TWI585534B - Polyimide-based positive photosensitive resin composition for amoled - Google Patents

Description

Poly-imine-based positive photosensitive resin composition for active organic light-emitting diode display (AMOLED) Field of invention

The present invention relates to a polyimide-based positive photosensitive resin composition for AMOLED (active-matrix organic light-emitting diode), and more particularly to a rigid structure by use. A rigid side chain monomer not only controls gas outgassing, but also maintains heat resistance and reduces packing density and maintains a taper angle of 30 to 35°. A positive photosensitive resin composition mainly composed of quinone.

Background of the invention

Recently, satellite and digital broadcasting have been officially promoted and the demand and attention for large-screen displays with high resolution have increased, so the expectation and role of flat panel displays are highly valued. At the same time, the demand for image information with high resolution but still high contrast and high vividness is further strengthened, and research on liquid crystal display and plasma display conforming to this is studied. And investment is actively taking place. Especially for organic light-emitting displays that are considered to be ideal displays The focus on the use of the organic light emitting display (AM) has been actively carried out for the research and investment of AM-OLED (active-matrix organic light-emitting diode) for realizing large screens.

The heat-sensitive photosensitive polyimide is widely used to form an interlayer insulating film or the like of such an organic light-emitting device.

The photosensitive polyimide contains excellent physical properties such as heat resistance and mechanical strength, excellent dielectric properties such as low dielectric constant and high insulating property, and also has excellent flattening properties of the coated surface and impurities which lower the reliability of the device. The content is very low, and the fine shape can be easily produced.

The above polyimine is classified into a negative-type photosensitive polyimide and a positive-type photosensitive polyimide, but has excellent resolution, low defect rate, cost saving, and environment. In the viewpoint of the protection, the research on the photosensitive polyimide of the positive type is actively carried out.

If the positive-type photosensitive polyimide composition as described above is to be applied to an AMOLED, heat resistance must be improved, and a taper angle is preferably as low.

For this reason, conventionally, in order to achieve a low tilt angle, a molecular weight is lowered or a monomer having a low glass transition temperature (Tg) is used, but here, there is a problem that heat resistance is lowered.

Therefore, there is a need for a novel composition capable of producing an insulating film having a low tilt angle and excellent heat resistance.

Summary of invention

In order to solve the above problems, the present invention provides a method of not only controlling gas outgassing, but also maintaining heat resistance and lowering packing density, and maintaining a taper angle of 30 to 35. The purpose of the poly-imide-based positive photosensitive resin composition is for the purpose.

The present invention also provides an insulating film produced by using the above-described positive photosensitive resin composition mainly composed of polyimine, and an active-matrix organic light-emitting diode comprising the insulating film. AMOLED) for the purpose.

In order to achieve the foregoing object, the present invention provides a polyimine-based positive photosensitive resin composition for AMOLED, which comprises a polyimine precursor, a hydroxystyrene polymer, and a PAC (photosensitive). a photoactive compound) and a solvent, and the polyimine precursor contains a monomer of the following chemical formula 1 or 2:

In the above formula, R ₁ is an alkyl group having 1 to 18 carbon atoms; and R ₂ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group.

Further, the present invention provides an insulating film produced by using the above-described positive photosensitive resin composition mainly composed of polyimine.

Further, the present invention provides an active organic light emitting display element (AMOLED) including the foregoing insulating film.

The polyimine-based positive photosensitive resin composition of the present invention maintains heat resistance and lowers packing density and tilts by using a monomer having a rigid side chain. The taper angle is maintained at 30 to 35 degrees. Further, since the free volume can be increased and reflow can be generated, it can be advantageously used for the insulating film and the active organic light-emitting display element including the insulating film.

Form for implementing the invention

The present invention relates to a polyimine which is capable of not only controlling gas evolution but also maintaining heat resistance and lowering packing density, and maintaining a taper angle of 30 to 35°. Type photosensitive resin composition.

The invention will be described in detail below.

The present invention relates to a polyimine-based positive photosensitive resin composition for AMOLED, which comprises a polyimine precursor, a hydroxystyrene polymer, a PAC (photosensitive compound, photo An active compound) and a solvent, and the aforementioned polyimide precursor contains a monomer of the following Chemical Formula 1 or 2:

In the above formula, R ₁ is an alkyl group having 1 to 18 carbon atoms; and R ₂ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group.

