KR20190109024A - Composition for forming multifunctional layer, multifunctional layer formed from the same, and protective layer comprising the multifunctional layer - Google Patents

Abstract

The present invention relates to a composition for forming a multi-functional film having significantly improved hardness, a multi-functional film formed therefrom and a protective film including the multi-functional film. The composition for forming a multi-functional film of the present invention comprises: a fluorinated acrylic copolymer containing a vinyl terminal functional group; and silica particles functionalized by a vinyl group.

Description

A multifunctional film-forming composition, a multifunctional film formed therefrom, and a protective film comprising the multifunctional film.

The present application is a multifunctional film-forming composition having a significantly improved hardness, a multifunctional film formed using the multifunctional film-forming composition, a protective film including the multifunctional film, and a display device including the protective film. It is about.

The touch display device means an apparatus including a display panel and a touch panel. Here, the display panel serves to provide a screen, such as a liquid crystal display (LCD), and the touch panel is a finger or a stylus pen (or a touch pen) to directly input information on the display. It serves to sense the touch of the back. Such touch display devices are applied to various electronic display products such as notebooks, monitors, TVs, large displays, and navigation devices from small mobile devices.

The top layer of the touch display device must be robust, durable, thin and light due to protection from the external environment such as human nails, keys in pockets, pens in bags. Therefore, the top layer of a touch display device is a very important factor in the lifetime and quality of the device.

The outermost layer of such a touch display device may be an anti-finger print hard coating. Since the user touches the anti-fingerprint hard coating film, the anti-fingerprint hard coating film has a high hardness characteristic. If the hardness of the anti-fingerprint hard coating film is insufficient, the film is damaged by the user's hand and the life of the device is shortened.

On the other hand, the hard coat film applied to a display device needs to have hardness, resistance to an external environment, anti-fingerprint, adhesiveness, and antireflection. However, when the adhesiveness is insufficient in the multilayer hard coating film having multiple functions such as hardness, anti-fingerprint, adhesion, and antireflection, the layer may be peeled off or the properties of the hard coating film may be degraded. In addition, due to the two-step process of the coating process for hardness and the coating process for hydrophobicity, there is a problem that the manufacturing process is complicated and the production cost is increased.

[Prior literature]

Republic of Korea Patent Publication No. 10-2017-0036166.

The present application is a multifunctional film-forming composition having a significantly improved hardness, a multifunctional film formed using the multifunctional film-forming composition, a protective film including the multifunctional film, and a display device including the protective film. To provide.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present disclosure provides a fluorinated acrylic copolymer containing vinyl terminal functional groups; And it provides a multifunctional film-forming composition comprising silica particles functionalized by a vinyl group.

The second aspect of the present application provides a multifunctional film, including a coating film formed using the multifunctional film-forming composition of the first aspect of the present application.

A third aspect of the present application provides a protective film, comprising the multifunctional membrane according to the second aspect of the present application.

A fourth aspect of the present application provides a device comprising a protective film according to the third aspect of the present application.

In the field of conventional touch display devices, studies have been conducted to prevent damage or contamination by fingerprints of the user of the uppermost layer of the touch display and to have high hardness characteristics. Accordingly, hardness, hydrophobicity, fingerprint resistance, and adhesion Functions such as frost and antireflection were provided in a multilayer hard coating. However, the hard coating film formed of the multilayer, when the adhesion between the layers is insufficient, the layer is peeled off or the properties of the hard coating film is reduced, the manufacturing process due to the two-step process of the coating process for hardness and the coating process for hydrophobicity, etc. There is a problem that this complexity and production cost is increased.

Thus, according to embodiments of the present application, by using a multifunctional film-forming composition comprising a fluorinated acrylic copolymer containing a vinyl terminal functional group and silica particles functionalized by a vinyl group, anti-fingerprint, adhesion with improved hardness The hard coating film, which is a multifunctional film having improved properties and / or antireflection properties, can be easily and efficiently produced in a one step process.

Specifically, according to the embodiments of the present invention, in the process of curing the multi-functional film-forming composition to form a multi-functional film, the vinyl contained in the fluorinated acrylic copolymer included in the multi-functional film-forming composition By crosslinking between the groups and the vinyl groups contained in the functionalized silica particles, the hardness of the multifunctional hard coating film formed using the multifunctional film-forming composition is improved, and the fluorinated acrylic copolymer The contact angle can be increased by the fluorine component contained therein, thereby improving anti-fingerprint, adhesiveness, and / or antireflection properties.

The hard coating film formed using the multifunctional film-forming composition according to embodiments of the present invention is a multifunctional film having properties of anti-fingerprint, adhesion, and / or antireflection to a substrate with improved hardness, It can have all of the properties of improved hardness, anti-fingerprint, adhesiveness, and anti-reflection to a single layer of film, which can be applied as a protective film of various devices to be an alternative to realize multifunctional thin and light devices. For example, the multi-functional hard coating film according to the embodiments of the present application can be used for the surface of wind generators, protective layers for displays and solar cells, automotive glass surface treatment for removing dust, water and oil, and various display or photovoltaic devices. It can be used as a protective film, and in particular, it can be applied as a protective film of various displays, such as a touch type display and a flexible display.

