TWI894155B - Positive photosensitive resin composition, positive photosensitive resin film and display device using the same - Google Patents

Abstract

The present invention relates to a positive-type photosensitive resin composition, a photosensitive resin film, and a display device using the same. The positive-type photosensitive resin composition of the present invention not only exhibits excellent sensitivity, chemical resistance, and heat resistance, but also significantly improves resolution, transmittance, and thermal discoloration resistance, enabling the production of high-brightness, high-resolution panels. Consequently, the composition can be effectively used in displays as interlayer insulating films, passivation insulating films, and gate insulating films, as well as planarizing films, banks, and pixel-defining layers.

Description

Positive photosensitive resin composition, photosensitive resin film, and display device using the same

The present invention relates to a positive-type photosensitive resin composition and a display using the same. More specifically, the present invention relates to a positive-type photosensitive resin composition having excellent resolution, photolithography process margin, and heat resistance.

In particular, the present invention relates to a positive-type photosensitive resin composition with excellent sensitivity and transparency and significantly improved adhesion, making it suitable for forming interlayer insulating films, PDLs (pixel definition layers), columnar spacers, etc. in the LCD and OLED manufacturing processes.

In the manufacturing process of TFT-type liquid crystal displays (LCDs) and organic light-emitting displays (OLEDs), interlayer insulating films are used to insulate the wiring between layers. However, the recent development of high-speed response and high-resolution devices requires high aperture ratios and low-resistance wiring technologies, resulting in reduced circuit widths and thicker layers, leading to a trend of increasing TFT height differences. In this case, the increased thickness of the interlayer insulating film used to achieve flattening results in decreased sensitivity and transparency, leading to reduced productivity and quality of display panels. Therefore, there is an urgent need to develop insulating films with excellent sensitivity and transparency.

This invention aims to provide a positive-type photosensitive resin composition with excellent resolution, photolithography process margin, and heat resistance, particularly excellent sensitivity and transparency, and significantly improved adhesion. This composition is suitable for forming interlayer insulating films, PDLs, columnar spacers, and other materials in LCD and OLED manufacturing processes.

In addition, the present invention aims to provide a display comprising a cured product of the positive photosensitive resin composition.

The positive-type photosensitive resin composition disclosed herein comprises: a) a first copolymer comprising i) repeating units derived from an ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protecting groups, ii) repeating units derived from an unsaturated carboxylic acid compound, and iii) repeating units derived from an ethylenically unsaturated compound; b) a second copolymer wherein at least a portion of the terminal hydroxyl groups are protected by acid-degradable protecting groups; c) a photoacid generator; and d) a solvent. The second copolymer comprises repeating units represented by the following chemical formulas 1 and 2.

In the above Chemical Formula 2, R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group.

The present invention also provides a photosensitive resin film comprising a cured product of the positive-type photosensitive resin composition described above.

The present invention also provides a display device comprising the above-mentioned photosensitive resin film.

Hereinafter, the positive photosensitive resin composition, photosensitive resin film, and display device according to specific embodiments of the present invention will be described in more detail.

The following embodiments are described in detail to facilitate implementation of the present invention by those skilled in the art. The embodiments can be implemented in various ways and are not limited to the specific embodiments described herein.

The present invention relates to a positive-type photosensitive resin composition that can be used in various fields, such as interlayer insulating films, passivation insulating films, gate insulating films, overcoats, columnar spacers, and PDL isolation walls, disposed between layers of displays such as liquid crystal displays (LCDs) and organic light-emitting displays (OLEDs).

1. Positive photosensitive resin composition

According to one embodiment of the present invention, a positive-type photosensitive resin composition comprises: a) a first copolymer comprising i) repeating units derived from an ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protecting groups, ii) repeating units derived from an unsaturated carboxylic acid compound, and iii) repeating units derived from an ethylenically unsaturated compound; and b) a second copolymer, at least a portion of whose terminal hydroxyl groups are protected by acid-degradable protecting groups. The first copolymer can be polymerized under conditions where, relative to 100 mol of the total monomer content used in the synthesis, the ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protecting groups contains 1 to 50 mol%, the unsaturated carboxylic acid compound contains 5 to 40 mol%, and the ethylenically unsaturated compound content is greater than or equal to 10 mol% and less than 70 mol%. A positive-type photosensitive resin composition can be provided, wherein the ethylenically unsaturated compound having a terminal hydroxyl group protected by an acid-decomposable protecting group can include at least one of the compounds represented by the following Chemical Formula 3 or 4, and the second copolymer includes any one of the main chains represented by the following Chemical Formulas 5 to 7.

In one embodiment of the present invention, the first copolymer of a) can be synthesized by a free radical reaction in the presence of i) an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protecting group, ii) an unsaturated carboxylic acid compound, and iii) a monomer of the ethylenically unsaturated compound, a solvent, and a polymerization initiator.

Specifically, the olefinically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group may include any of the compounds represented by the following Chemical Formula 3 or 4.

In the above Chemical Formula 3, _R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetyloxyethoxyethyl group. [Chemical Formula 4]

In the above Chemical Formula 4, _R2 is hydrogen or a C1 to C10 alkyl group, _R3 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, and n is an integer from 0 to 4.

Because the first copolymer, which includes as a monomer the aforementioned ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protecting groups, maximizes the difference in developer dissolution rates between exposed and unexposed areas when forming a photolithographic pattern, it can improve contrast. Therefore, an insulating film prepared from the positive photosensitive resin composition according to one embodiment of the present invention can achieve excellent sensitivity, resolution, transmittance, heat discoloration resistance, photolithographic process margin, adhesion, and heat resistance.

In contrast, if the first copolymer includes an ethylenically unsaturated compound whose terminal hydroxyl group is not protected by an acid-degradable protective group as a monomer during polymerization, there is a risk of poor sensitivity, resolution, and photolithography process margin.

Since the first copolymer comprises, as a monomer, an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-degradable protective group, the repeating unit derived from the ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-degradable protective group may comprise any of the repeating units represented by the following chemical formula 3-1 or 4-1.

In the above Chemical Formula 3-1, R ₁ ′ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group. [Chemical Formula 4-1]

In the above chemical formula 4-1, R ₂ ' is hydrogen or a C1 to C10 alkyl group, R ₃ ' is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, and n' is an integer from 0 to 4.

