KR102340745B1 - Low dielectirc insulating film and display device including the film - Google Patents

Abstract

The present invention relates to a low-k organic insulating film made of a binder resin in which porous supramolecules are introduced into side chains, and a display device including the organic insulating film. Since the organic insulating film of the present invention has a low dielectric constant, it can be used as a protective layer, an interlayer insulating film, or a bank layer for protecting the TFT of a display device, thereby reducing power consumption. In addition, the adhesion to the substrate is improved, so that it can be firmly attached to the substrate. Since the pattern of the organic insulating layer can be formed with a small amount of light in the patterning operation and folding and/or bending stress is low, it can be utilized in a flexible display device.

Description

Low dielectric insulating film and display device including same

The present invention relates to an insulating film used in a display device, and more particularly, to an insulating film having a low dielectric constant and excellent dispersion and adhesion characteristics, and a display device including the insulating film.

A flat panel display device such as an organic light emitting diode display employing a liquid crystal display (LCD) or an organic light emitting device (OLED) instead of the conventional CRT is widely used. A thin-film transistor (TFT) is typically used to implement an image in these flat panel display devices, but an insulating film is used to protect the TFT circuit from other elements.

The capacitance of the insulating film is proportional to the dielectric constant of the material and is inversely proportional to the distance between the two conductors, that is, the thickness of the insulating film. If the parasitic capacitance increases, the RC time is delayed in proportion to it, which not only reduces the switching speed of the device but also increases power consumption. Therefore, in order to reduce the parasitic capacitance caused by the insulating layer formed between the conductors of the display device, it is necessary to use a device having a low dielectric constant or increase the thickness of the insulating layer. When a material with a low dielectric constant is used as an insulator for the insulating film, parasitic capacitance does not increase even if the thickness of the insulating film is thin, and the on/off ratio can be improved to improve TFT driving characteristics.

Inorganic materials such as silicon oxide (SiOx) or silicon nitride (SiNx) are conventionally used as a material of a protective layer or insulating film for protecting the TFT circuit of a display device. However, the dielectric constants of silicon oxide and silicon nitride are relatively high at 3.9 to 7.0, respectively. Therefore, a display device using such an inorganic material as an insulating layer generates a lot of parasitic capacitance, which limits power consumption. Moreover, to apply these inorganic materials to a display device, a high-temperature process and vacuum equipment are required, and accordingly, there is a problem in that it is difficult to apply to a plastic substrate.

Therefore, recently, an organic material having a relatively low dielectric constant is used as an insulating film instead of an inorganic material. In general, as a material for an organic insulating film of a display device, a photoactive compound (PAC) that chemically reacts with light or an electron beam has been developed. The most widely used material as an organic insulating film material is a photoacrylic binder, which is a linear binder having a thermoplastic substituent derived from acrylic acid. However, the photoacrylic compound, which has been conventionally used as a material for the organic insulating film, has a linear structure and causes an increase in polarization, so the dielectric constant of the photoacrylic compound is relatively high, about 3.6.

In addition, since the photoacrylic compound has weak adhesion, when used as an organic insulating film, a hydroxyl group (-OH) is attached to the end of the photoacrylic compound to compensate for the adhesion. However, the dipole moment due to the lone pair of electrons present in the hydroxyl group, which is a hydrophilic functional group, increases, which increases the polarization rate and increases the dielectric constant value. In addition, there is a problem in that a dielectric constant value increases because moisture attacks a hydroxyl group, which is a hydrophilic functional group, and a leakage current occurs.

Therefore, in a display device using a photosensitive acrylic compound as an organic insulating layer, in order to reduce power consumption, the thickness of the organic insulating layer is increased to decrease the capacitance. Since the thickness of the organic insulating layer increases, there is a limit to its application to a thin display device. In addition, since a thick insulating film is employed, there is a limit to folding and bending, and thus it is difficult to be used in a flexible display device.

Accordingly, as an organic material having a low dielectric constant value, a polysiloxane resin is used as an organic insulating film material instead of the photosensitive acrylic compound. Polysiloxane resin has a higher modulus value than acrylic resin, and thus has good adhesion. However, when an organic insulating film is manufactured using polysiloxane resin, cracks are likely to occur at a predetermined thickness or more due to shrinkage stress generated in the curing process. In particular, when a tough material such as polysiloxane resin is used, cracks may occur in the organic insulating layer due to folding stress. Due to this, a leakage current may occur, which deteriorates the device, and thus there is a problem in that the life of the device is shortened.

SUMMARY OF THE INVENTION The present invention is to solve a problem that the prior art could not solve, such as securing a low dielectric constant and strong adhesion.

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic insulating film having a low dielectric constant and good dispersibility, and a display device including the same.

Another object of the present invention is to provide an organic insulating layer capable of reducing power consumption of a device and a display device including the same.

Another object of the present invention is to provide an organic insulating film having excellent adhesion to a substrate and a display device including the same.

Another object of the present invention is to provide an organic insulating layer with improved processability and good folding or bending characteristics, and a display device including the same.

According to one aspect of the present invention having the above object, the present invention provides a low-k organic insulating film including a binder resin in which porous supramolecules are introduced into side chains.

For example, the binder resin may be selected from the group consisting of (meth)acrylate resins, urethane resins, polysiloxane resins, and copolymers thereof.

The porous supramolecules may be selected from the group consisting of cyclodextrin, cucurbituril, calixarene, polycaprolactone, derivatives thereof, and combinations thereof.

According to another aspect of the present invention, a first substrate on which a plurality of signal lines are arranged, a thin film transistor positioned on the first substrate, an organic insulating film positioned on the thin film transistor, and positioned on the organic insulating film and a first electrode, wherein the organic insulating layer includes a binder resin in which porous supramolecules are introduced into side chains.

In one exemplary embodiment, the display device of the present invention may further include a second substrate facing the first substrate, and a liquid crystal layer interposed between the first substrate and the second substrate.

In this case, the display device of the present invention further includes a second electrode having a plurality of openings corresponding to the first electrode, and a protective layer positioned between the first electrode and the second electrode, wherein the protective layer includes the It may be made of the same material as the organic insulating layer.

In another exemplary embodiment, the display device of the present invention further includes a bank layer positioned on the first electrode, an organic light emitting layer, and a second electrode facing the first electrode, wherein the bank layer includes the organic insulating layer and the organic insulating layer. It may be made of the same material.

The organic insulating film of the present invention introduces molecules having a pore structure to lower the density of the thin film, thereby lowering the dielectric constant value, and the molecules of the pore structure are chemically bonded to and introduced into the binder resin, so that the dispersion characteristics are good. Accordingly, there is an advantage in that a low dielectric constant value can be uniformly secured over the entire insulating film.

By adopting the binder material having a low dielectric constant value, parasitic capacitance in the organic insulating film is reduced, thereby reducing the load of electric power applied to the display panel, thereby reducing power consumption of the device.

In addition, the binder material of the present invention not only has excellent adhesion to the substrate, but also can secure a sufficiently low dielectric constant even when the thickness of the insulating film is reduced due to a low dielectric constant value. Since the thickness of the insulating layer can be reduced as described above, it can be used in a flexible display device requiring folding or bending characteristics. In addition, since a desired pattern can be formed with a small amount of light in the patterning process of the insulating film, the efficiency of the process can be secured.

