KR101436018B1 - antifouling photo-curable resin composition containing per-fluoro polyether modified compound and antifouling transparent thin film for hard coating using the same - Google Patents

Abstract

The present invention relates to an antifouling photocurable resin composition comprising a perfluoropolyether-modified compound and a hard coat antifouling transparent thin film prepared using the same, wherein the photocurable perfluoropolyether-modified compound represented by Chemical Formula 1 according to the present invention Can be applied to an organic material such as a polymer, is excellent in compatibility with other organic chemicals, and can be applied to a roll to roll (R2R) process. In addition, the photocurable perfluoropolyether modified compound according to the present invention is capable of ultraviolet curing without the need for an additional radical initiator as compared with conventional photocurable compounds having a hydrocarbon-based double bond, Therefore, the photocurable resin composition containing the photocurable resin composition has high reactivity and is free from unreacted materials, and thus has excellent adhesion with a base material and excellent film-forming properties. Further, since the antifouling property due to the perfluoropolyether compound is remarkably excellent, it is possible to produce an antifouling transparent thin film for hard coat, so that the functional coating film for display, optical filter, frame or surface coating of electronic products, Waterproof paints used in household goods, construction, shipbuilding civil engineering fields, and the like.

Description

An antifouling photocurable resin composition comprising a perfluoropolyether-modified compound and an antifouling photo-curable resin composition containing the perfluoropolyether-modified compound and an antifouling transparent thin film using the same,

The present invention relates to an antifouling photocurable resin composition containing a perfluoropolyether-modified compound, and to an antifouling transparent film for a hard coat produced using the same.

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

At present, fluorinated functional materials are widely used as core materials of next generation technologies in optical communication, optoelectronics, semiconductors, automobiles, and computers in high-tech industries because they exhibit excellent performance that can not be realized by other materials due to contamination resistance, weather resistance, heat resistance, . Especially, in the field of consumer electronics, construction, shipbuilding, and civil engineering, which requires a conventional contamination surface property including an antifouling coating such as an outermost layer of a liquid crystal display or a frame of an elegant display, There has been a growing interest in fluorine-based functional materials because of the growing interest in anti-fouling coatings.

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

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

First, Patent Document 1 discloses a fluorine-silicon based surface coating agent comprising C ₈ F ₁₇ C ₂ H ₄ Si (NH) _3/2 , C ₄ F ₉ C ₂ H ₄ Si (NH) _3/2 or polysiloxane poly siloxazane) and the like. However, when these compounds are used alone, the fluorine compound is poor in durability against friction because of low reaction cross-linking property with the inorganic oxide as a base material, and when the fluorine compound alone is used, the decontamination property which is the inherent surface property of the fluorine compound is poor , And in the case of polysiloxazane compounds, the initial contamination prevention performance is poor because the surface energy is higher than that of the fluorine compound. In addition, sufficient crosslinking is not performed depending on the number of functional groups for forming a three-dimensional structure, so that the glass transition temperature is low, thereby accumulating or adhering contaminants and remaining fingerprints by hand. In addition, although silane having a perfluoro group is used as a glass surface modifier, such a coating also has a disadvantage that it can not exhibit sufficient water repellency, stain-proofing property and decontamination property at the same time.

Next, as means for solving the above problems, Patent Documents 2 to 5 disclose so-called silane coupling methods in which an inorganic material such as glass is bonded with an organic material. The silane coupling agent chemically bonded to the silane coupling agent as described in the above document can be used as a coating agent component having good film forming property, good adhesion to a substrate and durability. The compound having a silane coupling structure And the antifouling property (water repellency and oil repellency) is improved by fixing to the surface. However, the above compound has a limitation in the length of perfluoro group (molecular weight), and the oil-repelling performance is insufficient. Even if the length (molecular weight) of sufficient perfluoro group is satisfied, the proportion of the alkoxysilane group to the total molecular weight including the perfluoro group is lowered There is a drawback that it is insufficient in adhesiveness or adhesion durability.

These problems have been largely improved by the use of oligomeric perfluoroether-modified silane compounds having very good surface friction and decontamination properties due to their molecular structure properties.

First, Patent Document 6 discloses a perfluoroether-modified silane compound represented by the following formula.

Next, Patent Document 7 discloses a composition containing a carbon-carbon double bond including a triisocyanate obtained by trimerizing a diisocyanate, a perfluoropolyether having an active hydrogen, and a silane compound having an active hydrogen. However, the oligomer type perfluoroether-modified silane compound is suitable for imparting stain resistance to the surface of inorganic materials such as glass and ceramics. However, in order to impart stain resistance on the surface of organic and polymeric materials having much more applications than inorganic materials, , And it is fixed by van der Waals bond as a degree of network structure due to self crosslinking, so that surface bonding force and durability are insufficient. Secondly, since such a modified silane compound forms a coating by a sol-gel process at the time of coating, it takes a very long time to coat and form a film. Thirdly, the highly reactive silane or methoxysilane It is difficult to mix it with other reactive organic materials freely. In addition, it is difficult to adopt a roll-to-roll (R2R) process, which is the fourth most recent high-efficiency production type of IT parts.

Therefore, the inventors of the present invention have conducted research with interest on a compound that can be used as an antifouling coating composition capable of overcoming the above-mentioned problems, and have found that the photocuring for a hard coat containing a photocurable perfluoropolyether- The resin composition can be applied to an organic material like a polymer and is excellent in combinability with other organic medicines and can be applied to a roll to roll (R2R) process by coating and ultraviolet curing, It is possible to produce an antifouling transparent thin film for a hard coat which can be chemically bonded and has excellent durability, thus completing the present invention.

U.S. Patent No. 4,678,688; Japanese Patent Application Laid-Open No. 1983-167597; Japanese Patent Laid-Open No. 1983-122979; Japanese Patent Application Laid-Open No. 1998-232301; Japanese Patent Application Laid-Open No. 2000-143991; Korean Patent Publication No. 2009-0062760; U.S. Patent No. 6,906,115.

JAMES T. HILL, J. Macromol. Sci. Chem., A8, (3), 499 (1974).

It is an object of the present invention to provide a method for manufacturing a hydrocarbon-based substrate which can be applied to an organic material such as a polymer, has excellent compatibility with other organic medicines, can be applied to a roll to roll process by coating and ultraviolet curing, And which can be chemically bonded to provide an antifouling photocurable resin composition excellent in durability.

Another object of the present invention is to provide an antifouling transparent thin film for a hard coat comprising the antifouling photocurable resin composition.

It is still another object of the present invention to provide a film-coated antifouling base wherein the surface of the substrate is coated with the antifouling transparent film.

In order to achieve the above object,

The present invention relates to a photocurable perfluoropolyether-modified compound represented by the following general formula (1): 0.001-50 wt%; And

50 to 99.999% by weight of at least one hydrocarbon compound selected from the group consisting of polymerizable hydrocarbon-based divalent monomers, trivalent monomers, tetravalent monomers and oligomers, and mixtures thereof.

