KR102670959B1 - Primer composition, laminated film, and display device - Google Patents

Abstract

The primer composition according to the embodiment includes a binder resin, a trifunctional or higher polyvalent aziridine-based compound, and a solvent, and can strongly bond the substrate and the hard coating layer.

Description

Primer composition, laminated film, and display device {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 insulators, coatings, adhesives, extrusion resins, heat-resistant paints, heat-resistant plates, and heat-resistant materials. It is applied to adhesives, heat-resistant fibers, and heat-resistant films.

These polyimide resins are used in various fields. For example, polyimide resin is made in powder form and used as a coating agent for metals or magnet wires, and is mixed with other additives depending on the purpose. In addition, polyimide resin is used together with fluoropolymer as a paint for decoration and corrosion prevention, and serves to adhere the fluoropolymer to the metal substrate. Polyimide resin is also used to coat kitchen utensils, and because it has heat- and chemical-resistance characteristics, it is also used as a membrane for gas separation, and is used to filter contaminants such as carbon dioxide, hydrogen sulfide, and impurities in natural gas wells. It is also used in devices.

Recently, polyimide-based films that are less expensive and have excellent optical, mechanical, and thermal properties have been developed by converting polyimide-based resins into films.

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

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

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

Primer compositions according to embodiments include an acrylic binder resin; trifunctional or more polyvalent aziridine-based compounds; and solvent.

Laminated films according to embodiments include a substrate; A primer layer formed on the substrate from a primer composition containing an acrylic binder resin, a trifunctional or more polyvalent aziridine-based compound, and a solvent; 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 the viewing surface of the display panel, wherein the cover window includes a substrate, a primer layer formed on the substrate from a primer composition including an acrylic binder resin, a trifunctional or higher polyvalent aziridine compound, and a solvent. and a hard coating layer formed on the primer layer.

The primer composition according to the embodiment includes a trifunctional or more polyvalent aziridine-based compound, and can improve the adhesion between the substrate and the hard coating layer and improve the durability of the laminated film.

By using the trifunctional or more polyvalent aziridine-based compound with an acrylic resin, it is possible to strongly bond a polymer resin base film and a hard coating layer with antifouling and antistatic properties.

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 may not be easily separated by external stimuli, for example, even if applied to a flexible device and repeatedly deformed. Bonding between the hard coating layer and the substrate can be effectively maintained.

1 is a schematic exploded view of a display device according to one implementation.
Figure 2 is a schematic perspective view of a display device according to one implementation.
Figure 3 is a schematic cross-sectional view of a display device according to one implementation.

Hereinafter, the present invention will be described in detail through implementation examples. The embodiment is not limited to the content disclosed below and may be modified into various forms as long as the gist of the invention is not changed.

In this specification, when each film, window, panel, or layer is described as being formed “on” or “under” each film, window, panel, or layer, “on” “(on)” and “under” include those formed “directly” or “indirectly” through other components. In addition, the standards for the top and bottom of each component are explained based on the drawings. The size of each component in the drawings may be exaggerated for explanation and does not indicate the actual size.

In this specification, “includes” means that other components may be further included unless otherwise specified.

All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification should be understood as being modified by the term “about” in all cases unless otherwise specified.

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 only for the purpose of distinguishing one component from another.

In addition, in this specification, unless otherwise specified, "substituted" means deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine group, Hydrazone group, ester group, ketone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alicyclic oil means substituted with one or more substituents selected from the group consisting of a group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group, and the substituents listed above are connected to each other. A ring can be formed.

primer 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 polymerizing the (meth)acrylic acid-based compound. The (meth)acrylic acid-based compound may include (meth)acrylic acid and its derivatives. The derivative of (meth)acrylic acid may include, for example, a (meth)acrylic acid ester-based compound. As used herein, “(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-based compound is a (meth)acrylic acid ester substituted with an alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. It may include, and preferably, the alkyl group substituted in the ester compound may have 1 to 8 carbon atoms.

