TW202104293A - Positive photosensitive resin composition, positive photosensitive resin film and display device using the same - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition, a photosensitive resin film and a display device using the same. The positive photosensitive resin composition according to the present invention not only has excellent performances, such as sensitivity, chemical resistance, and heat resistance, but also greatly improves resolution, transmittance, heat discoloration resistance, etc., so that panels with a high brightness and a high resolution can be manufactured. Therefore, in a display, it can be effectively applied not only to interlayer insulating films, passivation insulating films, and gate insulating films, but also to planarization films, banks, pixel defining layers, and the like.

Description

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

The present invention relates to a positive photosensitive resin composition and a display using the same. More specifically, the present invention relates to a positive photosensitive resin composition with excellent resolution, lithography process margin, heat resistance, and the like.

In particular, the present invention relates to a positive photosensitive resin composition, which has excellent sensitivity and transparency and significantly improved adhesion, so that it is suitable for forming interlayer insulating films and PDL (pixel defining layer) in the manufacturing process of LCD and OLED. Columnar spacers, etc.

In the manufacturing process of a TFT type liquid crystal display device (LCD) and an organic light emitting display device (OLED), an interlayer insulating film is used to insulate the wirings arranged between the layers. However, since high-speed response and high-resolution devices have recently been developed, high aperture ratio and low resistance wiring technology are required, so the width of the circuit is reduced and the thickness of the formation is high, so there is a tendency for the height difference of TFT to become larger. . In this case, the thickness of the interlayer insulating film used for the degree of planarization will increase, which will cause the sensitivity and transparency to decrease, thereby causing the productivity and quality of the display device panel to decrease. Therefore, there is an urgent need to develop insulating films with excellent sensitivity and transparency.

The present invention aims to provide a positive photosensitive resin composition with excellent resolution, lithography process margin, heat resistance, especially sensitivity and transparency, and significantly improved adhesion, so it is suitable for LCD and OLED In the process, an interlayer insulating film, PDL, and columnar spacers are formed.

In addition, the present invention aims to provide a display including a cured product of the above-mentioned positive photosensitive resin composition.

The positive photosensitive resin composition disclosed in the present invention includes:

a) A first copolymer comprising i) a repeating unit derived from an ethylenically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group, ii) a repeating unit derived from an unsaturated carboxylic acid compound, and iii) a repeating unit derived from an olefin It is a repeating unit of an unsaturated compound;

b) The second copolymer, at least a part of its terminal hydroxyl group is protected by an acid-decomposable protective group;

c) Photoacid generator; and

d) solvent,

The above-mentioned second copolymer contains repeating units represented by the following chemical formulas 1 and 2.

[Chemical formula 1]

[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 silanoxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuran group, 2 , 3-Propylene carbonate group, methoxyethoxyethyl group or ethoxyethoxyethyl group.

The present invention also provides a photosensitive resin film containing a cured product of the above-mentioned positive photosensitive resin composition.

The present invention also provides a display device including 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 embodiments are described in detail below, so that those skilled in the art can easily implement the present invention. The embodiments can be implemented in various different ways and are not limited to the specific embodiments described herein.

The present invention relates to interlayer insulating films, passivation insulating films, gate insulating films, overcoats, etc. that can be used to be arranged between the various layers of displays such as liquid crystal display devices (LCD) and organic light emitting display devices (OLED). Positive photosensitive resin composition in various fields such as columnar spacers and PDL barriers.

1. Positive photosensitive resin composition

According to one embodiment of the present invention, the positive photosensitive resin composition comprises: a) a first copolymer, which comprises i) a repeating unit derived from an ethylenically unsaturated compound protected by an acid-decomposable protective group at the terminal hydroxyl group, Ii) a repeating unit derived from an unsaturated carboxylic acid compound and iii) a repeating unit derived from an ethylenically unsaturated compound; and b) a second copolymer in which at least a part of the terminal hydroxyl group is protected by an acid-decomposable protective group. The above-mentioned first copolymer can be polymerized as follows: relative to the total content of 100 mol of monomers used for synthesis, the content of the ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group is 1 to 50 mol% , Polymerization under the condition that the content of unsaturated carboxylic acid compound is 5-40 mol%, and the content of ethylenic unsaturated compound is greater than or equal to 10 mol% and less than 70 mol%. A positive photosensitive resin composition can be provided, wherein the ethylenically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protective group may include at least any one of the compounds represented by the following chemical formula 3 or 4, and the second copolymerization The substance contains any one of the main chains represented by the following chemical formulae 5 to 7.

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

Specifically, the above-mentioned ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group may include any one of the compounds represented by the following Chemical Formula 3 or 4.

[Chemical formula 3]

In the above chemical formula 3, 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-tetrahydrofuran group, 2 , One of 3-propylene carbonate, methoxyethoxyethyl or acetoxyethoxyethyl,

[Chemical formula 4]

In the above chemical formula 4, R ₂ is hydrogen or a C1 to C10 alkyl group, and R ₃ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, 2-tetrahydropyran One of a group, a vinyl ether group, a 2-tetrahydrofuran group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, and n is an integer from 0 to 4.

Since the first copolymer containing as a monomer contains an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group, when a photolithographic pattern is formed, the difference in the developer dissolving speed between the exposed part and the unexposed part is transmitted through Maximized, it can improve the contrast (Contrst), so the insulating film prepared from the positive photosensitive resin composition according to one embodiment of the present invention can achieve excellent sensitivity, resolution, transmittance, thermal discoloration resistance, light Engraving process margin, adhesion and heat resistance.

In contrast, if it contains the first copolymer of ethylenically unsaturated compounds whose terminal hydroxyl groups are protected by acid-decomposable protective groups as monomers during polymerization, sensitivity, resolution, and lithography process margins may appear. Bad technical problem.

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

[Chemical formula 3-1]

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 silanoxy group, 2-tetrahydropyranyl group, vinyl ether group, 2-tetrahydrofuran Group, 2,3-propylene carbonate group, methoxyethoxyethyl group or acetoxyethoxyethyl group,

[Chemical formula 4-1]

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

The above-mentioned first copolymer may be a copolymer obtained by copolymerizing a monomer mixture of the first copolymer, relative to the total monomer mixture of the first copolymer 100 mol%, the monomer mixture of the first copolymer contains more than 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% i) The above-mentioned ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group.

If the first copolymer is a copolymer obtained by copolymerizing a monomer mixture containing less than 1 mol% of the ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group, the photolithographic pattern is exposed to light. The difference between the dissolving speed of the developer in the part and the unexposed part is reduced, and it is impossible to improve the contrast (Contrst), so not only the sensitivity and resolution are deteriorated, but also the transmittance, heat discoloration resistance, lithography process margin, and adhesion And the technical problem of poor heat resistance.