1 is a cross-sectional view schematically illustrating a liquid crystal display as an example of a display device including a low-k organic insulating film according to an exemplary embodiment of the present invention.
2 is a cross-sectional view schematically illustrating an organic light emitting diode display as an example of a display device including a low-k organic insulating layer according to another exemplary embodiment of the present invention.
3A to 3C are photographs of whether or not the organic insulating film made of an acrylate-based binder resin is peeled off from the substrate according to the Cross-Cut tape test. The organic insulating film and pores in which porous supramolecules are introduced into the binder resin, respectively. An organic insulating film without added supramolecules and an organic insulating film containing simple porous supramolecules were targeted.
Figures 4a to 4c are photographs of whether the organic insulating film made of a urethane acrylate polysiloxane-based resin is peeled off from the substrate according to the Cross-Cut tape test, each of which is an organic insulating film in which porous supramolecules are introduced into binder resin; The organic insulating film to which porous supramolecules are not added and the organic insulating film in which porous supramolecules are simply mixed were targeted.
5A to 5C are graphs showing the results of measuring the peel strength of an organic insulating film made of an acrylate-based resin. The organic insulating film in which the porous supramolecules are introduced into the binder resin, the porous supramolecules, respectively. The organic insulating film that is not added and the organic insulating film in which porous supramolecules are simply mixed were targeted.
6A to 6C are graphs showing the results of measuring the peel strength of the organic insulating film made of the urethane acrylate polysiloxane-based resin. The organic insulating film in which the porous supramolecules are introduced into the binder resin, and the porous supramolecules are not added. It was targeted to an organic insulating film in which an untreated organic insulating film and a simple mixture of porous supramolecules were mixed.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings, if necessary.

[Low dielectric organic insulating film]

The low-k organic insulating film according to the present invention includes a binder resin in which porous supramolecules are introduced into side chains.

In an exemplary embodiment, the binder resin for manufacturing the organic insulating film may be at least one selected from the group consisting of (meth)acrylate resins, urethane resins, polysiloxane resins, and copolymers thereof. Unless otherwise defined herein, the term “meth(acrylate)” is used to include both acrylates and (meth)acrylates. In particular, as the binder resin of the present invention, a urethane resin, a urethane (meth)acrylate resin, a urethane polysiloxane resin, and a urethane (meth)acrylate polysiloxane resin may be preferable.

When the (meth)acrylate resin is used alone, the dielectric constant value increases when a hydroxyl group is introduced to improve adhesion. However, when a urethane resin, a urethane (meth)acrylate resin, a urethane polysiloxane resin, and a urethane (meth)acrylate polysiloxane resin are used, since the hydroxyl group can be reduced, there is an advantage in that the dielectric constant value can be reduced.

Illustratively, by using a binder resin in which a urethane resin and/or a polysiloxane resin having excellent toughness are copolymerized with the (meth)acrylate resin, the toughness of the organic insulating film can be improved, and the adhesion to the substrate It is possible to prevent peeling from the substrate by improving the

In particular, the polyurethane contained in the urethane resin, urethane (meth) acrylate resin, urethane polysiloxane resin, and urethane (meth) acrylate polysiloxane resin includes a urethane bond formed by addition polymerization of a polyol having a hydroxyl group and an isocyanate group and , an amine formed from carbamic acid formed by the reaction of water with isocyanate has a urea bond formed by reaction with isocyanate.

It is possible to obtain an adhesive whose flexibility can be controlled by a soft segment formed by a polyol used for synthesizing a urethane pre-polymer and a hard segment formed by an isocyanate. In addition, after obtaining a urethane prepolymer to form a urethane bond, a moisture curing process is performed to prepare a binder resin having excellent adhesion.

The binder resin may be synthesized from a curable component such as a monomer and/or oligomer constituting the resin through a photocuring process, a moisture curing process, and a thermosetting process. For example, the poly(meth)acrylate constituting the (meth)acrylate resin or the urethane (meth)acrylate resin is an alkyl (meth)acrylate having 1 to 20 carbon atoms and an alkenyl (di) having 2 to 20 carbon atoms. (meth)acrylate, C1-C20 alkoxy (di)(meth)acrylate, C1-C20 alkoxyalkyl (meth)acrylate, allyl alkoxylate; cycloaliphatic (meth)acrylate selected from at least one selected from cycloalkyl (meth)acrylate having 5 to 8 carbon atoms or N-acryloyl morphline; It is an oligomer and/or monomer that may be selected from the group consisting of epoxy (meth)acrylate, aryl (meth)acrylate, and combinations thereof. Poly(meth)acrylates can be formed by photocuring these (meth)acrylate oligomers and/or oligomers to form crosslinks between these monomers and/or oligomers.

A urethane prepolymer obtained by reacting a polyol with diisocyanate to form a urethane bond constituting a urethane resin, a urethane (meth)acrylate resin, a urethane polysiloxane resin, and a urethane (meth)acrylate polysiloxane resin can be used. Polyols for synthesizing urethane prepolymers include polyols obtained by reacting ethylene oxide or propylene oxide with glycerin, polyether polyols such as propylene glycol, tetramethylene glycol, and ethylene glycol polyether; and/or polycaprolactone polyol, polyester polyol obtained by dehydration condensation reaction of glycol or triol with adipic acid, which is a dibasic acid, and/or at least one kind may be selected. The diisocyanate compound for synthesizing the urethane prepolymer may be at least one selected from toluene diisocyanate (TDI), methylene diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), etc. . After synthesizing a urethane prepolymer by reacting these isocyanates with a polyol, a moisture curing process can be performed to obtain a polyurethane bond.

On the other hand, for example, the monomer for synthesizing the polysiloxane constituting the polysiloxane resin, the urethane (meth) acrylate polysiloxane resin, and the urethane polysiloxane resin includes a monomer containing a silanol group and/or a monomer containing a siloxane group. The monomer compound containing a silanol group includes ethylenically unsaturated alkoxy silanes such as (meth)acrylate-based alkoxy silanes; and/or an ethylenically unsaturated acyloxysilane including an ethylenically unsaturated acetoxysilane such as (meth)acrylate-based acetoxysilane or (meth)acrylatetopropyltriacetoxysilane.

Further, the monomer compound containing a siloxane group includes in particular a compound having a linear siloxane group. For example, the monomer compound having a linear siloxane group includes mono/di/tri/tetra/hexa/octasiloxane substituted with an alkyl group having 1 to 10 carbon atoms; mono/di/tri/tetra siloxane substituted with an alkoxy group having 1 to 4 carbon atoms; One or more types of alkylalkoxysilanes having 1 to 10 carbon atoms, vinylalkoxysilanes, aminoalkylalkoxysilanes, silanes substituted with methacryloxy groups or mercaptoalkyl groups are included, but the present invention is not limited thereto.

Polysiloxane can be obtained by thermosetting or photocuring a monomer for synthesizing polysiloxane. Illustratively, the unit units constituting the polysiloxane may be connected in a straight line form or may be connected in a cage form. Optionally, the polysiloxane may be in the form of a silsesquioxane.

The porous supramolecules introduced into the above-described binder resin have an empty space therein, and thus have a very low density. Since the empty space inside is filled with air having a low dielectric constant, the organic insulating film made of the binder resin in which the porous supramolecules are introduced can lower the dielectric constant.

