KR102311850B1 - Photosensitive resin composition and insulation pattern formed from the same - Google Patents

Abstract

The photosensitive resin composition according to embodiments of the present invention includes a binder resin including a cyclic ether-containing unit, a heterocyclic epoxy-containing unit and an alicyclic heterocyclic group-containing unit, a polymerizable compound, a photoinitiator, and a solvent. Through the composition of the binder resin, an insulating pattern having improved chemical resistance and low temperature curing characteristics may be formed.

Description

Photosensitive resin composition and insulating pattern formed therefrom

The present invention relates to a photosensitive resin composition and an insulating pattern formed therefrom. More particularly, it relates to a photosensitive resin composition including a binder resin and an insulating pattern formed therefrom.

For example, the photosensitive composition is used to form various photocurable insulating patterns such as photoresist, insulating film, protective film, black matrix, column spacer, and the like of a display device. After the photosensitive composition is applied, a photocurable pattern having a predetermined shape may be formed in a desired area through an exposure process and/or a developing process. The photosensitive composition has, for example, high sensitivity to ultraviolet light exposure and polymerization reactivity, and a pattern formed therefrom needs to have improved heat resistance, chemical resistance, and the like.

Recently, as a flexible display such as a flexible organic light emitting diode (OLED) device or a flexible liquid crystal display (LCD) device has been developed, a resin substrate such as polyimide is used as a base material. . In this case, since the base substrate may be damaged during the high-temperature curing process required for forming the insulating pattern, a photosensitive composition capable of securing sufficient degree of curing and mechanical properties even in the low-temperature curing process is required.

In addition, the insulating pattern is required to have chemical resistance to a developer, a peeling solution, and the like, and durability against various corrosive components generated during the display manufacturing process.

Therefore, there is a need for a composition for forming an insulating film that has sufficient hardness even in a low-temperature curing process and can also satisfy chemical resistance.

For example, Korea Patent No. 10-1302508 discloses a negative photosensitive resin composition comprising a copolymer polymerized using a cyclohexenyl acrylate monomer, but the above-described low-temperature curing characteristics cannot be sufficiently implemented. .

Korean Patent Registration No. 10-1302508

One object of the present invention is to provide a photosensitive resin composition having an improved degree of curing and chemical resistance.

One object of the present invention is to provide an insulating pattern formed from the photosensitive resin composition and having an improved degree of curing and reliability.

An object of the present invention is to provide an image display device including the insulating pattern.

1. A binder resin including a cyclic ether-containing unit, a heterocyclic epoxy-containing unit, and an alicyclic heterocyclic group-containing unit; polymerizable compounds; photoinitiator; and a solvent, the photosensitive resin composition.

2. The photosensitive resin composition according to the above 1, wherein the alicyclic heterocyclic group-containing unit is represented by the following Chemical Formula 1:

[Formula 1]

(In Formula 1, R ₁ is hydrogen or a methyl group, and X ₁ is an alicyclic heterocyclic group).

3. The photosensitive resin composition according to the above 2, wherein the ratio of the number of hydrogen atoms to the number of carbon atoms in the alicyclic heterocyclic group (number of hydrogen atoms/number of carbon atoms) is less than 1.8.

4. The photosensitive resin composition according to the above 1, wherein the alicyclic heterocyclic group-containing unit is derived from at least one of the compounds represented by the following Chemical Formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

(In Formulas 1-1 to 1-3, R ₂ is hydrogen or a methyl group).

5. The photosensitive resin composition according to the above 1, wherein the cyclic ether-containing unit is derived from at least one of the monomers represented by Formulas 2-1 to 2-4:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

(In Formulas 2-1 to 2-4, R ₃ is hydrogen or a methyl group).

6. The photosensitive resin composition of the above 1, wherein the heterocyclic epoxy-containing unit is derived from at least one of the monomers of Formula 3-1 or 3-2.

[Formula 3-1]

[Formula 3-2]

(In Formulas 3-1 and 3-2, R ₄ is hydrogen or a methyl group).

7. The photosensitive resin composition according to the above 1, wherein the molar ratio of the cyclic ether-containing unit in the binder resin is equal to or greater than the sum of the molar ratio of the alicyclic heterocyclic group-containing unit and the molar ratio of the heterocyclic epoxy-containing unit.

8. The photosensitive resin composition according to the above 1, wherein the molar ratio of the alicyclic heterocyclic group-containing unit in the binder resin is equal to or greater than the molar ratio of the heterocyclic epoxy-containing unit.

9. The photosensitive resin composition of 1 above, wherein the binder resin further comprises a carboxylic acid-containing unit.

10. The photosensitive resin composition according to the above 1, further comprising a polyfunctional thiol compound as a starting aid.

11. The above 10, in the total weight of the composition,

10 to 50% by weight of the binder resin; 5 to 40% by weight of the polymerizable compound; 0.1 to 10% by weight of the photoinitiator; And 40 to 80% by weight of the solvent, the photosensitive resin composition.

12. An insulating pattern formed from the photosensitive resin composition of any one of 1 to 11 above.

13. An image display device comprising the insulating pattern of 12 above.

The photosensitive resin composition according to embodiments of the present invention may include a binder resin including a cyclic ether-containing unit, a heterocyclic epoxy-containing unit, and an alicyclic heterocyclic group-containing unit. It is possible to secure low-temperature curability through the heterocyclic epoxy-containing unit and the cyclic ether-containing unit, and improve reliability such as chemical resistance through the alicyclic heterocyclic group-containing unit.