The first copolymer may be obtained by copolymerizing a monomer mixture of the first copolymer, wherein the monomer mixture of the first copolymer comprises greater than or equal to 1 mol% and less than or equal to 50 mol%, or greater than or equal to 1 mol% and less than or equal to 20 mol%, of i) the ethylenically unsaturated compound having a terminal hydroxyl group protected by an acid-degradable protecting group, relative to 100 mol% of the total monomer mixture of the first copolymer.

If the first copolymer is obtained by copolymerizing a monomer mixture containing less than 1 mol% of the aforementioned ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protecting groups, the difference in developer dissolution rates between exposed and unexposed areas during photolithographic pattern formation decreases, making it impossible to improve contrast. Consequently, not only does sensitivity and resolution deteriorate, but transparency, heat discoloration resistance, photolithographic process margin, adhesion, and heat resistance all suffer.

If the first copolymer is obtained by copolymerizing a monomer mixture containing greater than 50 mol% of the aforementioned ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protecting groups, the residual rate of the terminal acid-degradable protecting groups will be high during the exposure process when forming a photolithographic pattern, potentially leading to technical issues such as poor sensitivity, resolution, and poor photolithographic process margin.

Alternatively, the first copolymer may contain, relative to the total repeating units, greater than or equal to 1 mol% and less than or equal to 50 mol%, or greater than or equal to 1 mol% and less than or equal to 20 mol%, of repeating units derived from an ethylenically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group.

If the first copolymer contains less than 1 mol% of the aforementioned repeating units derived from an ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protecting groups, relative to the total number of repeating units, the difference in developer dissolution rates between exposed and unexposed areas during photolithographic pattern formation decreases, making it impossible to improve contrast. Consequently, not only does sensitivity and resolution deteriorate, but it also presents technical problems such as poor transmittance, heat discoloration resistance, photolithographic process margin, adhesion, and heat resistance.

If the first copolymer contains greater than 50 mol% of the repeating units derived from an olefinically unsaturated compound in which the terminal hydroxyl groups are protected by acid-degradable protecting groups, relative to the total number of repeating units, the residual rate of the terminal acid-degradable protecting groups will be high during the photolithographic pattern formation, even after the exposure process. This may lead to technical issues such as poor sensitivity, resolution, and poor photolithographic process margin.

The unsaturated carboxylic acid compound can be unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, methaconic acid, and itaconic acid; or their anhydrides, used alone or in combination of at least two. In particular, the use of acrylic acid, methacrylic acid, or maleic anhydride can improve copolymerization reactivity and solubility in alkaline aqueous developer solutions.

The unsaturated carboxylic acid compound may be mixed in an amount of greater than or equal to 1 mol% and less than or equal to 50 mol%, or greater than or equal to 20 mol% and less than or equal to 50 mol%, or greater than or equal to 25 mol% and less than or equal to 35 mol%, relative to 100 mol% of the total monomer mixture of the first copolymer. If the content of the unsaturated carboxylic acid compound is less than 1 mol%, it will be difficult to dissolve in an alkaline aqueous solution. If it is greater than 50 mol%, its solubility in an alkaline aqueous solution will become excessive.

Specifically, if the first copolymer is obtained by copolymerizing a monomer mixture containing greater than 50 mol% of the unsaturated carboxylic acid compound, its solubility in aqueous alkaline solutions becomes excessive, potentially leading to poor sensitivity, resolution, adhesion, heat resistance, and photolithography process margin.

The olefinically unsaturated compound may be methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, phenyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, phenyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, 1-cyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, 1-cyclopentan ... methacrylate), phenyl acrylate, benzyl acrylate, 2-hydroxy ethyl methacrylate, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, 1,3-butadiene, isoprene, or 2,3-dimethyl-1,3-butadiene, ethyl 2-[methacryloyloxy]-6-hydroxyhexanoate, 4-vinylphenol, 4-vinylcyclohexanol, 4-hydroxybenzyl methacrylate, methyl [[4-hydroxymethyl]cyclohexyl] methacrylate, 3-hydroxy-1-methacryloyloxyadamantanyl ester, 2-oxotetrahydrofuran-3-yl methacrylate methacrylate), 4-hydroxycyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl Benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, 3-ethyl-3-oxocyclobutyl methacrylate, 3-ethyl-3-oxocyclobutyl acrylate, 3-butyl-3-oxocyclobutyl methacrylate, 3-butyl methacrylate -butyl-3-oxocyclobutyl ester, 3-propyl-3-oxocyclobutyl methacrylate, 3-propyl-3-oxocyclobutyl acrylate, 3-oxocyclobutyl methacrylate, 3-oxocyclobutyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxybutyl acrylate and hydroxypropyl acrylate, etc. The above-mentioned compounds can be used alone or in combination of at least two.

The ethylenically unsaturated compound may be mixed in an amount of greater than or equal to 1 mol% and less than or equal to 50 mol%, or greater than or equal to 20 mol% and less than or equal to 50 mol%, or greater than or equal to 20 mol% and less than or equal to 30 mol%, relative to 100 mol% of the total monomer mixture of the first copolymer. When the content is within this range, swelling does not occur after development, and ideal solubility in the alkaline aqueous developer solution is maintained.

Specifically, if the first copolymer is obtained by copolymerizing a monomer mixture containing greater than 50 mol% of the aforementioned ethylenically unsaturated compound, developing speed and photosensitivity may be reduced, potentially leading to technical problems such as poor sensitivity, resolution, adhesion, heat resistance, and photolithography process margin.

In addition, for the first copolymer a) described above, its polystyrene-equivalent weight average molecular weight (Mw) may be greater than or equal to 3,000 g/mol and less than or equal to 30,000 g/mol.

Solvents used for solution polymerization of monomers include methanol, tetrahydroxyfuran, toluene, and dioxane. Free radical polymerization initiators can be used as polymerization initiators for solution polymerization. Specifically, they include 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobisisobutylate.

That is, the positive-type photosensitive resin composition of the above embodiment may include a first copolymer polymerized in the presence of 2 parts by weight to 24 parts by weight, 2 parts by weight to 10 parts by weight, or 5 parts by weight to 10 parts by weight of a free radical polymerization initiator, relative to 100 parts by weight of the total weight of the monomer mixture of the first copolymer.