In other words, by using the binder resin into which the porous supramolecules are introduced according to the present invention as a material for the organic insulating film, the density of the organic insulating film is lowered. Accordingly, the polarizability of the organic insulating layer is ultimately reduced, so that the dielectric constant value of the organic insulating layer can be lowered. In an exemplary embodiment, the porous supramolecules may be introduced into a side chain of a binder resin having a straight morphology, for example. As the porous supramolecules are introduced into the side chains of the linear binder resin, the increase in polarization can be suppressed, so that the dielectric constant value of the organic insulating film can be further lowered.

In addition, porous supramolecules are fairly bulky molecules. Therefore, when the porous supramolecules are introduced into the side chain of the binder resin, the roughness to the substrate increases due to the bulky porous supramolecules, so that the adhesion to the substrate can be further improved.

In addition, when the porous supramolecules are blended in the binder resin, it is difficult to uniformly disperse the porous supramolecules in the binder resin. Accordingly, an organic insulating film prepared by simply mixing porous supramolecules with a binder resin has a problem in that it does not have a uniformly low dielectric constant value throughout the insulating film. On the other hand, since the porous supramolecules of the present invention are bonded to the binder resin and formed integrally with the binder resin, there is no problem of dispersibility. Accordingly, the organic insulating film made of the binder resin into which the porous supramolecules are introduced according to the present invention can secure a uniformly low dielectric constant value throughout the insulating film.

As an exemplary embodiment, the urethane acrylate polysiloxane-based binder resin into which the porous supramolecules are introduced may have a repeating unit represented by the following formula (I).

(In Formula (I), R ₁ is hydrogen or a methyl group; R ₂ and R ₃ are each independently substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 4 to 20 carbon atoms, and selected from the group consisting of substituted or unsubstituted arylene having 6 to 20 carbon atoms; R ₄ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, selected from the group consisting of an acyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms; x is an integer from 2 to 10000; A is a binder resin porous supramolecules introduced into

For example, the porous supramolecules may be introduced in an amount of 5 to 100 parts by weight based on 100 parts by weight of the binder resin. When the content of the porous supramolecules exceeds 100 parts by weight based on the binder resin, the density of the binder resin may be too low, and thus the mechanical strength of the organic insulating film may be deteriorated. On the other hand, when the content of the porous supramolecules is less than 5 parts by weight based on the binder resin, the decrease in dielectric constant and/or improvement in adhesion to the substrate may be insignificant due to the introduction of the porous supramolecules.

In an exemplary embodiment, the porous supramolecules introduced into the side chain of the binder resin may be selected from the group consisting of cyclodextrin, cucurbituril, calixarene, polycaprolactone, derivatives thereof, and combinations thereof. can

Cyclodextrin, one of exemplary porous supramolecules introduced into the binder resin, can be obtained from carbohydrates such as starch by the action of enzymes, for example, alpha-, which is a sugar ring constituting carbohydrates. D-glucopyranoside (α-D-glucopyranoside) units are linked 1->4. For example, the cyclodextrin that can be used according to the present invention may have 5-8 alpha-D-glucopyranoside units. In particular, preferably, cyclodextrins usable as porous supramolecules include α-cyclodextrin (composed of 6 sugar rings), β-cyclodextrin (composed of 7 sugar rings), and γ-cyclodextrin (composed of 8 sugar rings). composition).

In an exemplary embodiment, cyclodextrin and/or a derivative thereof that can be introduced into the binder resin as a porous supramolecules according to the present invention may be represented by the following formula (II).

(In Formula (II), R ₅ to R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a hydroxyalkyl group having 1 to 20 carbon atoms. , a carboxyl group, or _{a silicon molecule represented by Si r1r2r3} , wherein r1, r2, and r3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms; It is an integer from 5 to 8 as the number of unit units)

In another exemplary embodiment, the other porous supramolecules incorporated into the side chains of the binder resin are cucurbituril. Cucurbituril is a porous supramolecules composed of glycoruril (=C ₄ H ₂ N ₄ O ₂ =) linked by a methylene bridge (-CH _{2 -).} Cucurbituril is named cucurbit[n]uril according to the number (n) of glycouryl units, which are structural units. Cucurbituril that can be incorporated into the binder resin according to the present invention is cucurbituril having 4-20 glycouryl units (i.e. cucurbit[4-20]uril), preferably 5-10 glycouryl units. cucurbituril (ie cucurbit[5-10]uril).

As an example of cucurbituril, cucurbit[6]uril can be synthesized in the following way. First, two molecules of urea and one molecule of dialdehyde are reacted to obtain an intermediate glycouryl by nucleophilic addition, and the obtained intermediate is condensed with formaldehyde at a temperature of 110° C. or higher to react with cucurbit [6] ]Can synthesize us. By lowering the temperature of the condensation reaction, it is possible to synthesize other cucurbiturils having a different number of glycoluril unit units.

Illustratively, cucurbituril and/or a derivative thereof may be represented by the following formula (III).

(In Formula (II), R ₈ and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an alkylthio group having 1 to 30 carbon atoms. , an alkylcarboxyl group having 1 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, nitro group, 1 to 30 carbon atoms of an alkylamine group, an amine group, an aminoalkyl group having 1 to 30 carbon atoms, a (hetero)cycloalkyl group having 5 to 30 carbon atoms, and a (hetero)aryl group having 6 to 15 carbon atoms; Y is O, S or NH n is the number of glycouryl unit units, and is an integer from 4 to 20, preferably an integer from 5 to 10)

According to another exemplary embodiment of the present invention, the compound that can be used as the porous supramolecules introduced into the side chain of the binder resin is calixarene and its derivatives. The callexarene compound is a compound in the form of a goblet-shaped macrocyle or cyclic oligomer including a benzene ring. Calixarene is formed by hydroxyalkylation of phenol, resorcinol, and pyrogallol, which are benzene compounds substituted with a hydroxyl group, and an aldehyde. A benzene ring substituted with a hydroxyl group bridges a methylene group. It is composed of unit units. According to the number of these unit units, it is named calix [p] arene (p is the number of unit units). In an exemplary embodiment, the calixarenes used as the porous supramolecules are calixarenes or derivatives thereof having 3 to 10 unit units (ie, calix[3-10]arenes and derivatives thereof).

In order to obtain a calixarene compound, for example, when phenol, which is a benzene compound substituted with one hydroxyl group, is used as an aromatic ring component, it can be synthesized by reacting with formaldehyde to induce a condensation reaction. On the other hand, when resorcinol or pyrogalyl having two or three hydroxyl groups is used as an aromatic ring component, it can generally be synthesized by reacting a relatively bulky aldehyde such as acetaldehyde. When an aromatic ring component and these aldehydes are reacted with an acid catalyst (eg, p-toluenesulfonic acid) or a base catalyst, an electrophilic aromatic substitution reaction occurs, followed by a continuous aromatic substitution reaction with the removal of water. A calixarene compound can be synthesized through the induced condensation reaction.

Illustratively, calixarene and/or a derivative thereof may be represented by the following formula (IV).

(In formula (IV), R ₁₀ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R ₁₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A silicon molecule represented by a carboxyl group having 1 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms or Si _r1r2r3 , wherein r1, r2, r3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms; o is an integer of 3 to 7 as the number of unit units)

Another exemplary porous supramolecules that can be introduced into the side chain of the binder resin according to the present invention are polycaprolactone or a derivative thereof. Polycaprolactone is a biodegradable polyester compound, and can be prepared by ring opening polymerization of ε-caprolactone, a heterocyclic compound, using a catalyst and heat. As the polycaprolactone derivative that can be introduced as a porous supramolecules into the binder resin according to the present invention, polycaprolactone dendrimer represented by the following formula (V) may be exemplified.

