polyester acrylate oligomer obtained by a reaction between a polyester polyol and (meth) acrylic acid, , But is not limited thereto.

The bifunctional or higher acrylate compound (A) is preferably contained in an amount of 5 to 95% by weight, more preferably 20 to 90% by weight based on the total solids content of the antifouling coating composition . When the content of the (A) bifunctional or higher acrylate compound is less than 20% by weight, the crosslinking density and hardness of the antifouling coating composition are affected. When the content is more than 90% by weight, the antifouling performance may not be sufficiently exhibited .

Preferably, the (A) bifunctional or higher acrylate compound may contain at least two or more acrylate monomers and urethane-modified acrylate oligomers. In this case, it is preferable that the acrylate monomer is contained in an amount of 40% by weight or less based on the total solids content of the antifouling coating composition. When the content is more than 40% by weight, the crosslinking property is increased, and the hard coat layer shrinks due to shrinkage during curing, and the coating layer may be broken.

The fluorine-containing acrylate compound (B) prevents the adherence of various contaminants to the hard coat layer formed by the antifouling coating composition of the present invention, and facilitates removal of contaminants. The fluorine-containing acrylate-based compound (B) contains fluorine which is highly electronegative so that contaminants do not easily adhere to the surface. The fluorine increases the water contact angle of the surface of the hard coat layer formed with the antifouling coating composition of the present invention to prevent contamination and improve gloss and transparency.

The fluorine-containing acrylate compound (B) is not particularly limited as long as it contains a fluorine atom and has a (meth) acrylate group as a UV curable functional group. For example, as the fluorine-containing acrylate compound (B), acrylate, methacrylate monomer and oligomer containing perfluoro group may be used, but the present invention is not limited thereto. At this time, the fluorine-containing acrylate compound (B) may contain 2 to 6 (meth) acrylate groups as functional groups.

The fluorine-containing acrylate compound (B) is preferably contained in an amount of 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, based on the total solids content of the antifouling coating composition. When the content of the fluorine-containing acrylate compound (B) is within the above range, the antifouling property and scratch resistance of the formed hard coat layer are improved and the miscibility with other compounds can be maintained, so that the surface properties and optical properties of the coating layer are maintained .

The silicone compound represented by the above formula (C) improves the antifouling property and the abrasion resistance of the hard coating layer formed by the antifouling coating composition of the present invention, thereby continuously maintaining the antifouling property even if physical damage is applied to the hard coating layer . This makes it possible to produce a hard coat layer which can be maintained stain-resistant continuously over time, unlike the conventional hard coat layer containing a fluorine-containing compound.

Here, the silicone compound contained in the antifouling coating composition of the present invention is a polysiloxane having at least two acrylate groups as a functional group, and specifically represented by the following formula (1).

[Chemical Formula 1]

Figure pat00002

Wherein R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a (meth) acrylate group, or an alkyl (meth) acrylate group having 1 to 10 carbon atoms. Acrylate group, R 2 is hydrogen or a methyl group, and n is an integer of 2 to 20. Preferably, R 1 may be an unsubstituted methyl group, a methacrylate group, or an acrylate group.

More specifically, the silicone compound represented by the above formula (C) includes a (meth) acrylate group at both terminals as a functional group. Here, it is more preferable that the silicone compound represented by the above formula (C) has 3 to 6 functional groups. When the number of functional groups is less than 3, hardness of the formed hard coating layer may be insufficient and it may be difficult to exhibit sufficient abrasion resistance. When the number of functional groups is more than 6, the flexibility of the hard coating layer is excessively lowered, , The solubility decreases, and it is difficult to dissolve in the solvent, so that the compatibility may be lowered.

The silicone compound (C) represented by the formula (1) is preferably contained in an amount of 5 to 90% by weight, more preferably 10 to 50% by weight, based on the total solid content of the antifouling coating composition. When the content of the silicone compound represented by the above formula (C) is less than 5% by weight, the antifouling property and the abrasion resistance of the formed hard coating layer are not sufficiently high. When the content of the silicone compound is more than 90% by weight, Or the optical properties of the hard coat layer may be deteriorated.

The antifouling coating composition of the present invention may further comprise a photoinitiator so as to be curable by ultraviolet rays. The type of the photoinitiator is not limited as long as it is a commonly used ultraviolet curing initiator, and examples thereof include 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, And at least one member selected from the group consisting of phosphorus oxyethyl ether, benzoin isopropyl ether, and benzoin butyl ether. Further, photoinitiators such as Daracur 1173, Irgacure 184 and Irgacure 907 (Ciba) may be used.

The photoinitiator is preferably contained in an amount of 0.1 to 10% by weight based on the total antifouling coating composition. When the content of the photoinitiator is less than 0.1% by weight, curing may not occur. When the content of the photoinitiator exceeds 10% by weight, cracks may occur on the surface of the hard coat layer due to over-curing or the un- Can be degraded.

