WO2022260325A1

WO2022260325A1 - Primer composition, laminated film, and display device

Info

Publication number: WO2022260325A1
Application number: PCT/KR2022/007602
Authority: WO
Inventors: 박준기; 우석종; 조형우; 편승용
Original assignee: 에스케이씨하이테크앤마케팅(주)
Priority date: 2021-06-08
Filing date: 2022-05-27
Publication date: 2022-12-15
Also published as: KR20220165586A

Abstract

A primer composition, according to an embodiment, comprises: an acrylic binder resin; a trifunctional or more polyvalent aziridine-based compound; and a solvent, thereby making it possible to strongly bond a substrate and a hard coating layer.

Description

Primer composition, laminated film and display device

Embodiments relate to primer compositions, laminated films, and display devices.

Polyimide-based resins such as polyamide-imide (PAI) have excellent friction, heat and chemical resistance, and are used as primary electrical insulation, coatings, adhesives, resins for extrusion, heat-resistant paints, heat-resistant plates, and heat-resistant materials. It is applied to adhesives, heat-resistant fibers, and heat-resistant films.

Such polyimide-based resins are utilized in various fields. For example, polyimide-based resin is made in the form of a powder and used as a coating agent for metal or magnet wire, etc., and is mixed with other additives depending on the use. In addition, polyimide-based resin is used as a paint for decoration and anti-corrosion along with fluoropolymer, and serves to adhere the fluoropolymer to a metal substrate. In addition, polyimide-based resin is used to coat kitchen utensils, and is used as a membrane used for gas separation due to its heat resistance and chemical resistance, and filters contaminants such as carbon dioxide, hydrogen sulfide and impurities in natural gas oil wells. Also used for devices.

Recently, a polyimide-based film having excellent optical, mechanical, and thermal properties at a lower cost has been developed by forming a polyimide-based resin into a film.

One embodiment provides a primer composition having excellent optical properties, mechanical properties and bonding properties.

One embodiment provides a laminated film having excellent optical and mechanical properties.

One embodiment provides a display device having excellent optical and mechanical properties.

A primer composition according to embodiments may include an acrylic binder resin; trifunctional or more polyvalent aziridine-based compounds; and a solvent.

A laminated film according to embodiments may include a substrate; a primer layer formed from a primer composition including an acrylic binder resin, a trifunctional or higher polyvalent aziridine-based compound, and a solvent on the substrate; and a hard coating layer formed on the primer layer.

A display device according to embodiments includes a display panel; and a cover window disposed on a viewing surface of the display panel, wherein the cover window includes a primer layer formed from a primer composition including a base material, an acrylic binder resin, a trifunctional or higher polyvalent aziridine compound, and a solvent on the base material; and and a hard coating layer formed on the primer layer.

The primer composition according to the embodiment may include a trifunctional or higher polyvalent aziridine-based compound to improve bonding strength between the substrate and the hard coating layer and improve durability of the laminated film.

By using the trifunctional or higher polyvalent aziridine-based compound together with an acrylic resin, the polymer resin base film and the hard coating layer having antifouling and antistatic properties can be strongly bonded.

Therefore, in the laminated film and display device including the primer layer formed from the primer composition, the hard coating layer is strongly bonded to the substrate and cannot be easily separated by external stimuli, for example, even if applied to a flexible device and repeatedly deformed Bonding between the hard coat layer and the substrate can be effectively maintained.

1 is a schematic exploded view of a display device according to an exemplary embodiment.

2 is a schematic perspective view of a display device according to an exemplary embodiment.

3 is a schematic cross-sectional view of a display device according to an exemplary embodiment.

100: laminated film, 110: hard coating layer, 120: primer layer, 122: first surface, 124: second surface, 130: substrate, 200: display panel

Hereinafter, various implementations and embodiments will be described in detail with reference to the drawings.

In describing the following embodiments, if it is determined that a detailed description of a related known configuration or function may obscure the subject matter, the detailed description will be omitted. In addition, the size of each component in the drawings may be exaggerated or omitted for description, and may differ from the actually applied size.

In this specification, the description that one component is formed above/under another component or is connected or coupled to each other includes all forms, connections, or couplings between these components directly or indirectly through another component. . In addition, it should be understood that the criterion for the top/bottom of each component may vary according to the direction in which the object is observed.

Terms referring to each component in this specification are used to distinguish them from other components, and are not intended to limit the scope of the implementation. Also, in this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

The term "comprising" in this specification is intended to specify specific properties, regions, steps, processes, elements and/or components, and unless otherwise stated, other characteristics, regions, steps, processes, elements and/or components. / or the presence or addition of ingredients is not excluded.

In this specification, terms such as first and second are used to describe various components, and the components should not be limited by the terms. The above terms are used for the purpose of distinguishing one component from another.

In the present specification, "substituted" means deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amido group, a hydrazine group, a hydrazone group, an ester group, unless otherwise specified. , ketone group, carboxyl group, substituted or unsubstituted C ₁ -C ₃₀ alkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₃₀ alkynyl group, substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, substituted or unsubstituted C ₆ -C ₃₀ alicyclic organic group, substituted or unsubstituted C ₄ -C ₃₀ heterocyclic group, substituted or unsubstituted C ₆ -C ₃₀ aryl group and substituted Alternatively, it means one substituted with one or more substituents selected from the group consisting of an unsubstituted C ₄ -C ₃₀ heteroaryl group, and two adjacent substituents may be linked to form a ring.

As is well known, the molecular weight of the compound or polymer described herein, such as number average molecular weight or weight average molecular weight, is a relative mass based on carbon-12 and does not describe the unit, but, if necessary, the same numerical molar mass (g/mol).

프라이머 조성물primer composition

Primer compositions according to embodiments include a binder resin, a trifunctional or higher polyvalent aziridine-based compound, and a solvent.

In some embodiments, the binder resin may include an acrylic resin.

The acrylic resin is an oligomer or polymer having a repeating unit derived from a (meth)acrylic acid-based compound, and may be formed by polymerization of the (meth)acrylic acid-based compound. The (meth)acrylic acid-based compound may include (meth)acrylic acid and derivatives thereof. The (meth)acrylic acid derivative may include, for example, a (meth)acrylic acid ester-based compound. In this specification, "(meth)acrylic acid" includes acrylic acid and methacrylic acid.

For example, the (meth)acrylic acid-based compound may include an ester compound in which (meth)acrylic acid is substituted with an alkyl group having 1 to 12 carbon atoms. For example, the (meth)acrylic acid ester compound is a (meth)acrylic acid ester substituted with an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. It may include, preferably, the number of carbon atoms of the alkyl group substituted in the ester compound may be 1 to 8.

For example, the (meth) acrylic acid compound is ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, (meth) acrylic acid, methyl (meth) acrylate, ethyl methacrylate, n-propyl (meth) )Acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butyl Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, glycidyl ( meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate lactate, 2-hydroxy-n-butyl (meth)acrylate, 3-hydroxy-n-butyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerin mono(meth)acrylate Acrylates, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2 -Hydroxyethyl phthalate, lactone-modified (meth)acrylate having a hydroxyl group at the terminal, and the like may be included, and these may be used alone or in combination of two or more.

