KR101406382B1 - Chemically amplified positive-imageable organic insulator composition and method of forming organic insulator using thereof - Google Patents

Abstract

The present invention relates to a chemically amplified positive photosensitive organic insulating film composition and a method of forming an organic insulating film using the same, in a chemically amplified positive photosensitive organic insulating film composition comprising a binder resin, the binder resin is acid-decomposable in a ring structure It comprises a monomer (moiety) containing a protecting group, it characterized in that it comprises a polymer or a copolymer containing the monomer.
According to the present invention, unlike the prior art, by constructing a ring structured acid-decomposable protecting group and a newly developed chemical structure in a copolymer form, not only the sensitivity is significantly increased, but also the film reduction of the unexposed portion during development can be significantly reduced, It is possible to significantly reduce the occurrence of volatile vapor during exposure, it is possible to realize a high resolution display, and has the advantage of maintaining a high transmittance.

Description

CHEMICALLY AMPLIFIED POSITIVE-IMAGEABLE ORGANIC INSULATOR COMPOSITION AND METHOD OF FORMING ORGANIC INSULATOR USING THEREOF}

The present invention relates to a chemically amplified positive photosensitive organic insulating film composition and a method of forming an organic insulating film using the same, and more specifically, in forming an organic insulating film such as a liquid crystal display device, not only significantly increases the sensitivity, It relates to a chemically amplified positive photosensitive organic insulating film composition having excellent properties such as low volatility, transparent film color (non-yellowish/non-redish), high residual rate, and high resolution, and a method of forming the organic insulating film using the same.

In a display device such as a thin film transistor (TFT) type liquid crystal display device, an inorganic protective film such as silicon nitride (SiOx or SiNx) is conventionally used as a protective film for protecting and insulating a thin film transistor (TFT) circuit. However, there is a problem in that it is difficult to improve the aperture ratio due to high cost and delay due to vacuum deposition and high dielectric constant, resulting in an increasing demand for a low-dielectric and coatable liquid organic insulating film. .

In addition, the organic insulating film applied at this time gives a photosensitive function to the insulating film itself, thereby enabling formation of a fine pattern that provides an interconnection path between circuits without a separate additional process, through which a separate photo using a photoresist over a conventional inorganic insulating film Since the process can be reduced, there is a higher productivity and cost saving effect, and the use is increasing.

As the organic insulating film, a photosensitive resin, which is a polymer compound in which solubility in a specific solvent is changed by chemical reaction by light and electron beam, is generally used, and micro-processing of the circuit pattern is polarity of the polymer caused by the photoreaction of the organic insulating film. By change or crosslinking reaction. In particular, the organic insulating film material uses a change property of solubility in a developing solution such as an aqueous alkali solution after exposure.

The organic insulating film is classified into a positive type and a negative type according to solubility for the phenomenon of the photosensitive portion. In the positive photoresist, the exposed portion is dissolved by the developer by polarity change, and in the negative photoresist, the exposed portion does not melt in the developer through a crosslinking reaction and the unexposed portion is dissolved to form a pattern.

Among them, the positive type organic insulating film is not only advantageous in terms of working environment because there is no problem in the compatibility of the developer, unlike the disadvantage of foreign matter generation when the negative type organic insulating film is mixed with an alkali developer widely used in the existing mass production process. As it has the advantage of improving the resolution because it can prevent the swelling of the part not exposed to ultraviolet rays. In addition, after the organic film is formed, it is easy to remove by the peeling solution, and thus, when a defective panel occurs during the process, the substrate recovery and reusability are significantly improved by removing the organic film.

For this reason, the positive type organic insulating film composition is a case in which a composition in which an acrylic polymer resin used as a representative binder resin and a quinonediazide-based photoactive compound (PAC) is mixed is actively used. In recent years, the insulating film has been widely applied, and various high-brightness devices through high aperture ratio have been released.

Sensitivity is mentioned as one of the important properties among the properties required for the organic insulating film. Since the improvement of sensitivity enables a significant reduction in the production time in industrial production of display devices, in the present situation where the demand for liquid crystal display devices and the like is remarkably increasing, sensitivity is the most required for this type of organic insulating film. It is recognized as one of the important characteristics.

However, conventionally used acrylic photosensitive resins and organic insulating film compositions using PAC have low transmittance to ultraviolet rays and lack sensitivity, and in particular, for this fundamental reason, the UV-irradiated portion and the non-irradiated portion In many cases, the difference in solubility is not so large that it does not have sufficient resolution.

For example, in Korean Patent Nos. 10-0867948 and 10-0737723 using quinone diazide as an alkali-soluble resin and a photosensitive compound (PAC), a high content of quinone diazide (at least 5 wt% or more) and accordingly There is a problem that it is difficult to improve the sensitivity (100 mJ/cm 2 or less) due to the high absorbance of exposure light.

In addition, U.S. Patent No. 4139391 discloses a photosensitive resin organic insulating film composition prepared using a copolymer of an acrylic acid compound and an acrylate compound as a binder resin and an acrylate compound as a multifunctional monomer. Among the non-exposed areas, which must remain, the dissolution inhibiting ability of the non-exposed areas is not high, so the difference in dissolution rate between the exposed and non-exposed areas is not large enough, resulting in poor development characteristics, thereby making it difficult to obtain fine patterns of 15 microns or less.

As described above, the conventional positive type organic insulating film not only satisfies the problem of sensitivity sufficiently, but also has a limitation in its resolution to cope with the miniaturization for high integration.

Although it is possible to improve the sensitivity by increasing the transmittance to exposure light or increasing the development time by minimizing the content of PAC for the polymer used, there is a limitation in this method, and the solubility of unexposed parts occurs together, resulting in overall The residual film rate is lowered, and this has a defect that causes film bleeding and pattern damage in a large display substrate.

Solubility in developer through polarity change by removing the protecting group of the polymer binder through acid catalyst reaction using acid generated through the exposed light in order to solve the sensitivity problem of the positive organic insulating film containing the PAC. A chemically amplified positive organic insulating film was introduced. (Republic of Korea registered patent No. 0964733)

However, here, the acid-decomposable acetal protecting group used in the polymer binder has a very small size of product generated by decomposition during exposure, so that it has a low boiling point, and because of its high volatility, a large amount of vapor is generated during exposure, which easily contaminates the expensive lens of the exposure machine. In addition, the film has a significant disadvantage in that the thickness of the film through volume contraction is relatively reduced due to the separation and volatilization of the protecting group during exposure.

This problem is caused not only in the exposure area during the exposure process, but also when the residual non-exposed part film is exposed to a high-temperature and high-humidity environment between post-processes. It has technical limitations that cause it and ultimately affect device operation.

Therefore, there is a need to develop a new organic insulating film material that can solve these problems.

The present invention is to solve the above problems, and, unlike the conventional one, by constructing a ring structured acid-decomposable protecting group and a newly developed chemical structure in a copolymer form, not only significantly increases the sensitivity, but also reduces the film of the unexposed portion during development. It is an object of the present invention to provide a chemically amplified positive photosensitive organic insulating film composition with significantly reduced and a method for forming an organic insulating film using the same.