On the other hand, the solvent used in the antifouling coating composition of the present invention is not particularly limited as long as it is a commonly used organic solvent, but it is not limited to benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol , Propyl alcohol, propylene carbonate, N-methylpyrrolidinone, N-vinylpyrrolidinone, N-acetylpyrrolidinone, N-hydroxymethylpyrrolidinone, N-butylpyrrolidinone, N-ethylpyrrolidinone , N- (N-octyl) pyrrolidinone, N- (N-dodecyl) pyrrolidinone, 2-methoxyethyl ether, xylene, cyclohexane, 3-methylcyclohexanone, ethyl acetate, , Tetrahydrofuran, methanol, amyl propionate, methyl propionate, propylene glycol methyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethyl formamide, ethylene glycol, hexafluoro Timothy carbonate may include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ether, and their cellosolve at least one selected from the group consisting of (cellosolve) derivative.

On the other hand, the solid component composed of (A) the bifunctional or higher acrylate compound, (B) the fluorine-containing acrylate compound and (C) the silicone compound represented by the formula (1) is 10 wt% to 70 wt% And more preferably 20% by weight to 50% by weight. When the solid content is less than 10% by weight, the hard coat layer may not have a sufficient thickness and functions can not be properly performed. When the solid content is more than 70% by weight, the surface properties and optical characteristics of the formed hard coat layer are deteriorated.

The antifouling coating composition of the present invention comprising the above-mentioned compounds may contain not only a fluorine-containing acrylate compound so as to prevent contaminants from adhering to the surface of the formed hard coat layer, but also a silicone- ≪ / RTI > As a result, the antifouling coating composition of the present invention can improve the initial water contact angle and prevent the decrease of the water contact angle as compared with the conventional antifouling coating composition, and can form a hard coat layer having more excellent antifouling property and abrasion resistance.

According to another aspect of the present invention, there is provided an antifouling coating composition which comprises a substrate sheet and a hard coat layer formed on at least one side of the substrate sheet, wherein the hard coat layer is formed using the antifouling coating composition and the hard coat layer has a thickness of 0.5 to 40 탆 , An antifouling sheet excellent in antifouling property and abrasion resistance is provided.

Various embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

1 is a schematic cross-sectional view of an antifouling sheet according to an embodiment of the present invention. Referring to FIG. 1, the antifouling sheet of the present invention has a structure in which a hard coating layer is formed on a substrate sheet.

Various materials can be used for the substrate sheet 110, without being limited by the use of the antifouling sheet 100. In particular, for use in a display device, a transparent substrate sheet 110 is used. For example, the substrate sheet 110 may be made of an acrylic resin, an acetylcellulose resin, a polycarbonate (PC) (PMMA) resin, a polyvinyl chloride (PVC) resin, a methyl methacrylate-styrene copolymer resin, an acrylonitrile butadiene styrene (ABS) resin, a polyethylene naphthalate resin, a polyethylene terephthalate resin and a polycyclohexylenedimethylene terephthalate And a phthalate resin. However, the present invention is not limited thereto.

The hard coat layer 120 is formed by curing an antifouling coating composition comprising a bifunctional or higher functional acrylate compound, a fluorine-containing acrylate compound, and a silicone compound represented by Formula 1 above. Since the antifouling coating composition is the same as that described above, detailed description thereof will be omitted.

As a method of coating the antifouling coating composition on the base sheet 110, a known coating method may be used. For example, a dip coating, a spin coating, a roll coating, a die coating , Bar coating, flow coating, 2 roll reverse coating, 3 roll reverse coating, gravure coating, micro gravure coating and the like can be used.

After coating, the composition coated by the above method is dried at 60 ° C to 110 ° C and cured with ultraviolet rays of 300 mJ / cm 2 to 1000 mJ / cm 2 to form the hard coat layer 120.

The thickness d 1 of the hard coat layer 120 formed by curing is preferably 0.5 μm to 40 μm, more preferably 5 μm to 20 μm. When the thickness d 1 of the hard coat layer 120 is less than 0.5 탆, hardness of the hard coat layer 120 is insufficient and antifouling property and abrasion resistance can not be sufficiently exhibited. When the thickness d 1 of the hard coat layer 120 is more than 40 탆, The hard coating layer 120 may be cracked and defective appearance may occur.

At this time, the hard coating layer 120 of the present invention is further improved in water contact angle as a standard for evaluating the antifouling property as compared with the conventional antifouling coating layer. Specifically, the water contact angle of the hard coat layer 120 is preferably 100 占 to 120 占 preferably 105 占 to 115 占 at 25 占 폚. When the water contact angle of the hard coat layer 120 is less than 100 °, it is vulnerable to contamination such as fingerprints or foreign matter. When the water contact angle exceeds 120 °, it is difficult to adhere the protective film to protect the coating layer. have.