In addition, by the embodiments of the present application, the multifunctional hard coating layer may improve adhesion to other treatment agents such as wear resistance, corrosion protection, printing paint, or photosensitive coating.

1A is a contact angle measurement photo of the hard coating film prepared according to Comparative Example 1, FIG. 1B is a contact angle measurement photo of the hard coating film prepared according to Comparative Example 2, FIG. 1C is a multifunctional hard coating film prepared according to Example 3 The contact angle measurement photograph is shown.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a part is said to be "connected" with another part, this includes not only the "directly connected" but also the "electrically connected" between other elements in between. do.

Throughout this specification, when a member is located “on” another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated. As used throughout this specification, the terms “about”, “substantially”, and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided, and an understanding of the present application may occur. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term “step of” or “step of” does not mean “step for”.

Throughout this specification, the term "combination (s) thereof" included in the expression of a makushi form refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of makushi form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.

Throughout this specification, the term "alkyl group" typically refers to 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 1 to Linear or branched alkyl groups having two carbon atoms. When the alkyl group is substituted with an alkyl group, it is also used interchangeably with "branched alkyl group". Substituents that may be substituted with the alkyl group include halo (eg, F, Cl, Br, I), haloalkyl (eg, CC1 ₃ or CF ₃ ), alkoxy, alkylthio, hydroxy, carboxy ( -C (O) -OH), alkyloxycarbonyl (-C (O) -OR), alkylcarbonyloxy (-OC (O) -R), amino (-NH ₂ ), carbamoyl (-NHC Or (O) OR- or -OC (O) NHR-), urea (-NH-C (O) -NHR-) and thiol (-SH). You may not. In addition, the alkyl group of 2 or more carbon atoms in the alkyl group described above may include at least one carbon to carbon double bond or at least one carbon to carbon triple bond, but may not be limited thereto. For example, it may include, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, or all possible isomer thereof.

Throughout this specification, the molecular weight of a polymer, a copolymer, an oligomer, etc. means the weight average molecular weight using the polystyrene conversion value by gel permeation chromatography.

Hereinafter, with reference to the accompanying drawings will be described embodiments and embodiments of the present application; However, the present disclosure may not be limited to these embodiments, examples, and drawings.

A first aspect of the present disclosure provides a fluorinated acrylic copolymer containing vinyl terminal functional groups; And it provides a multifunctional film-forming composition comprising silica particles functionalized by a vinyl group.

In one embodiment of the present disclosure, the functionalized silica particles may be nanoparticles.

In one embodiment of the present invention, the functionalized silica particles are functionalized by a vinyl group bonded to the Si element on the surface of the silica particles, or the following vinyl group-containing substituent bonded to the Si element or O element on the surface of the silica particles It may be functionalized by, but may not be limited to:

[Vinyl group-containing substituent]

또는

;

or

;

In the vinyl group-containing substituent, n is an integer of 1 to 5.

In one embodiment of the present application, the multi-functional film-forming composition may be cured to form a multi-functional hard coating film, wherein the hard coating film is functionalized by the vinyl group and the fluorinated acrylic copolymer containing the vinyl terminal functional group. It may have improved hardness by the silica particles.

In the embodiments of the present invention, in the process of curing the multi-functional film-forming composition to form a multi-functional film, the vinyl group contained in the fluorinated acrylic copolymer included in the multi-functional film-forming composition and the functionalization By crosslinking between the vinyl groups contained in the silica particles, the hardness of the multifunctional hard coating film formed using the multifunctional film-forming composition is improved, and the fluorine component contained in the fluorinated acrylic copolymer The contact angle can be increased to thereby improve anti-fingerprint, adhesion, and / or antireflection properties and the like.

In one embodiment of the present application, the content of the functionalized silica particles may be about 0.1 to about 10 parts by weight based on about 100 parts by weight of the multifunctional film-forming composition.

For example, based on about 100 parts by weight of the multifunctional film-forming composition, the content of the functionalized silica particles is about 0.1 to about 10 parts by weight, about 0.1 to about 8 parts by weight, about 0.1 to about 6 parts by weight Parts, about 0.1 to about 4 parts by weight, about 0.1 to about 2 parts by weight, about 0.1 to about 1 part by weight, about 1 to about 10 parts by weight, about 1 to about 8 parts by weight, about 1 to about 6 parts by weight, About 1 to about 4 parts by weight, about 1 to about 2 parts by weight, about 2 to about 10 parts by weight, about 2 to about 8 parts by weight, about 2 to about 6 parts by weight, about 2 to about 4 parts by weight, about 4 To about 10 parts by weight, about 4 to about 8 parts by weight, about 4 to about 6 parts by weight, about 6 to about 10 parts by weight, about 6 to about 8 parts by weight, or about 8 to about 10 parts by weight, but It may not be limited.

In one embodiment of the present application, the fluorinated acrylic copolymer may be to include those represented by the following formula (1):

[Formula 1]

;

;

In Formula 1, R ¹ and R ² are each independently a linear or branched C _1-6 alkyl group substituted by one or more F, R ³ is a linear or branched C _1-6 alkyl group, a and b is each independently a positive number.

In one embodiment of the present application, in Formula 1 representing the fluorinated acrylic copolymer, R ¹ and R ² may each independently include a linear or branched C _1-6 perfluoro alkyl group, but It may not be limited.