(In Formula (V), R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an acyl group having 2 to 30 carbon atoms, or a silicon molecule represented by _{Si r1r2r3 , r1} , r2, r3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms; p is an integer of 2 to 200)

The low-k organic insulating film according to the present invention includes, as an essential component, a binder resin in which porous supramolecules are introduced into, for example, side chains, and may include other functional additives. As the functional additive that may be included in the low-k organic insulating film, one or more types of photosensitizers, basic components, surfactants, adhesion improvers, light stabilizers, and the like may be selected.

For example, by adding a photosensitizer to the organic insulating film of the present invention to impart photosensitivity to the organic insulating film, the process of forming a pattern by applying a separate photoresist on the organic insulating film can be reduced, thereby simplifying the patterning process. can Regarding the pattern work, the organic insulating film material utilizes the property of changing solubility in a suitable developer such as an aqueous alkali solution after exposure. Unlike the negative type using an organic developer, the positive type can use an aqueous alkali solution as a developer, so workability is good, and it can be easily removed using a stripper after forming the organic insulating film.

In an exemplary embodiment, any photosensitizer may be used as the photosensitizer that can be blended with the binder resin into which the porous supramolecules are introduced. Illustratively, as the photosensitizer, a photoacid generator (PAG)-based photosensitizer may be used. For example, photosensitizers of the photoacid generator series include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, sulfonidiazomethanes, N-sulfonyloxyimides, benzoinsulfonates, nitro A photoacid generator selected from the group consisting of benzylsulfonate-based, sulfone-based, glyoxime-based, triazine-based and combinations thereof may be used. Particularly preferably, it is an onium salt-based photoacid generator that can be selected from diazonium salt-based, phosphonium salt-based, sulfonium salt-based, iodonium salt-based and combinations thereof.

For example, the photo-acid generator may be blended in an amount of 0.1 to 10 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin into which the porous supramolecules are introduced. If the content of the photoacid generator is less than this, chemical change due to acid catalysis does not occur, making it difficult to impart photosensitive characteristics. There are concerns.

The basic compound may be arbitrarily selected from those used as a chemically amplified resist. Basic compounds that can be used include alkyl amines; alicyclic amines; heterocyclic amines such as pyridine, imidazole, quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine and derivatives; quaternary ammonium hydroxy; At least one type may be selected from a quaternary ammonium salt of a carboxylic acid. The basic compound may be included in an amount of 0.01 to 1 parts by weight based on 100 parts by weight of the binder resin into which the porous supramolecules are introduced. When the content of the basic compound satisfies the above-described range, sufficient heat resistance may be secured and an organic insulating film having solvent resistance may be formed.

The surfactant is a component added to improve coating properties and prevent the formation of defects. The type of surfactant that can be used is not particularly limited, and one or two or more types of nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants may be used in combination. The surfactant may be included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the binder resin in which the porous supramolecules are introduced in the low-k organic insulating film. When the content of the surfactant satisfies the above-described range, the adhesion between the substrate and the low-k organic insulating layer may be maximized.

The adhesion improving agent improves the adhesion between an organic insulating film and an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, silicon nitride, or a metal such as gold, copper, and aluminum, and adjusts the taper angle with the substrate. also useful The type of the adhesion improving agent is not particularly limited, and specific examples thereof include a silane coupling agent or a thiol-based compound, and preferably a silane coupling agent.

As the silane coupling agent, a silane coupling agent having at least one reactive substituent selected from the group consisting of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group and an epoxy group can be used. In particular, γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane having an epoxy group with good adhesion to the substrate and/or γ-isocyanato having an isocyanate group for improving chemical resistance Propyltriethoxysilane may be used.

The adhesion improving agent may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin in which the porous supramolecules are introduced into the low-k organic insulating film. Accordingly, in particular, it is possible to improve the adhesion between the metal and the organic insulating film and maximize the effect of adjusting the taper angle with the substrate.

The light stabilizer is a component that improves the light resistance of the low-k organic insulating film. The type of light stabilizer is not particularly limited, and specific examples include one or two or more of benzotriazole-based, triazine-based, benzophenone-based, hindered aminoether-based, and hindered amine-based compounds. have. In the low-k organic insulating film, the light stabilizer may be included, for example, in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the binder resin into which the porous supramolecules are introduced. In this range, the light resistance improvement effect can be greatly improved.

On the other hand, the low-k organic insulating film according to the present invention may be prepared from a coating composition in which a binder resin into which porous supramolecules are introduced and other additives, if necessary, are dispersed in a solvent. The solvent included in the coating composition may be selected from the group consisting of alcohol-based, ether-based, ester-based, acetate-based, aromatic hydrocarbon-based, ketone-based, amide-based, lactone-based, and combinations thereof. Illustratively, the solvent in the coating composition may be added in a proportion of 200 to 400 parts by weight based on 100 parts by weight of the binder resin into which the porous supramolecules are introduced. When the content of the solvent satisfies the above-mentioned range, it is possible to properly maintain the content and viscosity of the solid content, for example, it is possible to secure sufficient coating properties when forming the organic insulating film through the coating process.

A process for manufacturing a low-k organic insulating film from a binder resin into which porous supramolecules are introduced according to the present invention will be described. First, the binder resin into which the porous supramolecules are introduced and, if necessary, a coating composition in which other additives are dispersed in a solvent are coated on a substrate, and the liquid coating composition is pre-bake at a predetermined temperature to obtain a solvent. is evaporated to form an organic insulating film. Then, the organic insulating film obtained is exposed and developed to form a pattern, and the organic insulating film on which the pattern is formed is subjected to heat treatment to post-bake, thereby forming an organic insulating film, a protective layer and/or a bank layer of a display device. .

Specifically, the coating composition in which the binder resin into which the porous supramolecules are introduced and, if necessary, other additives are dispersed in a solvent, is coated on an appropriate substrate. The substrate on which the coating composition is coated is not particularly limited. For example, the coating composition may be coated on a glass substrate, a transparent plastic substrate, a silicon wafer, a silicon oxide wafer or a silicon nitride wafer, etc., or a metal layer such as a source/drain electrode formed on an insulating substrate such as glass or plastic. , may be coated on top of a protective layer or an interlayer insulating film that may be made of silicon oxide or silicon nitride in a display device.

As a method of coating the coating composition on an appropriate substrate, spin coating such as a central drop spin method, roll coating, spray coating, bar coating, slit coating using a slit nozzle such as discharge nozzle type coating, etc. may be used, 2 It can be coated by combining more than one coating method. In this case, the thickness of the coated film may vary depending on the coating method, the concentration of solids in the photosensitive low-k organic insulating film composition, viscosity, etc., but may be applied so that the film thickness is 0.5 to 10 µm after drying.

Then, a pre-bake process is performed on the coating composition coated on the substrate. According to this process, the solvent is volatilized in the coating composition coated on the substrate to obtain a non-fluid coating film. This process usually applies appropriate heat to volatilize the solvent. For example, in the case of hot plate heating, it can be carried out at 60 ~ 130 ° C. for 10 ~ 300 seconds, and in the case of using a heat oven, 60 ~ It may be carried out at 140 ° C. for 20 to 500 seconds.