If the first copolymer is polymerized using less than 2 parts by weight of a free radical polymerization initiator, the first copolymer will be overpolymerized. Due to the polymerization into an acrylic copolymer with an excessively large molecular weight, the positive-type photosensitive resin composition containing the copolymer may suffer from poor photolithography process margin, adhesion, and heat resistance.

Conversely, if the first copolymer is polymerized using more than 24 parts by weight of a free radical polymerization initiator, the resulting acrylic copolymer may have an excessively low molecular weight. This may lead to technical issues such as poor photolithography process margin, poor adhesion, and poor heat resistance in the positive-type photosensitive resin composition containing the copolymer.

The monomers undergo a free radical reaction in the presence of a solvent and a polymerization initiator, and unreacted monomers are removed through precipitation, filtration, and vacuum drying to obtain a first copolymer having a polystyrene-equivalent weight-average molecular weight (Mw) of 3,000 to 20,000. For interlayer insulating films (organic insulating films) with a polystyrene-equivalent weight-average molecular weight of less than 3,000, developability and residual film rate may be reduced, or pattern development and heat resistance may be deteriorated. For interlayer insulating films with a polystyrene-equivalent weight-average molecular weight greater than 20,000, pattern development may be deteriorated.

On the other hand, the second copolymer in which at least a portion of the terminal hydroxyl groups are protected by an acid-decomposable protecting group may include repeating units derived from an olefinic compound in which the terminal hydroxyl groups are protected by an acid-decomposable protecting group; and repeating units derived from an olefinic compound having a terminal hydroxyl group, for example, repeating units represented by the following chemical formulas 1 and 2.

[Chemical formula 2]

In the above Chemical Formula 2, R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group.

Specifically, the second copolymer may include a main chain represented by the following Chemical Formula 5.

In the above Chemical Formula 5, a+b=100, a is 50 to 99, b is 1 to 50, and _R1 can be a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group.

Alternatively, the second copolymer may include a main chain represented by the following Chemical Formula 6 or Chemical Formula 7.

In the above Chemical Formula 6, a+b+c+d=100, b+d is 1 to 50, _R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, _R2 is hydrogen or a C1 to C10 alkyl group, and n can be an integer from 0 to 4.

In the above Chemical Formula 7, a+b+c+d=100, b+d is 1 to 50, _R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, _R2 is hydrogen or a C1 to C10 alkyl group, and n can be an integer from 0 to 4.

Preferably, the second copolymer in which at least a portion of the terminal hydroxyl groups are protected by an acid-decomposable protecting group may comprise a main chain represented by the above Chemical Formula 6 or Chemical Formula 7.

If the second copolymer includes the main chain represented by Chemical Formula 6 or Chemical Formula 7, it is more resistant to yellowing than the copolymer represented by Chemical Formula 5, achieving excellent transmittance and heat discoloration resistance.

In the above chemical formulas 5 to 7, a to d represent the molar ratios between the repeating units. Chemical formulas 5 to 7 do not restrict the order of the repeating units.

In addition, the second copolymer may include, relative to the total repeating units, greater than or equal to 0.01 mol% and less than or equal to 50 mol%, or greater than or equal to 1 mol% and less than or equal to 50 mol% of repeating units in which the terminal hydroxyl groups are protected by acid-degradable protecting groups.

When the olefinic copolymer contains more than 50 mol% of repeating units whose terminal hydroxyl groups are protected by acid-degradable protecting groups relative to the total number of repeating units, not only will sensitivity and resolution deteriorate, but transmittance, thermal discoloration resistance, and photolithography process margin will also be reduced.

The second copolymer may be included in an amount of greater than or equal to 1 part by weight and less than or equal to 50 parts by weight relative to 100 parts by weight of the total of the first copolymer and the second copolymer.

If the content of the second copolymer exceeds 50 parts by weight relative to a total of 100 parts by weight of the first and second copolymers, not only will sensitivity and resolution deteriorate, but transparency, thermal discoloration resistance, photolithography process margins, as well as adhesion and heat resistance will also decrease.

In addition, the second copolymer may have a polystyrene-equivalent weight average molecular weight (Mw) of greater than or equal to 3,000 g/mol and less than or equal to 30,000 g/mol.

According to one embodiment of the present invention, the positive-type photosensitive resin composition may further include c) a photoacid generator.

The photoacid generator c) may be included in an amount of greater than or equal to 0.1 parts by weight and less than or equal to 30 parts by weight relative to a total of 100 parts by weight of the first copolymer and the second copolymer.

There is no particular limitation on the type of photoacid generator c) mentioned above. For example, it may include at least one selected from the group consisting of oxime sulfonates, imide sulfonates, diazonium sulfonates, diazonium salts, disulfones, phosphonium salts, sulfonates, iodonium salts, o-nitrobenzyl sulfonates, and triazine compounds.

Specifically, the photoacid generator c) may include at least one of the compounds represented by the following chemical formulas 8 to 13.

[Chemical formula 11]

In the above Chemical Formulas 8 to 13, X is hydrogen or a C1 to C14 linear or branched alkyl group, and _R3 is a C1 to C18 aliphatic alkyl group, a C6 to C20 aryl group, a C7 to C20 aralkyl group, a C7 to C20 aryl group substituted with an acyl group, or a C1 to C8 halogenalkyl group.

In addition, according to one embodiment of the present invention, the positive photosensitive resin composition may further include d) a solvent.

The solvent d) mentioned above is used to apply the photosensitive resin composition to a substrate, etc. Specific examples include diethylene glycol dimethyl ether, diethylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl ether, ether), butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tert-butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethyl hexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl hexyl ether and dipropylene glycol methyl hexyl ether, etc., can be used alone or in combination of at least two.

The solvent d) may be included so that the solids content of the positive-working photosensitive resin composition reaches 10 to 50% by weight. If the solids content is less than 10% by weight, the coating thickness becomes thinner and the coating uniformity decreases. If the solids content is greater than 50% by weight, the coating thickness becomes thicker, which places a burden on the coating equipment during coating. When the solids content of the total composition is 10 to 25% by weight, it is convenient for use in a slit coater. When the solids content of the total composition is 25 to 50% by weight, it is convenient for use in a spin coater or a slit & spin coater.

The positive photosensitive resin composition can be prepared to have a solid concentration of 10 to 50% by weight and filtered using a 0.1-0.2 μm millipore filter or the like before use.

