KR102122269B1 - Fluoropolyether derivative, curable composition containing the same, and cured product thereof - Google Patents

Abstract

The present invention relates to a fluoropolyether derivative, a curable composition containing the same, and a cured product thereof. According to the present invention, it is possible to form a hard coat layer which is easy to form a solid thin film, and has excellent surface properties such as lubricity, flexibility, and antifouling properties. Accordingly, the fluoropolyether derivative is applied to the surface of various flat panel displays requiring high visibility, and can be advantageously used for various purposes in various industries by enabling adhesion inhibition and easy removal of contaminants or fingerprints.

Description

Fluoropolyether derivative, curable composition containing same, and cured product thereof{Fluoropolyether derivative, curable composition containing the same, and cured product thereof}

The present invention relates to a fluoropolyether derivative, a curable composition comprising the same, and a cured product thereof.

Polymer materials are increasingly used in various fields in recent years. Accordingly, according to each field, research on improved physical properties of a polymer material as a matrix, as well as research on control of its surface or interfacial properties, are becoming important. As an example of such a study on the control of surface or interfacial properties, a fluorine-based compound or a silicone-based compound is used as an additive material having low surface energy, and thus water-repellent, oil-repellent, anti-fouling, non-adhesive, peelable, releasable, slippery , Suggestions for improved properties such as wear resistance, anti-reflection properties, and chemical resistance.

Meanwhile, a plastic film having a hard coat layer for preventing damage is used on various flat panel display surfaces such as liquid crystal displays, plasma displays, and touch panels. Such a hard coat layer has a problem in that fingerprint marks or stains are easily attached, and the attached fingerprint marks or stains cannot be easily removed. For this reason, the visibility of the display image is significantly reduced or the aesthetics of the display is impaired. In particular, since the surface of the touch panel is directly touched by a person, it is particularly difficult to remove fingerprint marks and should be easy to remove even when fingerprint marks are attached.

Fluoroalkyl derivatives and the like are representative additive materials for forming a hard coat layer having a low surface energy. However, the cured product derived therefrom has excellent initial anti-pollution property but poor decontamination property. As an additive material capable of overcoming the disadvantages of the fluoroalkyl derivative, there may be mentioned a fluoropolyether derivative. The fluoropolyether derivative has an advantage derived from a fluoroalkyl derivative, as well as an advantage that it can simultaneously provide properties such as lubricity, that is, decontamination. In addition, it can provide excellent optical properties such as transparency and low refractive index properties [poly(hexafluoropropylene oxide), nD = 1.3010, T300 to 800 nm> 95%]. On the other hand, these fluoropolyether derivatives have a problem in that, in terms of physical properties, it is difficult to form and utilize a solid thin film as the liquid phase is maintained in almost the entire molecular weight region.

Accordingly, the development and application technology of additives for forming a hard coat layer that is easy to form a solid thin film and satisfies desired antifouling properties, flexibility, and excellent optical properties is still required.

JP 2007-264277 A JP 4784723 B2

An object of the present invention is to provide a novel fluoropolyether derivative for forming a hard coat layer that can easily form a solid thin film and satisfy excellent antifouling properties and lubricity at the same time.

The present invention is designed to contain a siloxane structure and a photopolymerizable structure in a fluoropolyether-modified compound, and an object thereof is to provide a fluoropolyether derivative excellent in light transparency and thermal stability and a surface treatment agent comprising the same.

The present invention aims to provide a cured product and a curable composition for realizing excellent hardness and numerical stability through rapid curing and simultaneously satisfying excellent antifouling properties and lubricity required by the hard coat layer of a flat panel display.

In order to achieve the above object, the present invention provides a fluoropolyether derivative represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

[In the above formula 1 and formula 2,

Rf ₁ is a monovalent fluoropolyether group;

Rf ₂ is a divalent fluoropolyether group;

X ₁ to X ₃ are independently of each other C ₁ -C ₇ alkylene, and -CH ₂ -of the alkylene is -O-, -S-, -C(=O)-, -NR- or a combination thereof And R is hydrogen or C _1-7 alkyl;

R'and R" are independently of each other triC ₁ -C ₂₀ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;

R ₁ to R ₆ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl or -OR ^a , and R ₁ and R ₅ may be connected to each other using -0- as a linking group to form a cyclic siloxane group, and R ^a is as defined for R'above;

L ₁ and L ₂ are each independently substituted or unsubstituted C ₁ -C ₂₀ alkylene, and the substitution is triC ₁ -C ₂₀ alkoxysilyloxy, acryloyloxy, methacryloyloxy, glycidyl One selected from oxy, aminocarbonyloxy, halogen, hydroxy, cyano, carboxyl, carboxylate, hydroxyC ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy and combinations thereof Or a substitution with two or more substituents, -CH ₂ -of L ₁ or L ₂ may be replaced by -O-, -S-, -NH-, -C(=O)- or a combination thereof;

a and b are each independently an integer selected from 0 to 20, and when a or b is an integer of 2 or more, the substituents of each repeating unit may be the same or different from each other.]

In the fluoropolyether derivative according to an embodiment of the present invention, Rf ₁ of Formula 1 may be represented by Formula 3 below.

[Formula 3]

Rf ₁₁ O-[Rf ₁₂ O] _m -[Rf ₁₃ O] _n -CF _2-

[In the above formula 3,

Rf ₁₁ is fluorosubstituted C ₁ -C ₄ alkyl;

Rf ₁₂ and Rf ₁₃ are different fluorosubstituted C ₁ -C ₄ alkylene;

m is an integer selected from integers from 0 to 10;

n is an integer selected from integers from 1 to 10.]

In the fluoropolyether derivative according to an embodiment of the present invention, Rf ₂ of Formula 2 may be represented by Formula 4 below.

[Formula 4]

-CF ₂ O-[Rf ₂₁ O] _m -[Rf ₂₂ O] _n -CF _2-

[In the above formula 4,

Rf ₂₁ is fluorosubstituted C ₂ -C ₄ alkylene;

Rf ₂₂ is fluorosubstituted C ₁ -C ₄ alkylene;

m is an integer selected from integers from 0 to 10;

n is an integer selected from integers from 1 to 10.]