[Chemical Formula 1]

(In the formula 1,

A and B are R _f or Y, where A is R _f , B is Y and A is Y, B is R _f ;

R _f is selected from R _f1 [CF ₂ O] _b [CF ₂ CF (CF ₃ ) O] _c [CF (CF ₃ ) O] _d [CF ₂ CF ₂ O] _e Z-, CF ₃ CF ₂ CF ₂ [ _{(CF 3) CF 2] a} OCF (CF 3) - or _{CF 3 CF 2 CF 2 O [} CF 2 CF 2 CF 2 O] f CF 2 CF 2 - , and wherein R _f1, and Z are each independently a C1- C5, and a, b, c, d, e, and f are integers from 0 to 100;

,

또는

이고, 이때 n은 1 내지 10의 정수이고; 및X is

,

or

, Wherein n is an integer from 1 to 10; And

,

,

,

또는

이고, 이때, X와 결합되는 Y의 결합자리는 아릴 고리상의 임의의 탄소이다).
Y is

,

,

,

or

, Wherein the bonding site of Y bonded to X is any carbon on the aryl ring.

The present invention also provides an antifouling transparent thin film for a hard coat formed by coating the antifouling photocurable resin composition.

Further, the present invention provides a film-coated antifouling base wherein the surface of the substrate is coated with the antifouling transparent thin film.

The antifouling photocurable resin composition containing the photocurable perfluoropolyether modified compound represented by Chemical Formula 1 according to the present invention can be applied to organic materials such as polymers and is excellent in compatibility with other organic medicines, to roll, R2R) process can be applied. In addition, the photocurable perfluoropolyether modified compound according to the present invention is capable of ultraviolet curing without the need for an additional radical initiator as compared with conventional photocurable compounds having a hydrocarbon-based double bond, Therefore, the photocurable resin composition containing the photocurable resin composition has high reactivity and is free from unreacted materials, and thus has excellent adhesion with a base material and excellent film-forming properties. Further, since the antifouling property due to the perfluoropolyether compound is remarkably excellent, it is possible to produce an antifouling transparent thin film for hard coat, so that the functional coating film for display, optical filter, frame or surface coating of electronic products, Waterproof paints used in household goods, construction, shipbuilding civil engineering fields, and the like.

1 is a graph comparing transmittances of antifouling transparent films for hard coatings prepared in Examples and Comparative Examples according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a photocurable perfluoropolyether-modified compound represented by the following general formula (1): 0.001-50 wt%; And

50 to 99.999% by weight of at least one hydrocarbon compound selected from the group consisting of polymerizable hydrocarbon-based divalent monomers, trivalent monomers, tetravalent monomers and oligomers, and mixtures thereof.

In Formula 1,

A and B are R _f or Y, where A is R _f , B is Y and A is Y, B is R _f ;

R _f is selected from R _f1 [CF ₂ O] _b [CF ₂ CF (CF ₃ ) O] _c [CF (CF ₃ ) O] _d [CF ₂ CF ₂ O] _e Z-, CF ₃ CF ₂ CF ₂ [ _{(CF 3) CF 2] a} OCF (CF 3) - or _{CF 3 CF 2 CF 2 O [} CF 2 CF 2 CF 2 O] f CF 2 CF 2 - , and wherein R _f1, and Z are each independently a C1- C5, and a, b, c, d, e, and f are integers from 0 to 100;

,

또는

이고, 이때 n은 1 내지 10의 정수이고; 및X is

,

or

, Wherein n is an integer from 1 to 10; And

,

,

,

또는

이고, 이때, X와 결합되는 Y의 결합자리는 아릴 고리상의 임의의 탄소이다.
Y is

,

,

,

or

, Wherein the bonding site of Y bonded to X is any carbon on the aryl ring.

Preferably,

Wherein R _f is _{CF 3 CF 2 CF 2 - [} OCF (CF 3) CF 2] a -OCF (CF 3) - , and wherein R _f1 is a perfluoroalkyl, and Z are independently of each other C1-C5, a is An integer from 1 to 100;

이고, 이때 n은 1 내지 10의 정수이고; 및X is

, Wherein n is an integer from 1 to 10; And

이다.
Y is

to be.

The antifouling photocurable resin composition containing the photocurable perfluoropolyether modified compound represented by Chemical Formula 1 according to the present invention can be applied to organic materials such as polymers and is excellent in compatibility with other organic medicines, to roll, R2R) process can be applied. In addition, the photocurable perfluoropolyether modified compound according to the present invention is capable of ultraviolet curing without the need for an additional radical initiator as compared with conventional photocurable compounds having a hydrocarbon-based double bond, Therefore, the photocurable resin composition containing the photocurable resin composition has high reactivity and is free from unreacted materials, and thus has excellent adhesion with a base material and excellent film-forming properties. Furthermore, the thin film produced by using the photocurable resin composition has a high contact angle, low surface energy, and low flow angle (see Experimental Example 1 and Experiment 2), and is excellent in anti-staining property and decontamination property (See Experimental Example 3 and Experimental Example 4), it has excellent antifouling property and transparency equivalent to that of a conventionally used transparent thin film (see Experimental Example 5), and thus is useful as an antifouling photocurable resin composition for hard coatings in various fields requiring antifouling properties Lt; / RTI >

At this time, the photocurable perfluoropolyether modified compound represented by Formula 1 according to the present invention can be produced by a coupling reaction between a heterocycloalkyl compound represented by Formula 2 and a compound represented by Formula 3 as shown in Reaction Scheme 1 below The compound represented by formula (4) may be added to prepare a compound represented by formula (1): < EMI ID =

[Reaction Scheme 1]

(Wherein, in the above Reaction Scheme 1, A and B are the same as defined in Formula 1, P is isocyanato, carboxylic acid or acid chloride, and Q is hydroxy or amine).

Hereinafter, a method of producing the photocurable perfluoropolyether modified compound according to the present invention will be described in more detail.

In the above production method according to the present invention, the heterocycloalkyl compound of formula (2) is a hydrocarbon-based compound having three reactors. The compound having three reactors represented by the above-mentioned general formula (2) is generally used in this field and is not particularly limited, but a hydrocarbon compound having a reactive group of isocyanato, carboxylic acid or acid chloride at the terminal thereof, Can be used. For example, a hexamethylene diisocyanate cyclic trimer (trade name: DESMODUR N3300) obtained by trimerizing a diisocyanate can be used.

In the above production method according to the present invention, any one of the compounds represented by Chemical Formulas 3 and 4 is a photo-curable perfluoropolyether compound having a reactive group at the terminal. The photo-curable perfluoropolyether compound having a reactive group at the terminal is not particularly limited, but a perfluoropolyether compound having a hydroxy or amine reactive group at the terminal thereof can be used. For example, perfluoropolyether-alcohol (PFPE-alcohol) can be used.