In one embodiment of the present application, in Chemical Formula 1 representing the fluorinated acrylic copolymer, a may be a number from 5 to 30, and b may be a number from 10 to 50, but may not be limited thereto. When the multifunctional film-forming composition comprising the fluorinated acrylic copolymer having the numerical range of a and b is cured to form a multifunctional hard coating film, the contact angle is determined by the fluorine component contained in the fluorinated acrylic copolymer. It is possible to improve the hydrophobicity and fingerprinting according to the increase, and by the crosslink between the vinyl group contained in the fluorinated acrylic copolymer and the vinyl group contained in the functionalized silica particles, the multifunctional membrane- Hardness of the hard coat film formed using the composition for forming can be improved, so that various properties of the final multifunctional hard coat film can be maintained or improved. Therefore, according to the embodiments of the present invention, by using the composition for multifunctional film-forming comprising the fluorinated acrylic copolymer containing the vinyl terminal functional group and the silica particles functionalized by the vinyl group, A multifunctional film having anti-finger print, adhesion, and / or anti-reflection properties can be easily produced as a single layer coating film in a one step process.

For example, in Chemical Formula 1, a is a number of 5 to 30, a number of 5 to 28, a number of 5 to 26, a number of 5 to 24, a number of 7 to 30, a number of 7 to 28, 7 to Number of 26, number of 7 to 24, number of 8 to 30, number of 8 to 28, number of 8 to 26, or number of 8 to 24; B is a number from 10 to 50, from 10 to 45, from 10 to 40, from 10 to 35, from 10 to 30, from 12 to 50, from 12 to 45, from 12 to 40 , 12 to 35, or 12 to 30.

In one embodiment of the present application, the fluorinated acrylic copolymer may have a molecular weight of about 5,000 to about 30,000. For example, the fluorinated acrylic copolymer can have a molecular weight of about 5,000 to about 30,000, about 6,000 to about 25,000, or about 7,000 to about 20,000. For example, the molecular weight of the fluorinated acrylic copolymer is about 5,000 to about 30,000, about 5,000 to about 28,000, about 5,000 to about 26,000, about 5,000 to about 24,000, about 5,000 to about 22,000, about 5,000 to about 20,000, about 5,000 To about 18,000, about 5,000 to about 16,000, about 5,000 to about 14,000, about 6,000 to about 30,000, about 6,000 to about 28,000, about 6,000 to about 26,000, about 6,000 to about 25,000, about 6,000 to about 24,000, about 6,000 to about 22,000, about 6,000 to about 20,000, about 6,000 to about 18,000, about 6,000 to about 16,000, about 6,000 to about 14,000, about 7,000 to about 30,000, about 7,000 to about 28,000, about 7,000 to about 26,000, about 7,000 to about 24,000, About 7,000 to about 22,000, about 7,000 to about 20,000, about 7,000 to about 18,000, about 7,000 to about 16,000, about 7,000 to about 15,000, or about 7,000 to about 14,000.

In one embodiment of the present application, the multifunctional film-forming composition may further comprise a curable monomer and a curing initiator. For example, the multifunctional film-forming composition further includes the curable monomer and a curing initiator together with a fluorinated acrylic copolymer containing vinyl terminal functional groups and silica particles functionalized by vinyl groups, such as photocuring or thermosetting. By hardening, a hard coat resin can be formed through a crosslinking reaction.

In one embodiment of the present application, the curable monomer may be a photocurable monomer such as a UV monomer or a thermosetting monomer.

In one embodiment of the present application, the curing initiator may include a photo initiator or a thermal initiator such as a UV initiator.

In one embodiment of the present application, the multifunctional film-forming composition may further include an organic solvent, a fluorinated acrylic copolymer containing the vinyl terminal functional group, silica particles functionalized by the vinyl group, the curable The monomer and the curing initiator may be mixed in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the components, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2 Ethyl hydroxypropionate, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxy ethyl acetate, 2-hydroxy-3-methylbutanemethyl 3-methoxy methyl propionate 3-methoxy ethyl propionate 3 -Ethoxy Propionate Methyl 3-ethoxy propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethyl formamide, N, N-dimethyl acetamide, N-methyl-2- It may include, but is not limited to, one selected from the group consisting of pyrrolidone, γ-butyrolactone, and combinations thereof.

In one embodiment of the present invention, based on about 100 parts by weight of the multifunctional film-forming composition, the fluorinated acrylic copolymer is about 5 to about 30 parts by weight, the curable monomer is about 30 to about 90 parts by weight, and The curing initiator may comprise about 1 to about 20 parts by weight.

For example, based on about 100 parts by weight of the multifunctional film-forming composition, the fluorinated acrylic copolymer is about 5 to about 30 parts by weight, about 5 to about 28 parts by weight, about 5 to about 26 parts by weight, about 5 to about 25 parts by weight, about 5 to about 20 parts by weight, about 7 to about 30 parts by weight, about 7 to about 28 parts by weight, about 7 to about 26 parts by weight, about 7 to about 25 parts by weight, about 7 to about About 20 parts by weight, about 10 to about 30 parts by weight, about 10 to about 28 parts by weight, about 10 to about 26 parts by weight, about 10 to about 25 parts by weight, or about 10 to about 20 parts by weight, but is not limited thereto. It may not be.