Next, in the selective exposure process, the obtained organic insulating film is exposed and developed to pattern it. Exemplary exposure process is excimer laser, deep ultraviolet, ultraviolet, visible light, electron beam, X-ray or g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), i-ray (wavelength 365 nm) or these It can be carried out by irradiating a mixed beam of For this purpose, exposure equipment such as a mask aligner, a stepper, and a scatterer may be used on the organic insulating film on which the pre-bake process has been completed. The exposure may be performed by a contact type, proximity type, projection type exposure method, or the like. The exposure energy is determined according to the sensitivity of the prepared organic insulating film, but may usually be in the range of 30 to 200 mJ/cm.

After the exposure process is completed, a desired pattern may be formed by immersing the substrate coated with the organic insulating film in a developer or spraying the developer on the substrate to remove the organic insulating film on the exposed portion. As the developer, an alkaline inorganic alkali compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, or potassium silicate, or an organic aqueous alkali solution such as triethylamine, triethanolamine, tetramethylammonium hydroxide, or tetraethylammonium hydroxide can be used For example, in manufacturing a liquid crystal display device, tetramethylammonium hydroxide is used in the form of 0.1 to 10 parts by weight of an aqueous solution for reasons of metal contamination, metal corrosion, etc., and then developed at 20 to 30° C. for 30 to 120 seconds, It is preferable to wash and dry for 60 to 120 seconds with ultrapure water.

Then, a post-baking process is performed on the photosensitive organic insulating film on which the pattern is formed. The post-baking process can be performed using a heating device such as a hot plate or an oven. The post-bake condition may be performed at 150 to 350° C. for 10 to 180 minutes, through which a photosensitive organic insulating film having a final pattern formed therein may be obtained.

By using the binder resin into which the porous supramolecules are introduced according to the present invention as a material for the organic insulating film, the density of the organic insulating film is lowered. Accordingly, the polarizability of the organic insulating layer is ultimately reduced, so that the dielectric constant value of the organic insulating layer can be lowered. As a result, parasitic capacitance of the display element can be reduced, thereby reducing a load applied to the display panel, and thus power consumption of the display element can be reduced. Since a sufficiently low dielectric constant value can be secured even if the thickness of the organic insulating layer is thin, a small amount of light is required in the patterning process of the organic insulating layer, so that the efficiency of the process can be increased. In addition, since stress due to folding or bending is low by adopting a thin organic insulating layer, it can be used in a flexible display device.

In addition, as the porous supramolecules were introduced into the side chain of the binder resin, roughness was increased, and adhesion to the substrate was improved. Therefore, the low-k organic insulating film including the binder resin into which the porous supramolecules of the present invention are introduced has an advantage that it can be firmly formed on elements constituting the display device.

[display device]

According to the present invention, the organic insulating film made of the binder resin into which the porous supramolecules are introduced has a low dielectric constant value. Accordingly, the low-k organic insulating layer according to the present invention may constitute an organic insulating layer, a protective layer, and/or a bank layer of a display device in which a thin film transistor (TFT) is formed. A non-limiting example of such a display device may include a liquid crystal display (LCD) or an organic light emitting display device. 1 schematically shows an exemplary fringe field switching mode liquid crystal display.

As shown in FIG. 1 , in the liquid crystal display 100 , a first substrate 101 and a second substrate 102 face each other, and a liquid crystal layer 110 is disposed between the substrates 101 and 102 . This is interposed. The first substrate 101 and the second substrate 102 may be made of plastic or glass, and a plurality of electrodes and wires are stacked on the first substrate 101 .

Looking in more detail with respect to the plurality of electrodes and wires stacked on the first substrate 101 , a plurality of gate wires (not shown) extend in one direction on the upper portion of the first substrate 101 , and the plurality of A plurality of data lines 170 are formed in the second direction to define a plurality of pixel areas P by crossing a gate line (not shown). A gate pad (not shown) is formed in the non-display area by being connected to one end of the gate line (not shown), and a data pad (not shown) is formed in the non-display area by being connected to one end of the data line 170 .

In each of the plurality of pixel regions P, a semiconductor layer 126 including a gate electrode 122 , a gate insulating layer 124 , an active layer 126a and an ohmic contact layer 126b , and source and drain electrodes 132 . , 134) is formed with a thin film transistor Tr. The gate electrode 122 is connected to a gate wiring (not shown) and is formed on the first substrate 101 . A gate insulating layer 124 made of an inorganic insulating material, for example, an inorganic insulating material such as silicon oxide (SiOx) or silicon nitride (SiNx), is formed on the gate wiring (not shown) and the gate electrode 122 .

An active layer 126a made of pure amorphous silicon is formed on the gate insulating layer 124 , and an ohmic contact layer 126b formed on the active layer 126a to expose the center of the active layer 126a and made of impurity amorphous silicon is formed. has been The active layer 126a and the ohmic contact layer 126b form the semiconductor layer 126 .

Source and drain electrodes 132 and 134) are formed on the semiconductor layer 126 to be spaced apart from each other and expose the center of the active layer 126a. The source electrode 132 is positioned on the semiconductor layer 126 and extends from the data line 170 , and the drain electrode 134 is positioned on the semiconductor layer 126 to be spaced apart from the source electrode 132 . The thin film transistor Tr is positioned in the switching region TrA.

In addition, a data line 170 extending in the second direction is formed on the gate insulating layer 124 to cross the gate line (not shown). The data line 170 extends from the source electrode 132 of the thin film transistor Tr located in the pixel region P. Meanwhile, although not shown in the drawings, in one exemplary embodiment, a common wiring (not shown) is formed along the second direction parallel to the data line 170 on the gate insulating layer 124 , and the gate wiring (not shown) ) intersect with In an alternative embodiment, the common wiring (not shown) may be formed on the same layer as the gate wiring (not shown) in parallel to the gate wiring (not shown).

Meanwhile, a first protective layer 128 covering the data line 170 , the source electrode 132 , the drain electrode 134 , and the common line (not shown) is formed. A drain contact hole 135 exposing the drain electrode 134 of the thin film transistor Tr is formed in the first passivation layer 128 . The first protective layer 128 may be an organic insulating layer, and may be composed of a low-k organic insulating layer made of a binder resin into which porous supramolecules are introduced according to the present invention. The first passivation layer 164 prevents the ohmic contact layer 126b from being damaged in the process of forming the pixel electrode 140 .

In addition, in each pixel region P, the pixel electrode 140 as a first electrode electrically connected to the drain electrode 134 of the thin film transistor Tr through the drain contact hole 135 and in contact with the organic organic material of the present invention. It is formed on the first protective layer 128, which may be composed of an insulating film. The pixel electrode 140 is made of a transparent conductive material and may have a plate shape in each pixel region P. For example, the transparent conductive material may be indium-tin-oxide (ITO) or indium-zinc-oxide (IZO). Although not shown in the drawings, a gate pad electrode and a data pad electrode made of the same transparent conductive material as the pixel electrode 140 are formed in the non-display area on the first passivation layer 128 . The gate pad electrode is the gate pad It is electrically connected to the gate pad through a contact hole (not shown), and the data pad electrode is electrically connected to the data pad through a data pad contact hole (not shown).