In addition, developability may be improved through the heterocyclic epoxy-containing unit to form an insulating pattern having a fine dimension. Barrier properties against external moisture and corrosive organic components may be improved through the alicyclic heterocyclic group-containing unit.

For example, a curable insulating pattern may be formed from the photosensitive resin composition at a temperature in the range of about 100 to 130° C., and the curable insulating pattern may be utilized as various insulating films and insulating patterns of a flexible display device.

1 is a conceptual diagram for explaining the definition of a bottom CD size of an insulating pattern.
2 and 3 are images of an insulating pattern without a developing residual film and an insulating pattern having a developing residual film, respectively.
4 and 5 are exemplary images for explaining the chemical resistance evaluation criteria for the aqueous methacrylic acid solution.

Examples of the present invention include a binder resin including a cyclic ether-containing unit, a heterocyclic epoxy-containing unit, and an alicyclic heterocyclic group-containing unit, and a photosensitive resin composition with improved reliability such as low-temperature curing properties and chemical resistance, and thereto An insulating film formed from

In addition, embodiments of the present invention provide an image display device including an insulating film or insulating pattern formed from the photosensitive resin composition.

In the present specification, chemical formulas include not only the structures represented by the respective formulas, but also the monomers, repeating units, and isomers of the compounds represented by the respective formulas.

Hereinafter, embodiments of the present invention will be described in detail.

<Photosensitive resin composition>

binder resin

The photosensitive resin composition according to embodiments of the present invention includes a binder resin as a base component. According to exemplary embodiments, the binder resin may be soluble in an alkaline developer, and may impart exposure and development characteristics of a coating film formed from the photosensitive resin composition.

According to exemplary embodiments, the binder resin may include a cyclic ether-containing unit, a heterocyclic epoxy-containing unit, and an alicyclic heterocyclic group-containing unit.

For example, the alicyclic heterocyclic group-containing unit may be represented by Formula 1 below.

[Formula 1]

In formula (1), R 1 is hydrogen or a methyl group, and X ₁ is an alicyclic heterocyclic group.

As used herein, the term "(meth)acryl-" is used to refer to "methacryl-", "acryl-", or both. In addition, "heterocyclic group" includes, for example, a bicyclic structure through a bridging carbon, a spiro structure through a junction carbon, and a fused structure in which two or more rings share a bond. can do.

According to exemplary embodiments, as the binder resin includes the alicyclic heterocyclic group, reliability such as chemical resistance and moisture resistance may be improved.

In some embodiments, the ratio of the number of hydrogen atoms to the number of carbon atoms in the alicyclic heterocyclic group (number of hydrogen atoms/number of carbon atoms) may be less than 1.8. If the ratio is 1.8 or more, the carbon content may not be ensured to achieve sufficient reliability. Therefore, it is difficult to realize sufficient resistance of the insulating film to a solution such as external moisture or a stripper.

The alicyclic heterocyclic group may include, for example, a tricyclodecanyl group or an isobornyl group. In some embodiments, X ₁ may be derived from a (meth)acrylate-based monomer including an alicyclic heterocyclic group.

For example, the alicyclic heterocyclic group-containing unit may be derived from at least one of the monomers represented by the following Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3, R ₂ may be hydrogen or a methyl group.

According to exemplary embodiments, the cyclic ether-containing unit may be provided as a functional unit implementing low-temperature curing characteristics by improving the thermosetting reactivity of the binder resin. In some embodiments, the cyclic ether-containing unit may not include a hydrocarbon heterocyclic structure.

In some embodiments, the cyclic ether-containing unit may include an oxiranyl group or an oxetanyl group as an alkyl substituent. In one embodiment, the cyclic ether-containing unit may be derived from at least one of the monomers represented by the following Chemical Formulas 2-1 to 2-4.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4, R ₃ may be hydrogen or a methyl group.

As described above, a low-temperature curing (eg, curing at 130° C. or lower) process of the composition may be implemented through the cyclic ether-containing unit. In the binder resin, the molar ratio (mol%) of the cyclic ether-containing unit may be greater than the molar ratio of the alicyclic heterocyclic group-containing unit. Accordingly, the low-temperature curing process characteristics can be effectively implemented.

The heterocyclic epoxy-containing unit may have a structure in which an epoxy group is fused together in a heterocyclic group. Accordingly, the reliability of the binder resin or the insulating film may be further improved through the heterocyclic group, and developability may be improved through the ring-opening reaction of the epoxy group.

In some embodiments, the heterocyclic epoxy-containing unit may be derived from at least one of the monomers of Formula 3-1 or 3-2 below.

[Formula 3-1]

[Formula 3-2]

In Formulas 3-1 and 3-2, R ₄ may be hydrogen or a methyl group.

The cyclic ether-containing unit, the heterocyclic epoxy-containing unit, and the alicyclic heterocyclic group-containing unit of the binder resin may be included as repeating units of the binder resin, respectively.

In some embodiments, the molar ratio (mol%) of the cyclic ether-containing unit in the binder resin may be equal to or greater than the sum of the molar ratio of the heterocyclic epoxy-containing unit and the molar ratio of the alicyclic heterocyclic group-containing unit. In one embodiment, the molar ratio (mol%) of the alicyclic heterocyclic group-containing unit may be greater than or equal to the molar ratio of the heterocyclic epoxy-containing unit.