In the fluoropolyether derivative according to an embodiment of the present invention, L ₁ and L ₂ are independently of each other C ₈ -C ₂₀ alkylene, -(C ₁ -C ₇ alkylene)-O-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-OC(=O)-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-OC(= O)-O-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-S-(C ₁ -C ₇ alkylene)-, -C(=O)-O-( C ₁ -C ₇ alkylene)-, -C(=O)-NH-(C ₁ -C ₇ alkylene)- or -(C ₁ -C ₇ alkylene)-C(=O)-O-( C ₁ -C ₇ alkylene)-C(=O)-O-(C ₁ -C ₇ alkylene)- and the like, and the alkylene is triC ₁ -C ₇ alkoxysilyloxy, acryloyloxy. , One or more selected from methacryloyloxy, glycidyloxy, aminocarbonyloxy, hydroxyC ₁ -C ₇ alkyl, C ₁ -C ₇ alkyl, C ₁ -C ₇ alkoxy and combinations thereof It may be one that can be substituted with a substituent.

In the fluoropolyether derivative according to an embodiment of the present invention, R'and R" are independently of each other triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocar Bonil or a combination thereof; wherein R ₁ to R ₆ are independently of each other hydrogen or C ₁ -C ₄ alkyl; wherein a and b are each independently an integer selected from 5 to 15, and the substituents of each repeating unit are It may be the same or different from each other.

In the fluoropolyether derivative according to an embodiment of the present invention, X ₁ to X ₃ are independently of each other C ₁ -C ₇ alkylene; R'and R" are independently of each other triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof; wherein R ₁ and R ₅ are -0 -Is a linking group to form a cyclic siloxane group; R ₃ is -OR ^a , and R ^a is tri C ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, Aminocarbonyl or a combination thereof; wherein R ₂ , R ₄ and R ₆ are independently of each other hydrogen or C ₁ -C ₄ alkyl; and a and b are each independently an integer selected from 1-3. When a or b is an integer of 2 or 3, the substituents of each repeating unit may be the same or different from each other.

In the fluoropolyether derivative according to an embodiment of the present invention, the fluoropolyether derivative may include a cyclic siloxane group represented by Formula 5 below.

[Formula 5]

[In the formula 5,

R ^b , R ^c and R ^d are independently of each other hydrogen or C ₁ -C ₄ alkyl;

R ^e is -OR ^a , wherein R ^a is triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;

x is an integer selected from 1 to 3, and when x is an integer of 2 or 3, the substituents of each repeating unit may be the same or different from each other.]

In the fluoropolyether derivative according to an embodiment of the present invention, Rf ₁ is a monovalent perfluoropolyether group; The Rf ₂ may be a divalent perfluoropolyether group.

In addition, the present invention provides a surface treatment agent comprising a fluoropolyether derivative.

In addition, the present invention provides a photopolymerizable composition comprising a fluoropolyether derivative, a photopolymerizable compound, a photoinitiator and a solvent.

Further, in the present invention, a cured product of the photopolymerizable composition described above is provided.

The cured product according to an embodiment of the present invention may be an optical film for preventing contamination or preventing reflection of a flat panel display.

The fluoropolyether derivative according to the present invention is capable of rapid curing with excellent sensitivity. Accordingly, it is possible to realize a low surface energy and a high oil contact angle during photocuring, thereby providing excellence in the properties derived therefrom. That is, according to the present invention, it is excellent in lubricity, flexibility, anti-pollution, and the like. In addition, despite maintaining the liquid phase in the entire molecular weight range in terms of physical properties, it is cured quickly and there is no disadvantage in forming a solid film.

In addition, the fluoropolyether derivative according to the present invention has the advantage of improving the adhesion between the substrate and the photopolymerization composition, and gives excellent compatibility with a conventional solvent.

Accordingly, according to the present invention, it is applied to the surface of various flat panel displays requiring high visibility, so that it is possible to suppress adhesion and easy removal of fingerprint marks or contaminants, and to prevent damage and provide excellent touch feeling.

The fluoropolyether derivative according to the present invention, the curable composition comprising the same and the cured product thereof will be described in detail below, but unless otherwise defined in the technical terms and scientific terms used at this time, the general knowledge in the technical field to which this invention belongs Description of known functions and configurations, which have meanings commonly understood by those who have, and may unnecessarily obscure the subject matter of the present invention, will be omitted in the following description.

As used herein, the term "fluoropolyether group" means a monovalent substituent in which at least one or more of the hydrogen atoms contained in the polyether group is replaced with fluoro (F).

In addition, the term "perfluoropolyether group" in the present specification means a monovalent substituent in which all of the hydrogen atoms contained in the polyether group are replaced with fluoro (F).

In addition, the term, "alkyl", "alkoxy" in the present specification, a substituent including alkyl means a monovalent substituent derived from a straight-chain or pulverized hydrocarbon. In addition, the alkoxy means *-O-alkyl.

In addition, the term "alkylene" in the present specification means a divalent substituent derived by removal of one hydrogen from the alkyl group.

In addition, the term "aminocarbonyl" in the present specification means *-(C=O)NH ₂ .

In addition, the term "halogen" as used herein means an F, Cl, Br or I atom.

Further, the term “average molecular weight” in the present specification may mean a number average molecular weight or a weight average molecular weight. Specifically, in the case of including fluoro, such as a fluoropolyether derivative, the number average molecular weight was confirmed by a value measured by ¹⁹ F-NMR. In addition, in the case of polysiloxane, the weight average molecular weight was confirmed by a value measured by gel permeation chromatography (GPC). At this time, the unit of the average molecular weight is g/mol.

In addition, in this specification, the expression "comprises" is an open-ended description having a meaning equivalent to expressions such as "have", "contains", "haves" or "makes a feature," and is not further enumerated. It does not rule out elements, materials or processes that are not.

In addition, the singular form used in the present specification may be intended to include the plural form unless otherwise specified in the context.

In addition, the units used without specific mention in the present specification are based on weight (g), and for example, units of% or ratio mean weight percent or weight ratio.

As described above, despite the fact that the conventional fluoropolyether derivative can provide excellent antifouling properties, it is difficult to form and utilize a solid thin film by maintaining the liquid phase in the entire molecular weight region.

While conducting research to solve this problem, the present inventors simultaneously introduced a substituent containing a predetermined siloxane group and a photopolymerizable substituent in the fluoropolyether-modified compound, thereby facilitating the formation of a solid thin film through rapid curing and being excellent. It was confirmed that a cured product having hardness and numerical stability could be provided. Accordingly, the present inventors propose the present invention to provide a novel fluoropolyether derivative molecularly designed as described above and use it as an additive material to effectively apply it to the hard coat layer of various flat panel displays.