According to another embodiment of the present invention, a positive-type photosensitive resin composition may be provided, further comprising at least one additive selected from the group consisting of e) an alkaline compound, f) an adhesion promoter, g) an antioxidant, and h) a photosensitizer.

When the positive-type photosensitive resin composition further comprises at least one additive selected from the group consisting of e) an alkaline compound, f) an adhesion promoter, g) an antioxidant, and h) a photosensitizer, the positive-type photosensitive resin composition may comprise, relative to 100 parts by weight of the first copolymer and the second copolymer, greater than or equal to 0.01 parts by weight and less than or equal to 3 parts by weight of e) an alkaline compound, greater than or equal to 0.5 parts by weight and less than or equal to 10 parts by weight of f) an adhesion promoter, greater than or equal to 0.1 parts by weight and less than or equal to 10 parts by weight of g) an antioxidant, and greater than or equal to 0.1 parts by weight and less than or equal to 10 parts by weight of h) a photosensitizer.

The alkaline compound may include at least one selected from the group consisting of trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, methyldicyclohexylamine, benzylamine, N,N-dimethylaniline, diphenylamine, pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexammonium hydroxide.

In addition, the adhesion promoter may include (3-glycyrrhetinol)trimethoxysilane, (3-glycyrrhetinol)triethoxysilane, (3-glycyrrhetinol)methyldimethoxysilane, (3-glycyrrhetinol)methyldiethoxysilane, (3-glycyrrhetinol)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, At least one member selected from the group consisting of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (3-isocyanatepropyl)triethoxysilane, and (3-isocyanatepropyl)trimethoxysilane.

In addition, the antioxidant may include at least one selected from the group consisting of phosphorus-based antioxidants, amides, hydrazides, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, and hydroxylamine derivatives.

In addition, the photosensitizer may include at least one selected from the group consisting of pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, and 9,10-dipropoxyanthracene.

2. Photosensitive resin film

According to one embodiment of the present invention, a photosensitive resin film can be provided, comprising a cured product of the positive-type photosensitive resin composition. The positive-type photosensitive resin composition comprises all of the above-mentioned components.

The above-mentioned cured product includes not only the case where all components with curable or cross-linkable unsaturated groups in the chemical structure are cured, but also the case where part of them are cured, cross-linked or polymerized.

The photosensitive resin film according to the above embodiment can be used not only as an interlayer insulating film, a passivation insulating film, and a gate insulating film, but also as a planarizing film, a bank, and a pixel define layer.

3. Display device

According to one embodiment of the present invention, a display device can be provided, comprising the above-mentioned photosensitive resin film. The above-mentioned photosensitive resin film includes all of the above-mentioned contents.

That is, when forming an insulating film in the display manufacturing process, the positive photosensitive resin composition according to one embodiment of the present invention can be used.

First, a positive-tone photosensitive resin composition is applied to the display panel substrate surface by spin coating, slit spin coating, slit coating, or roll coating. The solvent is then removed by pre-baking to form a coating film. The pre-baking can be performed at a temperature of 100°C to 120°C for 1 to 3 minutes. The resulting coating film is then irradiated with visible light, ultraviolet light, far-ultraviolet light, electron beams, X-rays, or other radiation according to a pre-prepared pattern. The film is then developed with a developer to remove unwanted areas, thereby forming the desired pattern.

The developer is preferably an aqueous alkaline solution. Specific examples include inorganic bases such as sodium hydroxide, potassium hydroxide, and sodium carbonate; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; alcoholamines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; or aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. The developer is prepared by dissolving the alkaline compound in a concentration of greater than or equal to 0.1 parts by weight and less than or equal to 10 parts by weight. A suitable amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may also be added.

After developing with a developer, the surface is rinsed with ultrapure water for 30 to 90 seconds to remove excess material, then dried to form a pattern. The resulting pattern is then irradiated with ultraviolet light or other light, and then heated in an oven or other heating device at 150 to 400°C for 30 to 90 minutes to obtain the final pattern.

The positive-type photosensitive resin composition according to the embodiment exhibits excellent planarization, transmittance, and outgassing properties, particularly excellent sensitivity. It also exhibits significantly improved adhesion, contrast, and chemical resistance under high temperature and high humidity conditions, making it suitable for forming interlayer insulating films and PDL isolation walls in LCD and OLED manufacturing processes.

According to embodiments, the positive photosensitive resin composition exhibits excellent resolution, photolithography process margin, and heat resistance, particularly excellent sensitivity and permeability, along with significantly improved adhesion. This makes it suitable for forming interlayer insulating films, PDLs, columnar spacers, and other materials in LCD and OLED manufacturing processes. Furthermore, the present invention provides a method for forming patterns on LCD and OLED substrates and display substrates using a cured product of the photosensitive resin composition. The patterns can be used as materials for passivation insulating films, gate insulating films, planarization films, columnar spacers, isolation walls, and other materials in TFT-LCDs, TSPs (touch screen panels), OLEDs, O-TFTs, EPDs, and EWDs.

Preferred embodiments are given below to help understand the present invention, but the following embodiments are only used to illustrate the present invention, and the scope of the present invention is not limited to the following embodiments.

Synthesis and Comparative Synthesis Example: Preparation of the First Copolymer

Synthesis Example 1: Preparation of the First Copolymer (A)

Tetrahydrofuran (THF) was prepared as a synthesis solvent in a flask equipped with a cooler and a stirrer. A mixed solution of an olefinically unsaturated compound represented by the following chemical formula (1A), methacrylic acid, styrene, and glycidyl methacrylate in a molar ratio of 30:20:20:30 was then added. The liquid composition was thoroughly mixed in a mixing vessel at 600 rpm, followed by the addition of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) to 100 parts by weight of the total monomers. The polymerization mixture was slowly heated to 55°C, maintained at this temperature for 48 hours, then cooled to room temperature and dried to completely remove the THF, thereby producing a first copolymer (A). The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured using GPC. The weight-average molecular weight is measured using a standard gel permeation chromatography (GPC) analysis method using a Waters e2695 Alliance Seperation Module.