On the other hand, the perfluoropolyether compound can be synthesized according to a known method as follows (Non-Patent Document 1). That is, it can be synthesized by reacting hexafluoropropylene (HFP), hexafluoropropylene oxide (HFPO) and cesium fluoride in a solvent. In this case, the solvent is not particularly limited and is generally used in the art, and for example, a solvent selected from triglyme, tetraglyme, butyl diglyme and ethyl diglyme can be used. The degree of polymerization (molecular weight) of the perfluoropolyether compound synthesized by the above method can be controlled by the introduction rate of hexafluoropropylene oxide (HFPO) and the reaction temperature, and can be controlled by a gel permeation chromatogram By measuring the molecular weight of the polyether compound, the polymerization degree can be confirmed. The degree of polymerization is an important parameter for determining the antifouling property, the adhesion property with the substrate and the durability of the compound of formula (1).

As an example of the perfluoropolyether compound, a perfluoropolyether compound having a terminal hydroxyl group, that is, a perfluoropolyether-alcohol (PFPE-alcohol) can be prepared by reacting the perfluoropolyether compound prepared above with, for example, methyl ester ≪ / RTI > and alcohols.

First, the reaction for methylesterification of the perfluoropolyether compound can be performed by mixing the perfluoropolyether compound with methanol and stirring at a temperature in the range of 20 to 30 ° C. Next, the reaction product is purified, vacuum-dried and sequentially carried out to obtain a perfluoropolyether-methyl ester compound.

Next, the alcohol conversion reaction of the methyl ester compound of the perfluoropolyether can be carried out using a known organic synthesis method. For example, sodium borohydride (NaBH ₄ ), a relatively stable compound, can be used to carry out the alcoholation reaction. That is, the reaction can be terminated by adding perfluoropolyether-methyl ester compound to a mixture of ethanol and sodium borohydride (NaBH ₄ ) / sodium ethoxide (C ₂ H ₅ ONa) . The progress of the reaction can be judged by gas chromatography or ¹ H-NMR analysis to confirm the conversion. Next, the reaction product is purified and dried sequentially to obtain a perfluoropolyether-alcohol compound.

Meanwhile, in the above production method according to the present invention, any one of the compounds represented by Chemical Formulas (3) and (4) is a benzophenone photo-binding compound having a reactive group at the terminal. The benzophenone-based compound can be chemically bonded to the hydrocarbon-based substrate by a photo-curing reaction without the need for an additional radical initiator. Therefore, when a film is formed with the coating composition containing the compound of Formula 1 according to the present invention, And it is an important parameter to determine the durability.

,

,

,

또는

를 사용할 수 있으며, 이때, 상기 화합물의 아릴 고리상의 임의의 탄소에는 반응기로서 하이드록시 또는 아민이 결합되어 있는 것이 바람직하다. 예를 들어, 4-하이드록시벤조페논(HBP)을 들 수 있다.
Specifically, the compound having a reactive group at the terminal is not particularly limited as it is generally used in the art, but a benzophenone compound

,

,

,

or

May be used. At this time, it is preferable that any carbon on the aryl ring of the compound is bonded to hydroxy or amine as a reactor. For example, 4-hydroxybenzophenone (HBP) can be mentioned.

Further, in the above production method of the present invention, the structure of the compound to be produced may vary depending on the composition ratio of the reactants. Specifically, in order to produce the compound represented by the formula (1), the molar ratio of the perfluoropolyether compound having a reactive group at the terminal to the hydrocarbon compound represented by the general formula (2) having three reactors is from 1: 1 to 1: 2 . When the molar ratio is less than 1: 1, a large amount of byproducts having a benzophenone compound adhere to all three reactors of the hydrocarbon-based compound represented by the formula (2), which have three reactors, , And when the ratio is more than 1: 2, a large amount of by-products in which perfluoropolyether compound adheres to all three reactors of the compound represented by the general formula (2) are generated so that a liquid impurity And the physical properties of the coating surface are lowered, which is undesirable.

Further, in the above production method according to the present invention, the molar ratio of the benzophenone compound having a reactive group at the terminal to the hydrocarbon compound represented by the general formula (2), which has three reactors, The ratio in which a reactive group can be substituted is suitable, for example, at a molar ratio of 1: (1 to 1.2 times the value obtained by subtracting the molar ratio of the terminal used and the perfluoropolyether compound having a reactive group to 3) Preferably 1.1 times the value obtained by subtracting the molar ratio of the perfluoropolyether compound having a reactive group to the end thereof used at 1: (3).

In the above production process according to the present invention, it is very important that the reactants mixed with the compounds of the formulas (2) to (4) form a homogeneous phase so that the reaction proceeds, and in particular, the selection of the reaction solvent is very important. Specifically, it is preferable to carry out the reaction in a mixed solvent of a fluorocarbon-based solvent and a hydrocarbon-based solvent. When only the fluorocarbon solvent is used, the solubility of the compound of formula (2) as the hydrocarbon compound and the benzophenone compound is poor and the reaction is difficult to proceed smoothly. When only the hydrocarbon solvent is used, the solubility in the perfluoropolyether compound It is not preferable because it is difficult to proceed smoothly.

At this time, the fluorocarbon solvent may be at least one selected from the group consisting of trifluorobenzene, 1,3-bistrifluorobenzene, 1,4-bistrifluorobenzene, trifluorotoluene, perfluoroheptane, perfluorohexane, m-xylene hexafluoride , Methyl and fluoro butyl ether, ethyl and fluoro butyl ether, perfluoro (2-butyltetrahydrofuran), 1,3-dichloro-1,1,2,2,3-pentafluoropropane, methoxy- nonafluoro Butane or ethoxy-nonafluorobutane can be used alone or in combination. As the hydrocarbon solvent, acetone, toluene, methyl isobutyl ketone (MIBK), tetrahydrofuran, or a mixed solution thereof can be used.

The mixing ratio of the fluorocarbon solvent to the hydrocarbon solvent may vary depending on the molecular weight of the perfluoropolyether to be used and the kind of the hydrocarbon compound represented by the general formula (2) having three reactors. For example, And 2 to 100 parts by weight of a hydrocarbon-based solvent may be used relative to 100 parts by weight of the fluorocarbon-based solvent.

In the above production method according to the present invention, the coupling reaction of the compound of Formula 2 with the compound of Formula 3 and Formula 4 may be a urethane reaction, an ester reaction or an amide reaction. For example, when perfluoropolyether-alcohol and 4-hydroxybenzophenone (HBP) are reacted with a hexamethylene diisocyanate cyclic trimer compound, a perfluoropolyether-modified compound of the formula (1) having a urethane linkage is prepared can do.

Further, in the above production method according to the present invention, the reaction temperature of the compound represented by the formula (2) and the mixture represented by the formula (3) and the formula (4) is preferably maintained at a room temperature to 50 ° C. When the reaction temperature is 50 ° C or higher, the polymerization reaction of the hydrocarbon compound itself represented by the formula (2) having three reactors occurs and it is difficult to obtain a compound having a desired structure and a polymer which is not dissolved in a solvent is produced. When the temperature is lower than room temperature, the reaction rate is not only slow, but the reaction may not be completed, which is not preferable.

On the other hand, the antifouling photocurable resin composition comprising the perfluoropolyether-modified compound represented by formula (1) according to the present invention is selected from the group consisting of polymerizable hydrocarbon-based divalent monomers, trivalent monomers, tetravalent monomers and oligomers At least one hydrocarbon compound.