If the first copolymer is copolymerized with a monomer mixture containing more than 50 mol% of the above-mentioned terminal hydroxyl group protected by an acid-decomposable protective group, the copolymer is obtained by copolymerization. In the exposure process, the residual rate of the above-mentioned terminal acid-decomposable protective groups will also be higher, and technical problems of poor sensitivity, resolution, and poor lithography process margins may occur.

Alternatively, with respect to the entire repeating unit, the first copolymer may include 1 mol% or more and 50 mol% or more, or 1 mol% or more and 20 mol% or more of the terminal hydroxyl group that is acid-free. Decomposition of the repeating unit protected by the protecting group derived from the ethylenically unsaturated compound.

Relative to the entire repeating unit, the first copolymer contains less than 1 mol% of the above-mentioned terminal hydroxyl group protected by an acid-decomposable protective group derived from an ethylenically unsaturated compound repeating unit, then when the photolithographic pattern is formed, the exposed part and The difference in the dissolving speed of the developer in the unexposed part is reduced, and it is impossible to improve the contrast (Contrst), so not only the sensitivity and resolution are deteriorated, but also the transmittance, heat discoloration resistance, lithography process margin, adhesion and heat resistance Technical problems with bad sex.

Relative to the entire repeating unit, the first copolymer contains more than 50 mol% of the above-mentioned terminal hydroxyl group protected by an acid-decomposable protective group derived from the ethylenically unsaturated compound repeating unit, then when the photolithographic pattern is formed, even if exposed During the manufacturing process, the residual rate of the above-mentioned terminal acid-decomposable protective groups will also be relatively high, and technical problems of poor sensitivity, resolution, and poor lithography process margin may occur.

The above-mentioned unsaturated carboxylic acid compounds may be unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, etc. , Citraconic acid, methaconic acid, itaconic acid, etc.; or their unsaturated dicarboxylic acid anhydrides, etc. are used alone or in combination of at least two. In particular, the use of acrylic acid, methacrylic acid, or maleic anhydride can improve the copolymerization reactivity and solubility in the alkaline aqueous solution of the developer.

Relative to the total monomer mixture of the first copolymer 100 mol%, the unsaturated carboxylic acid compound may be mixed to 1 mol% or more and 50 mol% or less, or 20 mol% or more and less than or equal to 50 mol%, or greater than or equal to 25 mol% and less than or equal to 35 mol%. If the content of the above-mentioned unsaturated carboxylic acid compound is less than 1 mol%, it will be difficult to dissolve in the alkali aqueous solution, and if it is more than 50 mol%, the solubility in the alkali aqueous solution will become too large.

Specifically, if the first copolymer is a copolymer obtained by copolymerizing a monomer mixture containing more than 50 mol% of the above-mentioned unsaturated carboxylic acid compound, the solubility to the aqueous alkali solution becomes too large, and sensitivity may occur. , Resolution, adhesion, heat resistance and lithography process margin are all poor technical problems.

The above-mentioned ethylenically unsaturated compound may be methylmethacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate (methylmethacrylate), ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentyl acrylate, methacrylic acid Dicyclopentenyl ester, dicyclopentyl methacrylate, 1-adamantyl acrylate (1-adamantyl acrylate), 1-adamantyl methacrylate, dicyclopentanyl oxyethyl methacrylate ), isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate , Phenyl acrylate, benzyl acrylate, 2-hydroxy ethyl methacrylate, styrene, o-methyl styrene, m-methyl styrene, p-methyl Styrene, vinyl toluene, p-methoxystyrene, 1,3-butadiene, isoprene, or 2,3-dimethyl 1,3-butadiene ( 2,3-dimethyl-1,3-butadiene), 2-[methacryloxy]6-hydroxyhexanoate, 4-vinylphenol, 4-vinylcyclohexanol, methacrylic acid 4- Hydroxybenzyl ester, [[4-hydroxymethyl]cyclohexyl] methyl methacrylate, 3-hydroxy-1-methacryloxyadamantyl ester, 2-oxotetrahydrofuran-3-yl methacrylate (2-oxotetrahydrofuran-3-yl methacrylate), 4-hydroxycyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate Ester, α-n-butyl glycidyl acrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-ethyl glycidyl acrylate, β-methacrylic acid Ethyl glycidyl ester, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-ring methacrylate Oxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, 3-ethyl-3-oxetanate methacrylate, 3-ethyl-3-oxetanate acrylate, 3-butyl-3-oxetanate methacrylate, 3-butyl acrylate 3-oxetanate, 3-propyl-3-oxetanate methacrylate, 3-propyl-3-oxetanate acrylate, 3-oxetanate methacrylate , 3-oxetanyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxybutyl acrylate and hydroxypropyl acrylate, etc. The mentioned compounds can be used singly or in combination of at least two.

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

Specifically, if the first copolymer is a copolymer obtained by copolymerizing a monomer mixture containing more than 50 mol% of the above-mentioned ethylenically unsaturated compound, the development speed and photosensitive characteristics may decrease, and sensitivity and resolution may occur. Technical problems with poor efficiency, adhesion, heat resistance, and lithography process margin.

In addition, for the aforementioned a) first copolymer, the weight average molecular weight (Mw) in terms of polystyrene may be greater than or equal to 3000 g/mol and less than or equal to 30,000 g/mol.

As a solvent used for solution polymerization of monomers, methanol, tetrahydroxyfuran, toluene, dioxane, etc. can be used. The polymerization initiator used for solution polymerization can be a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile (2,2-azobisisobutyronitrile), 2,2-azobis(2 ,4-Dimethylvaleronitrile), 2,2-Azobis(4-methoxy2,4-dimethylvaleronitrile), 1,1-Azobis(cyclohexane-1-nitrile) Or 2,2'-azobisisobutylate (2,2'-azobisisobutylate), etc.

That is, the positive photosensitive resin composition of the above-mentioned one embodiment may include a first copolymer polymerized as follows: relative to 100 parts by weight of the total weight of the monomer mixture of the first copolymer, 2 parts by weight or more and less than The first copolymer is polymerized in the presence of a radical polymerization initiator equal to 24 parts by weight, 2 parts by weight or more and 10 parts by weight or less, or 5 parts by weight or more and 10 parts by weight or less.

If the first copolymer is polymerized with less than 2 parts by weight of a free radical polymerization initiator, the first copolymer will be over-polymerized. Since it is polymerized into an acrylic copolymer with an excessively large molecular weight, a positive photosensitive containing the copolymer may appear. The technical problems of poor lithography process margin, adhesion and heat resistance of the flexible resin composition.