Synthesis Example 2: Preparation of the First Copolymer (B)

A first copolymer (B) was prepared by the same method as in Synthesis Example 1, except that the olefinically unsaturated compound represented by Chemical Formula 1A was replaced with the olefinically unsaturated compound represented by Chemical Formula 1B below. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC. The weight-average molecular weight was measured by standard gel permeation chromatography (GPC) using a Waters e2695 Alliance Separation Module.

Synthesis Example 3: Preparation of the First Copolymer (C)

A first copolymer (C) was prepared by the same method as Synthesis Example 1, except that the olefinically unsaturated compound represented by Chemical Formula 1A was replaced with the olefinically unsaturated compound represented by Chemical Formula 1C below. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC. The weight-average molecular weight was measured by standard gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Synthesis Example 4: Preparation of the First Copolymer (D)

A first copolymer (D) was prepared by the same method as in Synthesis Example 1, except that the olefinically unsaturated compound represented by Chemical Formula 2A was used instead of the olefinically unsaturated compound represented by Chemical Formula 1A. The weight-average molecular weight of the first copolymer was 12,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC. The weight-average molecular weight was measured by standard gel permeation chromatography (GPC) using a Waters e2695 Alliance Separation Module.

Synthesis Example 5: Preparation of the First Copolymer (E)

A first copolymer (E) was prepared by the same method as in Synthesis Example 1, except that the olefinically unsaturated compound represented by Chemical Formula 1A was replaced with the olefinically unsaturated compound represented by Chemical Formula 2B below. The weight-average molecular weight of the first copolymer was 12,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC. The weight-average molecular weight was measured by standard gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

[Chemical formula 2B]

Synthesis Example 6: Preparation of the First Copolymer (F)

A first copolymer (F) was prepared by the same method as Synthesis Example 1, except that the olefinically unsaturated compound represented by Chemical Formula 1A was replaced with the olefinically unsaturated compound represented by Chemical Formula 2C below. The weight-average molecular weight of the first copolymer was 12,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC. The weight-average molecular weight was measured by standard gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Synthesis Example 7: Preparation of the First Copolymer (G)

A first copolymer (G) was prepared by the same method as Synthesis Example 1, except that the olefinically unsaturated compound represented by Chemical Formula 2D below was used in place of the olefinically unsaturated compound represented by Chemical Formula 1A above. The weight-average molecular weight of the first copolymer was 13,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC, which is determined by standard analytical methods using a Waters e2695 Alliance Separation Module.

Synthesis Example 8: Preparation of the First Copolymer (H)

A first copolymer (H) was prepared by the same method as in Synthesis Example 1, except that the olefinically unsaturated compound represented by Chemical Formula 1A was replaced with the olefinically unsaturated compound represented by Chemical Formula 2E below. The weight-average molecular weight of the first copolymer was 12,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC. The weight-average molecular weight was measured by standard gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

[Chemical formula 2E]

Synthesis Example 9: Preparation of the First Copolymer (I)

A first copolymer (I) was prepared by the same method as in Synthesis Example 1, except that a mixed solution of the olefinically unsaturated compound represented by Chemical Formula 1A, methacrylic acid, styrene, and glycidyl methacrylate in a molar ratio of 50:30:10:10 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC, which is determined by standard analytical methods using a Waters e2695 Alliance Seperation Module.

Synthesis Example 10: Preparation of the First Copolymer (J)

A first copolymer (J) was prepared by the same method as Synthesis Example 1, except that a mixed solution of the olefinically unsaturated compound represented by Chemical Formula 1B, methacrylic acid, styrene, and 3-ethyl-3-oxobutyl acrylate in a molar ratio of 25:40:15:20 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Synthesis Example 11: Preparation of the First Copolymer (K)

A first copolymer (K) was prepared by the same method as Synthesis Example 1, except that a mixed solution of the olefinically unsaturated compound represented by Chemical Formula 1A, methacrylic acid, styrene, glycidyl methacrylate, and 3-ethyl-3-oxobutyl acrylate in a molar ratio of 5:15:35:25:20 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Synthesis Example 12: Preparation of the First Copolymer (L)

A first copolymer (L) was prepared by the same method as Synthesis Example 1, except that a mixed solution of the olefinically unsaturated compound represented by Chemical Formula 1A, methacrylic acid, styrene, and glycidyl methacrylate in a molar ratio of 40:15:30:15 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Synthesis Example 13: Preparation of the First Copolymer (M)

A first copolymer (M) was prepared by the same method as in Synthesis Example 1, except that a mixed solution of the ethylenically unsaturated compound represented by Chemical Formula 1A, methacrylic acid, styrene, glycidyl methacrylate, and hydroxyethyl acrylate in a molar ratio of 1:5:34:25:35 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by GPC. The weight-average molecular weight was measured by standard gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Synthesis Example 14: Preparation of the First Copolymer (N)

A first copolymer (N) was prepared by the same method as in Synthesis Example 1, except that 5 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) as a catalyst during the polymerization. The weight-average molecular weight of the first copolymer was 19,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Separation Module.

Synthesis Example 15: Preparation of the First Copolymer (O)

A first copolymer (O) was prepared by the same method as in Synthesis Example 1, except that 2 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) as a catalyst during the polymerization. The weight-average molecular weight of the first copolymer was 30,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Separation Module.

Synthesis Example 16: Preparation of the First Copolymer (P)

A first copolymer (P) was prepared by the same method as in Synthesis Example 1, except that 24 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of the 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) used as a catalyst during the polymerization. The weight-average molecular weight of the first copolymer was 3000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Separation Module.

Comparative Synthesis Example 1: Preparation of the First Copolymer (Q)

A first copolymer (Q) was prepared by the same method as Synthesis Example 1, except that a mixed solution of the olefinically unsaturated compound represented by Chemical Formula 1A, methacrylic acid, styrene, and glycidyl methacrylate in a molar ratio of 0:30:30:40 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Comparative Synthesis Example 2: Preparation of the First Copolymer (R)

A first copolymer (R) was prepared by the same method as in Synthesis Example 1, except that a mixed solution of the olefinically unsaturated compound represented by Chemical Formula 1A, methacrylic acid, styrene, and glycidyl methacrylate in a molar ratio of 52:13:15:20 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Comparative Synthesis Example 3: Preparation of the First Copolymer (S)

A first copolymer (S) was prepared by the same method as in Synthesis Example 1, except that a mixed solution of the ethylenically unsaturated compound represented by Chemical Formula 1A, methacrylic acid, styrene, glycidyl methacrylate, and hydroxyethyl acrylate in a molar ratio of 1:4:35:25:35 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Comparative Synthesis Example 4: Preparation of the First Copolymer (T)

A first copolymer (T) was prepared by the same method as Synthesis Example 1, except that a mixed solution of the olefinically unsaturated compound represented by Chemical Formula 1B, methacrylic acid, styrene, and 3-ethyl-3-oxobutyl acrylate in a molar ratio of 25:42:13:20 was added. The weight-average molecular weight of the first copolymer was 10,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Seperation Module.