Accordingly, it is possible to improve reliability such as chemical resistance and moisture resistance from the alicyclic heterocyclic group-containing unit while ensuring sufficient low-temperature curing properties through the cyclic ether-containing unit.

In some embodiments, the binder resin may further include an additional repeating unit copolymerized with the cyclic ether-containing unit, the heterocyclic epoxy-containing unit, and the alicyclic heterocyclic group-containing unit. For example, the repeating unit may include a carboxylic acid unit. By the carboxylic acid unit, developability of the binder resin and adhesion to the substrate may be further improved.

For example, the carboxylic acid unit is derived from a monomer such as (meth)acrylic acid, and may be represented by the following Chemical Formula 4 in one embodiment.

[Formula 4]

In Formula 4, R ₅ may be hydrogen or a methyl group.

In one embodiment, the binder resin may be substantially composed of the above-described cyclic ether-containing unit, heterocyclic epoxy-containing unit, alicyclic heterocyclic group-containing unit, and the carboxylic acid-containing unit. In this case, it is possible to maintain developability and adhesion while effectively implementing the above-described low-temperature curing characteristics and reliability improvement.

In some embodiments, the acid value of the binder resin may be in the range of about 20 to 200 (KOH mg/g), and in this case, it may have excellent developability and stability over time.

In some embodiments, the photosensitive resin composition may further include an additional binder resin commonly used in the field of resin compositions within a range that does not impair low-temperature curing characteristics and chemical resistance of the binder resin.

In some embodiments, the content of the binder resin may be about 10 to 50% by weight of the total weight of the composition. In the above range, solubility in a solvent or a developer is ensured, and sufficient mechanical reliability of the insulating film can be secured.

polymeric compound

The photosensitive resin composition according to exemplary embodiments may further include a polymerizable compound to secure additional crosslinking degree or hardness.

The polymerizable compound may include a monofunctional monomer, a difunctional monomer, and other polyfunctional monomers.

Examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. Examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol The bis(acryloyloxyethyl) ether of A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

Examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tri ( meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

These may be used alone or in combination of two or more. Preferably, a trifunctional or more functional monomer may be used to further secure chemical resistance.

The content of the polymerizable compound is not particularly limited, but may be, for example, about 5 to 40 wt % based on the total weight of the solid content in the photosensitive resin composition. In the above range, the mechanical and chemical reliability of the insulating film formed from the photosensitive resin composition may be further improved.

photoinitiator

According to exemplary embodiments, the photoinitiator may be used without particular limitation as long as it can induce a crosslinking reaction or polymerization reaction of the above-described polymerizable compound by generating radicals through an exposure process. For example, as the photoinitiator, at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, a thioxanthone-based compound, and an oxime ester-based compound may be used. can

In one embodiment, a thioxanthone-based compound represented by the following Chemical Formula 5 may be used as a photoinitiator.

[Formula 5]

In some embodiments, the content of the photoinitiator in the total weight of the photosensitive resin composition may be about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight. In the above range, it is possible to improve the resolution and sensitivity of the exposure process without impairing the reliability of the insulating film.

additive

Additional agents may be further included to improve polymerization properties, degree of curing, and surface properties of the insulating film formed from the photosensitive resin composition. For example, additives may be further included within a range that does not impair low-temperature curing characteristics and chemical resistance of the photosensitive resin composition according to embodiments of the present invention.

In some exemplary embodiments of the present invention, a polyfunctional thiol compound may be further included as an initiation adjuvant. As the curing reaction is more accelerated as the polyfunctional thiol compound is included, inhibition of oxygen on the surface of the cured film may be suppressed.

Examples of the polyfunctional thiol compound include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutylate) ), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.

In some embodiments, the polyfunctional thiol compound may include a compound represented by Formula 6 below.

[Formula 6]

In some embodiments, the photocurable composition may further include a surfactant. Through the surfactant, the coating uniformity of the composition and the surface uniformity of the cured film may be improved.

The surfactant is not particularly limited, and nonionic surfactants, cationic surfactants, anionic surfactants, etc. used in the art may be used.

On the other hand, additives such as antioxidants, leveling agents, curing accelerators, ultraviolet absorbers, aggregation inhibitors, and chain transfer agents may be further added to further improve properties such as curing degree, smoothness, adhesion, solvent resistance, and chemical resistance of the insulating film. .

For example, the content of the additive may be included in an amount of about 0.01 to 5% by weight based on the total weight of the photocurable composition.

solvent

In the photosensitive resin composition according to the exemplary embodiments, a solvent having sufficient solubility in the binder resin, the polymerizable compound, and the like may be used.

For example, the solvent is ethylene glycol monoalkyl ethers; diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetates; alkylene glycol alkyl ether acetates; propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers; propylene glycol alkyl ether propionates; butyldiol monoalkyl ethers; butanediol monoalkyl ether acetates; butanediol monoalkyl ether propionates; dipropylene glycol dimethyl ether, dipropylene glycol dialkyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones; alcohol; esters; cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as γ-butyrolactone. These may be used alone or in combination of two or more of them may be used.

The solvent is included in the remaining amount or an extra amount of the composition, for example, may be included in an amount of about 40 to 80% by weight of the total weight of the photosensitive resin composition. Within the above range, process easiness for application processes such as spin coating, slit coating, and inkjet printing may be improved.

<Insulation pattern and image display device>

The present invention provides an insulating pattern formed from the above-described photosensitive resin composition and a method for forming the same.