Preferably, the polyimine-based positive photosensitive resin composition is characterized by comprising: (1) 20 to 40 parts by weight of the polyimine precursor; (2) hydroxystyrene polymer 10 To 20 parts by weight; (3) 3 to 20 parts by weight of PAC; and (70) 70 to 90 parts by weight of the solvent.

The following will be explained for each component.

(1) Polyimine precursors

Generally, the polyimine precursor is produced by subjecting an amine-based or diamine-based monomer component to a dianhydride component in a polar organic solvent for two-stage condensation polymerization, and is produced by a terminal bonding protecting group. The polyimide precursor is characterized by containing a monomer of the following Chemical Formula 1 or 2:

In the above formula, R ₁ is an alkyl group having 1 to 18 carbon atoms; and R ₂ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group.

In the present invention, the above-mentioned single system is characterized by containing a rigid branch, whereby the gas-free emission can be maintained, the heat resistance can be maintained, the packing density can be lowered, and the inclination angle can be lowered.

Preferably, the polyimine precursor is preferably a precursor as shown in the following Chemical Formula 3.

In the above formula, X is a tetravalent organic group; Y is an organic group of the compound of Chemical Formula 1 or 2; and R is independently an epoxycyclohexylmethyl methacrylate (ECMMA) or (3-epoxypropyloxypropyl) Trimethoxy decane (GPTS); n is an integer from 3 to 100,000.

The above R is in the ratio of epoxycyclohexylmethyl methacrylate (ECMMA): (3-epoxypropyloxypropyl)trimethoxydecane (GPTS) in a molar ratio of 80 to 99:1~ 20 is better

More preferably, the aforementioned X-based 2,2-bis(3,4-dehydrated dicarboxyphenyl)hexafluoropropane (6FDA), 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3- a tetravalent organic group derived from cyclohexene-1,2-dicarboxylic anhydride (DOCDA) or 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA); one of the aforementioned Y Is 4,4'-diamine-3,3'-dimethyl-diphenylmethane (DADM) or 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (Bis-APAF) The derived divalent organic group is preferred.

In the present invention, the molecular weight of the polyimine precursor is preferably from 3,000 to 10,000, more preferably from 3,500 to 7,000. When it is within the above range, solubility adjustment, yield and sensitivity can be further improved.

Further, in the present invention, a solvent which is generally used in the technical field of the present invention can be used as the type of solvent used in the production of the above polyimine polymer.

In the present invention, the polyilylimine polymer content is preferably from 20 to 40 parts by weight, and when it is within the above range, heat resistance can be further improved.

(2) hydroxystyrene polymer

The hydroxystyrene polymer in the present invention is preferably used in a molecular weight of 4,000 to 20,000, and is preferably used in an amount of 10 to 20 parts by weight, and when it is within the above range, heat resistance can be further improved.

(3) PAC

The PAC used in the present invention can use a known PAC which can be used for an AMOLED insulating film, and in the present invention, the PAC is preferably 3 to 20 parts by weight.

(4) Solvent

In the present invention, a general solvent used in the field for producing a positive photosensitive composition mainly composed of polyimine can be used, and specifically, an alcohol such as methanol, ethanol, benzyl alcohol or hexanol can be used. Ethylene glycol alkyl ether acetate such as ethylene glycol methyl ether acetate or ethylene glycol ethyl ether acetate; ethylene glycol alkyl ether propionic acid such as ethylene glycol methyl ether propionate or ethylene glycol ethyl ether propionate; Esters; glycol monoethers such as ethylene glycol methyl ether and ethylene glycol ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol alkyl ether such as diethyl ether; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate or propylene glycol propyl ether acetate; propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether Propylene glycol alkane ether propionate such as propionate; propylene glycol monoalkyl ether such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether or propylene glycol butyl ether; dipropylene glycol alkyl ether such as dipropylene glycol dimethyl ether or dipropylene glycol diethyl ether; Butanediol monomethyl ether, butanediol monoethyl ether and other butanediol monomethyl ether Or dibutylene glycol dimethyl ether, diethylene glycol diethyl ether dibutyl glycol alkyl ethers; [gamma] -butyrolactone.

In the present invention, the solvent content is 70 to 90 parts by weight. Preferably, it is preferably contained in an amount such that the solid content of the photosensitive composition is 15 to 50% by weight.