For example, based on about 100 parts by weight of the multifunctional film-forming composition, the content of the curable monomer is about 30 to about 90 parts by weight, about 30 to about 85 parts by weight, about 30 to about 80 parts by weight, About 30 to about 75 parts by weight, about 30 to about 70 parts by weight, about 30 to about 65 parts by weight, about 30 to about 60 parts by weight, about 30 to about 55 parts by weight, about 30 to about 50 parts by weight, about 40 To about 90 parts by weight, about 40 to about 85 parts by weight, about 40 to about 80 parts by weight, about 40 to about 75 parts by weight, about 40 to about 70 parts by weight, about 40 to about 65 parts by weight, about 40 to about 60 parts by weight, about 40 to about 55 parts by weight, or about 40 to about 50 parts by weight, but may not be limited thereto.

For example, based on about 100 parts by weight of the multifunctional film-forming composition, the curing initiator is about 1 to about 20 parts by weight, about 1 to about 18 parts by weight, about 1 to about 16 parts by weight, about 1 To about 15 parts by weight, about 1 to about 10 parts by weight, about 5 to about 20 parts by weight, about 5 to about 18 parts by weight, about 5 to about 16 parts by weight, about 5 to about 15 parts by weight, or about 5 to about It may be about 10 parts by weight, but may not be limited thereto.

Therefore, in the content range of the fluorinated acrylic copolymer containing the vinyl terminal functional group, the silica particles functionalized by the vinyl group, the curable monomer, and the curing initiator, appropriate curing of the multifunctional film-forming composition is achieved, thereby improving the hardness and Together, a multifunctional hard coating film having anti-finger print, adhesion, and / or anti-reflection properties can be easily prepared as a single layer coating film by a one-step process. Can be.

In one embodiment of the present application, the curable monomer, the curing initiator, the curing method and the like can be carried out by selecting with reference to the documents known in the art, for example, reference Japanese Patent Laid-Open No. 2013-49802 See the disclosure in.

For example, the multi-functional hard coating film is applied to the surface of the substrate, the composition for forming the multi-functional film-forming, and dried, irradiated with an active energy ray, such as ultraviolet (UV), or cured by applying heat or hardening It may be formed by a method for forming, but may not be limited thereto.

In one embodiment of the present application, the UV monomer may be to include an acrylate monomer compound containing one or more functional groups, but may not be limited thereto. For example, the acrylate compound is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acryl Latene, nonyl acrylate, isodecyl acrylate, dodecyl acrylate, benzyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, Trimethylolpropane EO-modified triacrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane trioxyethyl acrylate, and From a group of combinations of these It may include one selected, but may not be limited thereto.

For example, the said acrylate type compound can use a well-known thing without a restriction | limiting in particular as long as the number of functional groups (number of ethylenically unsaturated double bonds) per molecule is 2 or more as a polyfunctional (meth) acryl compound.

As a bifunctional (meth) acrylate, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (meth) acrylate, long-chain aliphatic di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, hydroxy pivaric acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene diacrylate, glycerol (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol diacrylate, butylene glycol di (meth) acrylate, dicyclopentanyl diacrylate, polyethylene glycol di (meth) acrylate, Polypropylene diacrylate, triglycerol diacrylate, neopentyl glycol modified trimethylolpropanedi (meth) acryl Acrylate, allylated cyclohexyldi (meth) acrylate, methoxylated cyclohexyldi (meth) acrylate, acrylated isocyanurate, bis (acryloxy neopentylglycol) adipate, bisphenol A di (meth) acrylate, Tetrabromo bisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol (meth) acrylate, phthalic acid di (meth) acrylate, phosphate di (meth) acrylate, zinc di (meth) acrylic The rate etc. are mentioned.

As (meth) acrylate more than trifunctional, for example, trimetholpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxy ethyl) isocyanurate, tris (methacryloxy ethyl Isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipenta Erythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl modified dipentaery Erythritol may be a penta (meth) acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and the like.

Among these, dipentaerythritol hexaacrylate, dipentaerythritol penta acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like are preferable. It is preferable to use dipentaerythritol hexaacrylate (DPHA) which has many functional groups from a viewpoint of the scratch resistance which obtained the hardened coating film of especially high hardness.

In one embodiment of the present application, a photoinitiator such as a known UV initiator that can be decomposed by ultraviolet rays to generate radicals to initiate polymerization as the curing initiator is not particularly limited. In addition, a photosensitizer may be added if necessary.

As said photoinitiator, it can be broadly divided into an intramolecular cleavage type photoinitiator and a dehydrogenation type photoinitiator. As said intramolecular cleavage type photoinitiator, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl propane- 1-one, benzyl dimethyl ketal, 1- (4-isopropylphenyl)-, 2-hydroxy-2-methyl propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl Acetophenone type compounds, such as 2-morpholino (4-thiomethylphenyl) propane- 1-one and 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) butanone; Benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; And compounds such as benzyl and methylphenylglyoxyether.