Conversely, if the first copolymer is polymerized with more than 24 parts by weight of a radical polymerization initiator, it may be polymerized into an acrylic copolymer with a molecular weight that is too small. Technical problems of poor lithography process margin, adhesion and heat resistance.

The monomer undergoes a free radical reaction in the presence of a solvent and a polymerization initiator, and then the unreacted monomer is removed through the process of precipitation, filtration and vacuum drying, thereby obtaining the first copolymer, which is converted to polystyrene The weight average molecular weight (Mw) can be 3000 to 20000. For an interlayer insulating film (organic insulating film) with a weight average molecular weight of less than 3000 in terms of polystyrene, developability and residual film rate may be reduced or pattern development and heat resistance may be deteriorated. For an interlayer insulating film with a polystyrene-converted 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 part of the above-mentioned terminal hydroxyl group is protected by an acid-decomposable protective group may include a repeating unit derived from an olefinic compound in which the terminal hydroxyl group is protected by an acid-decomposable protective group; The repeating unit of the olefinic compound may include repeating units represented by the following chemical formulas 1 and 2, for example.

[Chemical formula 1]

[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 silanoxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuran group, 2 , 3-Propylene carbonate group, methoxyethoxyethyl group or ethoxyethoxyethyl group.

Specifically, the above-mentioned second copolymer may include a main chain represented by Chemical Formula 5 below.

[Chemical formula 5]

In the above chemical formula 5, a+b=100, a is 50 to 99, b is 1 to 50, and R ₁ can be a monovalent functional group derived from an acetal group, an alkyl group, an alkyl silyl group, or a silanoxy group. , 2-tetrahydropyranyl, vinyl ether, 2-tetrahydrofuranyl, 2,3-propylene carbonate, methoxyethoxyethyl, or acetoxyethoxyethyl.

Alternatively, the above-mentioned second copolymer may include a main chain represented by Chemical Formula 6 or Chemical Formula 7 below.

[Chemical formula 6]

In the above chemical formula 6, a+b+c+d=100, b+d is 1 to 50, and R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, One of 2-tetrahydropyranyl, vinyl ether, 2-tetrahydrofuran, 2,3-propylene carbonate, methoxyethoxyethyl, or acetoxyethoxyethyl, R ₂ It is hydrogen or a C1 to C10 alkyl group, and n may be an integer of 0 to 4.

[Chemical formula 7]

In the above chemical formula 7, a+b+c+d=100, b+d is 1 to 50, and R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, One of 2-tetrahydropyranyl, vinyl ether, 2-tetrahydrofuran, 2,3-propylene carbonate, methoxyethoxyethyl or acetoxyethoxyethyl, R ₂ is Hydrogen or C1 to C10 alkyl, n can be an integer of 0 to 4.

Preferably, the second copolymer in which at least a part of the terminal hydroxyl group is protected by an acid-decomposable protective group may include the main chain represented by the above Chemical Formula 6 or Chemical Formula 7.

If the above-mentioned second copolymer contains the main chain represented by the above-mentioned chemical formula 6 or the above-mentioned chemical formula 7, it is more favorable for yellowing than the above-mentioned chemical formula 5, and the technical effects of excellent transmittance and heat discoloration resistance can be achieved.

In the above chemical formulae 5 to 7, a to d represent the molar ratio between each repeating unit, and the chemical formulae 5 to 7 do not limit the order of each repeating unit.

In addition, with respect to the entire repeating unit, the second copolymer may include 0.01 mol% or more and 50 mol% or more, or 1 mol% or more and 50 mol%, and the terminal hydroxyl groups can be decomposed by acid. Repeating units protected by protecting groups.

Relative to the entire repeating unit, when the above-mentioned olefinic copolymer contains more than 50 mol% of the repeating unit in which the terminal hydroxyl group is protected by an acid-decomposable protective group, not only the sensitivity and resolution become poor, but also the permeability and heat-resistant discoloration are reduced. Performance and lithography process margin.

With respect to 100 parts by weight of the total of the first copolymer and the second copolymer, the second copolymer may be contained in an amount of 1 part by weight or more and 50 parts by weight or less.

Relative to the total 100 parts by weight of the first copolymer and the second copolymer, when the content of the second copolymer is greater than 50 parts by weight, not only the sensitivity and resolution will deteriorate, but also the transmittance, heat discoloration resistance and light will appear. The technical problems of reduced engraving process margin and reduced adhesion and heat resistance.

In addition, for the above-mentioned second copolymer, the weight average molecular weight (Mw) in terms of polystyrene may be greater than or equal to 3000 g/mol and less than or equal to 30,000 g/mol.

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

With respect to the total 100 parts by weight of the first copolymer and the second copolymer, the c) photoacid generator may be included in an amount of 0.1 parts by weight or more and 30 parts by weight or less.

The type of the above-mentioned c) photoacid generator is not very limited. For example, it may include selected from the group consisting of oxime sulfonate, imide sulfonate, diazodisulfonate, diazonium salt, disulfone, phosphonium salt, sulfur salt, At least one of iodonium salt, o-nitrobenzyl sulfonate, and triazine compound.

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

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

In the above chemical formulas 8 to 13, X is hydrogen or C1 to C14 linear or branched alkyl, R ₃ is C1 to C18 aliphatic hydrocarbon group, C6 to C20 aryl group, C7 to C20 aralkyl group, A C7 to C20 aryl group or a C1 to C8 haloalkyl group substituted by an acyl group.

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

In order to apply the photosensitive resin composition to a substrate or the like, the solvent of d) is used. Specific examples include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and propylene glycol methyl ether acetate (propylene glycol methyl ether). glycol methyl ether acetate), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate (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 (butylene glycol monomethyl ether), butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, two Butylene 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 Ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether and dipropylene glycol methylhexyl ether, etc., can be used alone or in combination of at least two.

The solvent of d) may be included so that the solid content of the positive photosensitive resin composition reaches 10 to 50% by weight. If the solid content is less than 10% by weight, the coating thickness will become thinner and the uniformity of the coating will decrease. If the solid content is greater than 50% by weight, the coating thickness will become thicker and the coating equipment will be Bring burden. When the solid content of the total composition is 10 to 25% by weight, it is convenient for use in a slit coater (Slit Coater), and when the solid content of the total composition is 25 to 50% by weight, it is convenient for spin coating. Machine (Spin Coater) or Slit & Spin Coater (Slit & Spin Coater).

The positive photosensitive resin composition can be made into a solid content of 10 to 50% by weight, and filtered with a 0.1~0.2㎛ millipore filter or the like before use.

According to another aspect of the present invention, a positive photosensitive resin composition can be provided, which further comprises at least one of e) a basic compound, f) an adhesion promoter, g) an antioxidant, and h) a photosensitizer An additive.