For example, the (meth)acrylic acid-based compounds include ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, (meth)acrylic acid, methyl (meth)acrylate, ethyl methacrylate, and n-propyl (meth)acrylate. ) 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, dicyclofentanyl (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 Latex, 2-hydroxy-n-butyl (meth)acrylate, 3-hydroxy-n-butyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, glycerin mono (meth) Acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-(meth)acryloyloxyethyl-2 -May include hydroxyethyl phthalate, lactone-modified (meth)acrylate having a hydroxyl group at the terminal, etc., 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 excluding the (meth)acrylic acid-based compound. The acrylic compound may include an ester compound (acrylic ester compound) of a carboxylic acid having 4 to 12 carbons and carbons 2 and 3 connected by a double bond. For example, the acrylic ester compound includes alkyl ester of crotonic acid, alkyl ester of isocrotonic acid, alkyl 2-petenoate, and alkyl 2-hexenoate ( Alkyl 2-hexanoate), etc. The carboxylic acid may preferably have 4 to 8 carbon atoms or 4 to 6 carbon atoms. 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 compounds include acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acrylonitrile, 3-(meth)acryloylpropyltrimethoxysilane, styrene, and α-methylstyrene. , p-methylstyrene, p-methoxystyrene, etc., and these may be used alone or in combination of two or more.

For example, the acrylic resin may include 50 to 97% by weight of the (meth)acrylic acid-based compound and 3 to 50% by weight of the comonomer, based on the total weight of monomers. The (meth)acrylic acid-based compound may be included in an amount of 60 to 97 wt%, 70 to 97 wt%, 80 to 97 wt%, or 90 to 97 wt%, and the comonomer may be included in an amount of 3 to 40 wt%, or 3 to 30 wt%. %, 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 g/mol. Specifically, the weight average molecular weight (Mw) of the acrylic resin is 20,000 to 150,000 g/mol, 30,000 to 150,000 g/mol, 40,000 to 150,000 g/mol, 15,000 to 100,000 g/mol, 20,000 to 100,000 g/mol, 000 to 100,000 g/mol, 40,000 to 100,000 g/mol, 15,000 to 80,000 g/mol, 20,000 to 80,000 g/mol, 30,000 to 80,000 g/mol, 40,000 to 80,000 g/mol, 15,000 to 60,00 0 g/mol, from 20,000 It may be 60,000 g/mol, 30,000 to 60,000 g/mol or 40,000 to 60,000 g/mol.

In some embodiments, the glass transition temperature (Tg) of the acrylic resin is 50 to 150 °C, 60 to 150 °C, 70 to 150 °C, 80 to 150 °C, 50 to 120 °C, 60 to 120 °C, 70 to It can be 120°C, 80 to 120°C, 50 to 100°C, 60 to 100°C, 70 to 100°C, 80 to 100°C, 50 to 90°C, 60 to 90°C, 70 to 90°C or 80 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 contain any functional groups other than an acrylic double bond and an ester group. In this case, the compatibility between the acrylic resin and the polyvalent aziridine-based compound described later can be improved, and the bonding characteristics of the primer composition can be improved.

In some embodiments, the acrylic resin may be formed from C ₁ to C ₄ alkyl crotonate and 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 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 ends of the molecular structure. For example, the aziridinyl group can improve the adhesion between the substrate and the hard coating layer by crosslinking the binder resin of the primer layer, 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 aziridinyl alkanoate-based moiety and a polyol-based moiety are ester bonded.

The aziridinyl alkanoate-based residue may be one in which an aziridinyl group is substituted for the alkyl group of the alkanoate-based residue. Preferably, the iziridinyl group may be substituted on the 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 hydroxy groups of the polyol-based residue may be ester bonded to the aziridinyl alkanoate-based residue, and in some embodiments, some of the hydroxy groups of the polyol-based residue may remain without ester bonding. Preferably, when a part of the hydroxy group remains, the hydroxy group may serve as a reaction site for the aziridinyl group of another polyvalent aziridine-based compound. Therefore, the crosslinking reaction can be promoted and the bonding strength between each layer of the laminated film can be improved.

The polyvalent aziridine-based compound may include a compound represented by the following formula (1).