According to the experiment of the present inventors, the hard coating layer 120 according to an embodiment of the present invention not only has excellent antifouling property but also excellent wear resistance. More specifically, as shown in Examples and Comparative Examples to be described later, the hard coat layer 120 of the antifouling sheet 100 was reciprocated by a cylindrical eraser having a diameter of 5 mm 1,500 reciprocal lengths of 30 mm to rub the surface of the hard coat layer 120 As a result of the evaluation test of the abrasion resistance, the rate of change of the water contact angle was 10% or less, preferably 8% or less. This shows that the hard coat layer 120 of the antifouling sheet 100 according to an embodiment of the present invention has durability that can minimize the deterioration of the antifouling performance even when abrasion occurs.

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

Manufacturing example  1 to 7

(A-TMM-3, Shin-Nakamura), a hexafunctional aliphatic urethane acrylate oligomer (U-6HA, Shin-Nakamura Co., Ltd.), a trifunctional acrylate monomer ), A fluorine-containing acrylate compound (Dainippon Ink & Chemicals, Inc.) and a silicone acrylate compound (SUO-S600NM, Shin-A Tien Co., Ltd.) were prepared in amounts as shown in Table 1 below based on the total solids content, To prepare a composition. The solvent was a mixture of methyl isobutyl ketone (MIBK, Daeshin Kagaku) and propylene glycol methyl ether (PGME, Daeshin K.K.) at a ratio of 1: 1, and the solid content was 50 wt% Respectively. At this time, Igacure 184 (Ciba) was added as a photopolymerization initiator in an amount of 4% by weight based on the total composition, and each component was stirred so as to be completely dissolved to prepare an antifouling coating composition.

division A1 (% by weight) A2 (% by weight) A3 (% by weight) B (% by weight) C (% by weight) Production Example 1 20.3 13.5 54.1 0.5 11.6 Production Example 2 19.4 12.9 51.8 4.8 11.1 Production Example 3 14.3 14.3 38.3 4.8 28.3 Production Example 4 23.4 15.6 61.0 - - Production Example 5 23.3 15.5 60.7 0.5 - Production Example 6 14.9 14.9 40.3 - 29.9

A1: 6-functional acrylate monomer

A2: Trifunctional acrylate monomer

A3: hexafunctional aliphatic urethane acrylate oligomer

B: Fluorine-containing acrylate compound

C: Silicone acrylate compound

Example  One

A 0.8 mm thick PMMA sheet was prepared as the base sheet, then the antifouling coating composition prepared in Preparation Example 1 was coated on the surface of the base sheet using a bar coater # 18 bar and then the solvent was dried at 80 DEG C for 2 minutes And irradiated with ultraviolet rays of 500 mJ / cm < 2 > to form a 20 [micro] m thick hard coat layer by curing the coated antifouling coating composition.

Example  2 to 3

An antifouling sheet was prepared in the same manner as in Example 1 except that the antifouling coating compositions were prepared in the same manner as in Preparation Examples 2 to 3, respectively.

Comparative Example  1 to 3

Antifouling sheets were prepared in the same manner as in Example 1, except that the antifouling coating compositions were prepared using the antifouling coating compositions prepared in Preparation Examples 4 to 6, respectively.

Property evaluation method - Experimental Example

(1) Pencil Hardness

Using a pencil hardness tester, the hard coat layer was tested three times under a load of 1.0 kg in accordance with the measurement standard JIS K5400, and the hardness without scratches was confirmed.

(2) Scratch resistance

Steel wool (# 0000) was mounted on a friction tester, and the hard coating layer was reciprocated 400 times under a load of 0.5 kg. Then, it was evaluated whether or not scratches were generated on the surface of the hard coating layer.

(3) Transmittance and haze

The transmittance and haze were measured using an integrating-point transmittance reflectance meter (CM-3700d, Konica Minolta).

(4) Water contact angle measurement

After dropping water droplets onto the surface of the hard coat layer at room temperature (25 ° C), the contact angle against water drops was measured five times using a contact angle meter (CAM100, KSV) to calculate the average value.

(5) Evaluation of abrasion resistance

The sheet prepared on the fixing plate was fixed using a rubbing tester (CORETECH), and then a cylindrical eraser having a diameter of 5 mm was mounted. The surface of the hard coating layer was rubbed 1,500 reciprocal lengths with a reciprocating length of 30 mm. And the average value of water contact angle before and after abrasion were compared.

(6)

After fingerprints were printed on the hard coat layer before and after the abrasion, 5 testers were printed with clean paper (product name: ULTIMA Ⅱ, Hansong Co., Ltd.) 10 times and gently wiped out.