When it further contains at least one additive of e) a basic compound, f) an adhesion promoter, g) an antioxidant, and h) a photosensitizer, relative to the total 100 parts by weight of the first copolymer and the second copolymer, The positive photosensitive resin composition may contain 0.01 parts by weight or more and 3 parts by weight or more e) alkaline compound, 0.5 parts by weight or more and 10 parts by weight or less f) adhesion assistant, 0.1 parts by weight or more And 10 parts by weight or less of g) antioxidant, and 0.1 parts by weight or more and 10 parts by weight or less of h) photosensitizer.

The above-mentioned basic compound may comprise selected from trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, methyl Dicyclohexylamine, benzylamine, N,N-xylidine, diphenylamine, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenyl Pyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetrahydroxide At least one of the group consisting of n-hexylammonium.

In addition, the above-mentioned adhesion promoter may comprise selected from (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) Propyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3 ,4-Epoxycyclohexyl) ethyl triethoxy silane, amine propyl trimethoxy silane, amine propyl triethoxy silane, 3-triethoxy silyl-N-(1,3- Dimethyl-butylene) propylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (3-isocyanatepropyl)triethoxysilane , At least one of the group consisting of (3-isocyanatepropyl)trimethoxysilane.

In addition, the above-mentioned antioxidant may include selected from phosphorus antioxidants, amides, hydrazines, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, At least one of the group consisting of sulfite, thiosulfate, and hydroxylamine derivative.

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

2. Photosensitive resin film

According to an embodiment of the present invention, it is possible to provide a photosensitive resin film including a cured product of the above-mentioned positive photosensitive resin composition. The above-mentioned positive photosensitive resin composition includes all of the above-mentioned contents.

The above-mentioned cured product includes not only the case where all the components of the curable or crosslinkable unsaturated group in the chemical structure are cured, but also the case where a part of it is cured, crosslinked or polymerized.

According to the above-mentioned one embodiment, the photosensitive resin film 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 defining layer (Pixel Define Layer). ).

3. Display device

According to an embodiment of the present invention, there can be provided a display device including 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 manufacturing process of a display, the positive photosensitive resin composition according to one embodiment of the present invention can be used.

First, the positive photosensitive resin composition is coated on the substrate surface of the display panel by spin coating, slit spin coating, slit coating, roll coating, etc., and the solvent is removed by prebaking to form a coating film. At this time, the pre-bake can be performed at a temperature of 100°C to 120°C for 1 minute to 3 minutes. Then, the formed coating film is irradiated with visible light, ultraviolet light, extreme ultraviolet light, electron beam, X-ray, etc. according to a pattern prepared in advance, and developed with a developer to remove unnecessary parts, thereby forming a predetermined pattern.

The developer preferably uses an aqueous alkali solution, specifically, 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, triethylamine, etc.; alcoholamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; or quaternary ammonium salt aqueous solutions such as tetramethylammonium hydroxide, Tetraethylammonium hydroxide. At this time, as a developer, the alkaline compound is dissolved in a concentration of 0.1 parts by weight or more and 10 parts by weight or less, and an appropriate amount of water-soluble organic solvents such as methanol and ethanol and surfactants can also be added.

In addition, after developing with a developer, rinse with ultrapure water for 30 to 90 seconds to remove excess parts, and then dry to form a pattern. After irradiating the formed pattern with light such as ultraviolet rays, pass it through a heating device such as an oven at 150°C. The pattern is heated at a temperature of ~400°C for 30 minutes to 90 minutes, so that the final pattern can be obtained.

The positive photosensitive resin composition according to the embodiment has excellent flatness, transmittance, outgassing properties (Outgas), especially has excellent sensitivity, and significantly improves the adhesion and contrast under high temperature and high humidity. , Chemical resistance, so it is suitable for forming interlayer insulating film and PDL isolation wall in LCD and OLED manufacturing process.

According to the embodiment, the positive photosensitive resin composition has excellent resolution, lithography process margin, heat resistance, especially excellent sensitivity, penetrability, and significantly improved adhesion, so it is suitable for LCD And the formation of interlayer insulating film and PDL, column spacers, etc. in the OLED manufacturing process. In addition, the present invention provides a method for patterning LCD and OLED substrates using a cured body of the photosensitive resin composition, and a display substrate of the photosensitive resin composition. The pattern can be used as a material for passivation insulating films, gate insulating films, planarization films, columnar spacers, partition walls, etc. of TFT-LCD, TSP (touch screen panel), OLED, O-TFT, EPD, EWD, etc.

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 Example and Comparative Synthesis Example: Preparation of the first copolymer

Synthesis Example 1: Preparation of the first copolymer (A)

A flask equipped with a cooler and a stirrer was used to prepare tetrahydrofuran as a synthesis solvent, and then mixed with the ethylenically unsaturated compound represented by the following chemical formula 1A, methacrylic acid, and benzene at a molar ratio of 30:20:20:30. A mixed solution of ethylene and glycidyl methacrylate. The above-mentioned liquid composition was thoroughly mixed in a mixing container at 600 rpm, and then 2,2-azobis(2,4-dimethylvaleronitrile) was added at a ratio of 10 parts by weight relative to 100 parts by weight of the total monomers. The above-mentioned polymerization mixed solution was slowly heated to 55° C., kept at this temperature for 48 hours and then cooled to normal temperature, and the tetrahydrofuran was completely removed through a drying process, thereby preparing the first copolymer (A). The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 1A]

Synthesis Example 2: Preparation of the first copolymer (B)

Except that the ethylenically unsaturated compound represented by the following chemical formula 1B was used instead of the ethylenically unsaturated compound represented by the above chemical formula 1A in the above Synthesis Example 1, the first copolymer was prepared by carrying out the same method as the above Synthesis Example 1.物(B). The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 1B]

Synthesis Example 3: Preparation of the first copolymer (C)

Except that the ethylenically unsaturated compound represented by the following chemical formula 1C was used instead of the ethylenically unsaturated compound represented by the above chemical formula 1A in the above Synthesis Example 1, the first copolymer was prepared by following the same method as in the above Synthesis Example 1.物(C). The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 1C]

Synthesis Example 4: Preparation of the first copolymer (D)

Except that the ethylenically unsaturated compound represented by the following chemical formula 2A was used instead of the ethylenically unsaturated compound represented by the above chemical formula 1A in the above-mentioned synthesis example 1, the first copolymer was prepared by carrying out the same method as the above-mentioned synthesis example 1.物(D). The weight average molecular weight of the above-mentioned first copolymer is 12,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 2A]

Synthesis Example 5: Preparation of the first copolymer (E)