[Formula 1]

In Formula 1, A is a tetravalent carbon atom or a residue represented by the following Formula 2, 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 In the case of a carbon atom, it may be 4, and in the case of a residue of the following formula (2), it may be 6. Preferably, n, m and l may be 1 to 4.

In some implementations, n and m can be the same. l may be larger than n and m, and in this case, the aziridinyl group of the compound of Formula 1 may be relatively free from steric hindrance effects. Therefore, the crosslinking ability of the compound of Formula 1 can be improved.

[Formula 2]

In Formula 2, k may be an integer of 1 to 6, and preferably, may be 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 to a uniform thickness and strong adhesion can be achieved. 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 to 20% by weight, and 0.5 to 10% by weight based on the total weight of the composition. , 0.5 to 5% by weight, 0.5 to 3% by weight, or 0.5 to 2% by weight.

In some embodiments, the polyhydric 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. Within the above content range, the adhesion between the substrate and the hard coating layer can be improved. Preferably, the polyvalent aziridine-based compound may be included in an amount of 0.01 to 2.5% by weight, 0.01 to 2% by weight, 0.03 to 2.5% by weight, or 0.03 to 2% by weight 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, the adhesion between the substrate and the hard coating layer can 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, for example, propylene glycol n-propyl ether (PNP), etc. The ketone-based compound may include methyl isobutyl ketone, etc. The ester-based compound may include an acetate-based compound, for example, n-butyl acetate. The hydrocarbon-based compound may include an aromatic hydrocarbon-based compound, for example, benzene, toluene, xylene, etc. Two or more of the exemplified solvents may be used in mixture.

laminated film

1 to 3 are schematic exploded views, perspective views, and cross-sectional views, respectively, of a display device according to an implementation example. Figure 3 is a cross-sectional view taken along the A-A' direction of Figure 2. Referring to FIGS. 1 to 3 , display devices according to implementation examples 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. Primer layer 120 may be formed from the primer composition described above. The primer layer 120 may be formed directly on the substrate 130, and the hard coating layer 110 may be formed directly on the primer layer 120.

The substrate 130 may include a polymer film. In some embodiments, the substrate 130 is a polyester resin such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; polycarbonate-based resin; Acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; Styrene-based resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin-based resins such as polyethylene, polypropylene, polyolefins with cyclo- or norbornene structures, and ethylene-propylene copolymers; Vinyl chloride-based resin; Amide resins such as nylon and aromatic polyamide; Imide-based resin; Polyamideimide-based resin; polyethersulfone-based resin; polyurethane-based resin; Sulfone-based resin; polyetheretherketone-based resin; Sulfated polyphenylene-based resin; Vinyl alcohol-based resin; Vinylidene chloride-based resin; Vinyl butyral resin; Allylate resin; polyoxymethylene-based resin; It may include epoxy resin, etc. These may be used alone or in combination of two or more.

The polyimide-based resin may be formed by reacting reactants including a diamine compound and a dianhyde compound simultaneously or sequentially. Specifically, the polyimide-based resin may include a polyimide polymer formed by polymerizing 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 further include a dicarbonyl compound and be polymerized, and may include a polyamide-imide polymer containing an amide repeating unit derived from polymerization of the diamine compound and the dicarbonyl compound. You 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 of Formula 1 below.

<Formula 1>

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 or different from each other.

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

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

More specifically, (E)e of Formula 1 may be a group represented by 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. At this time, the fluorine-containing substituent may be a fluorinated hydrocarbon group, and specifically, a trifluoromethyl group, but is not limited thereto.

In one embodiment, the diamine compound may be 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: '-diaminodiphenyl, TFDB), but is not limited thereto.

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

The dianhydride compound is not particularly limited, but may be an aromatic dianhydride compound containing an aromatic structure. For example, the aromatic dianhydride compound may be a compound of formula 2 below.

<Formula 2>

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 aromatic ring group, a substituted or unsubstituted tetravalent C ₄ -C ₃₀ hetero aromatic ring group, and the aliphatic ring group, the hetero aliphatic ring group, the aromatic ring group, or the hetero aromatic ring group exists alone. , are bonded to each other to form a condensed ring, or 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 the group represented by the following Formulas 2-1a to 2-9a, but is not limited thereto.