Hereinafter, the present invention will be described in detail.

It is noted that the novel fluoropolyether derivatives according to the present invention provide advantageous advantages for the formation of solid thin films, despite maintaining a liquid phase in the entire molecular weight range. According to the present invention, since the curing reaction is rapidly performed with excellent sensitivity during photo-curing, it is advantageous to form a solid thin film, and has the advantage of providing a cured product of high hardness with good numerical stability.

In addition, it is possible to minimize the optical loss due to absorption of CH during photo-curing, thereby improving the sensitivity by minimizing the optical progress loss, and by light, a transparent cured product having excellent water-repellent, oil-repellent, and anti-soiling properties can be obtained. Has the advantage of being.

In order to realize such an effect, the present invention provides a fluoropolyether derivative represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

[In the above formula 1 and formula 2,

Rf ₁ is a monovalent fluoropolyether group;

Rf ₂ is a divalent fluoropolyether group;

X ₁ to X ₃ are independently of each other C ₁ -C ₇ alkylene, and -CH ₂ -of the alkylene is -O-, -S-, -C(=O)-, -NR- or a combination thereof And R is hydrogen or C _1-7 alkyl;

R'and R" are independently of each other triC ₁ -C ₂₀ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;

R ₁ to R ₆ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl or -OR ^a , and R ₁ and R ₅ may be connected to each other using -0- as a linking group to form a cyclic siloxane group, and R ^a is as defined for R'above;

L ₁ and L ₂ are each independently substituted or unsubstituted C ₁ -C ₂₀ alkylene, and the substitution is triC ₁ -C ₂₀ alkoxysilyloxy, acryloyloxy, methacryloyloxy, glycidyl Substitution with one or more substituents selected from oxy, aminocarbonyloxy, halogen, hydroxy, cyano, carboxyl, carboxylate, hydroxyC ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkoxy, L -CH ₂ -of ₁ or L ₂ may be replaced by -O-, -S-, -NH-, -C(=O)-, or a combination thereof;

a and b are each independently an integer selected from 0 to 20, and when a or b is an integer of 2 or more, the substituents of each repeating unit may be the same or different from each other.]

With such a structural feature, the fluoropolyether derivative according to the present invention can realize a high water contact angle and an oil contact angle, as well as secure the numerical stability and durability. Specifically, the fluoropolyether derivative according to the present invention can be rapidly cured by light irradiation to form a mesh structure. Thus, it is possible to realize good numerical stability and durability in a short time.

In addition, the fluoropolyether derivative according to the present invention may be one containing a short-chain aliphatic fluoropolyether group in view of improving light stability and improving thermal stability at the same time as implementing the above-described effect. Thus, specifically, the fluoropolyether derivative according to the present invention may include a fluoropolyether group having an ether group having 7 or less carbon atoms in a repeating unit.

Specifically, in the fluoropolyether derivative according to an embodiment of the present invention, Rf ₁ of Formula 1 may be represented by Formula 3 below.

[Formula 3]

Rf ₁₁ O-[Rf ₁₂ O] _m -[Rf ₁₃ O] _n -CF _2-

[In the above formula 3,

Rf ₁₁ is fluorosubstituted C ₁ -C ₄ alkyl;

Rf ₁₂ and Rf ₁₃ are different fluorosubstituted C ₁ -C ₄ alkylene;

m is an integer selected from integers from 0 to 10;

n is an integer selected from integers from 1 to 10.]

For example, when the Rf ₁ in the formula (1) contains two repeating _{units, CF 3 O- [CF 2 O} ] m - [CF 2 CF 2 O] n -CF 2 -, CF 3 O- [CF 2 O] _m -[CF ₂ CF ₂ CF ₂ O] _n -CF ₂ -, CF ₃ O-[CF ₂ CF ₂ O] _m -[CF ₂ CF ₂ CF ₂ O] _n -CF ₂ -, CF ₃ CF ₂ O-[CF ₂ O] _m -[CF ₂ CF ₂ O] _n -CF ₂ -, CF ₃ CF ₂ O-[CF ₂ O] _m -[CF ₂ CF ₂ CF ₂ O] _n -CF _2- , CF ₃ CF ₂ O-[CF ₂ CF ₂ O] _m -[CF ₂ CF ₂ CF ₂ O] _n -CF ₂ -, CF ₃ O-[CF ₂ CF ₂ CF ₂ O] _m -[CF ₂ CF ₂ O] _n -CF ₂ -, CF ₃ O-[CF ₂ CF ₂ CF ₂ O] _m -[CF ₂ O] _n -CF ₂ -, CF ₃ CF ₂ O-[CF ₂ CF ₂ CF ₂ O] _m -[CF ₂ CF ₂ O] _n -CF ₂ -, CF ₃ CF ₂ O-[CF ₂ CF ₂ CF ₂ O] _m -[CF ₂ O] _n -CF ₂ -, CF ₃ CF ₂ O-[ CF ₂ CF ₂ O] _m -[CF ₂ O] _n -CF ₂ -and the like. At this time, the definition of m and n follows the formula (3). In addition, when at least one fluoro contained in the repeating unit is replaced by hydrogen, it may also be an aspect of the present invention.

For example, when the Rf ₁ in the formula (1) containing one repeating _{unit, CF 3 O- [CF 2 O} ] m -CF 2 -, CF 3 O- [CF 2 CF 2 O] m -CF 2 - , CF ₃ O-[CF ₂ CF ₂ CF ₂ O] _m -CF ₂ -, CF ₃ O-[CF(CF ₃ )CF ₂ O] _n -CF ₂ -, CF ₃ CF ₂ O-[CF ₂ O ] _m -CF ₂ -, CF ₃ CF ₂ O-[CF ₂ CF ₂ O] _m -CF ₂ -, CF ₃ CF ₂ O-[CF ₂ CF ₂ CF ₂ O] _m -CF ₂ -, CF ₃ CF ₂ O-[CF(CF ₃ )CF ₂ O] _n -CF ₂ -, and the like. At this time, m is an integer of 0, and the definition of n follows the formula (3). In addition, when at least one fluoro contained in the repeating unit is replaced by hydrogen, it may also be an aspect of the present invention.

Specifically, in the fluoropolyether derivative according to an embodiment of the present invention, Rf ₂ of Formula 2 may be represented by Formula 4 below.