Further, the photosensitive resin composition for AMOLED of the present invention may additionally contain a crosslinking agent and a surfactant.

Preferably, the crosslinking agent is preferably a melanin-based crosslinking agent, and the amount thereof is preferably from 1 to 30 parts by weight based on the photosensitive resin composition of the present invention.

In addition, examples of the surfactant include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, and F173 (trade name: Dainippon Ink Co., Ltd.), FC430, and FC431 (trade name: Sumitomo 3M Company, or KP341 (trade name: Shin-Etsu Chemical Co., Ltd.), etc. are used as an example, and it is preferable to contain 0.0001-2 weight part of the photosensitive resin composition of this invention.

Further, the present invention provides an insulating film produced using the above-described positive photosensitive resin composition mainly composed of polyimine for AMOLED, and an active organic light-emitting display element (AMOLED) containing the same.

The insulating film for an AMOLED manufactured by using the positive photosensitive polyimide film composition of the present invention can control not only gas release but also maintenance by using a rigid branched monomer of Chemical Formula 1 or 2. Heat resistance and reduced packing density, and lowering the tilt angle. Further, the aforementioned inclination angle is preferably 35 or less, more preferably 30 to 35, and the thermal decomposition temperature is 350 ° C or higher, more preferably 350 to 500 ° C.

The insulating film pattern forming method of the present invention is used in a method of forming an insulating film pattern in a display process, and the present invention is used. The above-mentioned positive-type photosensitive polyimide composition can be applied to a well-known method by other steps.

In the following, the preferred embodiments are set forth to understand the present invention, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following examples.

EXAMPLES: Production of Polyimide Photosensitive Precursors and Compositions

According to the content shown in the following Table 1, a positive photosensitive precursor and a composition mainly composed of polyimine were produced by the following method.

Example 1

100 g of DADM, 6-FDA of 50 g, 30 g of the monomer of Chemical Formula 1, and 70 g of γ-butyrolactone were placed in a reaction vessel in a 4-neck reaction vessel of 300 ml, and stirred for 1 hour to cause a reaction. In order to terminate the reaction at the end, PA2g was charged, and the reaction was further carried out at 20 ° C for 1 hour to prepare a polyimide intermediate having a solid content of 30%. Here, 100 mg of ECMMA as a protecting group substance was introduced, and after heating to 70 ° C, triethylamine (TEA) as a catalyst was added and allowed to react for 24 hours to produce a novel polyimine precursor.

30 parts by weight of the above-prepared polyimine precursor and 15 parts by weight of a hydroxystyrene polymer were mixed with 10 parts by weight of PAC. Thereafter, the γ-butyrolactone and propylene glycol monomethyl ether acetate (PGMEA) are mixed in a weight ratio of 50:50 in such a manner that the solid content of the mixture is 20% by weight. After the solvent was filtered through a 0.2 μm microporous filter, a positive photosensitive resin composition mainly composed of polyimine for AMOLED was produced.

Example 2

Except that the monomer of the chemical formula 2 was used instead of the above-mentioned monomer of the chemical formula 1 in the above Example 1, the same method as in the above Example 1 was carried out to produce a positive photosensitive film mainly for polyimine. Resin composition.

Comparative example 1

Except that 80 g of 6-FDA was used as the dianhydride in the above Example 1, and the monomer of Chemical Formula 1 or 2 was not used, the same method as in the above Example 1 was carried out to produce Polyurethane for AMOLED. An amine-based positive photosensitive resin composition.

Comparative example 2

In the same manner as in the above-mentioned Example 1, except that 30 g of EDA (ethylene diamine) was used instead of the above-mentioned monomer of the above Chemical Formula 1 in Example 1, a polyethylenimine-based positive type for AMOLED was produced. A photosensitive resin composition.

Test Example 1: Measurement of inclination angle

The photosensitive resin compositions produced in the above Examples 1 and 2 and Comparative Examples 1 and 2 were spin-coated on the ITO glass substrate to obtain a film having a thickness of 3.0 μm. Thereafter, prebaking was performed at 120 ° C for 2 minutes, and an exposure energy of 100 mJ/cm ^{2 was} irradiated at a wavelength of 365 nm through a mask having a line/space of 20 μm. Thereafter, it was developed with a 2.38% TMAH developing solution for 35 seconds, and then hardened in an oven at 230 ° C for 1 hour.