As said dehydrogen-type photoinitiator, benzophenone, o-benzoyl benzoic acid methyl-4-phenybenzophenone, 4,4'- dichloro benzophenone, hydroxy benzophenone, 4-benzoyl-4'-methyl-, for example Benzophenone type compounds, such as a diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'- tetra (t-butylperoxycarbonyl) benzophenone, and 3,3'- dimethyl- 4-methoxy benzophenone ; Thioxanthone compounds such as 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as 4,4'-diethylaminobenzophenone; And compounds such as 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone and camphor quinone. Among these, it is preferable that it is dehydrogen-type photoinitiator, such as benzophenone.

In one embodiment of the present disclosure, the photoinitiator may include a phosphine-based photoinitiator, the phosphine-based photoinitiator bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis ( 2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorbenzoyl)- 4-propylphenylphosphineoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and combinations thereof It may include that selected from the group consisting of.

In one embodiment of the present application, the multi-functional film-forming composition may further include a solvent for adjusting the viscosity in order to give applicability to the substrate. As said solvent, although a well-known thing can be used without a restriction | limiting in particular, For example, Aromatic hydrocarbons, such as toluene and xylene; Alcohols such as methanol, ethanol and isopropyl alcohol; Ester, such as ethyl acetate and an ethylene sorbate; Ketones, such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, etc. are mentioned. Especially, it is preferable to use the solvent of ketones and esters from a handling point and a dry point. These solvents may be used independently or may use 2 or more types together.

In one embodiment of the present application, the multi-functional film-forming composition may further include other photosensitive resins, additives other than the above components so long as the effects of the present application is not impaired. For example, urethane (meth) acrylate, polyester (meth) acrylate, etc. can be mix | blended as said photosensitive resin. As other additives, silicone-based, fluorine-based antifoaming agents, leveling agents, known thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, foaming agents, flame retardants, antistatic agents, anti-aging agents, antibacterial and anti-fog agents, and the like can be blended. .

The multifunctional hard coating film formed using the multifunctional film-forming composition according to the embodiments of the present invention may have all of the properties of improved hardness, anti-fingerprint, adhesion, and anti-reflection to a single layer film, Applied as a protective film of various devices, it can be an alternative to realize multi-functional thin and light devices. For example, the multi-functional hard coating film according to the embodiments of the present application may be used for the surface of a wind generator, the protective layer for display and solar cells, automotive glass surface treatment for removing dust, water and oil, and for various display or photovoltaic devices. It can be used as a protective film, and in particular, it can be applied as a protective film of various displays, such as a touch type display and a flexible display.

The second aspect of the present application provides a multifunctional film, including a coating film formed using the multifunctional film-forming composition of the first aspect of the present application. Although detailed descriptions of portions overlapping with the first aspect of the present application are omitted, the descriptions of the first aspect of the present application may be equally applied even if the description is omitted from the second side.

In one embodiment of the present application, the multi-functional film-forming composition may be cured to form a multi-functional hard coating film, wherein the hard coating film is functionalized by the vinyl group and the fluorinated acrylic copolymer containing the vinyl terminal functional group. It may have improved hardness by the silica particles.

In one embodiment of the present application, the multifunctional membrane may have one or more functionalities selected from the group consisting of anti-fingerprint, adhesion, and anti-reflection, with improved hardness.

In one embodiment of the present application, the multifunctional film may be formed by coating the multifunctional film-forming composition on a substrate and then photocuring or thermosetting.

In the embodiments of the present invention, in the process of curing the multi-functional film-forming composition to form a multi-functional film, the vinyl group contained in the fluorinated acrylic copolymer included in the multi-functional film-forming composition and the functionalization By crosslinking between the vinyl groups contained in the silica particles, the hardness of the multifunctional hard coating film formed using the multifunctional film-forming composition is improved, and the fluorine component contained in the fluorinated acrylic copolymer The contact angle may be increased to thereby improve fingerprint, adhesion, and / or antireflection properties.

For example, when the multifunctional film-forming composition is cured to form a multifunctional hard coat film, the contact angle may be increased by the fluorine component contained in the fluorinated acrylic copolymer, thereby improving hydrophobicity and fingerprinting. And by improving the hardness by crosslinking between the vinyl groups contained in the fluorinated acrylic copolymer included in the multifunctional film-forming composition and the vinyl groups contained in the functionalized silica particles. Maintain or improve properties. Thus, by embodiments of the present disclosure, using a multifunctional film-forming composition comprising a fluorinated acrylic copolymer containing a vinyl terminal functional group and silica particles functionalized by a vinyl group, it is possible to improve fingerprinting, adhesion with improved hardness. A multifunctional hard coat film having a property of anti-reflection and / or antireflection can be easily manufactured in a one step process.

In one embodiment of the present application, the multifunctional film-forming composition used for forming the multifunctional film is curable with the fluorinated acrylic copolymer containing the vinyl terminal functional group and the silica particles functionalized by the vinyl group. By further including a monomer and a curing initiator, a hard coating film can be formed through a crosslinking reaction by curing such as photocuring or thermosetting. For example, the curable monomer may include a photocurable monomer such as a UV monomer, and the curing initiator may include a photocuring agent such as a UV curing agent or a thermosetting agent, but may not be limited thereto. The curable monomer, the curing initiator, the curing method and the like can be carried out by selecting the contents described in the first aspect of the present application with reference to the documents known in the art, for example, reference Japanese Patent Application Laid-Open No. 2013-49802 See the disclosure in.