The acrylic resin may include a polymer of the (meth)acrylic acid-based compound and a comonomer. The comonomer may include an acrylic compound or a vinyl compound other than the (meth)acrylic acid compound. The acrylic compound may include an ester compound (acrylic ester compound) of carboxylic acid having 4 to 12 carbon atoms and carbon number 2 and carbon number 3 connected by a double bond. For example, the acrylic ester compound is an alkyl ester of crotonic acid, an alkyl ester of isocrotonic acid, an alkyl 2-petenoate, an alkyl 2-hexenoate ( alkyl 2-hexanoate) and the like. The number of carbon atoms of the carboxylic acid may be preferably 4 to 8 or 4 to 6. The alkyl group of the acrylic ester compound may be linear, branched or cyclic, and may have 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms.

Examples of the vinyl compound include acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acrylonitrile, 3-(meth)acryloylpropyltrimethoxysilane, styrene, and α-methylstyrene. , p-methylstyrene, p-methoxystyrene, and the like, which may be used alone or in combination of two or more.

For example, the acrylic resin may include 50 wt% to 97 wt% of the (meth)acrylic acid-based compound and 3 wt% to 50 wt% of the comonomer, based on the total weight of the monomers. The (meth)acrylic acid compound may be included in 60% to 97% by weight, 70% to 97% by weight, 80% to 97% by weight, or 90% to 97% by weight, and the comonomer is 3% by weight % to 40% by weight, 3% to 30% by weight, 3% to 20% by weight or 3% to 10% by weight.

For example, the weight average molecular weight (Mw) of the acrylic resin may be 15,000 to 150,000. Specifically, the weight average molecular weight (MW) of the acrylic resin is 20,000 to 150,000, 30,000 to 150,000, 40,000 to 150,000, 15,000 to 100,000, 20,000 to 100,000, 30,000 to 100,000, 40,000 to 100,000, 15,000 to 80,000, 20,000 to 80,000, 30,000 to 80,000, 40,000 to 80,000, 15,000 to 60,000, 20,000 to 60,000, 30,000 to 60,000 or 40,000 to 60,000.

In some embodiments, the glass transition temperature (Tg) of the acrylic resin is 50 ℃ to 150 ℃, 60 ℃ to 150 ℃, 70 ℃ to 150 ℃, 80 ℃ to 150 ℃, 50 ℃ to 120 ℃, 60 ℃ to 120°C, 70°C to 120°C, 80°C to 120°C, 50°C to 100°C, 60°C to 100°C, 70°C to 100°C, 80°C to 100°C, 50°C to 90°C, 60°C to 90°C °C, 70 °C to 90 °C or 80 °C to 90 °C.

In some embodiments, the acrylic resin may be formed from the (meth)acrylic acid-based compound and the acrylic ester compound, and may not include an acrylic double bond and other functional groups other than an ester group. In this case, compatibility between the acrylic resin and the polyvalent aziridine-based compound to be described later may be improved, and bonding properties of the primer composition may be improved.

In some embodiments, the acrylic resin may be formed from a C ₁ to C ₄ alkyl crotonate and a C ₁ to C ₈ alkyl (meth)acrylate. Preferably, the acrylic resin may be formed from methyl crotonate, methyl (meth)acrylate, butyl (meth)acrylate, octyl methacrylate and 2-ethylhexyl methacrylate.

The polyvalent aziridine-based compound may serve as a curing agent and/or a crosslinking agent of the primer composition.

In some embodiments, the polyvalent aziridine-based compound may include three or more aziridinyl groups (-N(CH ₂ )(CH ₂ )) at the terminal of the molecular structure. For example, the aziridinyl group may improve bonding strength between the substrate and the hard coating layer by cross-linking the binder resin of the primer layer with the polymer component of the substrate and the polymer component of the hard coating layer.

In some embodiments, the polyvalent aziridine-based compound may include a compound in which an aziridinylalkanoate-based moiety and a polyol-based moiety are ester-bonded.

The aziridinyl alkanoate-based residue may be obtained by substituting an aziridinyl group for an alkyl group of the alkanoate-based residue. Preferably, the diziridinyl group may be substituted on a terminal carbon atom of the alkanoate-based residue.

The polyol-based residue may include 2 to 10 hydroxyl groups, preferably 4 to 6 hydroxyl groups. All of the hydroxyl groups of the polyol-based residue may be ester-bonded with the aziridinylalkanoate-based residue, and in some embodiments, some of the hydroxyl groups of the polyol-based residue may remain without esterification. Preferably, when a part of the hydroxyl group remains, the hydroxyl group may be provided as a reaction site to an aziridinyl group of another polyvalent aziridine-based compound. Accordingly, the crosslinking reaction may be promoted, and bonding strength between the layers of the laminated film may be improved.

The polyvalent aziridine-based compound may include a compound represented by Formula I below.

[Formula I]

In Formula I, A is a tetravalent carbon atom or a residue represented by Formula Ia, n, m and l are each independently an integer of 1 to 6, y is an integer of 3 or more, and x+y is A It may be 4 in the case of a carbon atom and 6 in the case of a residue of the following formula (Ia). Preferably, n, m and l may be 1 to 4.

In some implementations, n and m can be the same. l may be greater than n and m, in which case the aziridinyl group of the compound of formula (I) may be relatively free from steric hindrance effects. Accordingly, the crosslinking ability of the compound of formula (I) can be improved.

[Formula Ia]

In Formula Ia, k may be an integer of 1 to 6, preferably, an integer of 1 to 4.

In some embodiments, the acrylic binder resin may be included in an amount of 0.1% to 20% by weight based on the total weight of the composition. Within the above content range, a primer film can be formed with a uniform thickness and strong adhesion can be realized. Preferably, the acrylic binder resin is 0.1% to 10% by weight, 0.1% to 5% by weight, 0.1% to 3% by weight, 0.1% to 2% by weight, 0.5% by weight based on the total weight of the composition. to 20% by weight, 0.5% to 10% by weight, 0.5% to 5% by weight, 0.5% to 3% by weight, or 0.5% to 2% by weight.

In some embodiments, the polyvalent aziridine-based compound may be included in an amount of 0.01% by weight or more and less than 3% by weight based on the total weight of the composition. It is possible to improve the bonding strength between the substrate and the hard coating layer in the above content range. Preferably, the polyhydric aziridine-based compound may be included in an amount of 0.01 wt% to 2.5 wt%, 0.01 wt% to 2 wt%, 0.03 wt% to 2.5 wt%, or 0.03 wt% to 2 wt% based on the total weight of the composition. .

In some embodiments, the polyvalent aziridine-based compound in the primer composition may be included in a smaller amount than the acrylic binder resin. In this case, bonding strength between the substrate and the hard coating layer may be improved.

In some embodiments, the solvent may be included in the remaining amount of the primer composition.