For example, after the above-described photosensitive resin composition is applied to a substrate, a preliminary insulating layer may be formed through a pre-bake process. The preliminary insulating layer may be formed through a process such as inkjet printing, spin coating, roll coating, or slit coating.

Thereafter, an exposure process may be performed on the preliminary insulating layer using a photomask including a light blocking portion and a transmitting portion.

The portion exposed through the exposure process may be cured and/or crosslinked. After the exposure process, a post-exposure baking (PEB) process may be further performed. In the exposure process, an ultraviolet light source such as a UV-A region (320 to 400 nm), a UV-B region (280 to 320 nm), or a UV-C region (200 to 280 nm) of a high-pressure mercury lamp may be used.

Thereafter, an unexposed portion of the preliminary insulating layer may be selectively removed using a developer. As the developer, for example, an alkaline solution such as tetramethylammonium hydroxide (TMAH) can be used.

Accordingly, an insulating pattern may be formed from the preliminary insulating layer. A post-bake process may be further performed on the insulating pattern.

The curing process including the exposure and baking processes may be performed at a low temperature of, for example, about 130° C. or less. As described above, the photosensitive resin composition according to the exemplary embodiments includes a binder resin including a cyclic ether-containing unit, an alicyclic heterocyclic group-containing unit, and a heterocyclic epoxy-containing unit, and thus is sufficient even through low-temperature curing An insulating pattern having chemical resistance and mechanical reliability can be formed.

Embodiments of the present invention provide an image display device including the insulating pattern.

The insulating pattern may be applied to various film structures or patterns of an image display device, and may be used, for example, as a photoresist, a black matrix, a column spacer pattern, or the like, but is not limited thereto.

For example, the image display device may include a flexible display such as a flexible OLED or a flexible LCD device. In the case of the flexible display, a resin substrate such as polyimide may be used as the back-plane substrate. The resin substrate may be disadvantageous compared to the glass substrate in terms of heat resistance. However, since the photosensitive resin composition or the insulating pattern according to the exemplary embodiments has excellent low-temperature curing properties, damage to the resin substrate due to high-temperature curing can be prevented.

The image display device includes various conductive and insulating structures in addition to the insulating pattern, and a photoresist pattern, an adhesive layer, and the like may be used to form the conductive and insulating structure.

For example, a basic organic cleaning solution may be used to remove the photoresist pattern, and organic acids such as acrylic acid may be eluted from the adhesive layer and propagate to the insulating pattern.

The photosensitive resin composition according to the exemplary embodiments has improved chemical resistance and moisture resistance through an alicyclic heterocyclic group-containing unit and a heterocyclic epoxy-containing unit, and thus has improved durability against the organic acid, the basic organic cleaning solution, and the like.

Hereinafter, experimental examples including preferred examples and comparative examples are presented to help the understanding of the present invention, but these examples are merely illustrative of the present invention and do not limit the appended claims, It is obvious to those skilled in the art that various changes and modifications can be made to the embodiments within the scope and spirit of the present invention, and it is natural that such variations and modifications fall within the scope of the appended claims.

Preparation Example 1: Synthesis of binder resin (A-1)

In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, and 200 g of diethylene glycol methyl ethyl ether was added and heated to 70° C. while stirring. Then, 44.0 g (0.20 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio of 50:50), 41.3 g (0.20 mol) of tricyclodecanyl acrylate, 71.1 g of glycidyl methacrylate ( 0.50 mol) and 8.6 g (0.10 mol) of methacrylic acid were dissolved in 200 g of diethylene glycol methyl ethyl ether to prepare a solution.

[Formula 7-1]

[Formula 7-2]

The prepared solution was dropped into the flask using a dropping funnel, and then 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 150 g of diethylene glycol methyl ethyl ether. The dissolved solution was dripped into the flask over 5 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, it was maintained at 70° C. for 10 hours, then cooled to room temperature, and a copolymer resin (A-) having a solid content of 32.5 mass% and an acid value of 61 mg-KOH/g (in terms of solid content) 1) was obtained. The weight average molecular weight (Mw) (in terms of polystyrene measured by GPC) of the obtained resin (A-1) was 16,400 and molecular weight distribution was 2.25.

Preparation Example 2: Synthesis of binder resin (A-2)

22.0 g (0.10 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50) in a diethylene glycol methyl ethyl ether solution, 61.9 g (0.30 mol) of tricyclodecanyl acrylate, glycidyl meta The same process as in Preparation Example 1 was performed except that 71.1 g (0.50 mol) of acrylate and 8.6 g (0.10 mol) of methacrylic acid were added. Thereby, a copolymer resin (A-2) having a solid content of 33.1 mass%, an acid value of 64 mg-KOH/g, a polystyrene reduced weight average molecular weight (Mw) of 16,800 measured by GPC, and a molecular weight distribution (Mw/Mn) of 2.50 was obtained. did.

Preparation Example 3: Synthesis of binder resin (A-3)

22.0 g (0.10 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50), 66.7 g (0.30 mol) of isobornyl acrylate, glycidyl methacrylate in diethylene glycol methyl ethyl ether solution The same process as in Preparation Example 1 was performed except that 71.1 g (0.50 mol) and 8.6 g (0.10 mol) of methacrylic acid were added. Accordingly, the binder resin (A-3) having a solid content of 32.4 mass%, an acid value of 62 mg-KOH/g, a polystyrene conversion weight average molecular weight (Mw) measured by GPC of 15,900, and a molecular weight distribution (Mw/Mn) of 2.30 ) was obtained.