The multifunctional film formed by using the multifunctional film-forming composition according to an embodiment of the present invention is a multi-step film having an improved hardness and anti-fingerprint, adhesion, and / or antireflective properties in a one step process. It can be easily manufactured as a coating film of a layer, and can be applied as a protective film of various devices to be an alternative to realize a multifunctional thin and light device. For example, the multifunctional membrane according to one embodiment of the present application is a surface of a wind generator, a protective layer for a display and a solar cell, an automotive glass surface treatment for removing dust, water and oil, and a protective film of various displays or photovoltaic devices. It can be used, and in particular, it can be applied as a protective film of various displays, such as a touch type display, a flexible display.

In addition, by the embodiments of the present application, the multifunctional hard coating layer may improve adhesion to other treatment agents such as wear resistance, corrosion protection, printing paint, or photosensitive coating.

In one embodiment of the present application, the multifunctional film may be formed by coating and curing the multifunctional film-forming composition on a base (base film).

Coating the multifunctional film-forming composition on the substrate may include, for example, spin-coating, slot-die coating, microgravure coating, web coating, double slit coating, dip coating, spray coating, insulating coating, or It may be performed by zone casting, but may not be limited thereto.

In one embodiment of the present application, the thickness of the multifunctional film may be about 0.1 μm to about 100 μm, but may not be limited thereto. For example, the thickness of the multifunctional membrane is about 0.1 μm to about 100 μm, about 0.1 μm to about 90 μm, about 0.1 μm to about 80 μm, about 0.1 μm to about 70 μm, about 0.1 μm to about 60 μm, About 0.1 μm to about 50 μm, about 0.1 μm to about 40 μm, about 0.1 μm to about 30 μm, about 0.1 μm to about 20 μm, about 0.1 μm to about 10 μm, about 1 μm to about 100 μm, about 1 Μm to about 90 μm, about 1 μm to about 80 μm, about 1 μm to about 70 μm, about 1 μm to about 60 μm, about 1 μm to about 50 μm, about 1 μm to about 40 μm, about 1 μm to About 30 μm, about 1 μm to about 20 μm, about 1 μm to about 10 μm, about 3 μm to about 100 μm, about 3 μm to about 90 μm, about 3 μm to about 80 μm, about 3 μm to about 70 Μm, about 1 μm to about 60 μm, about 3 μm to about 50 μm, about 3 μm to about 40 μm, about 3 μm to about 30 μm, about 3 μm to about 20 μm, or about 3 μm to about 10 μm Can be.

In one embodiment of the present application, the substrate is not particularly limited, but may be transparent, or may be transparent and flexible, for example, may include a glass, metal, oxide, silicon, or a polymer substrate However, this may not be limited. For example, the polymer substrate is polyethylsulfone (PES), PET, PC, PMMA, polyethylene phthalate, polymethylmethacrylate, polystyrene (PS), cyclic olefin air It includes a material selected from the group consisting of cyclic olefin copolymer, polyethylene naphthalate (PEN), polyimide, colorless polyimide (cPI), and combinations thereof It may be, but may not be limited thereto.

A third aspect of the present application provides a protective film, comprising the multifunctional membrane according to the second aspect of the present application. Portions overlapping with the first and second aspects of the present application have been omitted, but the same may be applied even if the description is omitted in the third aspect of the present application.

In one embodiment of the present application, the protective film may have one or more functionalities selected from the group consisting of anti-fingerprint, adhesiveness, and anti-reflection, with significantly improved hardness.

In one embodiment of the present application, the thickness of the protective film may be about 0.1 ㎛ to about 100 ㎛, but may not be limited thereto. For example, the protective film has a thickness of about 0.1 μm to about 100 μm, about 0.1 μm to about 90 μm, about 0.1 μm to about 80 μm, about 0.1 μm to about 70 μm, about 0.1 μm to about 60 μm, about 0.1 μm to about 50 μm, about 0.1 μm to about 40 μm, about 0.1 μm to about 30 μm, about 0.1 μm to about 20 μm, about 0.1 μm to about 10 μm, about 1 μm to about 100 μm, about 1 μm To about 90 μm, about 1 μm to about 80 μm, about 1 μm to about 70 μm, about 1 μm to about 60 μm, about 1 μm to about 50 μm, about 1 μm to about 40 μm, about 1 μm to about 30 μm, about 1 μm to about 20 μm, about 1 μm to about 10 μm, about 3 μm to about 100 μm, about 3 μm to about 90 μm, about 3 μm to about 80 μm, about 3 μm to about 70 μm About 1 μm to about 60 μm, about 3 μm to about 50 μm, about 3 μm to about 40 μm, about 3 μm to about 30 μm, about 3 μm to about 20 μm, or about 3 μm to about 10 μm Can be.

A fourth aspect of the present application provides a device comprising a protective film according to the third aspect of the present application. Portions overlapping with the first to third aspects of the present application have been omitted, but the same may be applied even if the description is omitted in the fourth aspect of the present application.

In one embodiment of the present application, the device includes the protective film having one or more functionalities selected from the group consisting of anti-fingerprint, adhesiveness, and anti-reflection, together with significantly improved hardness, thereby providing a long life and durability of the display. And the like can be significantly improved.