The hydrocarbon compound may be selected from the group consisting of 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-nucleic acid diol diacrylate, 1,6-nucleic acid diol monoacrylate Divalent monomers selected from the group consisting of monomethyl methacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylate, and alkoxylated cyclohexane dimethanol diacrylate; Glycerol triacrylate, trimethoxypropane triacrylate, ethoxylated triacrylate, propoxylated triacrylate, trimethylolpropane triacrylate, and tris (2-hydroxyethyl) isocyanurate A trifunctional monomer selected from the group consisting of triacrylate; Pentaerythritol tetraacrylate, eicosylated pentaerythritol tetraacrylate, and caprolactone-modified dipentaerythritol hexaacrylate such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, A tetravalent or higher-valent monomer selected from the group consisting of And oligomers selected from the group consisting of urethane acrylate, polyester acrylate, and epoxy acrylate; and at least one selected from the group consisting of urethane acrylate, polyester acrylate, and epoxy acrylate. Preferably, methyl methacrylate, trimethylol propane triacrylate (TMPTA), dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate can be used. But is not limited thereto.

Also, the antifouling photocurable resin composition according to the present invention is a resin composition comprising a photopolymerizable perfluoropolyether-modified compound represented by the general formula (1), a hydrocarbon-based divalent monomer, a trivalent monomer, a tetravalent or higher-valent monomer and an oligomer The at least one hydrocarbon compound may be prepared by mixing at a mixing ratio of 0.001-50 wt% to 50-99.999 wt%, preferably 0.01-10 wt% to 50-99.99 wt%.

When the content of the perfluoropolyether-modified compound is less than 0.001% by weight based on the total weight of the photocurable antifouling photocurable resin composition according to the present invention, the amount of the perfluoropolyether-modified compound exhibiting antifouling property is very small, It is difficult to anticipate effective antifouling effect. When the content of the perfluoropolyether-modified compound exceeds 50% by weight, the content of the polymerizable hydrocarbon compound is decreased. Therefore, the scratch resistance, abrasion resistance and hardness And the like.

In addition, the antifouling photocurable resin composition according to the present invention may further comprise a photocurable initiator and an organic solvent.

At this time, the photocurable initiator contained in the antifouling photocurable resin composition according to the present invention may be ethyl benzoin ether, isopropyl benzoin ether,? -Methyl benzoin ethyl ether, benzoin phenyl ether,? -Acyl oxime ester,? 2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, 2-ethyl anthra Quinone, 2-chloroanthraquinone, thioxanthone, isopropylthioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate, microclerketone and the like can be used. But is not limited to.

The organic solvent contained in the antifouling photocurable resin composition according to the present invention is a fluorocarbon solvent, a hydrocarbon solvent or a mixed solvent thereof. The fluorocarbon solvent may be at least one selected from the group consisting of trifluoro benzene, 1,3-bistrifluorobenzene, 1,4-bistrifluorobenzene, trifluoro toluene, perfluoroheptane, perfluorohexane, m-xylylene hexafluoride, (2-butyltetrahydrofuran), and the hydrocarbon solvent may be 3,3-dichloro-1,1,1,2,2-pentafluoropropane , Methoxy-nonafluorobutane, ethoxynonafluorobutane, petroleum benzene, mineral spirits, isoparaffin, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl glyme, methyl tri Glycerol, glyme, methyltetraglyme, tetrahydrofuran ethanol and the like, but not limited thereto.

The present invention also provides an antifouling transparent thin film formed by curing an antifouling photocurable resin composition comprising a perfluoropolyether-modified compound represented by the general formula (1).

In this case, in the transparent thin film according to the present invention, the method of applying the photocurable resin composition is not particularly limited to a method generally used in the art, and examples thereof include a spin coating method, a dip coating method, a curtain coating method , A spray coating method and the like can be used.

Further, in the antifouling transparent thin film according to the present invention, it is preferable that the thickness of the film has a thickness in the range of 0.005 to 50 mu m. When the thickness of the coating film is less than 0.005 μm, antifouling property against water or oil can not be manifested. When the thickness is more than 50 μm, the light transmittance may be decreased and the thickness may be uneven. It is preferable to maintain the thickness in the above range because a problem that an interference fringe occurs may occur.

The antifouling photocurable resin composition according to the present invention includes a perfluoropolyether compound having an antifouling property and can be applied to an organic material such as a polymer and is excellent in combined use with other organic medicines. (R2R) process. In addition, since the benzophenone-based compound is included, ultraviolet curing can be performed without the need for an additional radical initiator, and it is possible to chemically bond to a hydrocarbon-based substrate, It is possible to manufacture a transparent thin film. In addition, the antifouling transparent film produced by using the antifouling photocurable resin composition according to the present invention has high contact angle, low surface energy and low flow angle (see Experimental Example 1 and Experimental Example 2) (Refer to Experimental Example 3 and Experimental Example 4), and the thin film produced by using the thin film has excellent antifouling property and transparency equivalent to that of a transparent film conventionally used (see Experimental Example 5), so that antifouling properties are required And can be usefully used as an antifouling photocurable resin composition for hard coating in various fields.

The various fields requiring antifouling properties are not only usable in frames of functional coating films for display, optical filters and electronic products, which are rapidly in industrial demand, but also require antifouling property of waterproof and oil repellent. (PDP), an organic light emitting device (EL), a field emission display (FED), and the like, and the like. .

On the other hand, the present invention provides a film-coated antifouling base wherein the surface of the base is coated with the antifouling transparent thin film according to the present invention.

Specifically, in the film-adherence preventive base material of the present invention, the base material can be selected and used without limitation as long as it is a base material that requires antifouling property. For example, in order to impart antifouling properties to substrates of glass or plastic articles in all industrial fields, the antifouling photocurable resin composition containing the photocurable perfluoropolyether-modified compound represented by Formula 1 is cured So that a film formed thereon can be attached and used. More specifically, the present invention relates to a liquid crystal display device, a liquid crystal display device, a liquid crystal display device, a liquid crystal display device, a liquid crystal display device, a liquid crystal display device, Or objects that need to be provided with pollution prevention properties in the civil engineering field.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Experimental Examples. However, the following Production Examples, Examples and Experimental Examples are merely illustrative of the present invention, and the scope of the present invention is not limited to Examples and Experimental Examples.

< Manufacturing example  1> Overpayment  Synthesis of polyester-alcohol - 1

Step 1: Overpayment Of polyether-oxyfluoride (PFPE-COF)  synthesis

Tetraglyme (2.49 g), cesium fluoride (1.69 g), hexafluoropropylene (HFP, 35 g) and hexafluoropropylene oxide (HFPO, 165 g) were placed in a stainless steel high pressure reactor equipped with a stirrer, a cooling jacket, a thermometer and a pressure gauge. And reacted at -35 캜 for a total of 36 hours to obtain an oligomeric perfluoropolyether-oxyfluoride (PFPE-COF) represented by Formula 5 above. ¹⁹ F-NMR and Gel Permeation Chromatography (GPC) analysis of the prepared perfluoropolyether-oxyfluoride (PFPE-COF) was carried out and the results are shown below.