Comparative Synthesis Example 5: Preparation of the First Copolymer (U)

A first copolymer (U) was prepared by the same method as in Synthesis Example 1, except that 1.8 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) as a catalyst during the polymerization. The weight-average molecular weight of the first copolymer was 31,000. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Separation Module.

Comparative Synthesis Example 6: Preparation of the First Copolymer (V)

A first copolymer (V) was prepared by the same method as in Synthesis Example 1, except that 25 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) as a catalyst during the polymerization. The weight-average molecular weight of the first copolymer was 2800. The weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using a Waters e2695 Alliance Separation Module.

*Monomer i: An olefinically unsaturated compound with the terminal hydroxyl group protected by an acid-degradable protecting group

*Monomer ii: Unsaturated carboxylic acid compound

*Monomer iii: olefinically unsaturated compound

*Monomer iv: Unsaturated compound containing cross-linking groups

*MAA: methacrylic acid

*GMA: Glycidyl Methacrylate

*St: Styrene

*EOA: 3-Ethyl-3-oxocyclobutyl acrylate

*HEA: Hydroxyethyl acrylate

*ADVN: 2,2-azobis(2,4-dimethylvaleronitrile)

Examples, Comparative Examples, and Reference Examples: Preparation of Positive Photosensitive Resin Compositions

As shown in Table 2 below, the first copolymer prepared in the above synthesis example, the second copolymer represented by the following chemical formulas 3A to 5E, the photoacid generator represented by the following chemical formulas 12 to 28, an alkaline compound, an adhesion promoter, and an antioxidant were added, mixed and dissolved in propylene glycol methyl ether acetate to a solid content of 25% by weight, and then filtered through a 0.1 μm micropore filter to prepare a positive-working photosensitive resin composition.

In Table 2 below, the amounts of the first copolymer and the second copolymer are expressed in parts by weight relative to 100 parts by weight of the total of the first copolymer and the second copolymer. The amounts of the photoacid generator, alkaline compound, adhesion promoter, and antioxidant are expressed in parts by weight relative to 100 parts by weight of the total of the first copolymer and the second copolymer.

[Chemical Formula 3D] (Molecular weight: 8000 g/mol)

[Chemical formula 4E] (Molecular weight: 18000 g/mol)

[Chemical formula 5C] (Molecular weight: 12000 g/mol)

[Chemical formula 13]

[Chemical formula 18]

*DMA: N,N-dimethylaniline

*PP: Phenylpyridine

*TPA: tri-n-propylamine

*DEA: Diethylamine

*TEA: Triethanolamine

*APES: N-2-(aminoethyl)-3-aminopropyltriethoxysilane

*GOPMS: (3-glycidoxypropyl)trimethoxysilane

*DBMP: 2,6-di-tert-butyl-4-methylphenol

Experimental Example

The photosensitive resin compositions of the Examples and Comparative Examples were coated onto a glass substrate using a slot coater. The films were then subjected to a VCD (vacuum drying) process at a pressure of 40 Pa and pre-baked on a hot plate at 100°C for 2 minutes to form a film with a thickness of 4.0 μm.

The film's physical properties, including sensitivity, resolution, transmittance, thermal discoloration resistance, process margin, adhesion, and heat resistance, were measured and are shown in Table 3 below.

a) Sensitivity

The film formed above was irradiated with UV light at a broadband intensity of 20 mW/ ^cm² using a predetermined pattern mask with a standard dose of 10 μm contact hole size (CD). The film was then developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23°C for 1 minute and then rinsed with ultrapure water for 1 minute.

Next, the film was cured in an oven at 230°C for 30 minutes to produce a 3.0μm-thick patterned film. The sensitivity of the prepared patterned film was measured using the exposure energy (dose) required to form a 10μm contact hole pattern.

b) Resolution

The resolution is measured by the minimum size of the 10μm contact hole pattern formed when measuring the sensitivity in step a) above.

c) Transmittance

Transmittance was evaluated using a spectrophotometer to measure the transmittance at 400 nm of the patterned film formed during the sensitivity measurement in step (a) above. Transmittances of 97% or greater were marked with a ◎, 95% or greater with a ○, 90% or greater but less than 95% with a △, and less than 90% with an ×.

d) Resistance to heat discoloration

The substrate used in the transparency evaluation (c) was further cured twice in a 230°C oven for 30 minutes each time. Heat discoloration resistance was evaluated based on the change in transmittance at 400 nm of the patterned film before and after curing. Changes of less than 1% were marked with a ◎, less than 3% with a ○, 3% to 5% with a △, and greater than 5% with an ×.

e) PED (Post Exposure Delay) process margin

A patterned film was formed using the same sensitivity measurement method as in step (a) above. The CD variation rate based on the delay time after exposure and before the development process was measured, with a contact hole size of 10μm. A CD variation rate of less than 3% was indicated by ◎, less than 5% by ○, greater than or equal to 5% and less than 10% by △, and greater than or equal to 10% by ×.

f) Adhesion

The adhesion of the pattern film formed during the sensitivity measurement in step (a) above was evaluated based on whether the pattern was lost or not using the scope.

Pre-baking temperatures above 90°C indicate adhesion is guaranteed (◎), temperatures above 95°C indicate adhesion is guaranteed (○), temperatures between 100°C and 105°C indicate adhesion is guaranteed (∘), and temperatures above 105°C indicate adhesion is not guaranteed or pattern loss occurs (×).

g) Heat resistance

Heat resistance was measured using TGA. The patterned film formed during the sensitivity measurement in step (a) above was sampled and the temperature was raised from room temperature to 900°C at a rate of 10°C per minute using TGA. Cases where the temperature at which 5% weight loss occurred was higher than 300°C were marked with a circle, cases where the temperature at which 5% weight loss occurred was between 280°C and 300°C were marked with a triangle, and cases where the temperature at which 5% weight loss occurred was less than 280°C were marked with an x.