The solvent may include an aprotic polar solvent of at least one of an ether-based compound, a ketone-based compound, and an ester-based compound, or a non-polar solvent including an aromatic hydrocarbon-based compound. The ether-based compound may include an ether compound of a polyol compound, and may include, for example, propylene glycol n-propyl ether (PNP). The ketone-based compound may include methyl isobutyl ketone and the like. The ester-based compound may include an acetate-based compound, for example, n-butyl acetate and the like. The hydrocarbon-based compound may include an aromatic hydrocarbon-based compound, and may include, for example, benzene, toluene, xylene, and the like. Two or more of the exemplified solvents may be used in combination.

적층 필름laminated film

1 to 3 are schematic exploded views, perspective views, and cross-sectional views of a display device according to an embodiment, respectively. FIG. 3 is a cross-sectional view taken along the A-A′ direction of FIG. 2 . Referring to FIGS. 1 to 3 , a display device according to embodiments may include a laminated film 100 and a display panel.

The laminated film 100 may include a substrate 130 , a primer layer 120 formed on the substrate 130 , and a hard coating layer 110 formed on the primer layer 120 . The primer layer 120 may be formed from the above-described primer composition. The primer layer 120 may be directly formed on the substrate 130 , and the hard coating layer 110 may be directly formed on the primer layer 120 .

The substrate 130 may include a polymer film. In some embodiments, the substrate 130 may be a polyester-based resin such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, or polybutylene terephthalate; cellulosic resins such as diacetyl cellulose and triacetyl cellulose; polycarbonate-based resin; acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; styrenic resins such as polystyrene and acrylonitrile-styrene copolymer; polyolefin-based resins such as polyethylene, polypropylene, polyolefins having a cyclo-based or norbornene structure, and ethylene-propylene copolymers; vinyl chloride-based resins; amide resins such as nylon and aromatic polyamide; imide-based resins; polyamideimide-based resins; polyethersulfone-based resins; polyurethane-based resin; sulfone-based resins; polyether ether ketone-based resins; sulfurized polyphenylene-based resins; vinyl alcohol-based resin; vinylidene chloride-based resins; vinyl butyral-based resins; allylate-based resins; polyoxymethylene-based resin; Epoxy-based resins and the like may be included. These may be used alone or in combination of two or more.

The polyimide-based resin may be formed by simultaneously or sequentially reacting reactants including a diamine compound and a dianhydride compound. Specifically, the polyimide-based resin may include a polyimide-based polymer formed by polymerization of a diamine compound and a dianhydride compound. The polyimide-based resin may include an imide repeating unit derived from polymerization of a diamine compound and a dianhydride compound.

The polyimide-based resin may be polymerized by further including a dicarbonyl compound, and may include a polyamide-imide polymer including an amide repeating unit derived from polymerization of the diamine compound and the dicarbonyl compound. can

The diamine compound is not particularly limited, but may be, for example, an aromatic diamine compound containing an aromatic structure. For example, the diamine compound may be a compound represented by Formula 1 below.

In Formula 1,

E is a substituted or unsubstituted divalent C ₆ -C ₃₀ aliphatic ring group, a substituted or unsubstituted divalent C ₄ -C ₃₀ heteroaliphatic ring group, or a substituted or unsubstituted divalent C ₆ -C ₃₀ aromatic ring group , substituted or unsubstituted divalent C ₄ -C ₃₀ heteroaromatic ring group, substituted or unsubstituted C ₁ -C ₃₀ alkylene group, substituted or unsubstituted C ₂ -C ₃₀ alkenylene group, substituted or unsubstituted C ₂ -C ₃₀ Alkynylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, It may be selected from -C(CH ₃ ) ₂ - and -C(CF ₃ ) ₂ -.

e is selected from an integer of 1 to 5, and when e is 2 or more, E may be the same as or different from each other.

(E) _e of Formula 1 may be selected from the groups represented by Formulas 1-1a to 1-14a, but is not limited thereto.

Specifically, (E) _e of Formula 1 may be selected from the groups represented by Formulas 1-1b to 1-13b below, but is not limited thereto:

More specifically, (E) _e in Chemical Formula 1 may be a group represented by Chemical Formula 1-6b.

In one embodiment, the diamine compound may include a compound having a fluorine-containing substituent. Alternatively, the diamine compound may be composed of a compound having a fluorine-containing substituent. In this case, the fluorine-containing substituent may be a fluorinated hydrocarbon group, specifically a trifluoromethyl group, but is not limited thereto.

In one embodiment, the diamine compound may use one type of diamine compound. That is, the diamine compound may be composed of a single component.

For example, the diamine compound is 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-bis (trifluoromethyl) -4,4 having the following structure) '-diaminobiphenyl, TFDB), but is not limited thereto.

Since the dianhydride compound has a low birefringence value, it may contribute to improving optical properties such as transmittance of the film including the polyimide-based resin.

The dianhydride compound is not particularly limited, but may be an aromatic dianhydride compound having an aromatic structure. For example, the aromatic dianhydride compound may be a compound represented by Formula 2 below.

In Formula 2, G is a substituted or unsubstituted tetravalent C ₆ -C ₃₀ aliphatic ring group, a substituted or unsubstituted tetravalent C ₄ -C ₃₀ heteroaliphatic ring group, or a substituted or unsubstituted tetravalent C ₆ -C ₃₀ An aromatic ring group, a substituted or unsubstituted tetravalent C ₄ -C ₃₀ heteroaromatic ring group, and the aliphatic ring group, the heteroaliphatic ring group, the aromatic ring group, or the heteroaromatic ring group exists alone or , bonded to each other to form a condensed ring, a substituted or unsubstituted C ₁ -C ₃₀ alkylene group, a substituted or unsubstituted C ₂ -C ₃₀ alkenylene group, or a substituted or unsubstituted C ₂ -C ₃₀ alkynylene group , -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ - and -C(CF ₃ ) ₂ -.

G in Formula 2 may be selected from groups represented by Formulas 2-1a to 2-9a, but is not limited thereto.

For example, G in Chemical Formula 2 may be a group represented by Chemical Formula 2-8a.

In one embodiment, the dianhydride compound may include a compound having a fluorine-containing substituent. Alternatively, the dianhydride compound may be composed of a compound having a fluorine-containing substituent. In this case, the fluorine-containing substituent may be a fluorinated hydrocarbon group, specifically a trifluoromethyl group, but is not limited thereto.

In another embodiment, the dianhydride compound may consist of one single component or two mixed components.

For example, the dianhydride compound is 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride having the following structure (2,2'-bis- (3,4 -dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA), but is not limited thereto.

Polyamic acid may be produced by polymerization of the diamine compound and the dianhydride compound.

Subsequently, the polyamic acid may be converted into polyimide through a dehydration reaction.

The polyimide may include a repeating unit represented by Formula A below.

In Formula A, descriptions of E, G and e are as described above.

For example, the polyimide may include a repeating unit represented by Formula A-1 below, but is not limited thereto.