In addition, it is possible to significantly reduce the occurrence of volatile vapor during exposure, and also significantly reduce the exposure time, thereby reducing the process cost, realizing a high resolution display, and maintaining a high transmittance, chemically amplified positive photosensitive organic insulating film composition And it is an object to provide a method of forming an organic insulating film using the same.

In addition, by using an acid-decomposable protecting group having a ring structure, unlike conventional methods, it is bulky, thereby improving dissolution inhibiting power, and thereby, it is possible to maintain a higher residual film ratio in a non-exposed area, and thus an exposed portion and a nono It is an object of the present invention to provide a chemically amplified positive photosensitive organic insulating film composition capable of realizing a high-resolution pattern by increasing the difference in dissolution rate between the optical parts and a method of forming the organic insulating film using the same.

In addition, by using a ring-structured acid-decomposable protecting group, even when a small amount is added, compared with the prior art, the dissolution inhibiting effect is equal or superior, and thus an economical chemically amplified positive photosensitive organic insulating film composition and a method of forming the organic insulating film using the same It is aimed at providing.

The chemically amplified positive photosensitive organic insulating film composition according to the present invention for achieving the above object is a chemically amplified positive photosensitive organic insulating film composition comprising a binder resin, wherein the binder resin is an acid-decomposable protecting group having a ring structure It comprises a monomer (moiety) containing, characterized in that it comprises a polymer or a copolymer containing the monomer.

In addition, the unit is characterized in that it consists of at least one of the following formula 1-1 to 1-17.

<Formula 1-1> <Formula 1-2>

<Formula 1-3> <Formula 1-4>

<Formula 1-5> <Formula 1-6>

<Formula 1-7> <Formula 1-8>

<Formula 1-9> <Formula 1-10>

<Formula 1-11> <Formula 1-12>

<Formula 1-13> <Formula 1-14>

<Formula 1-15> <Formula 1-16>

<Formula 1-17>

In Formulas 1-1 to 1-17, R ₁ is a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group or a cyclic ether group, and R ₁ ^* Is a hydrogen group or a chain alkyl group, R ₂ is a chain alkyl group or a cyclic alkyl group, R ₃ is a hydrogen group or a chain alkyl group, R ₄ is a hydrogen group, a chain alkyl group or a cyclic alkyl group, R ₅ Is a chain alkene group or a cyclic alkene group, and R ₆ is a hydrogen group, a chain alkyl group, a cyclic alkyl group or an aryl group.

In addition, X is any one of a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group, or a cyclic ether group, and the same group as R ₁ may come. There, if no following the R ₁ X, if Y is coming, the X is left out, ends with no R ₁ X and Y is a group X is hydrogen.

In addition, Y is any one of a hydrogen group, a hydroxyl group, an epoxy group, an isocyanate group, an acryloyl group, an aryl group, a vinyl group, or an alkoxy group, and X ₁ ^* and X ₂ ^* are furan-based acid-decomposable protecting groups or pyran It is a (pyran)-based acid-decomposable protecting group.

In addition, the unit is characterized in that it consists of at least one of the following formula (2) or formula (3).

<Formula 2> <Formula 3>

In Formula 2 and Formula 3, G is the unit.

In addition, the polymer or the copolymer is characterized in that it further comprises at least one of the following formulas 4 to 7.

<Formula 4> <Formula 5>

<Formula 6> <Formula 7>

In the above formulas 4 to 7, R ₇ is a hydrogen group, a chain alkyl group, a cyclic alkyl group, a carbonyl group, an aromatic group containing at least one benzene ring, a chain olefin group, a cyclic olefin group, a chain ester group, a cyclic Ester group, chain ether group, cyclic ether group or any one of alkoxy, Z is hydrogen group, hydroxyl group, chain alkyl group, cyclic alkyl group, alkoxy group, acetoxy group, t-butoxy group or t-butoxy Any of the carbonyl groups, P is a carbonyloxy group (-COO-), methyl group (-CH ₂ -), methyloxy group (-CH ₂ O-) or oxygen group (-O-), m As a repeating unit of a monomer in a silver polymer, m≥0.

The polymer or the copolymer is characterized in that it further comprises at least one of the following formulas 8 to 10.

<Formula 8>

<Formula 9>

<Formula 10>

In Formulas 8 to 10, A and B are any one of a nitrogen group or an oxygen group, R ₈ is a hydrogen group, a hydroxyl group, an alkyl group or an epoxy group, n is a repeating unit of the monomer in the polymer, n≥1 to be.

In addition, the polymer or the copolymer is characterized in that any one of the following formula 11 to formula 12.

<Formula 11>

<Formula 12>

The binder resin has an average molecular weight of 2000 to 100000, and a dispersion degree of 1 to 10.

In addition, further comprising a dissolution inhibitor, the dissolution inhibitor is an alkali-soluble phenolic compound or a fluorene-based compound containing at least one phenol group, an alkali-soluble compound comprising at least one carboxylic acid group, or at least one Characterized in that at least one of the alkali-soluble compounds containing a benzoic acid group contains an acid-decomposable protecting group, in the dissolution inhibitor, the acid-decomposable protecting group is any one of the acid-decomposable protecting groups represented by the formulas 1-1 to 1-17. It is characterized by being.

In addition, further comprising a photoacid generator, the photoacid generator is made of at least one of an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid ester compound, or a traazine-based compound, based on 100 parts by weight of the binder resin, Characterized in that it comprises 0.1 to 10 parts by weight.

In addition, it characterized in that it further comprises a PhotoActiveCompound (PAC) containing a quinonediazide (quinonediazide) group, and further comprises an additive, the additive is a heat crosslinking agent, heat stabilizer, photocuring accelerator, surfactant, base quencher, Halle It characterized in that it consists of at least one of an anti-ionization agent, an adhesion aid, a light stabilizer or an antifoaming agent.

The thermal crosslinking agent is characterized by comprising a compound comprising at least one of a urea-based resin, melamine-based resin, isocyanate group, epoxy group, oxetane group, acrylate group, vinyl group, aryl group, hydroxy group or mercapto group The thermal stabilizer is characterized in that it is made of at least one of a phenol-based, lactone-based, amine-based, phosphorus-based or sulfur-based compound.

The light stabilizer is characterized in that it consists of at least one of a benzotriazole-based, triazine-based, benzophenone-based, hindered amino ether-based or hindered amine-based compound, and the adhesion aid is an isocyanate group, amino group, urea group, alkyl group , It is characterized by consisting of an alkoxy silane compound containing at least one of an epoxy group, an acrylate group, a vinyl group or a mercapto group.

The base quencher is a nitrogen-containing organic compound, and the nitrogen-containing organic compound is characterized in that it consists of at least one of a primary amine, a secondary amine, a tertiary amine or an amide compound.

Next, a method of forming an organic insulating film using the chemically amplified positive photosensitive organic insulating film composition according to the present invention includes the organic insulating film composition on a substrate, a source/drain or a silicon nitride layer formed on the substrate. Applying; Pre-bake the organic insulating film composition; Selectively exposing and then developing the organic insulating film composition to form a pattern; And forming an insulating protective film by fully exposing and curing the organic insulating film composition.

In addition, in the step of forming the pattern, a post-bake process is added between exposure and development.