Preparation Example 4: Synthesis of binder resin (A-4)

22.0 g (0.10 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50), 61.9 g (0.30 mol) of tricyclodecanyl acrylate, 3-ethyl in diethylene glycol methyl ethyl ether solution The same process as in Preparation Example 1 was performed except that 71.1 g (0.50 mol) of -3-oxetanyl methacrylate and 8.6 g (0.10 mol) of methacrylic acid were added. Thereby, a copolymer resin (A-4) having a solid content of 35.0 mass%, an acid value of 67 mg-KOH/g, a polystyrene reduced weight average molecular weight (Mw) of 16,600 measured by GPC, and a molecular weight distribution (Mw/Mn) of 2.15 was obtained. did.

Preparation Example 5: Synthesis of binder resin (A-5)

99.1 g (0.45 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50) in a diethylene glycol methyl ethyl ether solution, 30.9 g (0.15 mol) of tricyclodecanyl acrylate, glycidyl meta The same process as in Preparation Example 1 was performed except that 42.7 g (0.30 mol) of acrylate and 8.6 g (0.10 mol) of methacrylic acid were added. Accordingly, a copolymer resin (A-5) having a solid content of 34.3 mass%, an acid value of 58 mg-KOH/g, a weight average molecular weight (Mw) of 17,200 in terms of polystyrene measured by GPC, and a molecular weight distribution (Mw/Mn) of 2.73 obtained.

Preparation Example 6: Synthesis of binder resin (A-6)

66.1 g (0.30 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50), 20.6 g (0.10 mol) of tricyclodecanyl acrylate, 20.6 g (0.10 mol) of glycidyl meta in diethylene glycol methyl ethyl ether solution The same process as in Preparation Example 1 was performed except that 71.1 g (0.50 mol) of acrylate and 8.6 g (0.10 mol) of methacrylic acid were added. Thus, a copolymer resin (A-6) having a solid content of 33.7 mass%, an acid value of 62 mg-KOH/g, a polystyrene reduced weight average molecular weight (Mw) of 16,850 measured by GPC, and a molecular weight distribution (Mw/Mn) of 2.40 was obtained.

Preparation Example 7: Synthesis of binder resin (A-7)

22.0 g (0.10 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50), 35.5 g (0.30 mol) of vinyltoluene, 71.1 g of glycidyl methacrylate in diethylene glycol methyl ethyl ether solution (0.50 mol) and methacrylic acid 8.6 g (0.10 mol) was performed in the same manner as in Preparation Example 1, except that. Thus, a copolymer resin (A-7) having a solid content of 36.1 mass%, an acid value of 68 mg-KOH/g, a polystyrene reduced weight average molecular weight (Mw) of 14,800 measured by GPC, and a molecular weight distribution (Mw/Mn) of 2.15 was obtained.

Preparation Example 8: Synthesis of binder resin (A-8)

22.0 g (0.10 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50), 50.5 g (0.30 mol) of cyclohexyl methacrylate, and glycidyl methacryl in diethylene glycol methyl ethyl ether solution The same process as in Preparation Example 1 was performed except that the rate 71.1 g (0.50 mol) and methacrylic acid 8.6 g (0.10 mol) were added. Accordingly, a copolymer resin (A-8) having a solid content of 34.6 mass%, an acid value of 63 mg-KOH/g, a polystyrene reduced weight average molecular weight (Mw) measured by GPC of 15,700, and a molecular weight distribution (Mw/Mn) of 2.55 was obtained. .

Preparation Example 9: Synthesis of binder resin (A-9)

22.0 g (0.10 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50) in diethylene glycol methyl ethyl ether solution, 42.7 g (0.30 mol) of tert-butyl methacrylate, glycidyl meta The same process as in Preparation Example 1 was performed except that 71.1 g (0.50 mol) of acrylate and 8.6 g (0.10 mol) of methacrylic acid were added. Accordingly, a copolymer resin (A-9) having a solid content of 34.0 mass%, an acid value of 73 mg-KOH/g, a polystyrene conversion weight average molecular weight (Mw) of 16,200 measured by GPC, and a molecular weight distribution (Mw/Mn) of 2.46 was obtained.

Preparation 10: Synthesis of binder resin (A-10)

22.0 g (0.10 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50), 67.9 g (0.30 mol) of n-decyl methacrylate, glycidyl meta in diethylene glycol methyl ethyl ether solution The same process as in Preparation Example 1 was performed except that 71.1 g (0.50 mol) of acrylate and 8.6 g (0.10 mol) of methacrylic acid were added. Accordingly, a copolymer resin (A-9) having a solid content of 36.2 mass%, an acid value of 59 mg-KOH/g, a polystyrene reduced weight average molecular weight (Mw) measured by GPC of 14,300, and a molecular weight distribution (Mw/Mn) of 2.72 was obtained. .

Preparation Example 11: Synthesis of binder resin (A-11)

66.1 g (0.30 mol) of a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50), 123.8 g (0.60 mol) of tricyclodecanyl acrylate and 8.6 g of methacrylic acid in diethylene glycol methyl ethyl ether solution The same process as in Preparation Example 1 was performed except that g (0.10 mol) was added. Accordingly, a copolymer resin (A-11) having a solid content of 37.1 mass%, an acid value of 60 mg-KOH/g, a polystyrene reduced weight average molecular weight (Mw) measured by GPC of 17,000, and a molecular weight distribution (Mw/Mn) of 2.21 was obtained.