The inclination angle was measured using an SEM to measure the angle of the 2.5 μm pattern cross section, and was judged based on the criteria described in Table 2 below. The results are shown in Table 2 below.

Test example: Determination of thermal decomposition temperature

The thermal decomposition temperature was measured by thermogravimetric analysis (TGA) at a rate of 10 ° C/min under a nitrogen gas flow, and was determined based on the criteria described in Table 2 below. The results are shown in Table 2 below.

As shown in the above Table 2, it is understood that when the insulating film is formed by using the positive photosensitive resin composition mainly composed of polyimine of the present invention, The inclination angle is lowered to 35° or less, whereby the thermal decomposition temperature is increased to 350° C. or higher, and the heat resistance is excellent. On the other hand, in the case of Comparative Example 1, it was confirmed that the inclination angle was not lowered, and in the case of Comparative Example 2, the inclination angle was lowered, but the heat resistance could not be improved.

Claims (12)

A poly-imide-based positive photosensitive resin composition for AMOLED (active-matrix organic light-emitting diode) characterized by comprising a polyimide precursor, a hydroxystyrene polymer, and a PAC ( Photo active compound) and a solvent, and the aforementioned polyimine precursor is as shown in the following Chemical Formula 3: In the above formula, X is a tetravalent organic group; Y is an organic group of the compound of Chemical Formula 1 or 2; and R is independently an epoxycyclohexylmethyl methacrylate (ECMMA) or (3-epoxypropyloxypropyl) a monovalent organic group derived from trimethoxy decane (GPTS); and the aforementioned R-based epoxycyclohexylmethyl methacrylate (ECMMA): (3-epoxypropyloxypropyl)trimethoxydecane (GPTS) The ratio is 80 to 99:1 to 20 in terms of molar ratio; n is an integer from 3 to 100,000. A poly-imide-based positive photosensitive resin composition for AMOLED according to claim 1, which comprises (1) a polyimine precursor of 20 to 40 parts by weight; (2) 10 to 20 parts by weight of the hydroxystyrene polymer; (3) 3 to 20 parts by weight of the PAC; and (4) 70 to 90 parts by weight of the solvent. A poly-imide-based positive photosensitive resin composition for AMOLED according to the first aspect of the patent application, wherein X of the above Chemical Formula 3 is 2,2-bis(3,4-dehydrated dicarboxyphenyl) Hexafluoropropane (6FDA), 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA), or 2,3,3' , 4'-biphenyltetracarboxylic dianhydride (a-BPDA) derived tetravalent organic group. A poly-imide-based positive photosensitive resin composition for AMOLED according to the first aspect of the patent application, wherein a part of Y of the above Chemical Formula 3 is 4,4'-diamine-3,3' - Dimethyl-diphenylmethane (DADM) or 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (Bis-APAF) derived divalent organic group. A poly-imide-based positive photosensitive resin composition for AMOLED according to the first aspect of the invention, wherein 3 to 50 mol% of the above Y is an organic group derived from a compound of Chemical Formula 1 or 2. . The poly-imide-based positive photosensitive resin composition for AMOLED according to the first aspect of the patent application, wherein the hydroxystyrene polymer is 4000 in terms of polystyrene-equivalent weight average molecular weight (Mw). ~20000. The poly-imide-based positive photosensitive resin composition for AMOLED according to claim 1, wherein the solvent is selected from the group consisting of alcohols; ethylene glycol alkyl ether acetates; Alkanol ether propionate; B Glycol monoalkyl ethers; diethylene glycol alkyl ethers; propylene glycol alkyl ether acetates; propylene glycol alkyl ether propionates; propylene glycol monoalkyl ethers; dipropylene glycol alkyl ethers; butanediol monomethyl ethers; And at least one of a group consisting of dibutyl diol ethers and γ-butyrolactone. A poly-imide-based positive photosensitive resin composition for AMOLED according to the first aspect of the invention, which further comprises a crosslinking agent and a surfactant. An AMOLED insulating film is produced by using a polyimide-based positive photosensitive resin composition for AMOLED as in the first application of the patent application. The AMOLED insulating film of claim 9, wherein the insulating film has an inclination angle of 30 to 35°. The AMOLED insulating film according to claim 9, wherein the thermal decomposition temperature is 350 ° C or higher. An active organic light emitting display element (AMOLED) comprising an insulating film as in claim 9 of the patent application.