For example, G in Formula 2 may be a group represented by 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. At this time, the fluorine-containing substituent may be a fluorinated hydrocarbon group, and specifically, a trifluoromethyl group, but is not limited thereto.

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

For example, the dianhydride compound is 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2'-Bis-(3,4 -Dicarboxyphenyl)hexafluoropropane dianhydride, 6-FDA) may be included, but is not limited thereto.

The diamine compound and the dianhydride compound may polymerize to produce polyamic acid.

Subsequently, the polyamic acid can be converted to polyimide through a dehydration reaction.

The polyimide may include a repeating unit represented by the following formula (A).

<Formula A>

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

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

<Formula A-1>

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

The dicarbonyl compound is not particularly limited, but may be, for example, a compound of the following formula (3).

<Formula 3>

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 or different from each other.

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

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

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

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

In one embodiment, the dicarbonyl compound may be a mixture of at least two different dicarbonyl compounds. When two or more types of dicarbonyl compounds are used, (J) _j in Formula 3 may be two or more types selected from the group represented by Formulas 3-1b to 3-8b. there is.

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

For example, the dicarbonyl compound may include a first dicarbonyl compound and/or a second dicarbonyl compound that is 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 each an aromatic dicarbonyl compound, they contain a benzene ring, so the surface hardness and tensile strength of the film containing the produced polyamide-imide resin It can contribute to improving mechanical properties such as

The dicarbonyl compound is terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), 1'-biphenyl-4,4'-dicarbonyl dichloride ( 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 is used in appropriate combination as the first dicarbonyl compound and TPC is used as the second dicarbonyl compound, the film containing the produced polyamide-imide resin can have high oxidation resistance. there is.

Alternatively, the first dicarbonyl compound may include IPC (Isophthaloyl Chloride), and the second dicarbonyl compound may include TPC, but are not limited thereto.

Specifically, when IPC is used in appropriate combination as the first dicarbonyl compound and TPC is used as the second dicarbonyl compound, the film containing the produced polyamide-imide resin can have high oxidation resistance. And manufacturing costs can be reduced.

The diamine compound and the dicarbonyl compound may be polymerized to form a repeating unit represented by the following formula (B).

<Formula B>

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

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

<Formula B-1>

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

<Formula B-2>

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

The polyimide-based film may include filler.

The filler may be one or more selected from the group consisting of barium sulfate, silica, and calcium carbonate. By including the filler, the polyimide-based film can improve roughness and windability, as well as improve runability and scratch improvement effects during film production.

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

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

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, the 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/㎛ or more or 0.46 kgf/㎛ or more, but is not limited thereto.

The polyimide-based film may have a surface hardness of HB or higher. 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 has high oxidation resistance and can secure excellent optical properties such as high light transmittance, low haze, and low yellowness (YI). Furthermore, it can have excellent modulus, elongation, tensile properties, and elastic recovery force.

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

The coating can be performed through methods commonly used in the art, such as die coating.

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

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

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

The second surface 124 is a surface opposite to the substrate 130, and the second surface 124 may be located opposite to the surface where the primer layer 120 and the hard coating layer 110 are in 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 coating on the primer layer 120. The hard coating layer 110 may be bonded to 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 the mechanical and/or optical properties of the laminated film 100. The hard coating layer 110 may include anti-glare, anti-fouling, anti-static functions, etc.

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

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

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

Examples of the acrylic ester compounds include trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA), or dipentaerythritol hexaacrylate (DPHA), etc., but is 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 the terminal of a urethane compound formed by reacting a diisocyanate compound and 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 contains 2 to 4 hydroxy groups (-OH) and may be a straight-chain, branched, or cyclic aliphatic polyol compound with 4 to 12 carbon atoms or an aromatic polyol compound with 6 to 20 carbon atoms.