Preparation 12: Synthesis of binder resin (A-12)

132.2 g (0.60 mol), 42.6 g (0.30 mol) of glycidyl methacrylate and 8.6 g (0.30 mol) of methacrylic acid, in a solution of diethylene glycol methyl ethyl ether, a mixture of Chemical Formulas 7-1 and 7-2 (molar ratio 50:50) The same process as in Preparation Example 1 was performed except that g (0.10 mol) was added. Accordingly, a copolymer resin (A-12) having a solid content of 32.0 mass%, a solid content acid value of 65 mgKOH/g, a polystyrene conversion weight average molecular weight (Mw) of 15,500 measured by GPC, and a molecular weight distribution (Mw/Mn) of 1.97 was obtained.

Preparation Example 13: Synthesis of binder resin (A-13)

Except for adding 132.2 g (0.60 mol) of tricyclodecanyl acrylate, 42.6 g (0.30 mol) of glycidyl methacrylate and 8.6 g (0.10 mol) of methacrylic acid in diethylene glycol methyl ethyl ether solution The same process as in Preparation Example 1 was performed. Thus, a copolymer resin (A-13) having a solid content of 32.0 mass%, a solid content acid value of 70 mgKOH/g, a polystyrene reduced weight average molecular weight measured by GPC of 14,900 (Mw), and a molecular weight distribution (Mw/Mn) of 2.05 was obtained.

Preparation 14: Synthesis of binder resin (B)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was supplied at a flow rate of 0.02 L/min to form a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After raising the temperature to 100°C, 2,2'-azobis was added to a mixture containing 24.5 g (0.34 mol) of acrylic acid, 4.7 g (0.05 mol) of norbornene, 72.1 g (0.61 mol) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate. The solution to which 3.6 g of (2,4-dimethylvaleronitrile) was added was dripped at the flask over 4 hours from the dropping funnel, and it stirred at 100 degreeC for 12 hours further.

Then, the atmosphere in the flask was changed from nitrogen to air, and 28.4 g (0.20 mol) of glycidyl methacrylate (59 mol% with respect to the acrylic acid used in this reaction) was added into the flask, and the reaction was continued at 110° C. for 5 hours. and unsaturated group-containing resin (B) having a solid content acid value of 73 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 20,800, and the molecular weight distribution (Mw/Mn) was 3.40.

Examples and Comparative Examples

Photocurable compositions according to Examples and Comparative Examples were prepared with the components and contents (% by weight) shown in Tables 1 and 2 below.

division Example One 2 3 4 5 6 Binder resin (A) A-1 11.59 - - - - - A-2 - 11.59 - - - - A-3 - - 11.59 - - - A-4 - - - 11.59 - - A-5 - - - - 11.59 - A-6 - - - - - 11.59 A-7 - - - - - - A-8 - - - - - - A-9 - - - - - - A-10 - - - - - - A-11 - - - - - - A-12 - - - - - - A-13 - - Binder resin (B) 2.32 2.32 2.32 2.32 2.32 2.32 polymerizable compound (C) 9.28 9.28 9.28 9.28 9.28 9.28 Photoinitiator/Initiation Aid
(D) D-1 0.70 0.70 0.70 0.70 0.70 0.70 D-2 0.23 0.23 0.23 0.23 0.23 0.23 D-3 0.70 0.70 0.70 0.70 0.70 0.70 Antioxidant (E) 0.19 0.19 019 0.19 0.19 0.19 Solvent (F) F-1 26.25 26.25 26.25 26.25 26.25 26.25 F-2 48.74 48.74 48.74 48.74 48.74 48.74 Surfactant (G) 0.01 0.01 0.01 0.01 0.01 0.01

division comparative example One 2 3 4 5 6 7 Binder resin (A) A-1 - - - - - - - A-2 - - - - - - - A-3 - - - - - - - A-4 - - - - - - - A-5 - - - - - - - A-6 - - - - - - - A-7 11.59 - - - - - - A-8 - 11.59 - - - - - A-9 - - 11.59 - - - - A-10 - - - 11.59 - - - A-11 - - - - 11.59 - - A-12 - - - - - 11.59 - A-13 - - - - - - 11.59 Binder resin (B) 2.32 2.32 2.32 2.32 2.32 2.32 2.32 polymerizable compound (C) 9.28 9.28 9.28 9.28 9.28 9.28 9.28 Photoinitiator/Initiation Aid
(D) D-1 0.70 0.70 0.70 0.70 0.70 0.70 0.70 D-2 0.23 0.23 0.23 0.23 0.23 0.23 0.23 D-3 0.70 0.70 0.70 0.70 0.70 0.70 0.70 Antioxidant (E) 0.19 0.19 019 0.19 0.19 019 0.19 Solvent (F) F-1 26.25 26.25 26.25 26.25 26.25 26.25 26.25 F-2 48.74 48.74 48.74 48.74 48.74 48.74 48.74 Surfactant (G) 0.01 0.01 0.01 0.01 0.01 0.01 0.01

Specific ingredients listed in Tables 1 and 2 are as follows.