In one embodiment of the present application, the device may include a display or a photovoltaic device, but may not be limited thereto.

In one embodiment of the present application, the display is a touch type display, such as a touch screen panel, LCD display, LED display, OLED display, flat panel display, touch screen panel, plasma display, electroluminescent display, flexible display, touch type flexible Display or the like; Also, it may be a CRT display, a PDP display, a touch panel, or a digital paper, but may not be limited thereto.

In another embodiment of the present invention, the display device is a television receiver, various audio / video systems, home theater systems, desktop computer devices, computer monitor devices, camera devices, moving picture photographing devices, electronic signs or portable terminal devices. It may include a variety of devices capable of displaying a still image or a moving image, such as, but may not be limited thereto. For example, the portable terminal device may include various devices such as a notebook computer device, a cellular phone, a smart phone, a tablet PC, an e-book terminal device, a personal digital assistant device (PDA), a navigation terminal device, or a portable game machine. It may be, but may not be limited thereto.

In one embodiment of the present disclosure, the photovoltaic device may include various known photovoltaic devices capable of converting light energy into electrical energy or converting electrical energy into light energy. For example, the photoelectric device may include various known solar cells, but may not be limited thereto.

Hereinafter, the embodiments of the present application will be described in detail. However, the present application may not be limited thereto.

[ Example ]

< Multifunctional  Preparation of Film-Forming Composition>

In order to prepare the multifunctional-film forming composition in this embodiment, as a fluorinated acrylic copolymer (molecular weight: 7,000 to 20,000), dipentaerythritol hexaacrylate and pentaerythritol triacryl as UV monomers Pentaerythritol triacrylate, Irgacure 184 as a UV initiator and trimethylbenzoyl diphenylphosphine oxide (TPO), methyl ethyl ketone (MEK) as a solvent, and tetraethyl orthosilicate (TEOS) as silica particles. By mixing, a multifunctional film-forming composition was prepared. At this time, the content of the components are listed in Table 1 below.

< Example  1>

On vinyl  Functionalized by TEOS  Containing "silica particles A" Multifunctional  Preparation of Film-Forming Composition

Using the TEOS "silica particles A" functionalized by a vinyl group represented by the following formula, by mixing each component in the content shown in Table 1 to prepare a multi-functional film-forming composition:

[Silica Particles A]

.

.

< Example  2>

On vinyl  Functionalized by TEOS  Containing "silica particles B" Multifunctional  Preparation of Film-Forming Composition

Using the TEOS "silica particles B" functionalized by a vinyl group represented by the following formula, by mixing each component in the content shown in Table 1 to prepare a multi-functional film-forming composition:

[Silica Particles B]

.

.

< Example  3>

On vinyl  Functionalized by TEOS  Containing "silica particles C" Multifunctional  Preparation of Film-Forming Composition

Using the TEOS "silica particles C" functionalized by a vinyl group represented by the following formula, by mixing each component in the content shown in Table 1 to prepare a multi-functional film-forming composition:

[Silica Particles C]

.

.

< Comparative example  1>

The film-forming composition of Comparative Example 1 was prepared in the same manner as the components of the composition of Example 1, but without adding the functionalized silica particles.

< Comparative example  2>

The film-forming composition of Comparative Example 2 was prepared by adding the following "TEOS silica particles" in the same manner as the components of the composition of Example 1 above:

[TEOS silica particles]

.

.

< Multifunctional  hard Of coating film  Manufacture

The hard coating film was prepared using the multifunctional film-forming compositions prepared in Examples 1 to 3 and the film-forming compositions prepared in Comparative Examples 1 and 2, respectively.

First, a 125 μm-thick polyethylene terephthalate (PET) film (XG7PL2, Toray Advanced Materials Co., Ltd.), a bar coater, A ₄ paper, a fixed glass plate, an oven, and UV curing equipment were prepared. .

The PET film was cut to a 4 inch (10 × 10) size using a cutting machine and fixed to a fixed glass plate. After selecting the bar coater according to the desired thickness (mostly used are 3, 6, 9, 20, and 22 times), a pipette was used to prepare about 1 mL of each of the multifunctional membranes prepared in Examples 1 to 3 above- The composition for forming and the film forming composition prepared in Comparative Examples 1 and 2, respectively, were dropped on the film and then coated. The coated film was then dried in an oven at 80 ° C. for 10 minutes. At this time, the thickness of the film is 4 ㎛ to 5 ㎛.

The dried film is cured by irradiating ultraviolet (ultra-violet, UV) for 20 mJ / cm ² , 50 seconds (total 1,000 mJ) using a UV curing equipment, and the multi-functional hard coating film of Examples 1 to 3 and The hard coat films of Comparative Examples 1 and 2 were prepared respectively.

At this time, the ultraviolet irradiation is carried out using a medium pressure mercury lamp or a metal halide lamp in a nitrogen atmosphere, it may be irradiated in the range of 500 to 2,000 mJ / cm ² light, for example, the amount of ultraviolet radiation is 500 mJ / cm ² or less, insufficient chemical bonding of the UV fluorinated acrylic oligomer can not secure durability of the anti-fingerprint properties, if the amount of ultraviolet radiation irradiated is 2,000 mJ / cm ² or more, the curing is too advanced to multi-functional hard coating film The hardness of may decrease.