[Formula 4]

-CF ₂ O-[Rf ₂₁ O] _m -[Rf ₂₂ O] _n -CF _2-

[In the above formula 4,

Rf ₂₁ is fluorosubstituted C ₂ -C ₄ alkylene;

Rf ₂₂ is fluorosubstituted C ₁ -C ₄ alkylene;

m is an integer selected from integers from 0 to 10;

n is an integer selected from integers from 1 to 10.]

For example, when Rf ₂ of Formula 2 includes two repeating units, -CF ₂ O-[CF ₂ O] _m -[CF ₂ CF ₂ O] _n -CF ₂ -, -CF ₂ O-[ CF ₂ O] _m -[CF ₂ CF ₂ CF ₂ O] _n -CF ₂ -, -CF ₂ O-[CF ₂ CF ₂ O] _m -[CF ₂ CF ₂ CF ₂ O] _n -CF ₂ -, -CF ₂ O-[CF ₂ CF ₂ CF ₂ O] _m -[CF ₂ CF ₂ O] _n -CF ₂ -, -CF ₂ O-[CF ₂ CF ₂ CF ₂ O] _m -[CF ₂ O] _n -CF ₂ -, -CF ₂ O-[CF ₂ CF ₂ O] _m -[CF ₂ O] _n -CF ₂ -and the like. At this time, the definition of m and n follows the formula (4). In addition, when at least one fluoro contained in the repeating unit is replaced by hydrogen, it may also be an aspect of the present invention.

For example, when Rf ₂ of Formula 2 includes one repeating unit, -CF ₂ O-[CF ₂ O] _n -CF ₂ -, -CF ₂ O-[CF ₂ CF ₂ O] _n -CF ₂ -, -CF ₂ O-[CF ₂ CF ₂ CF ₂ O] _n -CF ₂ -, -CF ₂ O-[CFCF ₃ O] _n -CF ₂ -, -CF ₂ O-[CFCF ₃ CF ₂ O ] _n -CF ₂ -, -CF ₂ O-[CF ₂ CFCF ₃ O] _n -CF ₂ -, -CF ₂ O-[CF(CF ₃ )CF ₂ O] _n -CF ₂ -and the like. At this time, m is an integer of 0, and the definition of n follows the formula (4). In addition, when at least one fluoro contained in the repeating unit is replaced by hydrogen, it may also be an aspect of the present invention.

In the fluoropolyether derivative according to an embodiment of the present invention, L ₁ and L ₂ are independently of each other C ₈ -C ₂₀ alkylene, -(C ₁ -C ₇ alkylene)-O-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-OC(=O)-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-OC(= O)-O-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-S-(C ₁ -C ₇ alkylene)-, -C(=O)-O-( C ₁ -C ₇ alkylene)-, -C(=O)-NH-(C ₁ -C ₇ alkylene)- or -(C ₁ -C ₇ alkylene)-C(=O)-O-( C ₁ -C ₇ alkylene)-C(=O)-O-(C ₁ -C ₇ alkylene)- and the like, wherein the alkylene is triC ₁ -C ₇ alkoxysilyloxy, acryloyloxy, One or more substituents selected from methacryloyloxy, glycidyloxy, aminocarbonyloxy, hydroxyC ₁ -C ₇ alkyl, C ₁ -C ₇ alkyl, C ₁ -C ₇ alkoxy and combinations thereof It may be substituted with.

In addition, the fluoropolyether derivative according to the present invention has a linking group such as L ₁ and L ₂ as a spacer, thereby increasing adhesion to the substrate. That is, by performing a function of protecting the adhesive surface between the substrate and the fluoropolyether derivative from external environments such as mechanical friction and chemical contact such as moisture, it is possible to implement a more stable adhesive force and provide improved hardness.

For example, L ₁ and L ₂ may be independently of each other C ₈ -C ₂₀ alkylene, and the alkylene is C ₁ -C ₄ alkyl-acryloyloxy, C ₁ -C ₄ alkyl-methacryloyl jade Or glycidyloxy, or the like.

For example, L ₁ and L ₂ may be independently of each other -(C ₁ -C ₇ alkylene)-O-(C ₁ -C ₇ alkylene)-, and the alkylene is independently of each other C _1- C ₄ alkyl-acryloyloxy, C ₁ -C ₄ alkyl-methacryloyloxy, glycidyloxy and the like may be substituted or unsubstituted.

For example, X ₁ to X ₃ may be independently of each other C ₁ -C ₇ alkylene.

For example, the X ₁ to X ₃ are independently of each other -(C ₁ -C ₃ alkylene)-O-(C ₁ -C ₃ alkylene)-, -(C ₁ -C ₃ alkylene)-OC( =O)-(C ₁ -C ₃ alkylene)-, -(C ₁ -C ₃ alkylene)-OC(=O)-O-(C ₁ -C ₃ alkylene)-, -(C _1- C ₃ alkylene)-S-(C ₁ -C ₃ alkylene)-, -C(=O)-O-(C ₁ -C ₃ alkylene)-, -C(=O)-NH-(C ₁ -C ₃ alkylene)- or -(C ₁ -C ₃ alkylene)-C(=O)-O-(C ₁ -C ₃ alkylene)-C(=O)-O-(C _1- C ₃ alkylene)- and the like.

For example, X ₁ to X ₃ may be C ₂ -C ₄ alkylene at the same time.

More specifically, in a preferred embodiment of the fluoropolyether derivative according to an embodiment of the present invention, X ₁ to X ₃ are independently of each other C ₁ -C ₇ alkylene; R'and R" are independently of each other triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof; and R ₁ to R ₆ are independent of each other As hydrogen or C ₁ -C ₄ alkyl; the a and b are each independently an integer selected from 5 to 15, and the substituents of each repeating unit may be the same or different from each other.

In another embodiment, X ₁ to X ₃ are independently of each other C ₁ -C ₇ alkylene; R'and R" are independently of each other triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof; wherein R ₁ and R ₅ are -0 -Is a linking group to form a cyclic siloxane group; R ₃ is -OR ^a , and R ^a is tri C ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, Aminocarbonyl or a combination thereof; wherein R ₂ , R ₄ and R ₆ are independently of each other hydrogen or C ₁ -C ₄ alkyl; and a and b are each independently an integer selected from 1-3. When a or b is an integer of 2 or 3, the substituents of each repeating unit may be the same or different from each other.