As shown in Table 3 above, insulating films comprising cured products of the positive-type photosensitive resin compositions of Examples 1 to 75 of this application exhibited a sensitivity of 50 mJ and a resolution of 3 μm, confirming excellent sensitivity and resolution. Furthermore, they exhibited a transmittance of 95% or greater, a heat discoloration resistance of less than 3%, and a CD variation of less than 5%, confirming excellent transmittance, heat discoloration resistance, and photolithography process margin. Furthermore, adhesion was maintained even at temperatures as low as 95°C, and the temperature at which 5% weight loss occurred was greater than 300°C, confirming excellent adhesion and heat resistance. That is, the insulating film made of the positive photosensitive resin composition of the embodiment of the present application has excellent sensitivity, resolution, transmittance, resistance to thermal discoloration, photolithography process margin, adhesion, and heat resistance.

In particular, since the positive-type photosensitive resin compositions of Examples 52 to 67 and Example 75 further contain an alkaline compound, it was confirmed that the insulating films comprising the cured products of the positive-type photosensitive resin compositions of Examples 52 to 67 and Example 75 exhibited very excellent heat discoloration resistance, with a transmittance change rate of less than 1%.

Furthermore, since the positive-type photosensitive resin compositions of Examples 65 to 71 and Example 75 further contain an adhesion promoter, it was confirmed that the insulating film comprising the cured product of the positive-type photosensitive resin compositions of Examples 65 to 71 and Example 75 exhibited very excellent adhesion, maintaining adhesion at a pre-bake temperature of 90°C or higher.

Furthermore, since the positive-type photosensitive resin compositions of Examples 72 to 75 further contain an antioxidant, it was confirmed that the insulating films formed from the cured products of the positive-type photosensitive resin compositions of Examples 72 to 75 exhibited very excellent transmittance of 97% or greater and very excellent heat discoloration resistance with a transmittance change rate of less than 1%.

In contrast, the insulating film obtained from the positive-tone photosensitive resin composition of Comparative Example 1 of the present application, which includes the first copolymer Q of Comparative Synthesis Example 1 as a monomer, which does not include an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-degradable protective group, exhibited a sensitivity of 200 mJ and a resolution of 10 μm. Compared to the examples of the present application, this not only exhibited significantly inferior sensitivity and resolution, but also exhibited a CD variation of 10% or more, confirming that the photolithography process margin was also poor.

Furthermore, the insulating film obtained from the positive-type photosensitive resin composition of Comparative Example 2 of this application, which includes the first copolymer R of Comparative Synthesis Example 2 copolymerized with an ethylenically unsaturated compound whose terminal hydroxyl groups are protected by acid-degradable protective groups at a concentration of greater than 50 mol%, exhibited a sensitivity of 250 mJ and a resolution of 8 μm. Compared to the examples of this application, this exhibited significantly inferior sensitivity and resolution, as well as transmittance of less than 90%, heat discoloration resistance of greater than 5%, and CD variation of greater than 10%, confirming significantly poor transmittance, heat discoloration resistance, and photolithography process margin. Furthermore, pattern loss resulted in poor adhesion, with a 5% weight loss occurring at temperatures below 280°C, and poor heat resistance at 300°C.

Furthermore, the insulating film obtained from the positive-type photosensitive resin composition of Comparative Example 3 of the present application, which includes the first copolymer S of Comparative Synthesis Example 3 above, copolymerized with an excess of 70 mol% or more of an ethylenically unsaturated compound, exhibited a sensitivity of 200 mJ and a resolution of 8 μm. Compared to the examples of the present application, these films not only exhibited significantly lower sensitivity and resolution but also exhibited a CD variation of 10% or more, confirming significantly poor photolithography process margin. Furthermore, pattern loss resulted in poor adhesion, with a 5% weight loss observed even at temperatures below 280°C, and poor heat resistance at 300°C.

On the other hand, the insulating film obtained from the positive-type photosensitive resin composition of Comparative Example 4 of the present application, comprising the first copolymer T of Comparative Synthesis Example 4 copolymerized with an unsaturated carboxylic acid compound at a concentration greater than 40 mol%, exhibited a sensitivity of 60 mJ and a resolution of 5 μm. Compared to the examples of the present application, this exhibited not only inferior sensitivity and resolution but also a CD variation of 10% or greater, confirming significantly poor lithography process margin. Furthermore, pattern loss resulted in poor adhesion, with a 5% weight loss observed at temperatures below 280°C, and poor heat resistance at 300°C.

Furthermore, the insulating films obtained from the positive-type photosensitive resin compositions of Reference Examples 1 and 2 of the present application, which included the first copolymers U and V of Comparative Synthesis Examples 5 and 6 copolymerized with less than 2 parts by weight or more than 24 parts by weight of a free radical polymerization initiator, exhibited CD variation rates of 10% or greater, confirming relatively poor photolithography process margins. Furthermore, it was confirmed that the adhesion and heat resistance properties were also degraded.

In particular, the insulating film obtained from the positive-type photosensitive resin composition of Reference Example 1 of this application, which includes the first copolymer U of Comparative Synthesis Example 5, exhibited a sensitivity of 200 mJ and a resolution of 10 μm, indicating a decrease in sensitivity and resolution compared to the examples of this application. The insulating film obtained from the positive-type photosensitive resin composition of Reference Example 2 of this application, which includes the first copolymer V of Comparative Synthesis Example 6, was also measured to have a sensitivity of 120 mJ and a resolution of 8 μm, confirming a decrease in sensitivity and resolution compared to the examples of this application.

On the other hand, the insulating films obtained from the positive-type photosensitive resin compositions of Reference Examples 3 to 5 of this application, which do not contain the olefinic copolymer unique to the present invention, exhibited a sensitivity of 120 mJ and a resolution of 5 μm. Compared to the examples of this application, these films not only exhibited relatively poor sensitivity and resolution, but also exhibited a transmittance of less than 90%, a heat discoloration resistance of 5% or greater, and a CD variation of 10% or greater. These films were found to be somewhat inferior in transmittance, heat discoloration resistance, and photolithography process margin. Furthermore, some degradation in adhesion and heat resistance was observed.