In Formula A-1, n may be an integer from 1 to 400.

The dicarbonyl compound is not particularly limited, but may be, for example, a compound represented by Formula 3 below.

In Formula 3,

J is a substituted or unsubstituted divalent C ₆ -C ₃₀ aliphatic ring group, a substituted or unsubstituted divalent C ₄ -C ₃₀ heteroaliphatic ring group, or a substituted or unsubstituted divalent C ₆ -C ₃₀ aromatic ring group , substituted or unsubstituted divalent C ₄ -C ₃₀ heteroaromatic ring group, substituted or unsubstituted C ₁ -C ₃₀ alkylene group, substituted or unsubstituted C ₂ -C ₃₀ alkenylene group, substituted or unsubstituted C ₂ -C ₃₀ Alkynylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, It may be selected from -C(CH ₃ ) ₂ - and -C(CF ₃ ) ₂ -.

j is selected from an integer of 1 to 5, and when j is 2 or more, J may be the same as or different from each other.

X is a halogen atom. Specifically, X may be F, Cl, Br, I or the like. More specifically, X may be Cl, but is not limited thereto.

(J) _j in Chemical Formula 3 may be selected from the groups represented by Chemical Formulas 3-1a to 3-14a, but is not limited thereto.

Specifically, (J) _j in Chemical Formula 3 may be selected from the groups represented by Chemical Formulas 3-1b to 3-8b, but is not limited thereto:

More specifically, (J) _j in Chemical Formula 3 may be a group represented by Chemical Formula 3-1b, a group represented by Chemical Formula 3-2b, or a group represented by 3-3b.

In one embodiment, at least two dicarbonyl compounds that are different from each other may be mixed and used as the dicarbonyl compound. When two or more dicarbonyl compounds are used, two or more dicarbonyl compounds selected from the groups in which (J) _j in Formula 3 are represented by Formulas 3-1b to 3-8b may be used. have.

In another embodiment, the dicarbonyl compound may be an aromatic dicarbonyl compound including an aromatic structure.

For example, the dicarbonyl compound may include a first dicarbonyl compound and/or a second dicarbonyl compound different from the first dicarbonyl compound.

The first dicarbonyl compound and the second dicarbonyl compound may each be an aromatic dicarbonyl compound.

The first dicarbonyl compound and the second dicarbonyl compound may be different aromatic dicarbonyl compounds, but are not limited thereto.

When the first dicarbonyl compound and the second dicarbonyl compound are aromatic dicarbonyl compounds, respectively, since they contain a benzene ring, surface hardness and tensile strength of the film containing the prepared polyamide-imide resin It can contribute to improving mechanical properties such as

The dicarbonyl compound has the following structures: terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), 1'-biphenyl-4,4'-dicarbonyldichloride ( 1,1'-biphenyl-4,4'-dicarbonyl dichloride (BPDC) or a combination thereof, but is not limited thereto.

For example, the first dicarbonyl compound may include BPDC, and the second dicarbonyl compound may include TPC, but are not limited thereto.

Specifically, when BPDC as the first dicarbonyl compound and TPC as the second dicarbonyl compound are appropriately used in combination, the prepared film including the polyamide-imide resin may have high oxidation resistance. have.

Alternatively, the first dicarbonyl compound may include isophthaloyl chloride (IPC), and the second dicarbonyl compound may include TPC, but is not limited thereto.

Specifically, when IPC as the first dicarbonyl compound and TPC as the second dicarbonyl compound are appropriately used in combination, the prepared film including the polyamide-imide resin may have high oxidation resistance. And the manufacturing cost can be reduced.

The diamine compound and the dicarbonyl compound may be polymerized to form a repeating unit represented by Chemical Formula B below.

In Formula B, descriptions of E, J, e and j are as described above.

For example, the diamine compound and the dicarbonyl compound may be polymerized to form amide repeating units represented by Chemical Formulas B-1 and B-2.

In Formula B-1, x is an integer from 1 to 400.

In Formula B-2, y is an integer from 1 to 400.

The polyimide-based film may include a filler.

The filler may be at least one selected from the group consisting of barium sulfate, silica and calcium carbonate. By including the filler, the polyimide-based film can improve roughness and winding properties, as well as improve running properties and scratch improvement effects during film production.

The particle diameter of the filler may be greater than or equal to 0.01 μm and less than 1.0 μm. For example, the particle size of the filler may be 0.05 μm to 0.9 μm or 0.1 μm to 0.8 μm, but is not limited thereto.

The polyimide-based film may include the filler in an amount of 0.01 wt % to 3 wt % based on the total weight of the polyimide-based film. For example, the polyimide-based film may contain the filler in an amount of 0.05 wt% to 2.5 wt%, 0.1 wt% to 2 wt%, or 0.2 wt% to 1.7 wt% based on the total weight of the polyimide-based film. It may include, but is not limited thereto.

According to one embodiment, the haze of the polyimide-based film may be 3% or less. For example, the haze may be 2% or less, 1.5% or less, or 1% or less, but is not limited thereto.

According to one embodiment, the yellow index (YI) of the polyimide-based film may be 5 or less. For example, the yellowness may be 4 or less, 3.8 or less, 2.8 or less, 2.5 or less, 2.3 or less, or 2.1 or less, but is not limited thereto.

According to one embodiment, the modulus of the polyimide-based film may be 5 GPa or more. For example, the modulus may be 5.2 GPa or more, 5.5 GPa or more, 6.0 GPa or more, 10 GPa or less, 5 GPa to 10 GPa, or 7 GPa to 10 GPa, but is not limited thereto.

According to one embodiment, transmittance of the polyimide-based film may be 80% or more. For example, the transmittance may be 85% or more, 88% or more, 89% or more, 80% to 99%, 80% to 99%, or 85% to 99%, but is not limited thereto.

The compressive strength of the polyimide-based film may be 0.4 kgf/㎛ or more. Specifically, the compressive strength may be 0.45 kgf/μm or more or 0.46 kgf/μm or more, but is not limited thereto.

The surface hardness of the polyimide-based film may be greater than or equal to HB. Specifically, the surface hardness may be H or more or 2H or more, but is not limited thereto.

The polyimide-based film may have a tensile strength of 15 kgf/mm ² or more. Specifically, the tensile strength may be 18 kgf/mm ² or more, 20 kgf/mm ² or more, 21 kgf/mm ² or more, or 22 kgf/mm ² or more, but is not limited thereto.

The polyimide-based film may have an elongation of 15% or more. Specifically, the elongation may be 16% or more, 17% or more, or 17.5% or more, but is not limited thereto.

The substrate 130 according to one embodiment may have high oxidation resistance and secure excellent optical properties such as high light transmittance, low haze, and low yellowness (YI). Furthermore, it may have excellent modulus, elongation, tensile properties, and elastic restoring force.

The primer composition may be coated, dried, and cured on the substrate 130 to form the primer layer 120 .

The coating may be performed through a method commonly used in the art, such as die coating.