In the fluoropolyether derivative according to an embodiment of the present invention, if the fluoropolyether derivative includes a cyclic siloxane group, one aspect of the cyclic siloxane group may be represented by the following formula (5) have.

[Formula 5]

[In the formula 5,

R ^b , R ^c and R ^d are independently of each other hydrogen or C ₁ -C ₄ alkyl;

R ^e is -OR ^a , wherein R ^a is triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;

x is an integer selected from 1 to 3, and when x is an integer of 2 or 3, the substituents of each repeating unit may be the same or different from each other.]

In addition, in the fluoropolyether derivative according to an embodiment of the present invention, in terms of being excellent in water repellency, oil repellency, and antifouling property and stably maintaining it for a long period of time, Rf ₁ in Formula ₁ is a monovalent family A fluoropolyether group; In Formula 2, Rf ₂ may be a divalent perfluoropolyether group.

At this time, the fluoropolyether derivative according to the present invention is molecularly designed to simultaneously include a substituent containing a predetermined siloxane group and a photopolymerizable substituent in the fluoropolyether-modified compound, and even if it contains a perfluoropolyether group, adhesion to the substrate or The adhesive force can be extremely improved.

In addition, the fluoropolyether derivative according to the present invention may have an average molecular weight of 2,000 to 500,000.

Hereinafter, the use of the fluoropolyether derivative according to the present invention will be described.

The present invention provides the use of a fluoropolyether derivative as a surface treatment agent.

In addition, the present invention provides the use of the photopolymerizable composition as an additive. The fluoropolyether derivative according to the present invention serves as a surface treatment agent, a surface modifier, and the like in the photopolymerizable composition. That is, the fluoropolyether derivative according to the present invention is used in a variety of compositions, depending on the purpose, appropriately control the water repellency, oil repellency, antifouling properties, mechanical strength, refractive index, optical properties, etc., to easily modify the surface properties of the substrate can do.

Specifically, the photopolymerization composition according to the present invention may be one containing the above-described fluoropolyether derivative of the present invention, a photopolymerizable compound, a photoinitiator and a solvent.

In the photopolymerizable composition according to an embodiment of the present invention, the photopolymerizable compound may be used without limitation, such as a monofunctional polymerizable compound, a polyfunctional polymerizable compound, one or two selected from polymerizable compounds described below It can be used in the form of a mixture of the above.

For example, the photopolymerizable compound may be an acrylate-based monomer, and non-limiting examples thereof include methyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and isodecyl (Meth)acrylate, 2-dodecylthioethyl (meth)acrylate, octyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth) )Acrylate, hydroxybutyl (meth)acrylate, isooctyl (meth)acrylate, isodexyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, tetrafurfuryl ( Monofunctional monomers such as meth)acrylate, phenoxyethyl (meth)acrylate, urethane (meth)acrylate, aminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A-ethylene Glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di (Meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified diphosphate di(meth)acrylate, Bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, di(acryloxyethyl)isocyanurate, allylated cyclohexyldi(meth)acrylate, dimethyloldicyclopentane diacrylate, ethylene Bifunctional monomers such as oxide-modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, adamantane diacrylate; Trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane Trifunctional monomers such as tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, and glycerol tri(meth)acrylate ; Tetrafunctional monomers such as diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ditrimethylolpropanetetra(meth)acrylate; 5-functional monomers such as dipentaerythritol penta (meth)acrylate; And hexafunctional monomers such as dipentaerythritol hexa(meth)acrylate.

For example, the photopolymerizable compound may be an epoxy-based monomer, a non-limiting example of which is an epoxy compound having three or more epoxy groups, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, And dicyclopentadiene-type epoxy compounds, alicyclic epoxy compounds, and brominated epoxy compounds.

For example, the photopolymerizable compound may include an acrylic copolymer in which a (meth)acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a polymerizable monomer having a crosslinkable functional group are copolymerized.

In the photopolymerization composition according to an embodiment of the present invention, the photoinitiator may be used without limitation as long as it is a known one. For example, a cationic photoinitiator that produces a cationic species or Lewis acid, a photoinitiator that produces a radical, or a combination thereof. It can be used.

For example, the photoinitiator is one selected from benzoin derivatives, acetophenone derivatives, anthraquinone derivatives, thioxanthone derivatives, ketal derivatives, benzophenone derivatives, α-aminoacetophenone derivatives, acylphosphine oxide　 derivatives, and oxime ester derivatives. Can be. Non-limiting examples thereof include benzoin derivatives such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Acetophenone derivatives such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; Anthraquinone derivatives such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthone derivatives such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone derivatives such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone ; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one , 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone (commercially available Α-amino acetophenone derivatives such as Irugacure (registered trademark) 907, Irugacure 369, Irugacure 379, etc.) manufactured by Chiba Specialty Chemicals (currently, Chiba Japan). 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl Acylphosphine oxide　 derivatives such as phosphine oxide (a commercially available product, such as BASF Corporation's Lucilin (registered trademark) TPO, Chiba Specialty Chemical's Irugacure 819, etc.); 2-(acetyloxyiminomethyl)thioxanthen-9-one, (1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime)), (ethanone And oxime ester derivatives such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)).

In addition, the photoinitiator may be selected from onium salt-based derivatives, and non-limiting examples thereof include diaryl iodonium salt, triarylsulfonium salt, triaryl selenonium salt, tetraarylphosphonium salt, and aryldiazonium salt. Can be lifted.

In the photopolymerization composition according to an embodiment of the present invention, the solvent is an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene, ethylbenzene, tetralin; aliphatic or alicyclic hydrocarbon-based solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane; Halogen-based solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and ortho dichlorobenzene; Ester-based or ester ether-based solvents such as ethyl acetate, butyl acetate, methoxy butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; Ether-based solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; Ketone solvents such as acetone, 　methylethyl　ketone, methylisobutyl ketone, di-n-butyl ketone, and cyclohexanone; Alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethyl hexyl alcohol, benzyl alcohol, and ethylene glycol; Amide solvents such as N,N-dimethyl formamide and N,N-dimethyl acetamide; Sulfoxide solvents such as dimethyl sulfoxide; Heterocyclic compound-based solvents such as N-methyl-2-pyrrolidone; It can be used in the form of a mixture of one or more selected from the like.