According to the chemically amplified positive photosensitive organic insulating film composition and the method of forming the organic insulating film using the same, unlike the conventional method, the structure has a ring structured acid-decomposable protecting group and a newly developed chemical structure in the form of a copolymer, thereby significantly improving sensitivity. In addition, it has the advantage of significantly reducing the film reduction of the unexposed portion during development.

In addition, it is possible to significantly reduce the occurrence of volatile vapor during exposure, and also significantly reduce the exposure time, thereby reducing the process cost, realizing a high resolution display, and maintaining high transmittance.

In addition, by using an acid-decomposable protecting group having a ring structure, unlike conventional methods, it is bulky, thereby improving dissolution inhibiting power, and thereby, it is possible to maintain a higher residual film ratio in a non-exposed area, and thus an exposed portion and a nono There is an advantage in that a high resolution pattern can be realized by increasing a difference in dissolution speed between miners.

In addition, by using an acid-decomposable protecting group having a ring structure, even when a small amount is added, the dissolution inhibiting effect is equal or superior, which is economical, compared to the prior art.

1 is a cross-sectional view showing a unit cell device of a TFT-LCD having a high aperture ratio to which the chemically amplified positive photosensitive organic insulating film composition of the present invention is applied.
Figure 2a is a surface optical picture of the organic insulating film pattern evaluated for resolution according to the composition of Example 2-1 of the present invention
Figure 2b is a surface optical picture of the organic insulating film pattern evaluated for resolution according to the composition of Example 2-2 of the present invention
Figure 2c is a surface optical picture of the organic insulating film pattern evaluated for resolution according to the composition of Comparative Example 1 of the present invention
Figure 2d is a surface optical picture of the organic insulating film pattern to evaluate the resolution according to the composition of Comparative Example 2 of the present invention
<Description of drawing code>
1: Lower substrate
2: gate insulating film
3: gate electrode
4: Semiconductor layer
5: source electrode
6: drain electrode
7: Storage electrode
8: Data line
9: Organic insulating film
10: pixel electrode

Hereinafter, one preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings with respect to the chemically amplified positive photosensitive organic insulating film composition and the method of forming the organic insulating film using the same. The present invention can be better understood by the following examples, the following examples are for illustrative purposes of the present invention, and are not intended to limit the protection scope defined by the appended claims.

First, the chemically amplified positive photosensitive organic insulating film composition includes a binder resin, and the binder resin comprises a monomer containing a ring structured acid-decomposable protecting group, and a polymer or air containing the monomer Characterized in that it comprises a coalescence.

Here, the unit body means a minimum unit, including a monomer, and is defined to include any substance containing an acid-decomposable protecting group having a ring structure.

In addition, the unit is characterized in that it consists of at least one of the formulas 1-1 to 1-17 and at least one of the formulas 2 to 3. In addition, the copolymer is characterized in that it further comprises at least one of the formulas 4 to 7.

When the acid-decomposable protecting group having a ring structure represented by Chemical Formulas 1-1 to 1-17 is applied to an organic insulating film for a liquid crystal display, the organic insulating film remains after pattern formation to function as an insulating and protective film for wiring.

Accordingly, as a result of applying the acid-decomposable protecting group of the ring structure represented by the formulas 1-1 to 1-17 of the present invention to the organic insulating film, by serving to control the solubility in the composition, the sensitivity required for the organic insulating film, It was confirmed that the effect of improving the residual film rate, volatile vapor and resolution was very good.

In addition, it was confirmed that it shows a high transmittance characteristic in the visible light region of 400nm or more.

In addition, the crosslinked structures of Formulas 2 to 3 in the form in which the units are linked are more effective in suppressing solubility, and are effective for higher residual ratios and resolutions.

In the binder resin, when the copolymer further comprises the formulas 2 to 7 in addition to the unit, it is preferable because the properties of the organic insulating film can be further improved.

It may be formed by polymerizing any one of the formulas 2 to 14, or may be made by simply mixing the copolymers. However, when mixing each polymer, at least one acid-decomposable protecting group represented by Chemical Formulas 1-1 to 1-17 should be included.

In addition, the binder resin may be made of any one of the polymerized formulas 8 to 12, or may be made by simply mixing the copolymers. However, when mixing each polymer, at least one acid-decomposable protecting group represented by Chemical Formulas 1-1 to 1-17 should be included.

Here, the average molecular weight of the binder resin is preferably 2000 to 200000, more preferably 5000 to 30000 is effective. In addition, the dispersion degree of the binder resin is preferably 1 to 10, more preferably 1.1 to 5.0 is effective. When it is outside the range of the optimum average molecular weight and dispersion degree, there is a problem in that the properties of the organic insulating film are significantly lowered or the economic efficiency is poor.

In addition, the organic insulating film composition of the present invention, it is preferable to further include a solubility inhibitor, the solubility inhibitor is an alkali-soluble phenolic compound or a fluorene (fluorene)-based compound, at least one carbohydrate containing at least one phenol group It is preferable that at least one of an alkali-soluble compound containing an carboxylic acid group or an alkali-soluble compound containing at least one benzoic acid group contains an acid-decomposable protecting group. In the dissolution inhibiting agent, the acid-decomposable protecting group is preferably any one of the acid-decomposing protecting groups represented by Formulas 1-1 to 1-17.

Such a dissolution inhibiting agent is effectively mixed with the binder resin, thereby improving sensitivity and facilitating pattern formation.

The molecular weight of the dissolution inhibiting agent is preferably 5000 or less in the case of a monomolecular structure, and effective in the case of a polymer structure is 5000 to 30000.

As mentioned above, the binder resin of the present invention can be generated in the residual organic pattern film during or after the exposure process by using a minimum amount of an acid-decomposable protecting group to show sufficient dissolution inhibiting ability for a developer in a non-exposed part. The amount of volatile vapors can be significantly reduced, and the exposed part is deprotected at a very fast rate by catalytic reaction due to the action of the acid triggered from the photo acid generator (PAG) in the exposure process, solubility in the developer rapidly By increasing, the dissolving contrast of the organic insulating film composition is increased, and thus there is an advantage that a fine circuit pattern of high resolution can be formed even under a light source of i, g, and h-line composite wavelengths.

In addition, by adding at least one of a photoacid generator, an additive, and an organic solvent to the binder resin, its performance can be maximized.

First, the photoacid generator may be any material as long as it is capable of generating acid when exposed to a live-line radiation and does not degrade optical properties such as protective film formation and permeability, but preferably at a wavelength of 250 nm to 400 nm. It is effective to use a material that has adequate light absorption and can maintain excellent transmittance and transparent color of the organic insulating film in the visible light region of 400 nm or more.

Thus, in the present invention, after several experiments, it was confirmed that the photoacid generator, an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid ester compound, or a traazine-based compound is most suitable, and was used.

The onium heat compound is effective to use an iodonium salt, a forest phonium salt, a phosphonium salt, a diazonium salt, an ammonium salt or a pyridinium salt, and the halogen-containing compound is a haloalkyl group-containing hydrocarbon compound or a haloalkyl group-containing heterocyclic compound It is effective to use.