The drying and curing may be performed by heat treatment at a temperature of 80° C. to 160° C. for 1 minute to 20 minutes. In this case, the primer layer 120 capable of strongly bonding the substrate 130 and the hard coating layer 110 can be formed. Preferably, the temperature condition may be 100° C. to 140° C., and the heat treatment time may be 3 minutes to 12 minutes.

In some implementations, the thickness of the primer layer 120 can be between 20 nm and 200 nm. When the primer layer 120 has the above thickness, bonding strength between the substrate 130 , the primer layer 120 and the hard coating layer 110 may increase. Preferably, the thickness is 20 nm to 190 nm, 20 nm to 180 nm, 20 nm to 160 nm, 20 nm to 130 nm, 20 nm to 120 nm, 20 nm to 110 nm, 20 nm to 80 nm, 30 nm nm to 200 nm, 30 nm to 190 nm, 30 nm to 180 nm, 30 nm to 160 nm, 30 nm to 130 nm, 30 nm to 120 nm, 30 nm to 110 nm, 30 nm to 100 nm or 30 nm to may be 80 nm.

Referring to FIG. 3 , the primer layer 120 includes a first surface 122 and a second surface 124 . The first surface 122 is a surface opposite to the hard coating layer 110 and may be provided as an interface between the primer layer 120 and the hard coating layer 110 .

The second surface 124 is a surface facing the base material 130 , and the second surface 124 may be positioned opposite to a surface where the primer layer 120 and the hard coating layer 110 come into contact. The second surface 124 may serve as an interface between the primer layer 120 and the substrate 130 .

The hard coating layer 110 may be formed by being coated on the primer layer 120 . The hard coating layer 110 may be bonded on the primer layer 120 .

The hard coating layer 110 may include a curable resin. Specifically, the hard coating layer 110 may be a curable coating layer.

The hard coating layer 110 may improve mechanical properties and/or optical properties of the laminated film 100 . The hard coating layer 110 may include functions such as antiglare, antifouling, and antistatic.

The hard coating layer 110 may include an organic resin and/or an additive.

The organic resin may be a curable resin. The organic resin may be a binder resin. The organic resin may include at least one selected from the group consisting of a urethane acrylate-based compound, an acrylic ester-based compound, and an epoxy acrylate-based compound. Preferably, the organic resin may include a urethane acrylate-based compound and an acrylic ester-based compound.

The acrylic ester compound may be at least one selected from the group consisting of substituted or unsubstituted acrylates and substituted or unsubstituted methacrylates.

The acrylic ester-based compound may include 1 to 10 functional groups. The urethane acrylate-based compound may include 2 to 15 functional groups. The epoxy acrylate-based compound may include 1 to 10 functional groups.

Examples of the acrylic ester compound include trimethylolpropane triacrylate (TMPTA), trimethylolpropaneethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA), Or dipentaerythritol hexaacrylate (DPHA) and the like, but are not limited thereto.

The urethane acrylate-based compound includes a urethane bond as a repeating unit and may have a plurality of functional groups. The urethane acrylate-based compound may be one in which a terminal of a urethane compound formed by reacting a diisocyanate compound with a polyol is substituted with an acrylate group.

For example, the diisocyanate compound may include at least one of a straight-chain, branched or cyclic aliphatic diisocyanate compound having 4 to 12 carbon atoms and an aromatic diisocyanate compound having 6 to 20 carbon atoms. The polyol includes 2 to 4 hydroxyl groups (-OH) and may be a straight-chain, branched or cyclic aliphatic polyol compound having 4 to 12 carbon atoms or an aromatic polyol compound having 6 to 20 carbon atoms.

Terminal substitution with the acrylate group may be performed by an acrylate compound having a functional group capable of reacting with an isocyanate group (-NCO). For example, an acrylate compound having a hydroxyl group or an amine group may be used, and a hydroxyalkyl acrylate compound or an aminoalkyl acrylate compound having 2 to 10 carbon atoms may be used.

Examples of the urethane acrylate-based compound include a bifunctional urethane acrylate oligomer having a weight average molecular weight of 1400 to 25000, a trifunctional urethane acrylate oligomer having a weight average molecular weight of 1700 to 16000, a tetrafunctional urethane acrylate oligomer having a weight average molecular weight of 500 to 2000, 15 of hexafunctional urethane acrylate oligomers having a weight average molecular weight of 818 to 2600, 9 functional urethane acrylate oligomers having a weight average molecular weight of 2500 to 5500, 10 functional urethane acrylate oligomers having a weight average molecular weight of 3200 to 3900 or weight average molecular weights of 2300 to 20000 functional urethane acrylate oligomers and the like, but are not limited thereto.

In some embodiments, the glass transition temperature (Tg) of the urethane acrylate compound is -80 ° C to 100 ° C, -80 ° C to 90 ° C, -80 ° C to 80 ° C, -80 ° C to 70 ° C, -80 ℃ to 60 ℃, -70 ℃ to 100 ℃, -70 ℃ to 90 ℃, -70 ℃ to 80 ℃, -70 ℃ to 70 ℃, -70 ℃ to 60 ℃, -60 ℃ to 100 ℃, -60 ℃ to 90℃, -60℃ to 80℃, -60℃ to 70℃, -60℃ to 60℃, -50℃ to 100℃, -50℃ to 90℃, -50℃ to 80℃, -50℃ to 70°C or -50°C to 60°C.

Examples of the epoxy acrylate-based compound include a monofunctional epoxy acrylate oligomer having a weight average molecular weight of 100 to 300, a bifunctional epoxy acrylate oligomer having a weight average molecular weight of 250 to 2000, a tetrafunctional epoxy acrylate oligomer having a weight average molecular weight of 1000 to 3000, and the like. It may include, but is not limited thereto.

The weight average molecular weight (Mw) of the acrylic ester compound is about 500 to about 6,000, about 500 to about 5,000, about 500 to about 4,000, 1000 to about 6,000, about 1000 to about 5,000, about 1000 to about 4,000, 1500 to about 6,000, about 1500 to about 5,000 or about 1500 to about 4,000.

The acrylate equivalent weight of the acrylic ester compound is about 50 g/eq to about 300 g/eq, about 50 g/eq to about 200 g/eq, or about 50 g/eq to about 150 g/eq. may be in the range of

The epoxy equivalent weight of the epoxy acrylate-based compound is about 50 g/eq to about 300 g/eq, about 50 g/eq to about 200 g/eq, or about 50 g/eq to about 150 g/eq. may be in the range of

The content of the organic resin may be 30 wt% to 100 wt% based on the total weight of the hard coating layer 110 . Specifically, the content of the organic resin may be 40% to 90% by weight or 50% to 80% by weight based on the total weight of the hard coating layer 110 .

The hard coating layer 110 may optionally include a filler. Examples of the filler include silica, barium sulfate, zinc oxide or alumina. The particle diameter of the filler may be 1 nm to 100 nm. Specifically, the particle diameter of the filler may be 5 nm to 50 nm or 10 nm to 30 nm.