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

Examples of the urethane acrylate-based compounds include bifunctional urethane acrylate oligomers with a weight average molecular weight of 1,400 to 25,000, trifunctional urethane acrylate oligomers with a weight average molecular weight of 1,700 to 16,000, and tetrafunctional urethane acrylates with a weight average molecular weight of 500 to 2,000 g/mol. rate oligomer, hexa-functional urethane acrylate oligomer with a weight average molecular weight of 818 to 2600 g/mol, nine-functional urethane acrylate oligomer with a weight average molecular weight of 2500 to 5500 g/mol, ten-functional urethane with a weight average molecular weight of 3200 to 3900 g/mol Acrylate oligomers or 15-functional urethane acrylate oligomers with a weight average molecular weight of 2300 to 20000 g/mol may be included, but are not limited thereto.

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

Examples of the epoxy acrylate-based compounds include monofunctional epoxy acrylate oligomers with a weight average molecular weight of 100 to 300, bifunctional epoxy acrylate oligomers with a weight average molecular weight of 250 to 2000, or tetrafunctional epoxy acrylate oligomers with a weight average molecular weight of 1000 to 3000. Examples include, but are not limited to.

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

The acrylate equivalent weight of the acrylic ester-based compound may range from about 50 to about 300 g/eq, about 50 to about 200 g/eq, or about 50 to about 150 g/eq.

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

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 wt% to 90 wt% or 50 wt% to 80 wt% based on the total weight of the hard coating layer 110.

The hard coating layer 110 may optionally include 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 an inorganic filler having a different particle size distribution. For example, the filler may include a first inorganic filler having a d50 of 20 to 35 nm and a second inorganic filler having a d50 of 40 to 130 nm.

The content of the filler may be about 25 wt% or more, about 30 wt% or more, or about 35 wt% or more based on the total weight of the functional layer. Additionally, 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 contain an inorganic filler such as silica. In this case, for example, the adhesion between the base layer and the hard coating layer of the above-described composition can 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, Examples include, but are not limited to, 6-trimethylbenzoyl)-phosphine oxide or bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Additionally, commercial products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Esacure KIP 100F. The photoinitiator can be used alone or in a mixture of two or more different types.

In some implementations, the hard coating layer 110 may include an antifouling additive and/or 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 containing 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 a quaternary alkylammonium salt may include a halide such as chloride or bromide.

In comparative examples, when the primer layer according to the embodiments is not included, the hard coating layer to which antifouling and antistatic properties are imparted by the antifouling additive and the antistatic agent has adhesive strength with the substrate (particularly, polyimide-based film). may be low, and accordingly, when the laminated film is deformed or receives external stimulation, the hard coating layer may be easily separated from the substrate.

In the case of the laminated film 100 according to embodiments, by including the primer layer 120 described above, the bonding force between the base film and the hard coating layer having antifouling and antistatic properties can be improved.

The hard coating layer 110 may include other additives such as surfactants, UV absorbers, UV stabilizers, anti-yellowing agents, leveling agents, or dyes to improve color value. Additionally, the content of the additive can be adjusted in various ways within a range that does not deteriorate the physical properties of the hard coating layer 110. For example, the content of the additive may be from 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 1- to 2-functional fluorine-based acrylate, a fluorine-based surfactant, or a silicone-based surfactant. The surfactant may be included in the hard coating layer 110 in a dispersed or cross-linked form.

The UV absorber may include a benzophenone-based compound, a benzotriazole-based compound, or a triazine-based compound, and the UV stabilizer may 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 above-described organic resin, photoinitiator, antifouling additive, antistatic agent, other additives and/or solvent.

The organic solvent includes 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-based 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-based 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 alone or in combination.

The content of the organic solvent can be adjusted in various ways without deteriorating the physical properties of the coating composition, so it is not particularly limited. However, with respect to the solid content among the components included in the hard coating composition, the weight ratio of solid content: organic solvent is approximately It may be included in a ratio of 30:70 to about 99:1. When the organic solvent is within the above range, it can have appropriate fluidity and applicability.

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. According to the above composition, the mechanical properties, antifouling, and antistatic properties of the hard coating layer 110 can be improved.

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

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

Thereafter, 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 to about 20 μm, about 2 to about 15 μm, about 2 to about 10 μm, or about 3 to about 10 μm. It can have thickness.