A second passivation layer 129 is formed on the pixel electrode 140 . The second passivation layer 129 may be an organic insulating layer, and similarly to the above-described first passivation layer 128 may be composed of a low-k organic insulating layer according to the present invention.

Meanwhile, a common electrode 150 is formed on the second passivation layer 129 to overlap the plate-shaped pixel electrode 140 and have a plurality of slit-shaped holes (openings) 152 . Like the pixel electrode 140 , the common electrode 150 serving as the second electrode may be made of a transparent conductive material such as indium-tin-oxide (ITO) or indium-zinc-oxide (IZO). The common electrode 150 is formed over the entire display area in which the plurality of pixel areas P are formed. When a voltage is applied between the pixel electrode 140 , which may be a plate-shaped first electrode, and the common electrode 150 , which may be a second electrode having an opening 152 , a fringe field is formed to form a liquid crystal. By driving, the transmission efficiency is improved and a high-quality image is displayed.

Although not shown in the drawings, a black matrix, which is a light blocking member having an opening corresponding to each pixel region P, is formed under the second substrate 102 constituting the color filter substrate, and is formed between the lower portion of the black matrix and the black matrix. A color filter layer is formed under the second substrate 102 exposed through the opening. The color filter layer (not shown) includes red, green, and blue color filters corresponding to the pixel area P.

In addition, an overcoat layer (not shown) made of a material such as polyimide, polyacrylate, polyurethane, etc. is provided between the color filter layer (not shown) and the liquid crystal layer 110 to protect the color filter layer (not shown) and to planarize the surface. more can be formed.

As described above, since the organic insulating film of the present invention has a low dielectric constant, the parasitic capacitance value in the first passivation layer 128 and/or the second passivation layer 129 that can be formed of the organic insulating film is reduced. Therefore, power consumption can be reduced. In addition, the thickness of the first passivation layer 128 and/or the second passivation layer 129 formed from the low-k organic insulating film of the present invention may be reduced due to the low dielectric constant. Accordingly, it is possible to achieve a reduction in the thickness of the array substrate, and fine pattern work on these protective layers 128 and 129 is possible even with a low light quantity. Also, since stress for bending and folding is less, it may be used as a flexible display device. In addition, according to the present invention, the organic insulating film including the binder resin into which the porous supramolecules are introduced has improved adhesion to the substrate. Therefore, when the organic insulating film to which the organic material of the present invention is applied is used as the first protective layer 128 and/or the second protective layer 129, these protective layers 128 and 129 are not peeled off from the substrate even by a strong impact. It has the advantage of being able to be firmly attached to the substrate without it.

Meanwhile, the organic insulating film according to the present invention may be used as a material of an insulating film such as an interlayer insulating film, a protective layer, and/or a bank layer of an organic light emitting diode display device. FIG. 2 schematically shows an organic light emitting diode display 200 including an organic insulating film according to another exemplary embodiment of the present invention.

As shown in FIG. 2 , in the organic light emitting diode display 200 according to an exemplary embodiment of the present invention, a display area DR and a non-display area NDR are defined around the display area DR, The first substrate 201 and the second substrate 202 are spaced apart from each other and face each other. The first substrate 201 and/or the second substrate 202 constituting the organic light emitting diode display 200 may be formed of glass or flexible plastic.

For example, the first substrate 201 and the second substrate 202 may be formed of polyimide, polyethersulfone, polyetherimide (PEI) and/or polyethylene terephthalate (PET). material may be manufactured. By adopting such a plastic material, it can be applied as a flexible substrate.

A switching thin film transistor (not shown), a driving thin film transistor (DTr), and an organic light emitting diode (E) in each pixel region constituting the display region DR of the first substrate 201, which may be a glass or plastic substrate The organic light emitting device 210 including the is located. At this time, for encapsulation of the first substrate 201 and the organic light emitting device 210 , the second substrate 202 faces the first substrate 201 through an adhesive or a filling sealing material 290 . are cemented

An organic light emitting device 210 composed of a plurality of electrodes, signal wires, and layers is formed on the first substrate 201, which will be described in detail. A semiconductor layer 226 is formed in each pixel region of the display region DR of the first substrate 201 . The semiconductor layer 226 includes an active region 226a made of silicon and forming a channel in the central portion, and source and drain regions 226b and 226c doped with high concentrations of impurities on both sides of the active region 226a.

A gate insulating layer 224 is formed on the semiconductor layer 226 . In each pixel region in the display region DR, a gate electrode 222 is formed above the gate insulating layer 224 to correspond to the active region 226a of the semiconductor layer 226, and a gate wire (not shown) extending in one direction. is formed.

In particular, a first passivation layer 228 is formed on the upper entire surface of the gate electrode 262 and the gate wiring (not shown). The first passivation layer 228 may be an organic insulating layer, and may be composed of an organic insulating layer according to the present invention. The first passivation layer 228 and the gate insulating film 264 thereunder are formed to expose the source and drain regions 226b and 226c located on both sides of the active region 226a constituting the center of the semiconductor layer 226 , respectively. 1 and 2 semiconductor layer contact holes 227a and 227b are provided.

Although not shown in the drawings, on the first passivation layer 228 including the semiconductor layer contact holes 227a and 227b, it crosses a gate line (not shown), defines a pixel area, and includes a data line (not shown) made of a metal material. ) and spaced apart from each other, power wiring (not shown) is formed. Optionally, the power wiring (not shown) may be formed on the gate insulating layer 224 on which the gate wiring (not shown) is formed to be spaced apart from and parallel to the gate wiring (not shown).

In addition, in the display region DR, the first and second semiconductor layer contact holes 227a and 267b are spaced apart from each other on the first passivation layer 228 including the first and second semiconductor layer contact holes 227a and 227b. Source and drain electrodes 232 and 234 contacting the source and drain regions 226b and 226c exposed through the ?

A semiconductor layer 226 including source and drain electrodes 232 and 234 , source and drain regions 226b and 226c in contact with the electrodes 232 and 234 , and a gate insulating film formed on the semiconductor layer 226 . 224 and the gate electrode 222 constitute a driving thin film transistor DTr. Although not shown in the drawings, a data line defining a pixel area is formed by crossing the gate line (not shown). In addition, the switching thin film transistor (not shown) has the same structure as the driving thin film transistor DTr and is connected to the driving thin film transistor DTr.

In FIG. 2, a top gate type in which the semiconductor layer 226 is made of polysilicon is shown as an example in the form of a driving thin film transistor (DTr) and a switching thin film transistor (not shown), but the semiconductor layer is made of pure and impurities. It may be formed in a bottom gate type made of amorphous silicon.

A second passivation layer 229 is formed on the entire surface of the first substrate 201 including the driving thin film transistor DTr and the switching thin film transistor (not shown) in the display area DR. A drain contact hole 235 is formed in the second passivation layer 229 , and the first electrode 252 constituting the organic light emitting diode E is connected to the drain of the driving thin film transistor DTr through the drain contact hole 235 . It may be in electrical contact with the electrode 234 . The second protective layer 229 may be formed of, for example, an organic insulating material to have a flat surface, and may be formed of an organic insulating layer according to the present invention.