A-1: Binder resin of Preparation Example 1 (including tricyclodecanyl group: number of hydrogen atoms/number of carbon atoms ratio (H/C)=1.5)

A-2: Binder resin of Preparation Example 2 (including tricyclodecanyl group: H / C = 1.5)

A-3: Binder resin of Preparation Example 3 (including isobornyl group: H/C = 1.7)

A-4: Binder resin of Preparation Example 4 (including tricyclodecanyl group: H/C = 1.7)

A-5: Binder resin of Preparation Example 5 (including tricyclodecanyl group: H/C = 1.7)

A-6: Binder resin of Preparation Example 6 (including tricyclodecanyl group: H / C = 1.7)

A-7: Binder resin of Preparation Example 7 (including vinyl toluene group)

A-8: Binder resin of Preparation Example 8 (including cyclohexyl group: H/C = 1.8)

A-9: Binder resin of Preparation Example 9 (including tert-butyl group: H/C = 2.3)

A-10: Binder resin of Preparation 10 (including n-decyl group: H / C = 2.1)

A-11: Binder resin of Preparation Example 11 (without cyclic ether-containing unit)

A-12: Binder resin of Preparation Example 12 (without alicyclic heterocyclic group-containing unit)

A-13: Binder resin of Preparation Example 13 (without heterocyclic epoxy-containing unit)

B: Binder resin of Preparation Example 14

C: 6 functional acrylate compound (A-9550: manufactured by Shinjungbu Chemical Co., Ltd.)

D-1:2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

D-2: a compound of [Formula 5]

D-3: the compound of [Formula 6]

E: 4,4'-butylidene bis [6-tert-butyl-3-methylphenol]

F-1: methyl ethyl diethylene glycol

F-2: propylene glycol methyl ether acetate

G: SH8400 Fluid (manufactured by Dow-Corning-Toray)

Experimental example

A glass substrate having a width and length of 2 inches each (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol, and then dried. Each of the photosensitive resin compositions prepared in Examples and Comparative Examples were spin-coated on the glass substrate, and prebaked at 85° C. for 125 seconds using a hot plate to form a coating film. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was set to 150 μm, and light was irradiated with an exposure amount of 45 mJ/cm 2 (based on 365 nm) through an exposure machine (MA6 manufactured by MICOSUSS). The photomask had a square pattern with one side of 30 μm, and was formed on the same plane with an interval of 100 μm.

After the exposure process, the coating film was developed by immersing the coating film in a 2.38% tetramethylammonium hydroxide aqueous solution at 25° C. for 60 seconds, washing with water and drying, and post-baking at 130° C. for 40 minutes using a clean oven to form an insulating pattern. formed. The height of the formed insulating pattern was 2.0 mu m. The insulation pattern was evaluated for physical properties as follows, and the results are shown in Tables 3 and 4 below.

(1) Pattern Bottom CD size measurement

1 is a conceptual diagram for explaining the definition of a bottom CD size of an insulating pattern.

As described above, by observing the insulating pattern in which the hole is formed by the developing process with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), a point 5% of the total height from the bottom of the hole is defined as the Bottom CD. and the average value of the measured values in the horizontal and vertical directions was defined as the line width of the pattern.

(2) Pattern CD-Bias

As described above, the difference between the mask size and the bottom line width of the insulating pattern in which the hole is formed by the developing process was calculated as CD-bias. CD-bias is better as it approaches 0, and (+) means that the bottom CD value of the hole is smaller than the hole size of the mask, and (-) means that it is larger than the hole size of the mask.

(3) developing film

As described above, by measuring the insulating pattern in which the hole is formed by the developing process with a scanning electron microscope (Hitachi, S-4700), it was evaluated as follows by observing whether a residual film remains after development. Residual film refers to a residue in the form of reducing the line width of the bottom part while remaining in the hole.

○: No observed residual film (refer to FIG. 2)

×: generation of residual film (refer to Fig. 3)

(4) Evaluation of chemical resistance of the stripper

Each of the photosensitive resin compositions prepared in Examples and Comparative Examples were spin-coated on a silicon wafer having a width and length of 4 inches, respectively, and then pre-baked at 85° C. for 125 seconds using a hot plate to form a coating film. After cooling the prebaked substrate to room temperature, using an exposure machine (MA6 manufactured by MICOSUSS), the entire surface of the substrate is irradiated with light at an exposure dose of 45 mJ/cm2 (based on 365 nm), and the coating film is placed in a 2.38% tetramethylammonium hydroxide aqueous solution. After development by immersion at 25° C. for 60 seconds, washing with water and drying, post-baking was performed at 130° C. for 40 minutes using a clean oven to form an insulating pattern. The thickness of the obtained insulating pattern was 2.0 micrometers.

After measuring the thickness of the insulating pattern with a non-contact film thickness meter (Lambda Ace VM-1210; manufactured by Dainippon Screen MFG), it was immersed in a positive resist stripper, treated for 45 minutes/3 minutes, dried, and then the thickness of the insulation pattern was measured again. Thus, the film thickness change before/after the stripper treatment was confirmed.

As the positive resist stripper of the above experiment, 60 g of 2-amino-1-propanol dissolved in 60 g of N-methyl-2-pyrrolidone and 80 g of diethylene glycol methylbutyl ether was used.