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

display device

1 to 3 are schematic exploded views, perspective views, and cross-sectional views, respectively, of a display device according to an implementation example. Referring to FIGS. 1 to 3 , a display device according to implementation examples 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's 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 primer layer 120 described above may be used as the hard coating layer 110. When formed between the anti-fouling/antistatic hard coating layer and the substrate 130, the anti-fouling/antistatic hard coating layer and the substrate are strongly bonded, so that a display device that is durable even after repeated deformation can be provided.

The display panel 200 is a device that can display images and may have flexible characteristics.

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

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

The organic EL panel displays images through self-luminescence on a pixel basis. 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 dynamically 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 current can be applied to each of the organic electroluminescence units to drive the organic EL substrate.

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 explained 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 to these only.

Preparation Example 1: Preparation of primer composition

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

division ingredient weight% menstruum Propylene glycol n-propyl ether (PNP) 66.05% Methyl isobutyl ketone 28.31% Xylene 1.01% n-Butyl acetate 2.63% bookbinder Acrylic resin 1.96% Polyaziridine-based compounds Pentaerythritol tris(3-aziridin-1-ylpropionate)
[Pentaerythritol tris(3-aziridin-1-ylpropionate)] 0.04% Acrylic resin: copolymer of methyl crotonate, methyl methacrylate, butyl acrylate, octyl methacrylate, and 2-ethylhexyl methacrylate, Mw: about 50,000 g/mol, Tg: 85 ° C.

Preparation Examples 2 to 6

A primer composition was prepared in the same manner as 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 solvent content was decreased as the content of pentaerythritol tris(3-aziridin-1-ylpropionate) increased in the composition.

division Production example 2 Production example 3 Production example 4 Production example 5 Production example 6 Content of pentaerythritol tris(3-aziridin-1-ylpropionate) (% by weight) 1.5% 2.0% 2.5% 3.0% 3.5%

Preparation 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.

division ingredient weight% menstruum Isopropyl alcohol 5.00% Ethanol 32.50% Methyl isobutyl ketone 25.00% Propylene glycol methyl ether 12.50% organic resin Urethane Acrylate 13.50% acrylic ester 9.12% photoinitiator 1-Hydroxycyclohexyl phenyl ketone 1.13% antifouling additive (Perfluorohexyl)ethyl acrylate
[(Perfluorohexyl)ethyl Acrylate] 0.11% Antistatic agent Quaternary ammonium chloride 1.13% Urethane acrylate: Miramer MU9800 (Miwon Specialty Chemicals)
Acrylic ester: Miramer PS3010 (Miwon Specialty Chemicals)

Preparation Examples 8 to 10

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

Production example 7 Production example 8 Production example 9 Production example 10 Urethane Acrylate Miramer MU9800 Miramer PU340 (Miwon Specialty Chemicals) Miramer PU320
(Miwon Specialty Chemicals) Miramer SC2152
(Miwon Specialty Chemicals) acrylic ester Miramer PS3010 Photocryl DP344 (Miwon Specialty Chemicals) Miramer P261
(Miwon Specialty Chemicals) Miramer PS3010
(Miwon Specialty Chemicals)

Examples 1 to 9: Preparation of laminated films

The primer compositions of Preparation Examples 1 to 6 were applied on one side of a transparent polyimide film (manufactured by SKC) with a thickness of about 30 to 80 ㎛ using a die coating method. The solvent was dried by heat treatment at about 120°C for about 6 minutes, and curing was performed to form a primer layer with 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 die coating. The applied composition was dried at about 120°C for about 6 minutes and cured by applying a total of about 1 J/cm ² of energy through UV light with a wavelength of 375 nm to form a hard coating layer with a thickness of about 5 μm.

Examples 10 to 13

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

division Example 1 Example 7 Example 8 Example 9 Example 10 coating thickness 73nm 36nm 120 nm 156nm 182nm

Examples 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) with a thickness of about 40 μm was used as the primer composition instead of a polyimide film.