The curable composition according to an embodiment of the present invention, based on the total weight of the fluoropolyether derivative of the present invention 0.1 to 5% by weight, 5 to 60% by weight of the photopolymerizable compound, 0.01 to 3% by weight of the photoinitiator and the residual amount of solvent It may be to include. Specifically, the cohesive composition may be one containing 0.5 to 3% by weight of a fluoropolyether derivative of the present invention, 15 to 60% by weight of a photopolymerizable compound, 0.1 to 2% by weight of a photoinitiator, and a residual amount of a solvent. As the fluoropolyether derivative of the present invention, 1 to 3% by weight, 25 to 50% by weight of a photopolymerizable compound, 0.5 to 2% by weight of a photoinitiator, and residual solvent may be included.

In addition, the curable composition according to an embodiment of the present invention further includes additives such as inorganic binders, brighteners, wettability improvers, pigments, deodorants, antifoaming agents, antioxidants, organic flame retardants, thickeners, plasticizers, etc. in a range that does not lose inherent properties Of course it can. In this case, the additives may be included independently of each other and in an amount of 0.01 to 5 based on the total weight.

On the other hand, the present invention provides a cured product obtained from the curable composition described above.

Specifically, the cured product according to the present invention is obtained by photocuring the curable composition, and before or after application of the curable composition, a process such as drying or washing by heat treatment may be further performed.

For example, the cured product according to the present invention may be prepared in the form of a film by coating the curable composition on the substrate and forming a coating layer, followed by photocuring.

At this time, the photocuring may be performed through absorption of light energy such as electron beam, visible light or ultraviolet energy.

For example, in the case of photocuring performed through the ultraviolet energy, it is an ultraviolet region light source such as a UV-A region (320-400 nm), a UV-B region (280-320 nm), or a UV-C region (200-280 nm). Using a high pressure mercury lamp, the exposure process can be performed for 1 to 5 minutes.

As such, the cured product according to an embodiment of the present invention may be manufactured in the form of a film as mentioned. The film can be provided on the surface of various flat panel displays to characterize the surface with various aspects of physical properties.

For example, the film may be, for example, an anti-pollution or anti-reflection optical film of a flat panel display, but is not limited thereto.

For example, the film according to the present invention may have a water contact angle of 100 degrees or more.

In addition, the film according to the present invention satisfies the change rate within 0.1% even when measuring the water contact angle after maintaining for 72 hours in an atmosphere in which a 5% aqueous solution of NaCl is continuously sprayed in a salt sprayer maintained at 30°C.

For example, the oil contact angle of the film according to the present invention may be 66 degrees or more. In this case, the oil may be n-hexadecane.

Hereinafter, the present invention will be described in more detail through examples.

Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms in order to explain his or her invention in the best way. Based on the principle that it can be defined, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention. Therefore, the configuration shown in the embodiments and drawings described in this specification is only one of the most preferred embodiments of the present invention and does not represent all of the technical spirit of the present invention, and at the time of application, they can be replaced. It should be understood that there are various equivalents and variations.

(Assessment Methods)

1. Pencil hardness

The pencil hardness was measured at a load of 500 g using a pencil hardness tester (hardness tester, manufacturer: Chungbuk Tech). By changing the standard pencil (Mitshbishi) from 6B to 9H in accordance with ASTM 3363-74 while maintaining the 45° angle, the surface of the cured product obtained in Examples 4 to 6 and Comparative Examples 1 to 2 was scratched to change the surface. It was observed. Thereafter, each experimental value was measured 5 times and evaluated as an average value.

2. Water contact angle

When the distilled water was placed in the size of 3 µl on the surface of the cured product obtained in Examples 4 to 6 and Comparative Examples 1 to 2 using a contact angle meter (SEO), the angle between the surface and the water drop was measured. The numerical value measured by this method was evaluated as a water contact angle value.

In addition, using the same cured product, the water contact angle was re-measured after maintaining for 72 hours in an atmosphere in which a 5% aqueous solution of NaCl was continuously sprayed in a brine sprayer maintained at 30°C.

3.Erasing characteristics

The lines with the oil-based pen (name pen, manufacturer Monami) attached to the cured product obtained in Examples 4 to 6 and Comparative Examples 1 to 2 were wiped with a small force using kimwipes®, kimberly-clark, and Erasing characteristics were visually evaluated. The criteria are as follows.

○: Handwriting can be completely wiped.

△: Handwriting remains blurry.

×: Handwriting cannot be wiped.

4. Appearance

The surfaces of the cured products obtained in Examples 4 to 6 and Comparative Examples 1 to 2 were subjected to sensory evaluation. Specifically, five ordinary people were touched on the surface of each cured product with their fingers to perform sensory evaluation on the 5-point scale (minimum: 1 point, highest: 5 points).

(Example 1)

Step 1. Preparation of Compound A

After dissolving 300 g of a perfluoropolyether compound (average molecular weight of 4,000 with methylol groups at both ends) in 1500 g of hexafluoroxylene, 24 g of sodium hydroxide and 73 g of allyl bromide were added and stirred at 60 degrees for 12 hours. After the reaction was completely completed, it was cooled to room temperature (25 degrees), and then washed 3 times using distilled water. The organic layer was separated, and the unreacted compound and the solvent were completely removed by vacuum distillation to obtain 270 g of a transparent liquid compound A (yield=90%).

¹ H-NMR: 5.9 (m, 2H), 5.3 (d, 2H), 2.1 (m, 2H), 4.5 (m, 4H)

Step 2. Preparation of compound B

After dissolving 30 g of Compound A in 150 g of hexafluoroxylene, 42 g of polysiloxane having an average molecular weight of 700 is added to both ends, and then 0.03 g of a platinum chloride catalyst/vinylsiloxane complex (2,000 ppm containing platinum) is added and reacted. The temperature was raised to 90 degrees and stirred for 6 hours. After the reaction was completely completed, the polysiloxane used in excess was removed by extraction with hexane, and the catalyst and other foreign substances were removed using activated carbon, and then the solvent was removed by vacuum distillation to obtain 32 g of liquid compound B (yield = 86%). ).

¹ H-NMR: 4.5(m, 4H), 3.4(m, 4H), 1.5~1.3(m, 8H), 0.14~0.08(m, 90H)

Step 3. Preparation of compound C

After dissolving 30 g of Compound B in 150 g of hexafluoroxylene, 4 g of 2-(allyloxymethyl)-2-ethyl-1,3-propanediol was added, and 0.03 g of a platinum chloride catalyst/vinylsiloxane complex (2,000 ppm containing platinum) ) Was added and the reaction temperature was raised to 90 degrees and stirred for 6 hours. After the reaction is complete, 2-(allyloxymethyl)-2-ethyl-1,3-propanediol used in excess is removed by extraction with methanol, and the catalyst and other foreign substances are removed using activated carbon, followed by vacuum distillation. The solvent was removed with to obtain 25 g of liquid compound C (yield=75%).