On the other hand, the positive-type photosensitive resin compositions of Reference Examples 6 to 8 of this application contain greater than 50 parts by weight of the second copolymer relative to a total of 100 parts by weight of the first and second copolymers. The insulating films obtained from these positive-type photosensitive resin compositions exhibited sensitivities of 130 mJ or greater and resolutions of 5 μm. Compared to the examples of this application, these films not only exhibited relatively poor sensitivity and resolution, but also exhibited transmittances of less than 90%, heat discoloration resistances of 5% or greater, and CD variations of 10% or greater. These films demonstrated some deterioration in transmittance, heat discoloration resistance, and photolithography process margin. Furthermore, these films exhibited reduced adhesion and heat resistance.

without.

Claims (13)

A positive-type photosensitive resin composition comprises: a) a first copolymer comprising i) repeating units derived from an ethylenically unsaturated compound, the terminal hydroxyl groups of which are protected by acid-decomposable protecting groups, ii) repeating units derived from an unsaturated carboxylic acid compound, and iii) repeating units derived from an ethylenically unsaturated compound; b) a second copolymer, at least a portion of the terminal hydroxyl groups of which are protected by acid-decomposable protecting groups; c) a photoacid generator; and d) a solvent, wherein the second copolymer comprises repeating units represented by the following chemical formulas 1 and 2, wherein: The content of the olefinically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group is 1 to 50 mol%, the content of the unsaturated carboxylic acid compound is 5 to 40 mol%, and the content of the olefinically unsaturated compound is greater than or equal to 10 mol% and less than 70 mol%, relative to 100 mol% of the total monomers used to synthesize the first copolymer. The second copolymer contains greater than or equal to 0.01 mol% and less than or equal to 50 mol% of repeating units in which the terminal hydroxyl group is protected by an acid-decomposable protecting group, relative to the total repeating units. The content of the second copolymer is greater than or equal to 1 part by weight and less than or equal to 50 parts by weight, relative to 100 parts by weight of the first copolymer and the second copolymer. [Chemical Formula 1] [Chemical formula 2] In Chemical Formula 2, R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group. The positive-type photosensitive resin composition of claim 1, wherein the unsaturated carboxylic acid compound comprises at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, leuconic acid, meconic acid, itaconic acid, and anhydrides of unsaturated dicarboxylic acids thereof. The positive-type photosensitive resin composition as claimed in claim 1, wherein the olefinically unsaturated compound comprises a member selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl meth ... Cyclopentyloxyethyl ester, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, β-methyl glycidyl acrylate, β-methyl methacrylate Glycidyl ester, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxyhexyl methacrylate, 3,4-epoxyhexyl methyl methacrylate, 3,4-epoxyhexyl acrylate, 3,4-epoxyhexyl acrylate At least one member selected from the group consisting of oxadiazole methyl ester, 3-ethyl-3-oxadiazole butyl methacrylate, 3-ethyl-3-oxadiazole butyl acrylate, 3-butyl-3-oxadiazole butyl methacrylate, 3-butyl-3-oxadiazole butyl acrylate, 3-propyl-3-oxadiazole butyl methacrylate, 3-propyl-3-oxadiazole butyl acrylate, 3-oxadiazole butyl methacrylate, 3-oxadiazole butyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, and hydroxypropyl acrylate. The positive-type photosensitive resin composition of claim 1, wherein the ethylenically unsaturated compound having a terminal hydroxyl group protected by an acid-decomposable protective group comprises any one of the compounds represented by the following chemical formula 3 or chemical formula 4: [Chemical formula 3] In Chemical Formula 3, _R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetyloxyethoxyethyl group. [Chemical Formula 4] In Chemical Formula 4, _R2 is hydrogen or a C1 to C10 alkyl group, _R3 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, and n is an integer from 0 to 4. The positive photosensitive resin composition of claim 1, wherein the second copolymer comprises a main chain represented by any one of the following chemical formulas 5, 6, and 7: [Chemical Formula 5] In Chemical Formula 5, a+b=100, a is 50 to 99, b is 1 to 50, _R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetyloxyethoxyethyl group, [Chemical Formula 6] In Chemical Formula 6, a+b+c+d=100, b+d is 1 to 50, _R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, _R2 is hydrogen or a C1 to C10 alkyl group, and n is an integer from 0 to 4. [Chemical Formula 7] In Chemical Formula 7, a+b+c+d=100, b+d is 1 to 50, _R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanyloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, _R2 is hydrogen or a C1 to C10 alkyl group, and n is an integer from 0 to 4. The positive-type photosensitive resin composition of claim 1, wherein the first copolymer is polymerized in the presence of 2 parts by weight or more and 24 parts by weight or less of a free radical polymerization initiator relative to 100 parts by weight of the total weight of the monomers used to synthesize the first copolymer. The positive-type photosensitive resin composition of claim 1, wherein: relative to 100 parts by weight of the first copolymer and the second copolymer combined, the content of the photoacid generator is greater than or equal to 0.1 parts by weight and less than or equal to 30 parts by weight. The positive-working photosensitive resin composition of claim 1 further comprises: e) an alkaline compound, f) an adhesion promoter, g) an antioxidant, and h) at least one additive selected from the group consisting of a photosensitizer. The positive-type photosensitive resin composition of claim 8, wherein, relative to 100 parts by weight of the first copolymer and the second copolymer combined, the positive-type photosensitive resin composition comprises at least one of: 0.01 parts by weight to less than 3 parts by weight of the alkaline compound; 0.5 parts by weight to less than 10 parts by weight of the adhesion promoter; 0.1 parts by weight to less than 10 parts by weight of the antioxidant; and 0.1 parts by weight to less than 10 parts by weight of the photosensitizer. The positive-type photosensitive resin composition of claim 1, wherein the first copolymer has a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 30,000. The positive-working photosensitive resin composition of claim 1, wherein: the weight-average molecular weight (Mw) of the first copolymer, as measured in terms of polystyrene, is from 3,000 to 30,000; the weight-average molecular weight (Mw) of the second copolymer, as measured in terms of polystyrene, is from 3,000 to 30,000. A photosensitive resin film comprising a cured product of the positive photosensitive resin composition as described in any one of claims 1 to 11. A display device comprising the photosensitive resin film as described in claim 12.