Gel permeation chromatography (GPC) Measured value: 1700;

^{19 F-NMR (CDCl3, 300} MHz): δ - 83.8 (3F, s, C F 3 CF 2 CF 2), - 131.3 (2F, m, CF 3 C F 2 CF 2), - 83.2 [(2F, _{m, CF 3 CF 2 C F} 2), (3F, s, CF (C F 3) COF)], - 146.2 (1F, t, OC F (CF 3) CF 2), - 81.6 [(3F, m _{, OCF (C F 3) CF} 2), (m, 2F, OCF (CF 3) C F 2)], - 132.0 (1F, t, C F (CF 3) COF, + 25 [1F, s, - _{CF (CF 3) CO F]} .

Step 2: Overpayment Polyether - Methyl ester (PFPE-methyl ester)  synthesis

The perfluoropolyether-oxyfluoride (PFPE-COF) prepared in Step 1 was injected into a three-necked flask equipped with a bubble trap, and methanol was added slowly. At this time, the methanol was used more than twice as much as the molar ratio of the perfluoropolyether-oxyfluoride (PFPE-COF), and stirring was performed using a magnetic bar while methanol was slowly injected. At this time, the generation of hydrogen fluoride (HF) gas generated by the reaction of methanol and perfluoropolyether-oxyfluoride (PFPE-COF) could be confirmed through the bubble trap. The perfluoropolyether-oxyfluoride (PFPE-COF) showed a clear yellowish color, but it turned out to be opaque when methanol was added. The reaction was completed after stirring well for 3 hours or more. In order to remove the methanol used for the reaction, distilled water was added to the reaction mixture, and the reaction mixture was thoroughly mixed. Then, the reaction mixture was layered in a separating funnel, and then the PFPE-methyl ester portion of the lower layer was separated. Removal of methanol can be confirmed by gas chromatography (GC) analysis or ¹ H-NMR analysis. Next, a large amount of magnesium sulfate (MgSO ₄ ) was added in order to remove the distilled water used for removing the methanol, and the mixture was sufficiently stirred and filtered. The final compound, PFPE-methyl ester, obtained after vacuum drying to remove volatile substances remaining in the reactants, is a pale yellow transparent liquid. Gel permeation chromatography (GPC) analysis of the prepared polyether-methyl ester (PFPE-methyl ester) was performed, and the results are shown below.

Gel permeation chromatography (GPC) Measured value: 1700.

Step 3: Polyether -Alcohol( PFPE - alcohol ) Synthesis of

Ethanol and sodium borohydride (NaBH ₄ , 9.0 g) were added to the flask and stirred. Then, polyether-methyl ester (PFPE-methyl ester, molecular weight 1700, 200 g) was added to the flask using dropping funnel And slowly injected. The polyether-methyl ester (PFPE-methyl ester) was added over about 2 hours, and gas evolution continued after the completion of the addition. The reaction was carried out with stirring at room temperature overnight. It was confirmed that the reaction solution was free of gas and was semitransparent but maintained homogeneous phase, and the conversion was confirmed by gas chromatography or ¹ H-NMR analysis by sampling. After confirming the conversion rate, a 10% solution of hydrochloric acid (HCl) was added to separate the reaction into two layers, and it was confirmed that the polyether-alcohol (PFPE-alcohol) settled in the lower layer among the two separated layers. Then, a saturated solution of sodium hydrogencarbonate (NaHCO ₃ ) was added until the pH of the reaction solution became 7 to 8, and distilled water was added thereto to remove impurities such as ethanol, stirring and layer separation were repeated. Thereafter, a large amount of magnesium sulfate (MgSO ₄ ) was added to the distilled water to remove the used distilled water, and the resultant was thoroughly stirred and filtered. After vacuum drying, a final synthetic polyether-alcohol (PFPE-alcohol) %.

< Manufacturing example  2> Overpayment  Synthesis of polyester-alcohol - 2

The procedure of Step 1 of Preparation Example 1 was repeated except that hexafluoropropylene (HFP, 50 g) and hexafluoropropylene oxide (HFPO, 240 g) were used in Step 1 of Preparation Example 1, To obtain a polyether-oxyfluoride (PFPE-COF). At this time, producing a perfluoropolyether-fire cargo (PFPE-COF) is a ^{1 9} F-NMR measurement as a result, the perfluoropolyether prepared in Step 1 of Preparation 1 - fire cargo (PFPE-COF) with spectral data And the average molecular weight was 2500 by gel permeation chromatography (GPC) analysis.

Next, the perfluoropolyether-alcohol (PFPE-alcohol) of Production Example 2 was treated in the same manner as in Step 2 and Step 3 of Production Example 1 for perfluoropolyether-oxyfluoride (PFPE-COF) &Lt; / RTI &gt;

< Manufacturing example  3> Overpayment  Synthesis of polyester-alcohol - 3

The procedure of Step 1 of Preparation Example 1 was repeated except that hexafluoropropylene (HFP, 180 g) and hexafluoropropylene oxide (HFPO, 860 g) were used in Step 1 of Preparation Example 1, To obtain a polyether-oxyfluoride (PFPE-COF). At this time, producing a perfluoropolyether-fire cargo (PFPE-COF) is a ^{1 9} F-NMR measurement as a result, the perfluoropolyether prepared in Step 1 of Preparation 1 - fire cargo (PFPE-COF) with spectral data And the average molecular weight was 9000 as determined by Gel Permeation Chromatography (GPC) analysis.

Next, the perfluoropolyether-alcohol (PFPE-alcohol) of Production Example 3 was subjected to the same procedure as Step 2 and Step 3 of Production Example 1 for perfluoropolyether-acid fluoride (PFPE-COF) in Step 1, &Lt; / RTI &gt;

< Manufacturing example  4 to Manufacturing example  6> Light-curing type Overpayment Polyether  Synthesis of modified compounds

The hexamethylene diisocyanate cyclic trimer (DESMODUR N3300) and dibutyltin dilaurate (DBTDL) were mixed with a solution in which 1,3-bistrifluorobenzene and acetone were mixed according to the amount of the reagent shown in Table 1 below, Solution A was prepared. Then, a solution of 1,3-bistrifluorobenzene and acetone according to the amount of the reagent shown in Table 1 was prepared in the same manner as in the above-mentioned Reaction Solution A by adding the PFPE-alcohol ) Were mixed to prepare a reaction solution B. While stirring the reaction solution A containing the hexamethylene diisocyanate cyclic trimer (DESMODU N3300) prepared above, a reaction solution B containing a perfluoropolyether-alcohol (PFPE-alcohol) was added in a predetermined amount, . After the reaction mixture was mixed, 4-hydroxybenzophenone (4-HBP, 0.65 g) was added thereto, and the mixture was heated to 40 ° C and stirred. Unreacted materials were removed by precipitation and stirring in a mixture of cyclohexane and acetone. After removing the unreacted material for about 3 times, it was vacuum-dried to obtain the target compound, the photo-curable perfluoropolyether-modified compound, and the final composition was a white powder.