On the other hand, the first electrode 252 constituting the organic light emitting diode (E) and the organic light emitting layer 254 in the region for substantially displaying an image on the upper portion of the second passivation layer 229, which may be composed of the organic insulating film according to the present invention ) and the second electrode 256 are sequentially formed. The first electrode 252 is connected to the drain electrode 234 of the driving thin film transistor DTr.

Exemplarily, as the first electrode 252 , as an anode electrode, indium-tin-oxide (ITO), which is a material having a relatively high work function value, may be used. Meanwhile, the second electrode 256 may be a cathode electrode, and is made of aluminum (Al) or an aluminum alloy (AlNd), which is a material having a relatively low work function value.

The organic light emitting layer 254 stacked between the first electrode 252 and the second electrode 256 may be formed of a single layer made of a light emitting material. In an alternative embodiment, the organic light emitting layer 254 is formed of a hole injection layer (HIL), a hole transporting layer (HTL), an emitting material layer (EML), an electron transporting layer (ETL). ) and a multilayer of an electron injection layer (EIL), it is possible to maximize the luminous efficiency.

Accordingly, when a predetermined voltage is applied to the first electrode 252 and the second electrode 256 according to the color signal selected from the organic light emitting device 210, the holes injected from the first electrode 252 and the second electrode ( 256) is transferred to the organic light emitting layer 254 to form excitons, and when these excitons are transitioned from an excited state to a ground state, light is generated and emitted in the form of visible light. In this case, in the case of the bottom emission type, the emitted light passes through the transparent first electrode 252 and goes out, so that the organic light emitting device 210 realizes an arbitrary image.

Meanwhile, the first electrode 252 is formed for each pixel area, and a bank layer 253 is positioned between the first electrodes 252 formed for each pixel area. The bank layer 253 may be in the form of an organic insulating film, and the organic insulating film according to the present invention may constitute the bank layer 253 . For example, the bank layer 253 surrounds each pixel and overlaps the edge of the first electrode 252 , and may form a lattice shape having a plurality of openings throughout the display area DR. That is, the bank layer 253 is formed in a matrix type of a lattice structure as a whole of the first substrate 201, and the first electrode 252 is separated for each pixel area by using the bank layer 253 as a boundary for each pixel area. formed into a structure.

Optionally, a passivation layer 280 may be formed on the entire surface of the organic light emitting device 210 . Since the second electrode 256 alone cannot completely suppress the penetration of moisture into the organic light emitting layer 254 , by forming the passivation layer 280 on the entire surface of the organic light emitting diode 210 , the organic light emitting diode (E), especially It is possible to suppress penetration of moisture into the organic light emitting layer 254 .

In one exemplary embodiment, the passivation layer 280 may have a single-layer structure composed of an inorganic insulating material such as silicon oxide or silicon nitride. In another exemplary embodiment, the passivation layer 280 includes a first inorganic layer (not shown) laminated on the second electrode 256 using an inorganic insulating material such as silicon oxide or silicon nitride, and an olefin-based resin. , an organic layer (not shown) laminated on top of the first inorganic layer (not shown) using a polymer material such as epoxy resin, fluororesin, polyethylene terephthalate (PET), and polysiloxane, such as silicon oxide or silicon nitride It may have a multi-layered structure such as a second inorganic layer (not shown) stacked on top of an organic layer (not shown) using an inorganic insulating material.

Even in the display device 200 according to the second embodiment, the organic insulating layer having a low dielectric constant may form the first passivation layer 228 , the second passivation layer 229 , and/or the bank layer 253 . Therefore, power consumption in the organic light emitting device 210 can be reduced, and the thickness of the first protective layer 228 , the second protective layer 229 , and/or the bank layer 253 can be made thin. can match In particular, when forming the pattern of the first passivation layer 228, since a sufficiently fine pattern is possible even with a small amount of light, it can be applied to a high-definition display device. can be utilized.

In addition, according to the present invention, the organic insulating film including the binder resin into which the porous supramolecules are introduced has improved adhesion to the substrate. Therefore, when the organic insulating film to which the organic material of the present invention is applied is used as the first protective layer 228 , the second protective layer 229 and/or the bank layer 253 , these protective layers 228 and 229 even by strong impact ) and/or the bank layer 253 has an advantage that it can be firmly attached to the substrate without being peeled off from the substrate.

Hereinafter, the present invention will be described in more detail with reference to exemplary embodiments, but the present invention is not limited to the technical ideas described in the examples.

Example One: porosity supramolecules introduced Acrylates Organic Insulation Film Manufacturing

An acrylate-based organic insulating film into which cucurbituril was introduced as a porous supramolecule was prepared.

Example 2: porosity supramolecules introduced Urethane acrylate polysiloxane Organic Insulation Film Manufacturing

A urethane acrylate polysiloxane-based organic insulating film into which cucurbituril was introduced as a porous supramolecule was prepared.

comparative example One: porosity supramolecules not added Acrylates Organic Insulation Film Manufacturing

Compared to Example 1, the procedure of Example 1 was repeated except that an acrylate-based binder resin was used without adding porous supramolecules to prepare an acryl-based organic insulating film.

comparative example 2: porosity supramolecules blended Acrylates Organic Insulation Film Manufacturing

Compared with Example 1, the procedure of Example 1 was repeated, except that the porous supramolecules were simply blended into the acrylate-based binder resin to prepare an acrylic organic insulating film.

comparative example 3: porosity supramolecules not added Urethane acrylate polysiloxane Organic Insulation Film Manufacturing

Compared with Example 2, the procedure of Example 2 was repeated to prepare an organic insulating film, except that only a urethane acrylate polysiloxane-based binder resin was used without adding porous supramolecules.

comparative example 4: porosity supramolecules blended Urethane acrylate polysiloxane Organic Insulation Film Manufacturing

Compared with Example 2, the procedure of Example 2 was repeated, except that the porous supramolecules were simply mixed with the urethane acrylate polysiloxane-based binder resin without adding the porous supramolecules to prepare an organic insulating film.

Experimental example 1: dielectric constant measurement

The dielectric constant of the organic insulating layer was measured by measuring the capacitance of each of the organic insulating layers prepared in the above Examples and Comparative Examples. The dielectric constant of each photosensitive organic insulating film was measured using the following equation for measuring the capacitance.

In the formula, C represents the capacitance, ε _s represents the dielectric constant of each organic insulating film material, and ε ₀ is the dielectric constant in free space, which is 8.854 × 10 ^-2 . d is the distance between the conductors and is the thickness of the organic insulating film. A molybdenum dot pattern electrode was used as a lower electrode, and an aluminum square pattern electrode was used as an upper electrode. The dielectric constant measurement results for each photosensitive organic insulating film measured according to this experimental example are shown in Table 1 below. When the porous supramolecules were introduced into the binder resin, it was confirmed that the dielectric constant was significantly lowered compared to the case where the porous supramolecules were not introduced and the case where the porous supramolecules were simply mixed with the binder resin.

Experimental example 2: Adhesion test

The adhesive force of the organic insulating films prepared in Examples and Comparative Examples was measured. First, in order to find out a significant difference in the adhesive force of each organic insulating film to the substrate, a cross-cut tape test was performed. A sample was prepared by coating each organic insulating film to a thickness of 3 µm on a 630 nm-thick glass substrate, and depositing a titanium film to a thickness of 0.5 µm on the organic insulating film. A pressure cooker test (PCT) was performed at 2 atm, 120° C., and 100% relative humidity. The samples were repeated 4 times for 6 hours each, for a total of 24 hours. In order to perform the Cross-Cut Tape test, a 5 x 5 square pattern was formed on each sample at an equal interval of 2 mm using a cutter. 3M transparent double-sided tape was applied to the specimen and removed, and the pattern was repeated and compared.