In addition, it is effective to use β-ketosulfone, β-sulfonyl sulfone, or α-diazo compound thereof, and the sulfonic acid ester compound is an alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, arylsulfonic acid ester, imino sulfo It is effective to use nate or amide sulfonate.

In addition, the content of the photoacid generator, it is preferable to contain 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the binder resin, it is effective. If it is less than 0.1 part by weight, there is a problem that it is difficult to realize the sensitivity at a sufficient speed due to the limitation of the amount of acid generated during exposure, and when it exceeds 10 parts by weight, there may be a problem of deterioration in permeability and discoloration of the coating film.

Next, the additive is preferably made of at least one of a heat crosslinking agent, a heat stabilizer, a photocuring accelerator, a surfactant, a base quencher, an antihalation agent, an adhesion aid, a light stabilizer or an antifoaming agent.

The heat crosslinking agent is added to improve heat resistance and mechanical properties (hardness, strength) of the coating film by smoothly generating a crosslinking reaction between the binder resin and the heat crosslinking agent through an exposure heat treatment process when forming the organic insulating film. , Urea-based, melamine-based resin, isocyanate group, epoxy group, oxetane group, acrylate group, vinyl group, aryl group, hydroxy group or consisting of a compound containing at least one of mercapto groups is most effective in the present invention .

In addition, the thermal stabilizer is used to suppress discoloration and permeability deterioration caused by heat generated during the post-processing or device reliability conditions of the formed organic film, and at least one of phenol, lactone, amine, phosphorus or sulfur compounds It is most preferred in the present invention to consist of one.

The light stabilizer is used to maximize the light resistance of the organic insulating film composition, and the type of the light stabilizer having such properties is not particularly limited, but benzotriazole-based, triazine-based, benzophenone-based, hindered amino ether-based, or The use of at least one of the hindered amine-based compounds is most effective in the present invention.

In addition, the photo-curing accelerator may be any material that can promote acid generation during exposure, and the adhesion aid includes at least one of a socionate group, an epoxy group, an acrylate group, a vinyl group, or a mercapto group. It is preferably made of an alkoxy silane compound.

The base quencher serves to control the diffusion of the generated acid, and it is preferable to use a nitrogen-containing organic compound whose basicity does not change, more preferably a primary amine, secondary amine, tertiary amine or amide compound It is most effective to consist of at least one.

In addition, the surfactant (surfactant) is used to improve the coating properties and thickness uniformity through improved wetting characteristics (wetting) of the substrate and the organic insulating film composition, the type is not particularly limited, but preferably polyoxy lauryl ether , Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether or polyethylene glycol dilaurate. It is preferable that the content of these surfactants is 3 parts by weight or less based on 100 parts by weight of the positive organic insulating film composition of the present invention.

In addition, a commonly used photocuring accelerator, an antihalation agent (leveling agent), an antifoaming agent, and the like may be used, and if necessary, various other additives may be used to improve desired characteristics.

In addition, an organic solvent may be used for the organic insulating film composition, and the organic solvent is preferably at least one of an alcohol-based, acetate-based, ether-based, glycol-based, ketone-based, or carbonate-based organic solvent, and more preferably. It is most effective to use propylene glycol methyl ether acetate (PGMEA) because it has excellent coatability and excellent film thickness uniformity of the organic insulating film even on a large glass substrate.

In addition, R _1, R _2, R ₃ and the like defined in the above formulas are common to all formulas. That is, R _1, R _2, R ₃ and the like are not defined differently according to the formula.

Next, in the method of forming an organic insulating film using the chemically amplified positive photosensitive organic insulating film composition of the present invention, the organic insulating film composition is coated on the substrate, the source/drain or silicon nitride layer formed on the substrate. Step (S10), pre-bake the organic insulating film composition (S20), selectively exposing and developing the organic insulating film composition to form a pattern (S30) and the organic insulating film composition in front It comprises a step (S40) of forming an insulating protective film by exposure and heat treatment (cure bake).

As the substrate, glass or transparent plastic resins commonly used for flat panel displays (FPDs) such as liquid crystal displays (TFT-LCDs) and OLEDs are mainly used, but are not particularly limited depending on the characteristics of the display device used. For example, the organic insulating film is formed on an ITO metal film used as an anode for OLED, or on an EL layer of each RGB color, or on a metal film constituting a gate electrode on a substrate such as glass to protect and insulate. Can be used for purposes.

In the present invention, the method of applying the organic insulating film composition to the upper portion of the substrate, such as a spray coating method, a roll coating method, a coating method using a slit nozzle such as a discharge nozzle type coating method, a rotational coating method such as a central drop spin method, Extrusion coating method, bar coating method, and the like, can be coated by combining two or more coating methods.

The applied film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but is usually applied so that the film thickness is 0.5 to 10 μm after drying. The pre-baking step performed thereafter is a process of volatilizing the solvent by applying vacuum, infrared rays, or heat to obtain a coating film having no fluidity after forming the coating film. The heating conditions vary depending on the type or composition of each component, but in the case of heating a hot plate, the heating is performed at 60 to 130°C for 30 to 300 seconds, and when using a thermal oven to 60 to 150°C. It is common to heat for 30 to 1,000 seconds. Next, the selective exposure process is an excimer laser, far ultraviolet, ultraviolet, visible, electron beam, X-ray or g-ray (wavelength 436 nm), i-ray (wavelength 365 nm), h-ray (wavelength 405 nm) or mixed light thereof. It is carried out while investigating. The exposure may be performed by a contact method, a proximity method, a projection exposure method, or the like.

In the present invention, after performing the alkali development, it is characterized in that the step of performing an entire surface exposure and annealing the organic insulating film composition. A thermal crosslinking agent or the like is applied to the composition of the organic insulating film composition of the present invention for the high-temperature firing. The heat treatment step is performed for 30 minutes to 2 hours at a temperature of 150°C to 250°C using a heating device such as a hot plate or oven. After the heat treatment, a completely cross-linked cured pattern is obtained.

The organic insulating film formed in this way, as shown in the display device of Figure 1, the substrate 10, the gate electrode 20, the gate insulating film 30, a semiconductor layer 40 made of silicon nitride or the like, source 51 , In the stacked structure consisting of the drain 52 and the protective film 60, it is used for the gate insulating film 30 or the protective film 60.

Hereinafter, in the chemically amplified positive photosensitive organic insulating film composition of the present invention, a specific example of a method for polymerizing a Vine resin will be described.

Polymerization method of binder resin (first embodiment)

Example 1-1

A binder resin represented by Chemical Formula 13 below was prepared as follows. In Chemical Formula 13, a is 0.25, b is 0.10, c is 0.20, d is 0.10, e is 0.15, and f is 0.20.

<Formula 13>

4-acetoxystyrene 35 mol%, alpha-methylstyrene 20 mol%, methylmethacrylate 10 mol%, dicyclopentanyl acrylate 15 mol %, 45% by weight of a mixture of monomers consisting of 20 mol% of glycidyl methacrylate and propylene glycol methyl ether acetate (PGMEA), an organic solvent based on the weight of the mixture, is heated to 70°C to purge nitrogen. ) State and mix thoroughly.