The filler may include inorganic fillers having different particle diameter distributions. For example, the filler may include a first inorganic filler having a d50 of 20 nm to 35 nm and a second inorganic filler having a d50 of 40 nm to 130 nm.

The content of the filler may be about 25% by weight or more, about 30% by weight or more, or about 35% by weight or more based on the total weight of the functional layer. In addition, the content of the filler may be about 50 wt% or less, about 45 wt% or less, or about 40 wt% or less based on the total weight of the functional layer.

Preferably, the hard coating layer 110 may not include an inorganic filler such as silica. In this case, for example, bonding strength between the base layer and the hard coating layer having the above composition may be improved.

The hard coating layer 110 may further include a photoinitiator.

Examples of the photoinitiator include 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1-[4-(2-hydroxyethoxy ) Phenyl] -2-methyl-1-propanone, methylbenzoyl formate, α, α-dimethoxy-α-phenylacetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4- Morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone diphenyl (2,4, 6-trimethylbenzoyl)-phosphine oxide, or bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like, but are not limited thereto. In addition, commercial products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, Esacure KIP 100F, and the like. The photoinitiator may be used alone or in combination of two or more different types.

In some embodiments, the hard coating layer 110 may include at least one of an antifouling additive and an antistatic agent.

The antifouling additive may include a fluorine-substituted acrylate-based compound. For example, the antifouling additive may include an acrylate-based compound including a perfluoroalkyl group such as (perfluorohexyl)ethyl acrylate.

The antistatic agent may include an ionic surfactant. For example, the ionic surfactant may include an ammonium salt or a quaternary alkylammonium salt, and the ammonium salt and quaternary alkylammonium salt may include a halide such as chloride or bromide.

In Comparative Example, when the primer layer according to the embodiments is not included, the hard coating layer having antifouling and antistatic properties provided by the antifouling additive and the antistatic agent has adhesive strength with a substrate (in particular, a polyimide-based film). This may be low, and thus, when the laminated film is deformed or subjected to an external stimulus, the hard coat layer can be easily separated from the substrate.

In the case of the laminated film 100 according to embodiments, as the above-described primer layer 120 is included, bonding strength between the base film and the hard coating layer having antifouling and antistatic properties may be improved.

The hard coating layer 110 may include other additives such as a surfactant, a UV absorber, a UV stabilizer, an anti-yellowing agent, a leveling agent, or a dye for improving a color value. In addition, the content of the additive may be variously adjusted within a range that does not degrade the physical properties of the hard coating layer 110. For example, the content of the additive may be included in about 0.01 wt% to about 10 wt% based on the hard coating layer 110, but is not limited thereto.

The surfactant may be a mono- or bifunctional fluorine-based acrylate, a fluorine-based surfactant, or a silicone-based surfactant. The surfactant may be included in a dispersed or cross-linked form in the hard coating layer 110 .

Examples of the UV absorber include benzophenone-based compounds, benzotriazole-based compounds, and triazine-based compounds, and examples of the UV stabilizer include tetramethyl piperidine.

The hard coating layer 110 may be formed by applying a hard coating composition on the primer layer 120, drying, and curing.

The hard coating composition may include the aforementioned organic resin, photoinitiator, antifouling additive, antistatic agent, other additives and/or solvent.

Examples of the organic solvent include alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, and butanol; alkoxy alcohol solvents such as 2-methoxyethanol, 2-ethoxyethanol, and 1-methoxy-2-propanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, and cyclohexanone; Propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monopropyl ether ether solvents such as diethyl glycol monobutyl ether and diethylene glycol-2-ethylhexyl ether; aromatic solvents such as benzene, toluene, and xylene; etc. can be used individually or in mixture.

The content of the organic solvent is not particularly limited as it can be variously adjusted within a range that does not degrade the physical properties of the coating composition, but with respect to the solid content among the components included in the hard coating composition, the solid content: organic solvent weight ratio is about 30:70 to about 99:1. When the organic solvent is within the above range, appropriate fluidity and coating properties may be obtained.

The hard coating composition may include 10% to 30% by weight of an organic resin, 0.1% to 5% by weight of a photoinitiator, 0.01% to 2% by weight of an antifouling additive, and 0.1% to 10% by weight of an antistatic agent. can According to the above composition, the mechanical properties and antifouling and antistatic properties of the hard coating layer 110 can be improved together.

The hard coating composition is a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a micro gravure coating method, a comma coating method, a slot die coating method, a lip coating method, or a solution casting method It may be applied on the primer layer 120 through the like.

Thereafter, the organic solvent included in the hard coating composition may be removed through a drying process. The drying process may be performed at a temperature of 40°C to 100°C, preferably 40°C to 80°C, 50°C to 100°C, or 50°C to 80°C, for about 1 minute to 20 minutes, preferably 1 minutes to 10 minutes or 1 to 5 minutes.

Then, the hard coating composition layer may be cured by light and/or heat.

The cured hard coating layer 110 has a thickness of about 2 μm or more, or about 3 μm or more, for example, about 2 μm to about 20 μm, about 2 μm to about 15 μm, about 2 μm to about 10 μm, or about 3 μm to about 3 μm. It may have a thickness of about 10 μm.

In some embodiments, the laminated film may have a cross hatch adhesion test result value measured according to JIS K 5600 of 50/100 or more, 70/100 or more, 80/100 or more, 90/100 or more, or 95/100 or more. have.

디스플레이 장치display device

1 to 3 are schematic exploded views, perspective views, and cross-sectional views of a display device according to an embodiment, respectively. Referring to FIGS. 1 to 3 , a display device according to embodiments may include a laminated film 100 and a display panel 200 . The laminated film 100 may be provided as a cover window of a display device. The laminated film (cover window: 100) may be disposed on the viewer side with respect to the display panel 200 to protect the display panel 200.

In some embodiments, when the antifouling additive and the antistatic agent are included in the hard coating layer 110, the display device may have antifouling and antistatic properties, and the above-described primer layer 120 is the hard coating layer 110 When formed between the substrate 130 and the antifouling/antistatic hard coating layer and the substrate are strongly bonded, a display device having durability even when repeatedly deformed can be provided.

The display panel 200 is a device capable of displaying an image and may have a flexible characteristic.

The display panel 200 may be, for example, a liquid crystal display panel or an organic light emitting display panel. Specifically, the organic light emitting display panel may include a front polarizer and an organic EL panel, but is not limited thereto.

The front polarizing plate may be disposed on the front surface of the organic EL panel. Specifically, the front polarizing plate may be attached to a surface of the organic EL panel on which an image is displayed.

The organic EL panel displays an image by self-emission in pixel units. The organic EL panel may include an organic EL substrate and a driving substrate. The organic EL substrate may include a plurality of organic electroluminescent units each corresponding to a pixel. Specifically, each may include a cathode, an electron transport layer, a light emitting layer, a hole transport layer, and an anode. The driving substrate may be drivingly coupled to the organic EL substrate. That is, the driving substrate is coupled to apply a driving signal such as a driving current to the organic EL substrate, so that the organic EL substrate can be driven by applying a current to each of the organic electroluminescent units.