Production Example 4 Production Example 5 Production Example 6 Reaction solution A Hexamethylene diisocyanate cyclic trimer (DESMODU N3300) 3.00 3.00 3.00 1,3-bistrifluorobenzene 3.14 2.54 7.30 Acetone 0.79 0.64 1.83 Dibutyl tin dilaurate (DBTDL) 0.20 0.20 0.20 Reaction solution B Perfluoropolyether-alcohol (PFPE-alcohol) [molecular weight] 4.00 [2500] 2.50 [1700] 14.4 [9000] 1,3-bistrifluorobenzene 3.14 2.54 7.30 Acetone 0.79 0.64 1.83

< Example  1> Antifouling Photocuring  Preparation of Resin Composition - 1

The photocurable perfluoropolyether compound (0.025 g) prepared in Preparation Example 4 was dissolved in methyl methacrylate (2.45 g), Irgacure 184 (0.025 g) and 1,1,2,2-tetrafluoro- 1-propanol (2.5 g), and dispersed using a homogenizer (IKA, 10000-14000 rpm) to prepare an antifouling photocurable resin composition.

< Example  2> Antifouling Photocuring  Preparation of Resin Composition - 2

The photocurable perfluoropolyether compound (0.025 g) prepared in Preparation Example 6 was dissolved in trimethylolpropane triacrylate (TMPTA, 2.00 g), Irgacure 184 (0.025 g) and 1,1,2,2 -Tetrafluoro-1-propanol (2.95 g), and dispersed using a homogenizer (IKA, 10000-14000 rpm) to prepare an antifouling photocurable resin composition.

< Example  3> Antifouling Photocuring  Preparation of resin composition - 3

The photocurable perfluoropolyether compound (0.025 g) prepared in Preparation Example 4 was dissolved in a mixture of dipentaerythritol penta- / hexa-acrylate (2.50 g), Irgacure 184 (0.025 g) And 2.45 g of 1,1,2,2-tetrafluoro-1-propanol were mixed and dispersed using a homogenizer (IKA, 10000-14000 rpm) to obtain an antifouling photocurable resin A composition was prepared.

< Example  4> Antifouling Photocuring  Preparation of Resin Composition - 4

The photocurable perfluoropolyether compound (0.025 g) prepared in Preparation Example 6 was mixed with a resin (40% by weight) composed of pentaerythritol triacrylate and tetra (ethylene glycol) diacrylate; IgA Cure 184 (1 wt%); And a mixed solvent (59 wt%) consisting of ethanol, 2-ethoxyethanol and 4-methyl-2-propanone, and a homogenizer (IKA, 10000-14000 rpm) to prepare an antifouling photocurable resin composition.

< Example  5> Antifouling property Photocuring  Preparation of Resin Composition - 5

The photocurable perfluoropolyether compound (0.025 g) prepared in Preparation Example 4 was dissolved in a resin (70% by weight) composed of 2-hydroxypropyl acrylate; IgA Cure 184 (1 wt%); And a mixed solvent (2.475 g) comprising a mixed solvent of methyl ethyl ketone, toluene and xylene (29% by weight), and dispersed using a homogenizer (IKA, 10000-14000 rpm) Thereby preparing a photocurable resin composition.

< Example  6> Hard coat  Fabrication of antifouling transparent thin film - 1

The antifouling photocurable resin composition (0.3 mL) prepared in Example 1 was applied to a slide glass (Matsunami S-1111, 7.6 cm x 2.6 cm) by spin coating at 2000 rpm for 20 seconds. The coated composition was annealed in a vacuum oven at 54 ° C. for 10 minutes and then cured at 500 W for 30 to 300 seconds using an ARC Xe LAMP POWER SUPPLY, .

< Example  7> Hard coat  Fabrication of antifouling transparent film - 2

The procedure of Example 6 was repeated except that the antifouling photocurable resin composition prepared in Example 2 was used instead of the antifouling photocurable resin composition prepared in Example 1 To prepare a transparent thin film.

< Example  8> Hard coat  Fabrication of antifouling transparent film - 3

The procedure of Example 6 was repeated, except that the antifouling photocurable resin composition prepared in Example 3 was used instead of the antifouling photocured resin composition prepared in Example 1 To prepare a transparent thin film.

< Example  9> Hard coat  Fabrication of antifouling transparent film - 4

The procedure of Example 6 was repeated, except that the antifouling photocurable resin composition prepared in Example 4 was used instead of the antifouling photocurable resin composition prepared in Example 1 To prepare a transparent thin film.

< Example  10> Hard coat  Fabrication of antifouling transparent thin film - 5

The procedure of Example 6 was repeated, except that the antifouling photocurable resin composition prepared in Example 5 was used instead of the antifouling photocurable resin composition prepared in Example 1 To prepare a transparent thin film.

< Comparative Example  1> Hard coat  Fabrication of antifouling transparent thin film - 6

A transparent thin film was prepared in the same manner as in Example 6, except that the commercially available hard coating A was used instead of the antifouling photocurable resin composition prepared in Example 1.

< Experimental Example  1> Antifouling Photocuring  Of the film formed by curing the resin composition Contact angle  Measure

The following experiment was carried out in order to evaluate the degree of liquid wetting on the surface of the film formed by curing the photocurable resin composition containing the perfluoropolyether-modified compound according to the present invention.

The glass plates coated with the transparent thin films prepared in Examples 6 to 10 and the glass plates coated with the transparent thin film prepared in Comparative Example 1 were measured for contact angle with a contact angle meter (DSA100, manufactured by KRUSS) Water, hexadecane (HD) and diiodomethane (DIM) were measured at room temperature. The contact angle is determined by the surface free energy, and the higher the contact angle, the lower the surface energy, and the surface energy is calculated by the geometric mean method using the following equations (1) and (2). The measured contact angles and calculated surface energy values are shown in Table 2 below.

Example Comparative Example 1 6 7 8 9 10 Contact angle (°) water 106.7 108.0 111.2 108.9 100.3 79.48 DIM 95.5 95.8 98.4 94.9 86.1 49.12 HD 72.2 74.24 72.5 72.0 55.5 - Surface energy
[dyn / cm] 12.73 12.18 00.40 12.38 14.95 36.79

In Table 2, '-' indicates that measurement is impossible.

As shown in Table 2, the slide glasses coated with the transparent thin films prepared in Examples 6 to 10 according to the present invention had higher water and diiodes than the slide glasses coated with the transparent thin film prepared in Comparative Example 1, Methane (DIM) with a higher contact angle of about 20.82 ° - 31.72 ° and 36.98 ° - 49.28 °, respectively. In addition, the surface energy of the slide glass coated with the transparent thin film prepared in Examples 6 to 10 according to the present invention was significantly lower than that of the slide glass prepared in Comparative Example 1. From this, it can be seen that the transparent thin film according to the present invention has a high contact angle and low surface energy by using an antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound.