At this time, azonitrile-based initiator 2,2'-azobis (2,4-dimethyl-valeronitrile) (Vazo 52G) was added 4% by weight compared to the total monomer mixture and chain transfer agent 1-dodecanethiol 6% by weight PGMEA 20% by weight And dissolved, and reacted for 6 hours after dropping the mixture into the monomer mixture. Thereafter, an additional initiator (Vazo 52G) is added to 2% by weight of the total monomer, and after 3 hours of reaction, polymerization is terminated by adding 2,5-bis(1,1-dimethylbuthyl)hydroquinone.

Thereafter, 0.1% by weight of hydrochloric acid is added and mixed with respect to the weight of the polymer, followed by stirring at 45°C for 4 hours or more. Thereafter, the temperature was lowered to 25°C, and 3,4-dihydro-2H-pyran was added in an amount of 0.72 times the number of moles compared to the number of moles of 4-acetoxystyrene contained in the polymer resin, followed by stirring under a nitrogen atmosphere for 48 hours or more. Order.

When the reaction is completed, the temperature is lowered to room temperature to neutralize the sodium hydroxide by adding the same number of moles as the hydrochloric acid used above, and then extracting only the polymer resin portion with excess distilled water and then using distilled water several times. Wash the polymer resin. The finally obtained polymer resin is left to stand in a vacuum drying oven at 40° C. for 24 hours or more to remove moisture and dry.

Example 1-2

The binder resin represented by Chemical Formula 14 below was prepared as follows. In Formula 14, a is 0.25, b is 0.10, c is 0.20, d is 0.10, d is 0.15, and e is 0.20.

<Formula 14>

3, 3-diethyl-oxetane methacrylate and dicyclopentenyl acrylate, respectively, in place of glycidyl methacrylate and dicyclopentanyl acrylate used as monomers in the polymerization of the polymer resin. In addition, other polymerization methods were performed in the same manner as in Example 1-1, except that ethenoxy-methyl-benzene was used instead of 3,4-dihydro-2H-pyran.

Example 1-3

A binder resin represented by Chemical Formula 15 below was prepared as follows. In the following formula 15, a is 0.20, b is 0.10, c is 0.20, d is 0.10, e is 0.25, and f is 0.15.

<Formula 15>

When polymerizing the polymer resin, hydroxypropyl acrylate is substituted for methyl methacrylate used as a monomer, and 2-(2-Vinyloxy-ethyl)- instead of 3,4-dihydro-2H-pyran as an acid-decomposable protecting group. Other polymerization methods were performed in the same manner as in Example 1-1, except that naphthalene was used in an amount of 0.68 times mole number compared to the mole number of 4-acetoxystyrene used in the polymerization of the polymer resin.

Example 1-4

The binder resin represented by Chemical Formula 16 below was prepared as follows. In the following Chemical Formula 16, a is 0.30, b is 0.05, c is 0.20, d is 0.10, e is 0.20, and f is 0.15.

<Formula 16>

Instead of glycidyl methacrylate used as a monomer during polymerization of the polymer resin, benzyl methacrylate is added, and as an acid-decomposable protecting group, 3,4-dihydro-2H-pyran. instead of 1,4-cyclohexanemethanol Other polymerization methods were performed in the same manner as in Example 1-1, except that vinyl ether was used in an amount of 0.86 times the number of moles compared to the number of moles of 4-acetoxystyrene used in the polymerization of the polymer resin.

Example 1-5

The binder resin represented by Chemical Formula 17 below was prepared as follows. In Chemical Formula 17, a is 0.25, b is 0.10, c is 0.20, d is 0.20, and e is 0.25.

<Formula 17>

In place of 4-acetoxystyrene and methyl methacrylate used as monomers in the polymerization of the polymer resin, methacrylic acid and 2-hydroxypropyl acrylate are respectively added and used. The other polymerization method was the same as in Example 1-1, except that 3,4-dihydro-2H-pyran was used as a degradable protecting group in an amount of 1.2 times the number of moles compared to the number of moles of methacrylic acid used in polymerizing the polymer resin. Was performed.

Example 1-6

The binder resin represented by Chemical Formula 18 below was prepared as follows. In Chemical Formula 18, a is 0.25, b is 0.10, c is 0.15, d is 0.25, and e is 0.25.

<Formula 18>

When polymerizing the polymer resin, carboxytetracyclododecyl methacrylate is used in place of 4-acetoxystyrene, except for alphamethylstyrene used as a monomer, and 3,4-dihydro-2H-pyran is used as an acid-decomposable protecting group when polymerizing the polymer resin. Other polymerization methods were carried out in the same manner as in Example 1-1, except that the molar number of carboxytetracyclododecyl methacrylate used was 0.72 times the number of moles.

Example 1-7

A binder resin represented by Chemical Formula 19 below was prepared as follows. In Chemical Formula 19, a is 0.15, b is 0.25, c is 0.15, d is 0.20, and e is 0.25.

<Formula 19>

In place of the polymerization of the polymer resin, a methacrylic acid is used instead of the methyl methacrylate used as a monomer, and 3,4-dihydro-2H-pyran is used as an acid-decomposable protecting group in 4-acetoxy style used in the polymerization of the polymer resin. Other polymerization methods were performed in the same manner as in Example 1-1, except that they were used in an amount of 1.2 times the mole number compared to the total mole number of the ren and methacrylic acid sheet.

Example 1-8

The binder resin represented by Chemical Formula 20 below was prepared as follows. In Chemical Formula 20, a is 0.20, b is 0.10, c is 0.20, d is 0.25, and e is 0.25.

<Formula 20>

Except for the hydroxypropyl acrylate used as a monomer in the polymerization of the polymer resin, as the acid-decomposable protecting group, bisphenol A-diethoxy divinyl ether is used instead of 3,4-dihydro-2H-pyran. Other polymerization methods were carried out in the same manner as in Example 1-5, except that they were used in an amount of 0.68 times mole number compared to the mole number of the acid.

Example 1-9

A binder resin represented by Chemical Formula 21 below was prepared in the following manner. In the following Chemical Formula 21, a is 0.20, b is 0.15, c is 0.15, d is 0.10, d is 0.20, and e is 0.20.

<Formula 21>

As an acid-decomposable protecting group, 1,4-cyclohexanedimethanol divinyl ether instead of 3,4-dihydro-2H-pyran was used in an amount of 0.58 times mole number compared to the mole number of 4-acetoxystyrene used in the polymer resin polymerization. The polymerization method was carried out according to the case of Example 1-1.

Example 1-10

The polymer resins represented by Chemical Formulas 13 and 17 were prepared as described above, and binder resins prepared by mixing each polymer resin in a weight ratio of 60:40 were prepared.

Example 1-11

Polymer resins represented by the following Chemical Formulas 22 and 23 were prepared as follows, and a binder resin was prepared by mixing the polymeric resin represented by Chemical Formula 22 and the polymeric resin represented by Chemical Formula 23 in a weight ratio of 60:40.

In the following Chemical Formula 22, a is 0.30, b is 0.25, c is 0.20, d is 0.25, and in Chemical Formula 23, a is 0.45 and b is 0.55.

<Formula 22>

The other polymerization method was carried out according to the case of Example 1-5, except for the hydroxypropyl acrylate used as a monomer in the polymerization of the polymer resin, polymerization was carried out to terminate the reaction.