According to one embodiment, an adhesive layer may be included between the display panel 200 and the laminated film 100 . The adhesive layer may be an optically transparent adhesive layer, and is not particularly limited.

The above will be described in more detail by the following examples. However, the following examples are only for illustrating the invention, and the scope of the examples is not limited only to these.

제조예 1: 프라이머 조성물의 제조Preparation Example 1: Preparation of Primer Composition

A primer composition was prepared by mixing each component according to the composition shown in Table 1 below.

구분division	성분ingredient	중량%weight%
용매menstruum	프로필렌 글리콜 n-프로필 에테르(PNP)Propylene glycol n-propyl ether (PNP)	66.05%66.05%
	메틸 이소부틸 케톤(Methyl isobutyl ketone)Methyl isobutyl ketone	28.31%28.31%
	자일렌(Xylene)Xylene	1.01%1.01%
	n-부틸 아세테이트(n-Butyl acetate)n-Butyl acetate	2.63%2.63%
바인더bookbinder	아크릴계 수지acrylic resin	1.96%1.96%
다가 아지리딘계 화합물Polyvalent aziridine-based compound	펜타에리트리톨 트리스(3-아지리딘-1-일프로피오네이트) [Pentaerythritol tris(3-aziridin-1-ylpropionate)]Pentaerythritol tris(3-aziridin-1-ylpropionate) [Pentaerythritol tris(3-aziridin-1-ylpropionate)]	0.04%0.04%
아크릴계 수지: 메틸 크로토네이트/메틸 메타크릴레이트/부틸 아크릴레이트/옥틸 메타크릴레이트/2-에틸헥실 메타크릴레이트의 공중합체, Mw: 약 50,000, Tg: 85℃Acrylic resin: copolymer of methyl crotonate/methyl methacrylate/butyl acrylate/octyl methacrylate/2-ethylhexyl methacrylate, Mw: about 50,000, Tg: 85°C

제조예 2 내지 6Preparation Examples 2 to 6

A primer composition was prepared in the same manner as in Preparation Example 1, except that the content of pentaerythritol tris(3-aziridin-1-ylpropionate) in the primer composition was adjusted as shown in Table 2 below. The content of the solvent was decreased by the increase in the content of pentaerythritol tris(3-aziridin-1-ylpropionate) in the composition.

구 분division	제조예 2Preparation Example 2	제조예 3Preparation Example 3	제조예 4Production Example 4	제조예 5Preparation Example 5	제조예 6Preparation Example 6
펜타에리트리톨 트리스(3-아지리딘-1-일프로피오네이트)의 함량(중량%)Content of pentaerythritol tris(3-aziridin-1-ylpropionate) (% by weight)	1.5%1.5%	2.0%2.0%	2.5%2.5%	3.0%3.0%	3.5%3.5%

제조예 7: 하드코팅 조성물의 제조Preparation Example 7: Preparation of hard coating composition

A hard coating composition was prepared by mixing each component in the composition shown in Table 3 below.

구 분division	성분ingredient	중량%weight%
용매menstruum	이소프로필 알코올(Isopropyl alcohol)Isopropyl alcohol	5.00%5.00%
	에탄올(Ethanol)Ethanol	32.50%32.50%
	메틸 이소부틸 케톤(Methyl isobutyl ketone)Methyl isobutyl ketone	25.00%25.00%
	프로필렌글리콜 메틸 에테르(Propylene glycol methyl ether)Propylene glycol methyl ether	12.50%12.50%
유기 수지organic resin	우레탄 아크릴레이트 Urethane Acrylate	13.50%13.50%
유기 수지organic resin	아크릴 에스테르acrylic ester	9.12%9.12%
광개시제photoinitiator	1-하이드록시사이클로헥실 페닐 케톤(1-Hydroxycyclohexyl phenyl ketone)1-Hydroxycyclohexyl phenyl ketone	1.13%1.13%
방오 첨가제antifouling additives	(퍼플로로헥실)에틸 아크릴레이트[(Perfluorohexyl)ethyl acrylate](Perfluorohexyl)ethyl acrylate [(Perfluorohexyl)ethyl acrylate]	0.11%0.11%
대전방지제antistatic agent	4급 암모늄 염화물quaternary ammonium chloride	1.13%1.13%
우레탄 아크릴레이트: Miramer MU9800(미원 스페셜티 케미칼)아크릴 에스테르: Miramer PS3010(미원 스페셜티 케미칼)Urethane Acrylate: Miramer MU9800 (Miwon Specialty Chemical) Acrylic Ester: Miramer PS3010 (Miwon Specialty Chemical)

제조예 8 내지 10Preparation Examples 8 to 10

A hard coating composition was prepared in the same manner as in Preparation Example 7, except that urethane acrylate and acrylic ester were respectively changed to the compounds shown in Table 4 below.

	제조예 7Preparation Example 7	제조예 8Preparation Example 8	제조예 9Preparation Example 9	제조예 10Preparation Example 10
우레탄 아크릴레이트Urethane Acrylate	Miramer MU9800Miramer MU9800	Miramer PU340(미원 스페셜티 케미칼)Miramer PU340 (Miwon Specialty Chemical)	Miramer PU320(미원 스페셜티 케미칼)Miramer PU320 (Miwon Specialty Chemical)	Miramer SC2152(미원 스페셜티 케미칼)Miramer SC2152 (Miwon Specialty Chemical)
아크릴 에스테르acrylic ester	Miramer PS3010Miramer PS3010	Photocryl DP344(미원 스페셜티 케미칼)Photocryl DP344 (Miwon Specialty Chemical)	Miramer P261(미원 스페셜티 케미칼)Miramer P261 (Miwon Specialty Chemical)	Miramer PS3010(미원 스페셜티 케미칼)Miramer PS3010 (Miwon Specialty Chemical)

실시예 1 내지 9: 적층 필름의 제조Examples 1 to 9: Preparation of laminated films

The primer compositions of Preparation Examples 1 to 6 were applied on one surface of a transparent polyimide film (manufactured by SKC) having a thickness of about 30 to 80 μm by a die coating method. Heat treatment was performed at about 120° C. for about 6 minutes to dry the solvent and curing was performed to form a primer layer having a thickness of about 70 to 90 nm.

The hard coating compositions of Preparation Examples 7 to 10 were applied on the primer layer by a die coating method. The applied composition was dried at about 120° C. for about 6 minutes and cured by applying a total energy of about 1 J/cm ² through UV with a wavelength of 375 nm to form a hard coating layer having a thickness of about 5 μm.

실시예 10 내지 13Examples 10 to 13

A laminated film was prepared in the same manner as in Example 1, except that the thickness of the primer layer was changed as shown in Table 5 below.