Therefore, the transparent thin film according to the present invention can be produced by using the antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound, thereby obtaining a transparent thin film prepared using a resin composition containing no perfluoropolyether- The transparent thin film produced according to the present invention is excellent in water repellency and oil repellency, and thus can be used as a functional coating film for displays, an optical filter, a frame or surface coating of electronic products, Water repellent coatings, optical product coatings, and waterproof paints used in daily necessities, construction, shipbuilding and civil engineering fields.

< Experimental Example  2> Antifouling Photocuring  Of the film formed by curing the resin composition Flow angle  Measure

In order to evaluate the antifouling property of the film formed by curing the photocurable resin composition containing the perfluoropolyether-modified compound according to the present invention, the following experiment was conducted.

The flow angle of liquid droplets was measured on the transparent thin film coated glass prepared in Examples 6 to 10 and the transparent glass coated slide glass prepared in Comparative Example 1. In general, the contact angle has been used as a criterion for evaluating the degree of hydrophobicity of the surface. However, since the flow angle to the surface having a high contact angle does not always have a low value, it is not sufficient to measure the flow property of the water droplet on the surface only by the contact angle. Therefore, with respect to hydrophobicity, the measurement of the flow angle to the droplet should be performed separately from the contact angle. The flow angle is a critical angle when a droplet having a specific weight starts to flow on an inclined surface. The flow angle of liquid by the surface is defined by Wolfram as shown in Equation (3).

30 μL of hexadecane at room temperature was dropped on the slide glass surface coated with the transparent thin film prepared in Examples 6 to 10 and Comparative Example 1, and the respective flow angles were measured using a contact angle meter (DSA100, KRUSS) Respectively.

Example Comparative Example 1 6 7 8 9 10 Flow angle of hexadecane
[deg, 30 [mu] l] 7.2 12.2 5.4 6.9 18.5 -

In Table 3, '-' indicates that measurement is impossible.

As shown in Table 3, in the case of the slide glass coated with the transparent thin film prepared in Examples 6 to 10 according to the present invention, the flow angle was found to have a low flow angle of about 5 to 18 °. On the other hand, in the case of the slide glass coated with the transparent thin film prepared in Comparative Example 1, the flow angle was considerably high and it was found that the measurement of the value was impossible. It can be seen that the transparent thin film according to the present invention has a low flow angle by using an antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound.

Therefore, the transparent thin film according to the present invention can be produced by using the antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound, thereby obtaining a transparent thin film prepared using a resin composition containing no perfluoropolyether- The transparent thin film produced according to the present invention is excellent in water repellency and oil repellency, and thus can be used as a functional coating film for displays, an optical filter, a frame or surface coating of electronic products, a fiber water repellent coating , Coatings for optical products, and waterproof paints used in household products, construction, shipbuilding and civil engineering fields.

< Experimental Example  3> Antifouling Photocuring  Of the film formed by curing the resin composition Pollution prevention property  evaluation

In order to evaluate the antifouling property of the thin film formed by curing the photocurable resin composition containing the perfluoropolyether-modified compound according to the present invention, the following experiment was conducted.

The anti-fouling test was performed on the transparent thin film coated glass prepared in Examples 6 to 10 and the transparent glass coated slide glass prepared in Comparative Example 1. When the monitor screen is contaminated with fingerprints or oily substances, a new optical thin film having a different refractive index is formed on the surface of the substrate to provide an unfavorable image as well as an increase in eye fatigue, The product is provided with pollution prevention function. However, there is no established standard for assessing the degree of pollution prevention and it is impossible to quantify it.

In this experiment, a commercially available black name pen (Monami) was used to prepare a slide glass cured coating film coated with the transparent thin film prepared in Examples 6 to 10 and a slide glass coated with the transparent thin film prepared in Comparative Example 1 I have drawn a line on the surface. Then, the dirt adhered by visual inspection was judged according to the following criteria, and the results are shown in Table 4 below.

Contaminant attachment Preventiveness  Criteria

○: The ink hardly fills the coating surface.

△: Some ink is buried on the coated surface.

X: The ink is buried well on the coated surface.

Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Pollution prevention property
(Oil-based ink) △ - ○ ○ ○ ○ ○ ×

As shown in Table 4, in the case of the slide glass coated with the transparent thin film prepared in Examples 6 to 10 according to the present invention, after drawing a line with a black namepen, the ink was hardly or hardly observed on the coated surface It was confirmed with the naked eye. On the other hand, in the case of the slide glass coated with the transparent thin film prepared in Comparative Example 1, it was visually confirmed that the ink of the black namepen appeared on the coated surface considerably. From this, it can be seen that the transparent thin film according to the present invention has antifouling adhesion by using an antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound.

Therefore, the transparent thin film according to the present invention can be produced by using the antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound, thereby obtaining a transparent thin film prepared using a resin composition containing no perfluoropolyether- The transparent thin film produced according to the present invention is remarkably excellent in antifouling property. Therefore, it is possible to provide a functional coating film for display, an optical filter, a frame or surface coating of an electronic product, a fiber water repellent Coatings, coatings for optical products, and waterproof paints used in daily necessities, construction, shipbuilding and civil engineering fields.

< Experimental Example  4> Antifouling Photocuring  Of the film formed by curing the resin composition Decontamination property  evaluation

In order to evaluate the antifouling property of the thin film formed by curing the photocurable resin composition containing the perfluoropolyether-modified compound according to the present invention, the following experiment was conducted.

The ink of the black neimpen attached in Experimental Example 3 were wiped off the dirt on the treated surface by the reciprocating five times using a Kimwipe to 1 kg of the force _f. Then, according to the following criteria, the dirt adhered by visual inspection was determined, and the results are shown in Table 5 below.

Property criteria for wiping contaminants

○: Dirt can be wiped off

△: The dirt can be almost wiped off, but a little trace remains.

X: The dirt remains and the trace remains clearly

Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Wipe-out property
(Oil-based ink) △ △ - ○ ○ ○ △ ×

As shown in Table 5, in the case of the slide glass coated with the transparent thin film prepared in Examples 6 to 10 according to the present invention, it was visually confirmed that all of the ink remaining on the coated surface with respect to the namepen ink could be wiped off . On the other hand, in the case of the slide glass coated with the transparent thin film manufactured in Comparative Example 1, the dirt was not removed and the slide glass remained dirty, and it was visually confirmed that the trace remained clearly. From this, it can be seen that the transparent thin film according to the present invention has decontamination property by using an antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound.

Therefore, the transparent thin film according to the present invention can be produced by using the antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound, thereby obtaining a transparent thin film prepared using a resin composition containing no perfluoropolyether- The transparent thin film produced according to the present invention is remarkably excellent in antifouling property. Therefore, it is possible to provide a functional coating film for display, an optical filter, a frame or surface coating of electronic products, a fiber water repellent coating , Coatings for optical products, and waterproof paints used in household products, construction, shipbuilding and civil engineering fields.

< Experimental Example  5> Antifouling property Photocuring  Evaluation of transparency of a film formed by curing a resin composition

The following experiment was conducted to measure the transmittance of the thin film formed by curing the photocurable resin composition containing the perfluoropolyether-modified compound according to the present invention.