Except that the ethylenically unsaturated compound represented by the following chemical formula 2B was used instead of the ethylenically unsaturated compound represented by the above chemical formula 1A in the above synthesis example 1, the first copolymer was prepared by performing the same method as the above synthesis example 1.物(E). The weight average molecular weight of the above-mentioned first copolymer is 12,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 2B]

Synthesis Example 6: Preparation of the first copolymer (F)

Except that the ethylenically unsaturated compound represented by the following chemical formula 2C was used in place of the ethylenically unsaturated compound represented by the above chemical formula 1A in the above Synthesis Example 1, the first copolymer was prepared by following the same method as in the above Synthesis Example 1.物(F). The weight average molecular weight of the above-mentioned first copolymer is 12,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 2C]

Synthesis Example 7: Preparation of the first copolymer (G)

Except that the ethylenically unsaturated compound represented by the following chemical formula 2D was used instead of the ethylenically unsaturated compound represented by the above chemical formula 1A in the above Synthesis Example 1, the first copolymer was prepared by carrying out the same method as the above Synthesis Example 1.物(G). The weight average molecular weight of the above-mentioned first copolymer is 13,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 2D]

Synthesis Example 8: Preparation of the first copolymer (H)

Except that the ethylenically unsaturated compound represented by the following chemical formula 2E was used instead of the ethylenically unsaturated compound represented by the above chemical formula 1A in the above Synthesis Example 1, the first copolymer was prepared by carrying out the same method as in the above Synthesis Example 1.物(H). The weight average molecular weight of the above-mentioned first copolymer is 12,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

[Chemical formula 2E]

Synthesis Example 9: Preparation of the first copolymer (I)

In addition to the addition of a mixed solution of the ethylenically unsaturated compound represented by the above-mentioned chemical formula 1A, methacrylic acid, styrene, and glycidyl methacrylate at a molar ratio of 50:30:10:10 in Synthesis Example 1, In addition, the first copolymer (I) was prepared by following the same method as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Synthesis Example 10: Preparation of the first copolymer (J)

In addition to the addition of the ethylenically unsaturated compound represented by the above chemical formula 1B in the above synthesis example 1 at a molar ratio of 25:40:15:20, methacrylic acid, styrene and acrylic acid 3-ethyl-3-oxa Except for the mixed solution of cyclobutyl ester, the first copolymer (J) was prepared by following the same method as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Synthesis Example 11: Preparation of the first copolymer (K)

In addition to adding a molar ratio of 5:15:35:25:20, the ethylenically unsaturated compound represented by the above chemical formula 1A in Synthesis Example 1 above, methacrylic acid, styrene, glycidyl methacrylate, and acrylic acid are mixed. Except for the mixed solution of 3-ethyl-3-oxetanate, the first copolymer (K) was prepared in the same manner as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Synthesis Example 12: Preparation of the first copolymer (L)

In addition to the addition of a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A, methacrylic acid, styrene, and glycidyl methacrylate at a molar ratio of 40:15:30:15 in the above Synthesis Example 1, In addition, the first copolymer (L) was prepared by following the same method as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Synthesis Example 13: Preparation of the first copolymer (M)

In addition to adding a molar ratio of 1:5:34:25:35, the ethylenically unsaturated compound represented by the above chemical formula 1A in Synthesis Example 1 above, methacrylic acid, styrene, glycidyl methacrylate and acrylic acid are mixed. Except for the mixed solution of hydroxyethyl ester, the first copolymer (M) was prepared by following the same method as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Synthesis Example 14: Preparation of the first copolymer (N)

Except that 5 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) were used instead of 10 parts by weight of 2,2-azobis(2,2-azobis(2, Except for 4-dimethylvaleronitrile), the first copolymer (N) was prepared in the same manner as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 19,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Synthesis Example 15: Preparation of the first copolymer (O)

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(2,2-azobis(2, Except for 4-dimethylvaleronitrile), the first copolymer (O) was prepared in the same manner as in Synthesis Example 1 above. The weight average molecular weight of the above-mentioned first copolymer is 30,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Synthesis Example 16: Preparation of the first copolymer (P)

In addition to using 24 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) instead of 10 parts by weight of 2,2-azobis(2,2-azobis(2, Except for 4-dimethylvaleronitrile), the first copolymer (P) was prepared in the same manner as in Synthesis Example 1 above. The weight average molecular weight of the above-mentioned first copolymer is 3,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Comparative Synthesis Example 1: Preparation of the first copolymer (Q)

In addition to the addition of a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A, methacrylic acid, styrene, and glycidyl methacrylate at a molar ratio of 0:30:30:40 in the above Synthesis Example 1, In addition, the first copolymer (Q) was prepared by following the same method as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Comparative Synthesis Example 2: Preparation of the first copolymer (R)

In addition to the addition of a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A, methacrylic acid, styrene, and glycidyl methacrylate at a molar ratio of 52:13:15:20 in Synthesis Example 1, In addition, the first copolymer (R) was prepared by following the same method as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Comparative Synthesis Example 3: Preparation of the first copolymer (S)

In addition to adding a molar ratio of 1:4:35:25:35, the ethylenically unsaturated compound represented by the above chemical formula 1A in Synthesis Example 1 above, methacrylic acid, styrene, glycidyl methacrylate and acrylic acid are mixed. Except for the mixed solution of hydroxyethyl ester, the first copolymer (S) was prepared by following the same method as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Comparative Synthesis Example 4: Preparation of the first copolymer (T)

In addition to adding 25:42:13:20 at a molar ratio of 25:42:13:20, the ethylenically unsaturated compound represented by the above chemical formula 1B in the synthesis example 1, methacrylic acid, styrene and acrylic acid 3-ethyl-3-oxa Except for the mixed solution of cyclobutyl ester, the first copolymer (T) was prepared in the same manner as in Synthesis Example 1 above. The weight average molecular weight of the first copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Comparative Synthesis Example 5: Preparation of the first copolymer (U)

In addition to using 1.8 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) instead of 10 parts by weight of 2,2-azobis(2,2-azobis(2, Except for 4-dimethylvaleronitrile), the first copolymer (U) was prepared in the same manner as in Synthesis Example 1 above. The weight average molecular weight of the above-mentioned first copolymer is 31,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC, and the weight average molecular weight is the standard analysis method of gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

Comparative Synthesis Example 6: Preparation of the first copolymer (V)

Except for using 25 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) instead of 10 parts by weight of 2,2-azobis(2,2-azobis(2, Except for 4-dimethylvaleronitrile), the first copolymer (V) was prepared in the same manner as in Synthesis Example 1 above. The weight average molecular weight of the above-mentioned first copolymer was 2,800. At this time, the weight average molecular weight is the weight average molecular weight measured by GPC in terms of polystyrene, and the weight average molecular weight is the standard analysis method using gel permeation chromatography (GPC) using the e2695 Alliance Seperation Module of Waters Corporation. Measured.