< Multifunctional  hard Of coating film  Characterization>

1. Contact angle measurement: The model name is Phoenix 150, and deionized water was applied to each of the multifunctional hard coating film prepared according to Examples 1 to 3 and the hard coating film prepared according to Comparative Examples 1 and 2, respectively. Drop was dropped and the angle was measured.

2. Hardness: A multi-functional hard coating film prepared according to Examples 1 to 3 and a Pencil (4H) based on each of the hard coating films prepared according to Comparative Examples 1 and 2 were 45 ° to 1 kg load. After fixing with, 5 cm or more was drawn to determine the presence of scratches. If there were some scratches with the naked eye, the measurement was made again using a pencil with a lower grade.

Table 1 below shows the results of measuring the properties of the multi-functional hard coating film according to each of Examples 1 to 3 and the hard coating film according to Comparative Examples 1 and 2, respectively.

A contact angle measurement photograph of the prepared films is shown in FIG. 1, FIG. 1A is a contact angle measurement photograph of a hard coating film prepared according to Comparative Example 1, and FIG. 1B is a contact angle measurement photograph of a hard coating film prepared according to Comparative Example 2, FIG. 1c shows a photograph of the contact angle of the multi-functional hard coating film prepared according to Example 3.

As shown in Table 1 and Figure 1, compared to Comparative Example 1 containing no silica particles and Comparative Example 2 containing TEOS particles not functionalized by the vinyl group, containing the TEOS particles functionalized by the vinyl group Examples 1 to 3, it can be confirmed that both the hardness and the contact angle of the formed multi-functional hard coating film is improved.

As a result of the above, the hard coating film formed by using the multifunctional film-forming composition according to the embodiments, the cross-linking between the vinyl group contained in each of the fluorinated acrylic copolymer and the functionalized silica particles. It was found that the hardness was improved, and the hydrophobicity was improved by the fluorine component contained in the fluorinated acrylic copolymer.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

Claims (20)

Fluorinated acrylic copolymers containing vinyl terminal functional groups; And
Vinyl functionalized silica particles
Comprising a multi-functional film-forming composition.
The method of claim 1,
The functionalized silica particles are nanoparticles, multifunctional film-forming composition.
The method of claim 1,
The functionalized silica particles are functionalized by a vinyl group bonded to the Si element on the surface of the silica particles, or functionalized by the following vinyl group-containing substituent bonded to the Si element or O element on the surface of the silica particles. Functional film-forming composition:
[Vinyl group-containing substituent]

or

;
In the vinyl group-containing substituent, n is an integer of 1 to 5.
The method of claim 1,
The fluorinated acrylic copolymer is represented by the following formula (1), multifunctional film-forming composition:
[Formula 1]

;
In Chemical Formula 1,
R ¹ and R ² are each independently a linear or branched C _1-6 alkyl group substituted by one or more F,
R ³ is a linear or branched C _1-6 alkyl group,
a and b are each independently a positive number.
The method of claim 4, wherein
The fluorinated acrylic copolymer has a molecular weight of 5,000 to 30,000, multifunctional film-forming composition.
The method of claim 4, wherein
Wherein a is a number of 5 to 30, b is a number of 10 to 50, the multifunctional film-forming composition.
The method of claim 1,
The content of the functionalized silica particles, 0.1 to 10 parts by weight based on 100 parts by weight of the multifunctional film-forming composition, multifunctional film-forming composition.
The method of claim 1,
The cross-linking between the fluorinated acrylic copolymer and the vinyl groups contained in the functionalized silica particles, respectively, which is used for forming a multifunctional hard coating layer having an improved hardness. Formation composition.
The method of claim 1,
The multifunctional film-forming composition may have a hardness; And it is used to form a multi-functional hard coating film having at least one functionality selected from the group consisting of anti-fingerprint, adhesive and anti-reflective, multifunctional film-forming composition.
The method of claim 1,
A composition for forming a multifunctional film, further comprising a curable monomer and a curing initiator.
A multifunctional film comprising a coating film formed using the multifunctional film-forming composition of any one of claims 1 to 10.
The method of claim 11,
And a multifunctional hard coating film having improved hardness by crosslinking between the fluorinated acrylic copolymer containing the vinyl terminal functional group and the vinyl groups contained in the silica particles functionalized by the vinyl group, respectively.
The method of claim 11,
The multifunctional membrane has a hardness; And a multifunctional hard coating film having one or more functionalities selected from the group consisting of anti-fingerprint, adhesiveness and antireflection.
A protective film comprising the multifunctional film according to claim 11.
The method of claim 14,
The protective film is hardness; And at least one functional group selected from the group consisting of anti-fingerprint, adhesiveness, and antireflection.
A device comprising the protective film according to claim 14.
The method of claim 16,
Wherein the device comprises a display or a photovoltaic device.
The method of claim 17,
Wherein the display comprises a touch type display or a touch type flexible display.
The method of claim 17,
Wherein the display comprises a liquid crystal display, a light emitting diode display, an organic light emitting diode display, a plasma display, or an electroluminescent display.
The method of claim 17,
Wherein the photovoltaic device comprises a solar cell.

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