 <Formula 23>

After dissolving 50 g of polyhydroxystyrene (weight average molecular weight 12,000) resin in 150 g of PGMEA, 23.33 g equivalent to 0.45 times the number of moles of hydroxystyrene in the polymer resin with 3,4-dihydro-2H-pyran. added and 12M hydrochloric acid (HCl ) Was dropped 0.4 g and reacted by stirring at 25° C. for more than 48 hours under a nitrogen atmosphere. When the reaction is completed, the temperature is lowered to room temperature to neutralize the sodium hydroxide by adding the same number of moles as the hydrochloric acid used above, and then extracting only the polymer resin portion with excess distilled water and then using distilled water several times. Wash the polymer resin. The finally obtained polymer resin is left to stand in a vacuum drying oven at 40° C. for 24 hours or more to remove moisture and dry.

Example 1-12

The polymer resin represented by Chemical Formula 24 below and the acid-decomposable dissolution inhibitor represented by Chemical Formula 25 are prepared as follows, and the polymer resin represented by Chemical Formula 24 and the acid-decomposable dissolution inhibitor represented by Chemical Formula 25 below are mixed in a weight ratio of 75:25. A binder resin was prepared.

In Chemical Formula 24, a is 0.15, b is 0.25, c is 0.20, d is 0.20, and e is 0.20.

<Formula 24>

Except for the alpha methyl styrene used as a monomer during polymerization of the polymer resin, 0.7 times the number of moles compared to the total number of moles of 4-acetoxystyrene used for polymerization of 3,4-dihro-2H-pyran as an acid-decomposable protecting group. Other polymerization methods were performed in the same manner as in Example 1-1, except that the reaction was carried out.

<Formula 25>

10 g of bisphenol fluorene is dissolved in 110 g of ethyl aceate, dissolved, and ethenoxy-methyl-benzene as an acid-decomposable protecting group is added 2.5 times the number of moles of bisphenol fluorene, and 0.1 g of 12M HCl is added dropwise to react at 25°C for 24 hours or more. . After neutralization and purification with aqueous sodium bicarbonate solution, a dissolution inhibitor protected with the acid-decomposable protecting group was extracted through petroleum ether.

Example 1-13

The polymer resin represented by Chemical Formula 26 below and the acid-decomposable dissolution inhibitor represented by Chemical Formula 27 are prepared as follows, and the polymer resin represented by Chemical Formula 26 and the acid-decomposable dissolution inhibitor represented by Chemical Formula 27 are mixed in a weight ratio of 70:30. A binder resin was prepared.

In the following formula 26, a is 0.30, b is 0.25, c is 0.20, and d is 0.25.

<Formula 26>

 Except for the alpha methyl styrene used as a monomer in the polymerization of the polymer resin, p-tert-butoxystyrene was added instead of 4-acetoxy styrene to hydrolyze p-tert-butoxystyrene using concentrated hydrochloric acid after polymerization. Other polymerization methods were carried out according to the case of Example 1-1, except that the reaction proceeds to the hydrolysis reaction and terminates.

<Formula 27>

After dissolving 10 g of α,α-Bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl)-ethylbenzene in 110 g of ethyl aceate and dissolving it, 1,4-cyclohexanedimethanol divinyl ether and Cyclohexyl vinyl ether was added 0.45 times and 0.3 times the number of moles of α,α-Bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl)-ethylbenzene, and 0.1 g of 12M HCl was added dropwise to 25 It reacts for 24 hours or more at ℃. After neutralization and purification with an aqueous sodium bicarbonate solution, a dissolution inhibitor protected with the acid-decomposable protecting group was extracted through a mixed solvent of methanol and distilled water.

Evaluation of physical properties of the organic insulating film by the organic insulating film composition (second example)

Next, an organic insulating film composition is prepared by adding a photoacid generator, an organic solvent, a crosslinking agent, and other additives together with the binder resin prepared by the polymerization method, and the results of evaluating the physical properties of the organic insulating protective film formed therethrough are described. Shall be

On the substrate, the organic insulating film compositions prepared in Examples 2-1 to 2-8 below were applied onto the substrate, spin-coated at a rotational speed of 500 to 1,500 rpm per minute, exposed on a hot plate, and at a temperature of 90°C. It was dried for 90 seconds to form a coating film. The formed coating film formed a thickness of 1.0 to 5㎛ depending on the rotation speed.

Example 2-1

With respect to 100 parts by weight of the organic solvent (PGMEA), the binder resin of Formula 12 polymerized by Example 1-1 is 31.96 parts by weight, the photo-acid generator N-hydroxynaphthalimide triflate is 0.64 parts by weight, and triethylamine (base quencher) triethylamine) 0.09 parts by weight, and 0.10 parts by weight of surfactant F-475 (Dainippon Ink & Chemicals) for coating properties, completely dissolved, and rotated on a glass substrate at a rotation speed of 500 rpm to 1000 rpm for 90 seconds on a hot plate for 90 seconds. After drying at ℃ ℃ to form a coating film of 3.5㎛ ~ 4.0㎛ thickness, after exposure by the amount of light after developing in 2.38wt% TMAH (tetramethylammonium hydroxide) developer at 23 ℃ to 24 ℃ for 80 seconds and the thickness of the coating film and 20㎛ L The exposure dose for implementing the /S pattern was confirmed, and the minimum line width that could be resolved was confirmed.

Subsequently, the total thickness of the coating film formed through a curing bake process for 1 hour in an oven at 220° C. and the light transmittance at a wavelength of 450 nm was measured after exposure to ultraviolet rays on the organic film at an exposure dose of 500 mJ/cm 2 to 700 mJ/cm 2.

Example 2-2

As a binder resin, an experiment was conducted in the same manner as in Example 2-1, except that the binder resin of Formula 14 polymerized by Example 1-3 was used.

Example 2-3

As a binder resin, experiments were carried out in the same formulation and method as in Example 2-1, except that the binder resin of Formula 16 polymerized by Example 1-5 was used.

Example 2-4

The experiment was conducted in the same manner as in Example 2-1, except that the binder resin of Formula 18 polymerized by Example 1-7 was used as the binder resin.

Example 2-5

Experiments were conducted in the same manner as in Example 2-1, except that the binder resin of Formula 19 polymerized by Example 1-8 was used as the binder resin.

Example 2-6

Experiments were conducted in the same manner as in Example 2-1, except that the binder resin of Chemical Formula 20 polymerized by Example 1-9 was used as the binder resin.

Example 2-7

As the binder resin, the examples except that the copolymers of the formulas 21-1 and 21-2 polymerized/synthesized according to Examples 1-11 and the dissolution inhibitor were used in a binder resin mixed at a weight ratio of 60:40. The experiment was conducted in the same formulation and method as in 2-1.

Example 2-8

As the binder resin, the examples except that the copolymers of the formulas 22-1 and 22-2 polymerized/synthesized according to Examples 1-12 and the dissolution inhibitor were used in a binder resin mixed at a weight ratio of 75:25. The experiment was carried out in the same formulation and method as in 2-1.