¹ H-NMR: 4.5(m, 4H), 3.4~3.2(m, 20H), 1.5~1.2(m, 20H), 0.14~0.08(m, 96H)

Step 4. Preparation of compound D (title compound 1)

After dissolving 20 g of Compound C in 100 g of hexafluoroxylene, 2.8 g of triethylamine was added and the reaction temperature was maintained at 10 degrees or less. 2.5 g of acroyl chloride was slowly added to the reactor. After the injection was completed, the reaction mixture was raised to room temperature and stirred for 5 hours. After the reaction was completed, the mixture was washed three times with distilled water, and the solvent and unreacted compound were removed by vacuum distillation to obtain 22 g of compound D (title compound 1) (yield=79%).

¹ H-NMR: 6.5 (m, 4H), 6.1 (m, 4H), 5.8 (m, 4H), 4.5 (m, 4H), 4.1 (br, 8H), 3.4~3.2 (m, 20H), 1.5 ~1.2(m, 20H), 0.14~0.08(m, 96H)

(Example 2)

Step 1. Preparation of compound E

After dissolving 30 g of Compound A obtained in Step 1 of Example 1 in 150 g of hexafluoroxylene, 15 g of tetramethylcyclotetrasiloxane was added, and then 0.03 g of a platinum chloride catalyst/vinylsiloxane complex (2,000 ppm containing platinum) was added. And the reaction temperature was raised to 90 degrees and stirred for 6 hours. After the reaction was completely completed, the tetrasiloxane used in excess was removed by extraction with hexane, the catalyst and other foreign substances were removed using activated carbon, and then the solvent was removed by vacuum distillation to obtain 29 g of liquid compound E (yield=80%). ).

¹ H-NMR: 4.5(m, 4H), 3.4(m, 4H), 1.5~1.3(m, 8H), 0.2~0.13(m, 24H)

Step 2. Preparation of compound F (title compound 2)

After dissolving 20 g of Compound E in 100 g of hexafluoroxylene, 9 g of undecenol was added, and then 0.02 g of a platinum chloride catalyst/vinylsiloxane complex (2,000 ppm containing platinum) was added, and the reaction temperature was raised to 90 degrees for 6 hours. While stirring. After the reaction was completely completed, the alcohol used in excess was removed by extraction with methanol, the catalyst and other foreign substances were removed using activated carbon, and then the solvent was removed by vacuum distillation to obtain 21 g of liquid compound F (yield=84%). .

¹ H-NMR: 4.5(m, 4H), 3.5~3.4(m, 16H), 1.5~1.2(m, 128H), 0.14(br, 24H)

Step 3. Preparation of compound G (title compound 2)

After dissolving 20 g of Compound F in 100 g of hexafluoroxylene, 3.9 g of triethylamine was added and the reaction temperature was maintained at 10 degrees or less. 3 g of acroyl chloride was slowly added to the reactor. After the addition was completed, the reaction was raised to room temperature and stirred for 5 hours. After the reaction was completely completed, after washing three times with distilled water, the solvent and unreacted compound were removed by vacuum distillation to obtain 22 g of compound G (title compound 2) (yield=78%).

¹ H-NMR: 6.5(m, 6H), 6.1(m, 6H), 5.8(m, 6H), 4.5(m, 4H), 4.2(m, 12H), 3.5~3.4(m, 4H), 1.5 ~1.2(m, 128H), 0.14(br, 24H)

(Example 3)

Step 1. Preparation of compound H (title compound 3)

After dissolving 20 g of Compound E obtained in Step 1 of Example 2 in 100 g of hexafluoroxylene, 6 g of allyl glacidyl ether was added and 0.02 g of a platinum chloride catalyst/vinylsiloxane complex (2,000 ppm containing platinum) was added. And the reaction temperature was raised to 90 degrees and stirred for 6 hours. After the reaction was completely completed, the ether used in excess was removed by extraction with methanol, the catalyst and other foreign matter were removed using activated carbon, and then the solvent was removed by vacuum distillation to obtain 18 g of liquid compound H (title compound 3) ( Yield=88%).

¹ H-NMR: 4.5(m, 4H), 3.5~3.2(m, 52H), 2.9~2.5(m, 18H), 1.5~1.2(m, 140H), 0.14(br, 24H)

(Production Example 1)

Step 1. Preparation of compound I

50 g of perfluorohexylethyl methacrylate, 50 g of isobornyl methacrylate and 5 g of azobisisobutyronitrile (AIBN) were dissolved in 400 g of methylethyl ketone, the reactor temperature was raised to 80 degrees and stirred for 12 hours to compound I was obtained (average molecular weight: 12000 Pd: 2.3).

(Production Example 2)

Step 1. Preparation of compound J

After dissolving 50 g of perfluorohexylethyl methacrylate, 45 g of isobornyl methacrylate, 5 g of glycinyloxy methacrylate and azobisisobutyronitrile in 400 g of methylethyl ketone, the reactor temperature was raised to 80 degrees for 12 hours. The compound J was obtained by stirring (average molecular weight: 9700 Pd: 2.1).

(Examples 4 to 6 and Comparative Examples 1 to 2)

A curable composition (100 g) was prepared to include the components shown in Table 1 below, and photocured to prepare a cured product.

Specifically, after dissolving the photopolymerizable compound and the photoinitiator in a solvent, each Example or Preparation Example compound was further added and stirred for 24 hours to prepare a curable composition. Each curable composition was removed with a 0.4um syringe filter, then bar coated on a PET film, and then the solvent was removed for 30 minutes in an 80 degree oven. The coated film from which the solvent was removed was exposed for 2 minutes using a high pressure mercury lamp (Litzen Co., Ltd. model name: LZ-U101) to obtain a cured product.

Through the above evaluation method, the surface properties of each cured product were confirmed, and the results are shown in Table 2 below.