구분division	실시예 1Example 1	실시예 7Example 7	실시예 8Example 8	실시예 9Example 9	실시예 10Example 10
코팅 두께coating thickness	73 nm73 nm	36 nm36 nm	120 nm120 nm	156 nm156 nm	182 nm182 nm

실시예 14 내지 17Examples 14 to 17

Laminated films were prepared in the same manner as in Examples 1 to 4, except that a polyethylene terephthalate film (TU94, 50 μm thick; manufactured by SKC) having a thickness of about 40 μm was used as the primer composition instead of the polyimide film.

비교예comparative example

thickness 73 The hard coating composition of Preparation Example 7 was directly applied on one surface of a ㎛ transparent polyimide film by a die coating method, and the coated composition was dried at about 120 ° C. for about 6 minutes, and a total of about 1 A laminated film in which a hard coating layer was laminated was prepared by curing by applying energy of J/cm ² .

실험예: 크로스 해치 접착력 테스트Experimental Example: Cross Hatch Adhesion Test

Adhesion tests were conducted on the laminated films of Examples and Comparative Examples according to JIS K 5600 using a cross hatch adhesion tester (Elcometer, 107-1542).

Specifically, sheaths were formed in two directions orthogonal to each other on the surface of the sample on which the hard coating layer was formed using a cross hatch cutter to form 10 x 10 cutting units. An adhesive tape (Nitto, 31B) was attached so as to cover all of the cutting units, and the tape was peeled off at a speed of about 2500 mm/min or more in the 90 ^° direction. The number of cut units remaining without being peeled off by the tape among the total cut units was evaluated as a ratio and shown in Table 6 below.

구분division	기재write	프라이머층의 조성Composition of the primer layer	프라이머층의 두께(nm)Thickness of primer layer (nm)	하드코팅층 조성Composition of hard coat layer	크로스 해치 접착력cross hatch adhesion
실시예 1Example 1	PIPI	제조예 1Preparation Example 1	7373	제조예 7Preparation Example 7	100/100100/100
실시예 2Example 2	PIPI	제조예 2Preparation Example 2	7373	제조예 7Preparation Example 7	100/100100/100
실시예 3Example 3	PIPI	제조예 3Preparation Example 3	7373	제조예 7Preparation Example 7	100/100100/100
실시예 4Example 4	PIPI	제조예 4Production Example 4	7373	제조예 7Preparation Example 7	100/100100/100
실시예 5Example 5	PIPI	제조예 5Preparation Example 5	7373	제조예 7Preparation Example 7	80/10080/100
실시예 6Example 6	PIPI	제조예 6Preparation Example 6	7373	제조예 7Preparation Example 7	50/10050/100
실시예 7Example 7	PIPI	제조예 1Preparation Example 1	7373	제조예 8Preparation Example 8	100/100100/100
실시예 8Example 8	PIPI	제조예 1Preparation Example 1	7373	제조예 9Preparation Example 9	100/100100/100
실시예 9Example 9	PIPI	제조예 1Preparation Example 1	7373	제조예 10Preparation Example 10	100/100100/100
실시예 10Example 10	PIPI	제조예 1Preparation Example 1	3636	제조예 7Preparation Example 7	100/100100/100
실시예 11Example 11	PIPI	제조예 1Preparation Example 1	120120	제조예 7Preparation Example 7	95/10095/100
실시예 12Example 12	PIPI	제조예 1Preparation Example 1	156156	제조예 7Preparation Example 7	80/10080/100
실시예 13Example 13	PIPI	제조예 1Preparation Example 1	182182	제조예 7Preparation Example 7	70/10070/100
실시예 14Example 14	PETPET	제조예 1Preparation Example 1	7373	제조예 7Preparation Example 7	100/100100/100
실시예 15Example 15	PETPET	제조예 2Preparation Example 2	7373	제조예 7Preparation Example 7	100/100100/100
실시예 16Example 16	PETPET	제조예 3Preparation Example 3	7373	제조예 7Preparation Example 7	100/100100/100
실시예 17Example 17	PETPET	제조예 4Production Example 4	7373	제조예 7Preparation Example 7	100/100100/100
비교예comparative example	PIPI	--	--	제조예 7Preparation Example 7	0/1000/100

Referring to Table 6, in the case of laminated films of Examples including a primer layer prepared by including a trifunctional or higher polyvalent aziridine-based compound, the polyamide-based base film and the hard coating layer having antifouling and antistatic performance are strongly adhered. It was confirmed that there is

Specifically, when the thickness of the primer layer was 200 nm or less, it was confirmed to have excellent adhesive strength, and when the content of the trifunctional or higher polyvalent aziridine-based compound in the primer composition was less than 3% by weight, it was confirmed that the adhesive strength was improved.

Claims

acrylic binder resin;

trifunctional or more polyvalent aziridine-based compounds; and

A primer composition comprising a solvent.
According to claim 1,

The polyvalent aziridine-based compound comprises three or more aziridinyl groups at the terminal of the molecular structure, the primer composition.
According to claim 1,

The polyvalent aziridine-based compound includes a compound in which an aziridinyl alkanoate-based residue and a polyol-based residue are ester-bonded, the primer composition.
According to claim 1,

The polyvalent aziridine-based compound comprises a compound represented by Formula I below, a primer composition:

[Formula I]

In Formula I, A is a tetravalent carbon atom or a residue represented by Formula Ia, n, m and l are each independently an integer of 1 to 6, y is an integer of 3 or more, and x+y is A 4 for a carbon atom and 6 for a moiety of formula Ia;

[Formula Ia]

In the above formula (Ia), k is an integer from 1 to 6.
According to claim 1,

A primer composition comprising 0.1% to 20% by weight of the acrylic binder resin and 0.01% by weight or more and less than 3% by weight of the polyvalent aziridine-based compound based on the total weight of the composition.
According to claim 1,

Wherein the solvent comprises a non-polar solvent containing at least one aprotic polar solvent or an aromatic hydrocarbon-based compound selected from among ether-based compounds, ketone-based compounds and ester-based compounds.
write;

a primer layer formed from a primer composition including an acrylic binder resin, a trifunctional or higher polyvalent aziridine-based compound, and a solvent on the substrate; and

A laminated film comprising a hard coating layer formed on the primer layer.
According to claim 7,

The hard coating layer comprises at least one of a urethane acrylate-based compound and an acrylic ester-based compound, the laminated film.
According to claim 7,

Wherein the hard coating layer includes at least one of an antifouling additive and an antistatic agent.
According to claim 9,

The antifouling additive comprises a fluorine-substituted acrylate-based compound, the laminated film.
According to claim 9,

Wherein the antistatic agent comprises an ionic surfactant.
According to claim 9,

The thickness of the primer layer is 20 nm to 200 nm, the laminated film.
According to claim 9,

A laminated film having a cross hatch adhesion test result value of 50/100 or more measured according to JIS K 5600.
display panel; and

A cover window disposed on the viewing surface of the display panel;

The cover window includes a substrate, a primer layer formed from a primer composition containing an acrylic binder resin, a trifunctional or more polyvalent aziridine-based compound and a solvent on the substrate, and a hard coating layer formed on the primer layer. Display device.