Comparative Example 1

 Polymerized as shown in the following formula 28 using ethoxyethoxystyrene (aka PEES) monomer using ethylvinyl ether as an acid-decomposable protecting group of hydroxystyrene. The experiment was conducted in the same formulation and evaluation method as in Example 2-1, except that the copolymer was used as the binder resin. In the following formula 28, a is 0.30, b is 0.10, c is 0.20, d is 0.10, e is 0.10, and f is 0.20.

<Formula 28>

Comparative Example 2

Experiment with the same evaluation method as in Example 2-1, except that an existing organic insulating film composition (JSR 411B) composed of a PAC compound containing an alkali-soluble acrylic resin and a quinonediazide group as a binder resin was used. Was performed.

Using the patterns formed in the above Examples and Comparative Examples, an appropriate exposure amount (Eop), a residual film rate after development, a residual film rate after cure bake, thermal contraction rate, resolution, and total light transmittance can be measured by the following method. Did.

1) Optimal exposure amount (Eop)

When the width (CD) is observed by an optical microscope (optical microscopy) after the exposure (UV exposure) and development (development) process using a photomask (photomask) with a pattern of 20㎛ is engraved when the 20㎛ pattern is realized The exposure dose of was confirmed.

2) Residual rate after development%

The thickness of the coated organic film before development and the residual organic film after development were measured, and the residual film rate after development was calculated using the following equation. Here, the residual film ratio after the development is derived by a calculation formula of (thickness of the coated film after development)/(thickness of the coated film before development)x100(%).

3) Residual rate after cure bake%

After the development, the residual organic film was left in an oven at 220° C. for 1 hour to undergo a cure bake process, and then the thickness of the residual organic film was measured, and the residual film rate after cure bake was calculated using the following formula. Here, the residual film rate after the cure bake is derived by the calculation formula of (thickness of the coating film after cure bake) / (thickness of the coating film before development) x 100 (%).

4) Heat shrinkage (shrinkage %)

After development, the thickness of the residual organic film and the thickness of the residual organic film after cure bake were measured, respectively, and the heat shrinkage ratio was calculated using the following equation. Here, the thermal contraction rate is derived by a calculation formula of (thickness of the coating after development-thickness of the coating after curing bake)/(thickness of the coating after development)x100(%).

5) Resolution

Based on the 1:1 line&space (L/S) pattern, the pattern width (CD) that can be most finely formed without distortion or tear-off of the pattern after development was measured. The optical micrograph of the pattern is as shown in FIGS. 2A to 2D.

6) Total light transmittance (%)

After performing the final cure bake process, the organic film having a thickness of 2.5 µm was measured for light transmittance at a wavelength of 450 nm using a UV-Visible-Spectrometer and PDA UV-Vis Spectro (Scinco).

Table 1 below shows the appropriate exposure amount (Eop), the residual film rate after development, the residual film rate after curing bake, the thermal shrinkage rate, the resolution, and the light transmittance for the thin films coated by Examples 2-1 to 2-8. It shows the results of the evaluation.

Example Appropriate exposure amount (mJ/cm2) After development
Residual rate (%) After cure bake
Residual rate (%) Heat shrinkage rate
(%) resolution
(㎛) Light transmittance
(%) Example 2-1 40 99.1 81.0 18.26 ~3 94.29 Example 2-2 35 100.0 84.3 15.70 ~3 95.26 Example 2-3 40 98.5 80.3 18.48 ~3 95.49 Example 2-4 50 99.0 78.6 20.61 ~3 94.76 Example 2-5 60 100.0 86.6 13.40 ~3 95.02 Example 2-6 55 100.0 85.9 14.10 ~3 95.58 Example 2-7 30 98.5 82.4 16.34 ~3 96.05 Example 2-8 45 99.2 82.1 17.24 ~3 94.23 Comparative Example 1 55 97.8 74.5 23.82 ~4 93.89 Comparative Example 2 160 93.5 82.0 12.30 ~10 93.37

As shown in <Table 1>, the pattern according to the embodiment of the present invention has excellent sensitivity in the range of exposure amount of 35 to 60 mJ/cm2, and the residual film rate is also excellent.

Particularly, when compared with Comparative Example 1 (chemically amplified organic insulating film having a chain structure acid-decomposable protecting group), the residual film rate after cure bake is relatively high, which is caused by acid catalytic reaction during exposure or high temperature (220° C.) heat treatment. The reason why the heat shrinkage is low is that the volume shrinkage is limited by the low volatility of the dropped ring structure protecting groups.

Not only is the volatility of the deprotecting group of the ring structure itself lower than that of the chain structure, but the deprotecting group of the ring structure has a relatively high inhibitory ability to dissolve in the developing solution, while maintaining a low concentration of the acid-decomposable protecting group in the binder resin while providing sufficient pattern realization ability. Since it can be realized, it is possible to keep the concentration of by-products that may occur from the binder resin low.

In addition, the dissolution inhibiting ability of the non-exposed part is higher than that of the chain-structured acid-decomposable protector, so that the ring-structured acid-decomposable protector is higher, further maximizing the dissolution contrast between the exposed part and the non-exposed part, thereby providing a higher level of resolution. Enables the implementation of

Therefore, it can be seen that by providing photosensitivity to the organic insulating film itself produced by the composition, the process of using a separate photoresist in the conventional inorganic insulating layer can be reduced, and thus a fine pattern can be formed more easily.

Although the preferred embodiments of the present invention have been described above, the present invention can use various changes, modifications, and equivalents. It is clear that the present invention can be equally applied by appropriately modifying the above embodiments. Therefore, the above description is not intended to limit the scope of the present invention as defined by the following claims.

Claims (19)

In the chemically amplified positive photosensitive organic insulating film composition comprising a binder resin,
The binder resin is made of a monomer (moiety) containing a ring-structured acid-decomposable protecting group, the binder resin comprises a polymer or copolymer containing the unit,
The unit is a chemically amplified positive photosensitive organic insulating film composition comprising at least one of the following formulas 1-1 to 1-17

<Formula 1-1><Formula1-2>

<Formula 1-3><Formula1-4>

<Formula 1-5><Formula1-6>

<Formula 1-7><Formula1-8>

<Formula 1-9><Formula1-10>

<Formula 1-11><Formula1-12>

<Formula 1-13><Formula1-14>

<Formula 1-15><Formula1-16>

<Formula 1-17>

In Formulas 1-1 to 1-17, R ₁ is a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group or a cyclic ether group, and R ₁ ^* Is a hydrogen group or a chain alkyl group, R ₂ is a chain alkyl group or a cyclic alkyl group, R ₃ is a hydrogen group or a chain alkyl group, R ₄ is a hydrogen group, a chain alkyl group or a cyclic alkyl group, R ₅ Is a chain alkene group or a cyclic alkene group, and R ₆ is a hydrogen group, a chain alkyl group, a cyclic alkyl group or an aryl group.
In addition, X is any one of a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group, or a cyclic ether group, and the same group as R ₁ may come. There, if no following the R ₁ X, if Y is coming, the X is left out, ends with no R ₁ X and Y is a group X is hydrogen.
In addition, Y is any one of a hydrogen group, a hydroxyl group, an epoxy group, an isocyanate group, an acryloyl group, an aryl group, a vinyl group, or an alkoxy group, and X ₁ ^* and X ₂ ^* are furan-based acid-decomposable protecting groups or pyran It is a (pyran)-based acid-decomposable protecting group.
In the chemically amplified positive photosensitive organic insulating film composition comprising a binder resin,
The binder resin is made of a monomer comprising a ring structured acid-decomposable protecting group (moiety), the binder resin comprises a polymer or copolymer containing the unit,
The unit is a chemically amplified positive photosensitive organic insulating film composition comprising at least one of the following Chemical Formula 2 or Chemical Formula 3
<Formula 2><Formula3>