(Table 1)

(Table 2)

As shown in Table 2, it was confirmed that the cured product obtained from the curable composition comprising the fluoropolyether derivative according to the present invention has very good erasing properties to the surface pollutant source by an oil-based pen. In general, the surface contaminant caused by oil-based pens, etc., requires wipe resistance by wiping using tissues or wipes containing organic solvents represented by ethanol and acetone. According to the present invention, it has an advantage over the prior art in that it can provide the advantage of being able to remove the surface contamination source by an oily pen or the like without using an organic solvent as well as wiping resistance to the use of the organic solvent.

In addition, according to the present invention, the excellent water contact angle is realized as well as it is stably maintained. On the other hand, in the case of the comparative example, only the initial water contact angle was excellent.

In addition, according to the present invention, it was confirmed that a smooth appearance can be realized as the light is rapidly cured with high sensitivity. That is, the numerical stability is excellent. Thus, it can be stably attached to the surface of a large area used for a flat panel display, thereby providing a hard coat layer having excellent surface properties such as anti-pollution and anti-reflection. As mentioned, the fluoropolyether derivative according to the present invention is capable of realizing improved sensitivity and thus provides a transparent cured product that realizes excellent surface characteristics and satisfies high pencil hardness even with a small amount of use compared to the compound of the preparation example. .

As described above, although the embodiments of the present invention have been described in detail, those of ordinary skill in the art to which the present invention pertains may view the present invention without departing from the spirit and scope of the present invention as defined in the appended claims. The invention may be modified in various ways. Therefore, changes to the embodiments of the present invention are also included within the protection scope of the present invention.

Claims (12)

Fluoropolyether derivative represented by the following formula (2):
[Formula 2]

[In the formula 2,
Rf ₂ is a divalent fluoropolyether group;
X ₂ and X ₃ are independently of each other C ₁ -C ₇ alkylene, and -CH ₂ -of the alkylene is -O-, -S-, -C(=O)-, -NR- or combinations thereof And R is hydrogen or C _1-7 alkyl;
R'and R" are independently of each other triC ₁ -C ₂₀ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;
R ₁ to R ₆ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl or -OR ^a , and R ₁ and R ₅ may be connected to each other with -0- as a linking group to form a cyclic siloxane group, and R ^a is as defined for R'above;
L ₁ and L ₂ are each independently substituted or unsubstituted C ₁ -C ₂₀ alkylene, and the substitution is triC ₁ -C ₂₀ alkoxysilyloxy, acryloyloxy, methacryloyloxy, glycidyl One selected from oxy, aminocarbonyloxy, halogen, hydroxy, cyano, carboxyl, carboxylate, hydroxyC ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy and combinations thereof Or a substitution with two or more substituents, and -CH ₂ -of L ₁ or L ₂ may be replaced by -O-, -S-, -NH-, -C(=O)- or a combination thereof;
a and b are each independently an integer selected from 0 to 20, and when a or b is an integer of 2 or more, the substituents of each repeating unit may be the same or different from each other. delete According to claim 1,
Rf ₂ of Formula 2 is,
A fluoropolyether derivative represented by Formula 4 below:
[Formula 4]
-CF ₂ O-[Rf ₂₁ O] _m -[Rf ₂₂ O] _n -CF _2-
In Chemical Formula 4,
Rf ₂₁ is fluorosubstituted C ₂ -C ₄ alkylene;
Rf ₂₂ is fluorosubstituted C ₁ -C ₄ alkylene;
m is an integer selected from integers from 0 to 10;
n is an integer selected from integers from 1 to 10. According to claim 1,
L ₁ and L ₂ are independently of each other C ₈ -C ₂₀ alkylene, -(C ₁ -C ₇ alkylene)-O-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkyl Ren)-OC(=O)-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-OC(=O)-O-(C ₁ -C ₇ alkylene)-, -(C ₁ -C ₇ alkylene)-S-(C ₁ -C ₇ alkylene)-, -C(=O)-O-(C ₁ -C ₇ alkylene)-, -C(=O) -NH-(C ₁ -C ₇ alkylene)- or -(C ₁ -C ₇ alkylene)-C(=O)-O-(C ₁ -C ₇ alkylene)-C(=O)-O -(C ₁ -C ₇ alkylene)-, wherein the alkylene is triC ₁ -C ₂₀ alkoxysilyloxy, acryloyloxy, methacryloyloxy, glycidyloxy, aminocarbonyloxy, hydroxy Fluoropolyether derivatives, which may be substituted with one or more substituents selected from C ₁ -C ₇ alkyl, C ₁ -C ₇ alkyl, C ₁ -C ₇ alkoxy and combinations thereof. According to claim 1,
R'and R" are independently of each other triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;
R ₁ to R ₆ are independently of each other hydrogen or C ₁ -C ₄ alkyl;
The a and b are each independently an integer selected from 5 to 15, and the substituents of each repeating unit are the same or different from each other, a fluoropolyether derivative. According to claim 1,
X ₂ and X ₃ are independently of each other C ₁ -C ₇ alkylene;
R'and R" are independently of each other triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;
R ₁ and R ₅ are connected to each other with -0- as a linking group to form a cyclic siloxane group;
R ₃ is -OR ^a and R ^a is triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;
R ₂ , R ₄ and R ₆ are independently of each other hydrogen or C ₁ -C ₄ alkyl;
The a and b are each independently an integer selected from 1 to 3, and when a or b is an integer of 2 or 3, the substituents of each repeating unit are the same or different from each other, a fluoropolyether derivative. The method of claim 6,
The fluoropolyether derivative,
A fluoropolyether derivative comprising a cyclic siloxane group represented by Formula 5 below:
[Formula 5]

In Chemical Formula 5,
R ^b , R ^c and R ^d are independently of each other hydrogen or C ₁ -C ₄ alkyl;
R ^e is -OR ^a , wherein R ^a is triC ₁ -C ₄ alkoxysilyl, acryloyl, methacryloyl, glycidyl, aminocarbonyl or a combination thereof;
x is an integer selected from 1 to 3, and when x is an integer of 2 or 3, the substituents of each repeating unit may be the same or different from each other. According to claim 1,
The Rf ₂ is a divalent perfluoropolyether group, a fluoropolyether derivative. Surface treatment agent comprising the fluoropolyether derivative according to claim 1. A curable composition comprising the fluoropolyether derivative according to claim 1, a photopolymerizable compound, a photoinitiator and a solvent. Cured product of the curable composition according to claim 10. The method of claim 11,
The cured product,
Hardened material, which is an optical film for preventing contamination or reflection of flat panel displays.