A: No fingerprints left. B: There are a few print marks left. C: There are a lot of polished marks left.

division Pencil hardness Abrasion resistance Transmittance (%) Hayes Abrasion resistance evaluation Before wear After wear Initial water contact angle (°) Water contact angle after wear (°) Contact Angle Change Rate (%) Example 1 4H radish 92.3 0.12 110.5 103.2 6.6 A A Example 2 4H radish 92.1 0.13 115.3 106.4 7.7 A A Example 3 4H radish 92.4 0.12 114.6 108.2 5.6 A A Comparative Example 1 4H U 92.1 0.12 64.2 63.8 0.6 C C Comparative Example 2 4H radish 92.0 0.11 110.2 85.1 22.8 A B Comparative Example 3 4H radish 92.3 0.12 103.6 93.2 10.0 A B

As shown in Table 2, when Examples 1 to 3 and Comparative Examples 1 to 3 were compared, the hardness of the hard coat formed with the antifouling coating composition containing both the fluorine-containing acrylate compound and the silicone compound represented by Formula 1 The coating layer had excellent pencil hardness, scratch resistance and optical properties. In addition, the hard coat layer formed on the antifouling sheet of Examples 1 to 3 had a very low initial water contact angle of 109 ° or more and a very low value of less than 8% after the evaluation of abrasion resistance I could.

Although the embodiments of the present invention have been described in detail with reference to the accompanying drawings, it is to be understood that the present invention is not limited to those embodiments and various changes and modifications may be made without departing from the scope of the present invention. . Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

100: Antifouling sheet
110: substrate sheet
120: hard coat layer

Claims (4)

Bifunctional acrylate compounds;
Fluorine-containing acrylate compounds; And
1. An antifouling coating composition comprising a silicone compound represented by the following formula (1).
[Chemical Formula 1]
Figure pat00003

Wherein R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a (meth) acrylate group, or an alkyl (meth) acrylate group having 1 to 10 carbon atoms. Acrylate group, R 2 is hydrogen or a methyl group, and n is an integer of 2 to 20. The method according to claim 1,
Wherein the silicone-based compound is included in an amount of 5 wt% to 90 wt% based on the total solid content. A base sheet; And
And a hard coating layer formed on at least one side of the substrate sheet,
Wherein the hard coat layer is formed by curing an antifouling coating composition comprising an acrylate compound having two or more functional groups, a fluorine-containing acrylate compound, and a silicone compound represented by the following formula (1)
Wherein the hard coat layer has a thickness of 0.5 to 40 占 퐉.
[Chemical Formula 1]
Figure pat00004

Wherein R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a (meth) acrylate group, or an alkyl (meth) acrylate group having 1 to 10 carbon atoms. Acrylate group, R 2 is hydrogen or a methyl group, and n is an integer of 2 to 20. The method of claim 3,
Wherein the hard coat layer has a water contact angle of not less than 110 DEG C at 25 DEG C and a water contact angle change rate of not more than 10% after the evaluation of abrasion resistance.
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JP2018202697A (en) * 2017-06-01 2018-12-27 大日本印刷株式会社 Hard coat film, touch panel including the hard coat film, and image display device including the touch panel
CN109880411A (en) * 2018-12-21 2019-06-14 宁波激智科技股份有限公司 A kind of hardened layer coating fluid and a kind of cured film
RU2708587C1 (en) * 2019-07-29 2019-12-09 Николай Николаевич Петров Method of forming a protective coating having anti-fouling effect in an aqueous medium, a composition for forming a coating on a protected surface and use thereof
KR102177988B1 (en) * 2020-03-03 2020-11-12 주식회사 광성텍 Manufacturing method of rubber roll having low-friction, high-isolation, anti-contamination performance for transferring sheet material and rubber roll thereof

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CN101279212B (en) 2008-04-15 2011-05-18 中国石油化工股份有限公司 Preparation of intercrossed network water dealcoholizing pervaporation membrane

Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2018202697A (en) * 2017-06-01 2018-12-27 大日本印刷株式会社 Hard coat film, touch panel including the hard coat film, and image display device including the touch panel
CN109880411A (en) * 2018-12-21 2019-06-14 宁波激智科技股份有限公司 A kind of hardened layer coating fluid and a kind of cured film
RU2708587C1 (en) * 2019-07-29 2019-12-09 Николай Николаевич Петров Method of forming a protective coating having anti-fouling effect in an aqueous medium, a composition for forming a coating on a protected surface and use thereof
KR102177988B1 (en) * 2020-03-03 2020-11-12 주식회사 광성텍 Manufacturing method of rubber roll having low-friction, high-isolation, anti-contamination performance for transferring sheet material and rubber roll thereof

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