In Formula 2 and Formula 3, G is the unit, and R ₁ is a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group or a cyclic ether group , R ₂ is a chain alkyl group or a cyclic alkyl group, R ₃ is a hydrogen group or a chain alkyl group.
Moreover, X is any of a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group, or a cyclic ether group.
delete delete The method according to claim 1 or 2,
The polymer or the copolymer is a chemically amplified positive photosensitive organic insulating film composition further comprising at least one of the following formulas 4 to 7
<Formula 4><Formula5>

<Formula 6><Formula7>

In Chemical Formulas 4 to 7, R ₃ is a hydrogen group or a chain alkyl group, R ₇ is a hydrogen group, a chain alkyl group, a cyclic alkyl group, a carbonyl group, an aromatic group containing at least one benzene ring, a chain olefin group, a ring Type olefin group, chain ester group, cyclic ester group, chain ether group, cyclic ether group or any one of alkoxy, Z is a hydrogen group, hydroxyl group, chain alkyl group, cyclic alkyl group, alkoxy group, acetox Time, t-butoxy group or t-butoxycarbonyl group, P is a carbonyloxy group (-COO-), methyl group (-CH ₂ -), methyloxy group (-CH ₂ O-) or oxygen group (-O-), m is a repeating unit of the monomer in the polymer, m≥0.
The method according to claim 1 or 2,
The polymer or the copolymer is a chemically amplified positive photosensitive organic insulating film composition, characterized in that any one of the following formulas 8 to 10
<Formula 8>

<Formula 9>

<Formula 10>

In Formulas 8 to 10, A and B are any one of a nitrogen group or an oxygen group, R ₈ is a hydrogen group, a hydroxyl group, an alkyl group or an epoxy group, n is a repeating unit of the monomer in the polymer, n≥1 to be.
Further, R ₁ is a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group or a cyclic ether group, and R ₁ ^* is a hydrogen group or a chain alkyl group , R ₂ is a chain alkyl group or a cyclic alkyl group, R ₃ is a hydrogen group or a chain alkyl group,
In addition, X is any one of a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group, or a cyclic ether group, and the same group as R ₁ may come. There, if no following the R ₁ X, if Y is coming, the X is left out, ends with no R ₁ X and Y is a group X is hydrogen.
In addition, Y is any one of a hydrogen group, a hydroxyl group, an epoxy group, an isocyanate group, an acryloyl group, an aryl group, a vinyl group, or an alkoxy group, and X ₁ ^* and X ₂ ^* are furan-based acid-decomposable protecting groups or pyran It is a (pyran)-based acid-decomposable protecting group.
The method according to claim 1 or 2,
The polymer or the copolymer is a chemically amplified positive photosensitive organic insulating film composition, characterized in that any one of the following formula 11 to formula 12
<Formula 11>

<Formula 12>

In Formulas 11 to 12, A and B are any one of a nitrogen group or an oxygen group, R ₈ is a hydrogen group, a hydroxyl group, an alkyl group or an epoxy group, n is a repeating unit of the monomer in the polymer, n≥1 to be.
Further, R ₁ is a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group or a cyclic ether group, and R ₂ is a chain alkyl group or a cyclic alkyl group , R ₃ is a hydrogen group or a chain alkyl group,
In addition, X is any one of a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group, or a cyclic ether group, and the same group as R ₁ may come. There, if no following the R ₁ X, if Y is coming, the X is left out, ends with no R ₁ X and Y is a group X is hydrogen.
Moreover, Y is any of a hydrogen group, a hydroxyl group, an epoxy group, an isocyanate group, an acryloyl group, an aryl group, a vinyl group, or an alkoxy group.
The method according to claim 1 or 2,
The average molecular weight of the binder resin is 2000 to 200000, and the dispersion degree is 1 to 10, characterized in that the chemically amplified positive photosensitive organic insulating film composition
The method according to claim 1 or 2,
It further comprises a solubilizing agent, the solubilizing agent is an alkali-soluble phenolic compound or a fluorene-based compound containing at least one phenol group, an alkali-soluble compound comprising at least one carboxylic acid group or at least one benzoic acid group Chemically amplified positive photosensitive organic insulating film composition comprising at least one of the alkali-soluble compounds containing an acid-decomposable protecting group
delete The method according to claim 1 or 2,
Further comprising a photoacid generator, the photoacid generator is made of at least one of an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid ester compound, or a traazine-based compound, and based on 100 parts by weight of the binder resin, 0.1 to Chemically amplified positive photosensitive organic insulating film composition comprising 10 parts by weight
The method according to claim 1 or 2,
Chemically amplified positive photosensitive organic insulating film composition further comprising PhotoActiveCompound (PAC) containing a quinonediazide group
The method according to claim 1 or 2,
It further includes an additive, and the additive is a chemically amplified positive photosensitive type comprising at least one of a heat crosslinking agent, a heat stabilizer, a photocuring accelerator, a surfactant, a base quencher, an antihalation agent, an adhesion aid, a light stabilizer or an antifoaming agent. Organic insulating film composition
The method of claim 13,
The thermal crosslinking agent is characterized by comprising a compound comprising at least one of a urea-based resin, melamine-based resin, isocyanate group, epoxy group, oxetane group, acrylate group, vinyl group, aryl group, hydroxy group or mercapto group Chemically amplified positive photosensitive organic insulating film composition
The method of claim 13,
The thermal stabilizer, a chemically amplified positive photosensitive organic insulating film composition comprising at least one of a phenol-based, lactone-based, amine-based, phosphorus-based or sulfur-based compound
The method of claim 13,
The light stabilizer, a chemically amplified positive photosensitive organic insulating film composition, characterized in that at least one of a benzotriazole-based, triazine-based, benzophenone-based, hindered amino ether-based or hindered amine-based compound
The method of claim 13,
The adhesion aid is a chemically amplified positive photosensitive organic insulating film composition comprising an alkoxy silane compound containing at least one of isocyanate group, amino group, urea group, alkyl group, epoxy group, acrylate group, vinyl group or mercapto group.
The method of claim 13,
The base quencher is a nitrogen-containing organic compound, the nitrogen-containing organic compound is a chemically amplified positive photosensitive organic insulating film composition, characterized in that consisting of at least one of a primary amine, secondary amine, tertiary amine or amide compound
A method for forming an organic insulating film using the chemically amplified positive photosensitive organic insulating film composition of claim 1 or 2,
Coating the organic insulating film composition on a substrate of a display device, and on a source/drain or silicon nitride layer formed on the substrate;
Pre-bake the organic insulating film composition;
Selectively exposing and then developing the organic insulating film composition to form a pattern;
A method of forming an organic insulating film comprising the steps of: exposing and curing the organic insulating film composition to form an insulating protective film.

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