3A is an organic insulating film in which porous supramolecules are introduced into an acrylate-based binder resin (Example 1), FIG. 3B is an organic insulating film using only an acrylate-based binder resin (Comparative Example 1), and FIG. 3C is an acrylate-based binder resin. The cross-cut tape test results for the organic insulating film (Comparative Example 2) in which porous molecules were simply mixed with In addition, FIG. 4A is an organic insulating film in which porous supramolecules are introduced into a urethane acrylate polysiloxane-based binder resin (Example 2), FIG. 4B is an organic insulating film using only a urethane acrylate polysiloxane-based binder resin (Comparative Example 3), and FIG. 3C is a cross-cut tape test result for an organic insulating film (Comparative Example 4) in which porous molecules are simply mixed with a urethane acrylate polysiloxane-based binder resin. The measurement results are also shown in Table 1 below. According to the embodiment, the organic insulating film in which the porous supramolecules were introduced into the binder resin was not peeled off from the glass substrate. It was confirmed that peeling from the interface of the glass substrate from the second time.

Subsequently, the peel strength through a peel test was measured for the organic insulating films prepared in Examples and Comparative Examples, respectively. Each organic insulating film was applied to a thickness of 3 μm on a 630 nm thick glass substrate, and the strength when each organic insulating film was peeled off from the glass substrate was measured.

5A is an organic insulating film in which porous supramolecules are introduced into an acrylate-based binder resin (Example 1), FIG. 5B is an organic insulating film using only an acrylate-based binder resin (Comparative Example 1), and FIG. 5C is an acrylate-based binder resin. It is a graph showing the results of measuring the peel strength of the organic insulating film (Comparative Example 2) in which porous molecules were simply mixed with the . 6A is an organic insulating film in which porous supramolecules are introduced into a urethane acrylate polysiloxane-based binder resin (Example 2), FIG. 6B is an organic insulating film using only a urethane acrylate polysiloxane-based binder resin (Comparative Example 3), FIG. 6C is a graph showing the results of measuring the peel strength of the organic insulating film (Comparative Example 4) in which porous molecules are simply mixed with a urethane acrylate polysiloxane-based binder resin. The measurement results are also shown in Table 1 below. It was confirmed that the strength of the organic insulating film in which the porous supramolecules were introduced into the binder resin was greatly increased, and the adhesion to the substrate was greatly improved in the organic insulating film in which the porous supramolecules were introduced into the binder resin.

Dielectric constant and adhesion test of organic insulating film permittivity cross-cut Peel strength (N/m) Example 1
(Introduced porous supramolecules into acrylic resin) 3.01±0.2 no peeling 411 Example 2
(Introduced porous supramolecules to urethane acrylic siloxane resin 2.66±0.3 no peeling 550 Comparative Example 1 (acrylic resin) 3.38±0.1 slightly torn 339 Comparative Example 2
(Simple mixing of porous supramolecules in acrylic resin) 3.21±1.3 About 5% torn 336 Comparative Example 3 (urethane acrylic siloxane resin) 3.12±0.1 slightly torn 116 Comparative Example 4
(Simple mixing of porous supramolecules with urethane acrylic siloxane resin) 2.98±1.0 slightly torn 106

In the above, the present invention has been described based on exemplary embodiments and examples of the present invention, but the present invention is not limited to the technical ideas described in the above-described embodiments and examples. Rather, those skilled in the art to which the present invention pertains can easily propose various modifications and changes based on the above-described embodiments and examples. However, the fact that the scope of the present invention includes such modifications and variations will become more apparent from the appended claims.

100, 200: display device 101, 201: first substrate
102, 202: second substrate 110: liquid crystal layer
122, 222: gate electrodes 124, 224: gate insulating film
126, 226: semiconductor layer 128, 228: first protective layer
129, 229: second passivation layer 132, 232: source electrode
134, 234: drain electrode 140: pixel electrode
150: common electrode 210: organic light emitting device
252: first electrode 253: bank layer
254: organic light emitting layer 256: second electrode
280: passivation layer Tr: thin film transistor
TrA: switching area P: pixel area
DR: visible area NDR: non-display area
DTr: driving thin film transistor E: organic light emitting diode

Claims (11)

delete delete delete a first substrate on which a plurality of signal lines are arranged;
a thin film transistor positioned on the first substrate;
an organic insulating film positioned on the thin film transistor; and
a first electrode positioned on the organic insulating film;
The organic insulating layer includes a binder resin in which porous supramolecules selected from the group consisting of cyclodextrin, cucurbituril, calixarene, derivatives thereof, and combinations thereof are introduced into side chains.
5. The method of claim 4,
The binder resin is a (meth) acrylate resin, a urethane resin, a polysiloxane resin, and a display device selected from the group consisting of copolymers thereof.
delete 6. The method according to any one of claims 4 to 5,
The display device further comprising: a second substrate facing the first substrate; and a liquid crystal layer interposed between the first substrate and the second substrate.
8. The method of claim 7,
A display further comprising: a second electrode having a plurality of openings corresponding to the first electrode; and a protective layer positioned between the first electrode and the second electrode, wherein the protective layer is made of the same material as the organic insulating layer Device.
6. The method according to any one of claims 4 to 5,
It further comprises a bank layer, an organic light emitting layer, and a second electrode facing the first electrode positioned on the first electrode,
The bank layer is made of the same material as the organic insulating layer. 6. The method according to claim 4 or 5,
The binder resin is a display device having a repeating unit represented by the following formula (I).

(In formula (I), R ₁ is hydrogen or a methyl group; R ₂ and R ₃ are each independently substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 4 to 20 carbon atoms, And selected from the group consisting of a substituted or unsubstituted arylene having 6 to 20 carbon atoms, R ₄ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms , an acyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms; x is an integer from 2 to 10000; A is a binder A porous supramolecules introduced into the resin, selected from the group consisting of cyclodextrin, cucurbituril, calixarene, derivatives thereof, and combinations thereof)
6. The method according to claim 4 or 5,
The porous supramolecules include at least one compound represented by the following Chemical Formulas (II) to (IV).

(In Formula (II), R ₅ to R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a hydroxyalkyl group having 1 to 20 carbon atoms. , a carboxyl group, or _{a silicon molecule represented by Si r1r2r3} , wherein r1, r2, and r3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms; It is an integer from 5 to 8 as the number of unit units)

(In formula (III), R ₈ and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an alkylthio group having 1 to 30 carbon atoms. , an alkylcarboxyl group having 1 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, nitro group, 1 to 30 carbon atoms of an alkylamine group, an amine group, an aminoalkyl group having 1 to 30 carbon atoms, a (hetero)cycloalkyl group having 5 to 30 carbon atoms, and a (hetero)aryl group having 6 to 15 carbon atoms; Y is O, S or NH n is the number of glycouryl unit units, and is an integer from 4 to 20)

(In formula (IV), R ₁₀ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R ₁₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A silicon molecule represented by a carboxyl group having 1 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms or Si _r1r2r3 , wherein r1, r2, r3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms; o is an integer of 3 to 7 as the number of unit units)

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