【Table 1】 First copolymer Weight average molecular weight Monomer i (mole ratio) Monomer ⅱ (mole ratio) Monomer ⅲ (mole ratio) Monomer ⅳ (mole ratio) Catalyst (parts by weight) Synthesis example 1 A 10000 Chemical formula 1A (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 2 B 10000 Chemical formula 1B (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 3 C 10000 Chemical formula 1C (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 4 D 12000 Chemical formula 2A (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 5 E 12000 Chemical formula 2B (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 6 F 12000 Chemical formula 2C (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 7 G 13000 Chemical formula 2D (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 8 H 12000 Chemical formula 2E (30) MAA(20) St(20) GMA(30) ADVN(10) Synthesis Example 9 I 10000 Chemical formula 1A (50) MAA(30) St(10) GMA(10) ADVN(10) Synthesis Example 10 J 10000 Chemical formula 1B (25) MAA(40) EOA (20) St(15) - ADVN(10) Synthesis Example 11 K 10000 Chemical formula 1A (5) MAA(15) St(35) EOA (20) GMA(25) ADVN(10) Synthesis Example 12 L 10000 Chemical formula 1A (40) MAA(15) St(30) GMA(15) ADVN(10) Synthesis Example 13 M 10000 Chemical formula 1A (1) MAA(5) HEA(35) ST(34) GMA(25) ADVN(10) Synthesis Example 14 N 19000 Chemical formula 1A (30) MAA(20) St(20) GMA(30) ADVN(5) Synthesis Example 15 O 30000 Chemical formula 1A (30) MAA(20) St(20) GMA(30) ADVN(2) Synthesis Example 16 P 3000 Chemical formula 1A (30) MAA(20) St(20) GMA(30) ADVN(24) Comparative Synthesis Example 1 Q 10000 - MAA(30) St(30) GMA(40) ADVN(10) Comparative Synthesis Example 2 R 10000 Chemical formula 1A (52) MAA(13) St(15) GMA(20) ADVN(10) Comparative Synthesis Example 3 S 10000 Chemical formula 1A (1) MAA(4) St(35) HEA(35) GMA(25) ADVN(10) Comparative Synthesis Example 4 T 10000 Chemical formula 1B (25) MAA(42) EOA (20) St(13) - ADVN(10) Comparative Synthesis Example 5 U 31000 Chemical formula 1A (30) MAA(20) St(20) GMA(30) ADVN(1.8) Comparative Synthesis Example 6 V 28000 Chemical formula 1A (30) MAA(20) St(20) GMA(30) ADVN(25)

*Monomer i: an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group

*Monomer ⅱ: Unsaturated carboxylic acid compound

*Monomer ⅲ: ethylenically unsaturated compound

*Monomer iv: unsaturated compound containing crosslinking group

*MAA: Methacrylic acid

*GMA: Glycidyl methacrylate

*St: Styrene

*EOA: 3-ethyl-3-oxetanyl acrylate

*HEA: Hydroxyethyl acrylate

*ADVN: 2,2-Azobis(2,4-Dimethylvaleronitrile)

Examples, Comparative Examples and Reference Examples: Preparation of positive photosensitive resin composition

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, the basic compound, After the adhesion promoter and antioxidant are added, they are mixed and dissolved with propylene glycol methyl ether acetate to have a solid content of 25% by weight, and then filtered with a 0.1 ㎛ microporous filter to prepare a positive photosensitive resin composition.

In Table 2 below, the content of the first copolymer and the second copolymer is relative to 100 parts by weight of the sum of the first copolymer and the second copolymer, the photoacid generator, the basic compound, and the adhesion promoter And the content of the antioxidant is relative to 100 parts by weight of the sum of the first copolymer and the second copolymer.

[Chemical formula 3A] (Molecular weight: 10000g/mol)

[Chemical formula 3B] (Molecular weight: 12000g/mol)

[Chemical formula 3C] (Molecular weight: 5000g/mol)

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

[Chemical formula 3E] (Molecular weight: 16000g/mol)

[Chemical formula 3F] (Molecular weight: 11000g/mol)

[Chemical formula 3G] (Molecular weight: 22000g/mol)

[Chemical formula 4A] (Molecular weight: 6000g/mol)

[Chemical formula 4B] (Molecular weight: 3000g/mol)

[Chemical formula 4C] (Molecular weight: 27000g/mol)

[Chemical formula 4D] (Molecular weight: 9000g/mol)

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

[Chemical formula 5A] (Molecular weight: 25000g/mol)

[Chemical formula 5B] (Molecular weight: 8000g/mol)

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

[Chemical formula 5D] (Molecular weight: 20000g/mol)

[Chemical formula 5E] (Molecular weight: 15000g/mol)

[Chemical formula 12]

[Chemical formula 13]

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

[Chemical formula 17]

[Chemical formula 18]

[Chemical formula 19]

[Chemical formula 20]

[Chemical formula 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical formula 25]

[Chemical formula 26]

[Chemical formula 27]

[Chemical formula 28]