Comparative example

Thickness 73 The hard coating composition of Preparation Example 7 was applied directly to one side of the ㎛ transparent polyimide film using a die coating method. The applied composition was dried at about 120°C for about 6 minutes, and a total of about 1 was applied using UV with a wavelength of 375 nm. A laminated film with a hard coating layer was manufactured by curing by applying energy of J/cm ² .

Experimental Example: Cross Hatch Adhesion Test

Using a cross hatch adhesion tester (Elcometer, 107-1542), an adhesion test was performed on the laminated films of Examples and Comparative Examples according to JIS K 5600.

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

division write Composition of primer layer Thickness of primer layer (nm) Hard coating layer composition cross hatch adhesion Example 1 PI Manufacturing Example 1 73 Production example 7 100/100 Example 2 PI Production example 2 73 Production example 7 100/100 Example 3 PI Production example 3 73 Production example 7 100/100 Example 4 PI Production example 4 73 Production example 7 100/100 Example 5 PI Production example 5 73 Production example 7 80/100 Example 6 PI Production example 6 73 Production example 7 50/100 Example 7 PI Manufacturing Example 1 73 Production example 8 100/100 Example 8 PI Manufacturing Example 1 73 Production example 9 100/100 Example 9 PI Manufacturing Example 1 73 Production example 10 100/100 Example 10 PI Manufacturing Example 1 36 Production example 7 100/100 Example 11 PI Manufacturing Example 1 120 Production example 7 95/100 Example 12 PI Manufacturing Example 1 156 Production example 7 80/100 Example 13 PI Manufacturing Example 1 182 Production example 7 70/100 Example 14 PET Manufacturing Example 1 73 Production example 7 100/100 Example 15 PET Production example 2 73 Production example 7 100/100 Example 16 PET Production example 3 73 Production example 7 100/100 Example 17 PET Production example 4 73 Production example 7 100/100 Comparative example PI - - Production example 7 0/100

Referring to Table 6, in the case of the laminated film of the examples including a primer layer prepared including a trifunctional or more polyvalent aziridine-based compound, the polyamide-based base film and the hard coating layer having anti-fouling and anti-static properties are strongly adhered. It has been confirmed that it exists.

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

100: Laminated film 110: Hard coating layer
120: primer layer 122: first side
124: Second page 130: Description
200: display panel

Claims (14)

delete delete delete delete delete delete polyimide-based film;
A primer layer formed on the polyimide-based film from a primer composition containing an acrylic binder resin, a trifunctional or more polyvalent aziridine-based compound, and a solvent; and
It includes a hard coating layer formed on the primer layer,
The acrylic binder resin has a weight average molecular weight of 15,000 to 150,000 g/mol and a glass transition temperature of 50 to 150 ℃,
The primer composition includes 0.1 to 10% by weight of the acrylic binder resin based on the total weight of the composition,
The thickness of the primer layer is 30 to 120 nm,
A laminated film with a cross hatch adhesion test result of 95/100 or higher as measured in accordance with JIS K 5600.
According to claim 7,
The hard coating layer is a laminated film comprising at least one of a urethane acrylate-based resin and an acrylic ester-based resin.
According to claim 7,
The hard coating layer includes at least one of an antifouling additive and an antistatic agent.
According to clause 9,
The laminated film wherein the antifouling additive includes a fluorine-substituted acrylate-based compound.
According to clause 9,
The laminated film wherein the antistatic agent includes an ionic surfactant.
delete delete display panel; and
It includes a cover window disposed on the viewing surface of the display panel,
The cover window includes a polyimide-based film, a primer layer formed on the polyimide-based film from a primer composition comprising an acrylic binder resin, a trifunctional or more polyvalent aziridine-based compound, and a solvent, and a hard coating layer formed on the primer layer. ,
The acrylic binder resin has a weight average molecular weight of 15,000 to 150,000 g/mol and a glass transition temperature of 50 to 150 ℃,
The primer composition includes 0.1 to 10% by weight of the acrylic binder resin based on the total weight of the composition,
The thickness of the primer layer is 30 to 120 nm,
The cover window is a display device having a cross hatch adhesion test result value of 95/100 or more as measured according to JIS K 5600.