Using the UV / Vis spectroscopy (JASCO, V-650), the transparent glass-coated glass prepared in Examples 6 to 10 and the transparent glass-coated slide glass prepared in Comparative Example 1 were exposed to air The transmittance values at 550 nm were measured under the conditions of 350 nm to 800 nm under the conditions shown in Table 6 and Fig.

Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Permeability (%) 90.6 91.3 90.0 91.1 90.0 91.4

As shown in Table 6 and FIG. 1, the transparency of the transparent thin film-coated slide glass prepared in Examples 6 to 10 according to the present invention was found to be 90% or more. It can be seen that this value is not lowered and the equivalent transmittance is shown as compared with the transmittance of the slide glass coated with the transparent thin film prepared in Comparative Example 1 which is conventionally used by using the resin composition for hard coat. From the above, even when the transparent thin film according to the present invention is produced by using the antifouling photocurable resin composition containing the photo-curable perfluoropolyether-modified compound, it can be seen that the transparency of the transparent thin film is equivalent to that of the conventional transparent thin film .

Therefore, the transparent thin film according to the present invention can be produced by using the antifouling photocurable resin composition containing a photo-curable perfluoropolyether-modified compound, thereby obtaining a transparent thin film prepared using a resin composition containing no perfluoropolyether- A low surface energy and a low flow angle, as well as a remarkably excellent antifouling property and decontamination property, the transparent thin film produced according to the present invention is remarkably excellent in antifouling property. In addition, since the transparency of the transparent thin film is comparable to that of a conventional transparent thin film, the functional coating film, optical filter, frame or surface coating of electronic products, optical fiber coating, optical product coating, , Waterproof paints used in shipbuilding and civil engineering fields, and the like.

Claims (12)

0.001-50% by weight of a photocurable perfluoropolyether-modified compound represented by the following formula (1); And
50 to 99.999% by weight of at least one hydrocarbon compound selected from the group consisting of polymerizable hydrocarbon-based divalent monomers, trivalent monomers, tetravalent monomers and oligomers, and the like.
[Chemical Formula 1]

(In the formula 1,
A and B are R _f or Y, where A is R _f , B is Y and A is Y, B is R _f ;
R _f is selected from R _f1 [CF ₂ O] _b [CF ₂ CF (CF ₃ ) O] _c [CF (CF ₃ ) O] _d [CF ₂ CF ₂ O] _e Z-, CF ₃ CF ₂ CF ₂ [ _{(CF 3) CF 2] a} OCF (CF 3) - or _{CF 3 CF 2 CF 2 O [} CF 2 CF 2 CF 2 O] f CF 2 CF 2 - , and wherein R _f1, and Z are each independently a C1- C5, and a, b, c, d, e, and f are integers from 0 to 100;
X is

,

or

, Wherein n is an integer from 1 to 10; And
Y is

,

,

,

or

, Wherein the bonding site of Y bonded to X is any carbon on the aryl ring.
The method according to claim 1,
Wherein R _f is _{CF 3 CF 2 CF 2 - [} OCF (CF 3) CF 2] a -OCF (CF 3) - , and wherein R _f1 is a perfluoroalkyl, and Z are independently of each other C1-C5, a is An integer from 1 to 100;
X is

, Wherein n is an integer from 1 to 10; And
Y is

Wherein the perfluoropolyether-modified compound is a perfluoropolyether-modified compound.
The method according to claim 1,
The photo-curable perfluoropolyether-modified compound represented by Formula 1 may be represented by the following Formula 1 while performing a coupling reaction between a heterocycloalkyl compound represented by Formula 2 and a compound represented by Formula 3, Wherein the compound represented by the general formula (1) is prepared by adding a compound represented by the following general formula
[Reaction Scheme 1]

(Wherein, in the above Reaction Scheme 1, A and B are the same as defined in claim 1;
P is isocyanato, carboxylic acid or acid chloride; And
Q is hydroxy or an amine.
The method according to claim 1,
The hydrocarbon compound may be selected from the group consisting of 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol monoacrylonitrile monomethyl Divalent monomers selected from the group consisting of methacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylate, and alkoxylated cyclohexane dimethanol diacrylate; Glycerol triacrylate, trimethoxypropane triacrylate, ethoxylated triacrylate, propoxylated triacrylate, trimethylolpropane triacrylate, and tris (2-hydroxyethyl) isocyanurate A trifunctional monomer selected from the group consisting of triacrylate; Dipentaerythritol pentaacrylate, pentaerythritol triacrylate, eicoxylated pentaerythritol tetraacrylate, and caprolactone-modified dipentaerythritol hexaacrylate as the main component A tetravalent or higher-valent monomer selected from the group consisting of And an oligomer selected from the group consisting of urethane acrylate, polyester acrylate and epoxy acrylate. The antifouling photocurable resin composition according to claim 1,
The method according to claim 1,
Wherein the photocurable resin composition further comprises a photocurable initiator and an organic solvent.
6. The method of claim 5,
The photo-curable initiator may be selected from the group consisting of ethyl benzoin ether, isopropyl benzoin ether,? -Methyl benzoin ethyl ether, benzoin phenyl ether,? -Acyl oxime ester,?,? -Diethoxy acetophenone, Phenanthrone, phenanthone, phenanthrene, phenanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, Wherein the photo-curable resin composition is at least one member selected from the group consisting of benzoic acid, thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate and microclerketone.
6. The method of claim 5,
The organic solvent may be at least one selected from the group consisting of trifluoro benzene, 1,3-bistrifluorobenzene, 1,4-bistrifluorobenzene, trifluorofluorene, perfluoroheptane, perfluorobutane, m-xylene hexafluoride, , At least one fluorocarbon solvent selected from the group consisting of ethyl and fluoro butyl ether and perfluoro (2-butyltetrahydrofuran); 3,3-dichloro-1,1,1,2,2-pentafluoropropane, methoxy-nonafluorobutane, ethoxynonafluorobutane, petroleum benzene, mineral spirits, isoparaffin, toluene, xylene, acetone , At least one hydrocarbon solvent selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylglyme, methyltriglyme, methyltetraglyme, tetrahydrofuran and ethanol, or a mixed solvent thereof And the photo-curable resin composition is an antifouling photocurable resin composition.
An antifouling transparent thin film for a hard coat formed by coating the photocurable resin composition of claim 1.
9. The method of claim 8,
Wherein the transparent thin film has a film thickness in the range of 0.005 to 50 占 퐉.
9. The method of claim 8,
The transparent thin film is used for a waterproof paint used in a functional coating film for display, an optical filter, a frame or a surface coating of an electronic product, a fiber water repellent coating, an optical product coating or a household product, Dust-proof transparent thin film.
11. The method of claim 10,
Wherein the display is one selected from the group consisting of a liquid crystal, a flat panel display (PDP), an organic light emitting device (EL), and a field emission display (FED).
An antifouling substrate with a film, characterized in that the surface of the substrate is coated with the antifouling transparent thin film of claim 8.

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