【Table 2】 First copolymer Second copolymer Photoacid generator Basic compound Adhesive additives Antioxidants Example 1 A 50 3A 50 Chemical formula 12 5 - - - - - - Example 2 B 70 3A 30 Chemical formula 13 10 - - - - - - Example 3 C 90 3A 10 Chemical formula 14 15 - - - - - - Example 4 D 50 3B 50 Chemical formula 15 20 - - - - - - Example 5 E 70 3B 30 Chemical formula 16 25 - - - - - - Example 6 F 90 3B 10 Chemical formula 17 30 - - - - - - Example 7 G 50 3C 50 Chemical formula 18 0.1 - - - - - - Example 8 H 70 3C 30 Chemical formula 19 5 - - - - - - Example 9 I 90 3C 10 Chemical formula 20 10 - - - - - - Example 10 J 50 3D 50 Chemical formula 21 15 - - - - - - Example 11 K 70 3D 30 Chemical formula 22 20 - - - - - - Example 12 L 90 3D 10 Chemical formula 23 25 - - - - - - Example 13 M 50 3E 50 Chemical formula 24 30 - - - - - - Example 14 N 70 3E 30 Chemical formula 25 0.1 - - - - - - Example 15 O 90 3E 10 Chemical formula 26 5 - - - - - - Example 16 P 50 3F 50 Chemical formula 27 10 - - - - - - Example 17 A 70 3F 30 Chemical formula 28 15 - - - - - - Example 18 B 90 3F 10 Chemical formula 12 20 - - - - - - Example 19 C 50 4A 50 Chemical formula 13 25 - - - - - - Example 20 D 70 4A 30 Chemical formula 14 30 - - - - - - Example 21 E 90 4A 10 Chemical formula 15 0.1 - - - - - - Example 22 F 50 4B 50 Chemical formula 16 5 - - - - - - Example 23 G 70 4B 30 Chemical formula 17 10 - - - - - - Example 24 H 90 4B 10 Chemical formula 18 15 - - - - - - Example 25 I 50 4C 50 Chemical formula 19 20 - - - - - - Example 26 J 70 4C 30 Chemical formula 20 25 - - - - - - Example 27 K 90 4C 10 Chemical formula 21 30 - - - - - - Example 28 L 50 4D 50 Chemical formula 22 0.1 - - - - - - Example 29 M 70 4D 30 Chemical formula 23 5 - - - - - - Example 30 N 90 4D 10 Chemical formula 24 10 - - - - - - Example 31 O 50 5A 50 Chemical formula 25 15 - - - - - - Example 32 P 70 5A 30 Chemical formula 26 20 - - - - - - Example 33 A 90 5A 10 Chemical formula 27 25 - - - - - - Example 34 B 50 5B 50 Chemical formula 28 30 - - - - - - Example 35 C 70 5B 30 Chemical formula 12 0.1 - - - - - - Example 36 D 90 5B 10 Chemical formula 13 5 - - - - - - Example 37 E 50 5C 50 Chemical formula 14 10 - - - - - - Example 38 F 70 5C 30 Chemical formula 15 15 - - - - - - Example 39 G 90 5C 10 Chemical formula 16 20 - - - - - - Example 40 H 50 5D 50 Chemical formula 17 25 - - - - - - Example 41 I 70 5D 30 Chemical formula 18 30 - - - - - - Example 42 J 90 5D 10 Chemical formula 19 0.1 - - - - - - Example 43 K 95 3A 5 Chemical formula 20 5 - - - - - - Example 44 L 95 4A 5 Chemical formula 21 5 - - - - - - Example 45 M 95 5A 5 Chemical formula 22 5 - - - - - - Example 46 N 97 3B 3 Chemical formula 23 5 - - - - - - Example 47 O 97 4B 3 Chemical formula 24 5 - - - - - - Example 48 P 97 5B 3 Chemical formula 25 5 - - - - - - Example 49 A 99 3C 1 Chemical formula 26 5 - - - - - - Example 50 B 99 4C 1 Chemical formula 27 5 - - - - - - Example 51 C 99 5C 1 Chemical formula 28 5 - - - - - - Example 52 A 50 3A 50 Chemical formula 12 3 DMA 0.01 - - - - Example 53 B 70 3A 30 Chemical formula 12 5 DMA 0.1 - - - - Example 54 C 90 3A 10 Chemical formula 12 10 DMA 1 - - - - Example 55 D 50 3B 50 Chemical formula 16 3 2-PP 0.01 - - - - Example 56 E 70 3B 30 Chemical formula 16 5 3-PP 0.1 - - - - Example 57 F 90 3B 10 Chemical formula 16 10 4-PP 1 - - - - Example 58 G 50 3C 50 Chemical formula 19 3 TPA 0.01 - - - - Example 59 H 70 3C 30 Chemical formula 19 5 TPA 0.1 - - - - Example 60 I 90 3C 10 Chemical formula 19 10 TPA 1 - - - - Example 61 J 50 3D 50 Chemical formula 20 3 DEA 0.01 - - - - Example 62 K 70 3D 30 Chemical formula 20 5 DEA 0.1 - - - - Example 63 L 90 3D 10 Chemical formula 20 10 DEA 1 - - - - Example 64 M 50 3E 50 Chemical formula 25 20 TEA 3 - - - - Example 65 N 70 3E 30 Chemical formula 25 3 TEA 0.01 APES 0.5 - - Example 66 O 90 3E 10 Chemical formula 25 5 TEA 0.1 GOPMS 2 - - Example 67 P 50 3F 50 Chemical formula 25 10 TEA 2 APES 5 - - Example 68 A 50 3A 50 Chemical formula 12 5 - - GOPMS 0.5 - - Example 69 D 70 4A 30 Chemical formula 12 10 - - GOPMS 2 - - Example 70 G 90 5C 10 Chemical formula 12 15 - - APES 5 - - Example 71 G 90 5C 10 Chemical formula 12 5 - - APES 10 - - Example 72 A 50 3A 50 Chemical formula 12 10 - - - - DBMP 0.1 Example 73 D 70 4A 30 Chemical formula 12 15 - - - - DBMP 5 Example 74 G 90 5C 10 Chemical formula 12 5 - - - - DBMP 10 Example 75 G 90 5C 10 Chemical formula 12 10 TEA 2 APES 10 DBMP 5 Comparative example 1 Q 50 3A 50 Chemical formula 12 30 - - - - - - Comparative example 2 R 60 3B 40 Chemical formula 13 25 - - - - - - Comparative example 3 S 70 3C 30 Chemical formula 14 20 - - - - - - Comparative example 4 T 80 3D 20 Chemical formula 15 15 - - - - - - Reference example 1 U 90 3E 10 Chemical formula 16 10 - - - - - - Reference example 2 V 95 3F 5 Chemical formula 17 5 - - - - - - Reference example 3 A 70 3G 30 Chemical formula 18 20 - - - - - - Reference example 4 A 70 4E 30 Chemical formula 19 20 - - - - - - Reference example 5 A 70 5E 30 Chemical formula 20 20 - - - - - - Reference example 6 A 49 3A 51 Chemical formula 12 31 - - - - - - Reference example 7 A 48 3B 52 Chemical formula 12 32 - - - - - - Reference example 8 A 47 3C 53 Chemical formula 12 33 - - - - - -

*DMA: N,N-xylene amine

*PP: Phenylpyridine

*TPA: Tri-n-propylamine

*DEA: Diethylamine

*TEA: Triethanolamine

*APES: N-2-(aminoethyl)-3-aminopropyl triethoxysilane

*GOPMS: (3-glycidoxypropyl) trimethoxysilane

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

Experimental example

The photosensitive resin compositions of the above examples and comparative examples were coated on a glass substrate with a slit coater, and then implemented a VCD (vacuum drying) process to a pressure of 40 Pa, and placed on a hot plate at a temperature of 100°C. Pre-baking was performed for 2 minutes to form a film with a thickness of 4.0 μm.