(5) Chemical resistance of aqueous methacrylic acid solution

An APC (99% Ag; Furuya Metal Co., Ltd.) film with a thickness of 2000 Å is formed on a glass substrate (Eagle 2000; Corning Co., Ltd.) having a thickness of 2 inches each of width and length by sputtering, and on the glass substrate, the Examples and Comparative Examples Each of the photosensitive resin compositions prepared in Example was spin-coated and then pre-baked at 85° C. for 125 seconds using a hot plate to form a coating film. After cooling the prebaked substrate to room temperature, irradiate the entire surface of the substrate with light at an exposure dose of 45 mJ/cm 2 (based on 365 nm) using an exposure machine (MICOSUSS MA6), and apply the coating film to 2.38% tetramethylammonium hydroxide aqueous solution. was immersed at 25° C. for 60 seconds to develop, washed with water and dried, and then post-baked at 130° C. for 40 minutes using a clean oven to form an insulating pattern. Thereafter, the substrate on which the insulating pattern was formed was immersed in 1.5 wt% of an aqueous methacrylic acid solution and left for 10 hours while heating to 85° C.

○: No change in the surface appearance of the coating film or insulation pattern (refer to FIG. 4)

×: peeling of the surface of the coating film or the insulating pattern was observed (refer to FIG. 5)

Meanwhile, FIGS. 2 to 5 are reference images for explaining the evaluation criteria, and are not used as images showing actual experimental results of Examples and Comparative Examples in this Experimental Example.

division Example One 2 3 4 5 6 photo etching
(Lithography)
characteristic Hole CD (㎛) 29.6 28.3 27.2 30.1 27.7 24.4 CD-Bias (μm) -0.4 -1.7 -2.8 +0.1 -2.3 -5.6 development residue ○ ○ ○ ○ ○ ○ Stripper chemical resistance
* Film thickness change (㎛) 0.19 0.08 0.14 0.18 0.59 0.28 Chemical resistance of aqueous methacrylic acid solution ○ ○ ○ ○ × ×

division comparative example One 2 3 4 5 6 7 photo etching
(Lithography)
characteristic Hole CD (㎛) 19.8 17.2 21.9 8.1 18.3 25.6 15.5 CD-Bias (μm) -10.2 -12.8 -8.1 -21.9 -11.7 -4.4 -14.5 development residue ○ × ○ × × ○ × Stripper chemical resistance
* Film thickness change (㎛) 0.24 0.30 0.41 0.71 0.25 0.32 0.20 Chemical resistance of aqueous methacrylic acid solution × × × × ○ × ○

Referring to Tables 3 and 4, in the case of Examples including a binder resin including a cyclic ether-containing unit, a heterocyclic epoxy-containing unit, and an alicyclic heterocyclic group-containing unit, overall better photoetching properties and resistance than Comparative Examples showed chemistry.

On the other hand, in Example 5, in which the molar ratio of the alicyclic heterocyclic group-containing unit (derived from tricyclodecanyl acrylate) and the cyclic ether-containing unit (derived from glycidyl methacrylate) was somewhat reduced, and the alicyclic heterocyclic group-containing unit In the case of Example 6 in which the molar ratio was smaller than the molar ratio of the heterocyclic epoxy-containing unit, the chemical resistance was slightly lowered.

Claims (13)

a binder resin including a cyclic ether-containing unit, a heterocyclic epoxy-containing unit, and an alicyclic heterocyclic group-containing unit;
polymerizable compounds;
photoinitiator; and
contains a solvent;
The molar ratio of the alicyclic heterocyclic group-containing unit in the binder resin is greater than or equal to the molar ratio of the heterocyclic epoxy-containing unit, the photosensitive resin composition.
The method according to claim 1, wherein the alicyclic heterocyclic group-containing unit is represented by the following formula (1), the photosensitive resin composition:
[Formula 1]

(In Formula 1, R ₁ is hydrogen or a methyl group, and X ₁ is an alicyclic heterocyclic group).
The method according to claim 2, The ratio of the number of hydrogen atoms to the number of carbon atoms in the alicyclic heterocyclic group (number of hydrogen atoms / number of carbon atoms) is less than 1.8, the photosensitive resin composition.
The photosensitive resin composition of claim 1, wherein the alicyclic heterocyclic group-containing unit is derived from at least one of compounds represented by the following Chemical Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

(In Formulas 1-1 to 1-3, R ₂ is hydrogen or a methyl group).
The method according to claim 1, wherein the cyclic ether-containing unit is derived from at least one of the monomers represented by Formulas 2-1 to 2-4, the photosensitive resin composition:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

(In Formulas 2-1 to 2-4, R ₃ is hydrogen or a methyl group).
The photosensitive resin composition of claim 1, wherein the heterocyclic epoxy-containing unit is derived from at least one of the monomers of Formula 3-1 or 3-2.
[Formula 3-1]

[Formula 3-2]

(In Formulas 3-1 and 3-2, R ₄ is hydrogen or a methyl group).
The photosensitive resin composition of claim 1, wherein the molar ratio of the cyclic ether-containing unit in the binder resin is equal to or greater than the sum of the molar ratio of the alicyclic heterocyclic group-containing unit and the molar ratio of the heterocyclic epoxy-containing unit.
delete The photosensitive resin composition of claim 1, wherein the binder resin further comprises a carboxylic acid-containing unit.
The photosensitive resin composition according to claim 1, further comprising a polyfunctional thiol compound as an initiating aid.
11. The method of claim 10, wherein in the total weight of the composition,
10 to 50% by weight of the binder resin;
5 to 40% by weight of the polymerizable compound;
0.1 to 10% by weight of the photoinitiator; and
A photosensitive resin composition comprising 40 to 80% by weight of the solvent.
An insulating pattern formed from the photosensitive resin composition of any one of claims 1 to 7 and 9 to 11.
An image display device comprising the insulating pattern of claim 12 .

Images