The physical properties such as sensitivity, resolution, transmittance, heat discoloration resistance, process margin, adhesion, and heat resistance were measured for the film, and are shown in Table 3 below.

a) Sensitivity

Using a predetermined pattern mask on the film formed as above, irradiating a broadband (Broadband) with an intensity of 20mW/cm ² of ultraviolet rays with a contact hole size (Contact Hole CD) of 10μm (Contact Hole CD) and a standard dose (Dose), and then using Sijia An aqueous solution containing 2.38% by weight of ammonium hydroxide was developed at 23° C. for 1 minute, and then washed with ultrapure water for 1 minute.

Next, it was cured in an oven at 230°C for 30 minutes to obtain a patterned film with a thickness of 3.0 μm. For the prepared pattern film, the exposure energy (dose) when a 10 μm contact hole pattern (pattern) was formed was measured as the sensitivity.

b) Resolution

The resolution is measured with the smallest size of a 10 μm contact hole pattern (pattern) formed when measuring the sensitivity of a) above.

c) Transmittance

Transmittance evaluation The transmittance of the pattern film at 400 nm was measured using a pattern film formed when the sensitivity of the above a) was measured using a spectrophotometer. At this time, the case where the transmittance is 97% or more is indicated as ⊚, the case of 95% or more is indicated as ○, the case of 90% or more and less than 95% is indicated as △, and the case of less than 90% is indicated as ×.

d) Heat discoloration resistance

The measurement substrate for evaluating the transparency of c) was further cured twice for 30 minutes in an oven at 230° C., and the heat discoloration resistance was evaluated based on the change in the 400 nm transmittance of the pattern film before and after curing. At this time, the case where the rate of change is less than 1% is indicated as ◎, the case of less than 3% is indicated as ○, the case of 3% to 5% is indicated as △, and the case of greater than 5% is indicated as ×.

e) PED (Post Exposure Delay) process margin

The pattern film is formed by the same method as the sensitivity measurement of a) above, and the CD change rate based on the delay time before the development process after exposure is measured based on the contact hole size of 10μm (Contact Hole CD) . At this time, the case where the rate of change is less than 3% is indicated as ⊚, the case of less than 5% is indicated as ○, the case of 5% or more and less than 10% is indicated as △, and the case of 10% or more is indicated as ×.

f) Adhesion

The pattern film formed during the measurement of the sensitivity of a) above is used to evaluate the adhesive force based on whether the pattern is lost or not through the scope of the film.

When the pre-bake temperature is 90℃ or higher, the adhesive force is guaranteed as ◎, when the temperature is 95℃ or higher, the adhesive force is guaranteed as ○, and when the adhesive force is guaranteed at 100℃~105℃, it is indicated as when it is greater than 105℃. The case of ensuring adhesion or pattern loss is expressed as ×.

g) Heat resistance

The heat resistance is measured by TGA. After sampling the pattern film formed when measuring the sensitivity of the above a), the temperature was increased from room temperature to 900°C by TGA, at a rate of 10°C per minute. The case where the temperature of the loss of 5 wt% is higher than 300°C is indicated as ○, the case of the temperature of the loss of 5 wt% of 280°C to 300°C is indicated as △, and the case of the loss of 5 wt% is lower than 280°C is indicated as ×.

【table 3】 Sensitivity (mJ) Resolution (μm) Transparency Heat discoloration resistance PED process margin Adhesion Heat resistance Example 1 50 3 ○ ○ ○ ○ ○ Example 2 50 3 ○ ○ ○ ○ ○ Example 3 50 3 ○ ○ ○ ○ ○ Example 4 50 3 ○ ○ ○ ○ ○ Example 5 50 3 ○ ○ ○ ○ ○ Example 6 50 3 ○ ○ ○ ○ ○ Example 7 50 3 ○ ○ ○ ○ ○ Example 8 50 3 ○ ○ ○ ○ ○ Example 9 50 3 ○ ○ ○ ○ ○ Example 10 50 3 ○ ○ ○ ○ ○ Example 11 50 3 ○ ○ ○ ○ ○ Example 12 50 3 ○ ○ ○ ○ ○ Example 13 50 3 ○ ○ ○ ○ ○ Example 14 50 3 ○ ○ ○ ○ ○ Example 15 50 3 ○ ○ ○ ○ ○ Example 16 50 3 ○ ○ ○ ○ ○ Example 17 50 3 ○ ○ ○ ○ ○ Example 18 50 3 ○ ○ ○ ○ ○ Example 19 50 3 ○ ○ ○ ○ ○ Example 20 50 3 ○ ○ ○ ○ ○ Example 21 50 3 ○ ○ ○ ○ ○ Example 22 50 3 ○ ○ ○ ○ ○ Example 23 50 3 ○ ○ ○ ○ ○ Example 24 50 3 ○ ○ ○ ○ ○ Example 25 50 3 ○ ○ ○ ○ ○ Example 26 50 3 ○ ○ ○ ○ ○ Example 27 50 3 ○ ○ ○ ○ ○ Example 28 50 3 ○ ○ ○ ○ ○ Example 29 50 3 ○ ○ ○ ○ ○ Example 30 50 3 ○ ○ ○ ○ ○ Example 31 50 3 ○ ○ ○ ○ ○ Example 32 50 3 ○ ○ ○ ○ ○ Example 33 50 3 ○ ○ ○ ○ ○ Example 34 50 3 ○ ○ ○ ○ ○ Example 35 50 3 ○ ○ ○ ○ ○ Example 36 50 3 ○ ○ ○ ○ ○ Example 37 50 3 ○ ○ ○ ○ ○ Example 38 50 3 ○ ○ ○ ○ ○ Example 39 50 3 ○ ○ ○ ○ ○ Example 40 50 3 ○ ○ ○ ○ ○ Example 41 50 3 ○ ○ ○ ○ ○ Example 42 50 3 ○ ○ ○ ○ ○ Example 43 50 3 ○ ○ ○ ○ ○ Example 44 50 3 ○ ○ ○ ○ ○ Example 45 50 3 ○ ○ ○ ○ ○ Example 46 50 3 ○ ○ ○ ○ ○ Example 47 50 3 ○ ○ ○ ○ ○ Example 48 50 3 ○ ○ ○ ○ ○ Example 49 50 3 ○ ○ ○ ○ ○ Example 50 50 3 ○ ○ ○ ○ ○ Example 51 50 3 ○ ○ ○ ○ ○ Example 52 50 3 ○ ○ ◎ ○ ○ Example 53 50 3 ○ ○ ◎ ○ ○ Example 54 50 3 ○ ○ ◎ ○ ○ Example 55 50 3 ○ ○ ◎ ○ ○ Example 56 50 3 ○ ○ ◎ ○ ○ Example 57 50 3 ○ ○ ◎ ○ ○ Example 58 50 3 ○ ○ ◎ ○ ○ Example 59 50 3 ○ ○ ◎ ○ ○ Example 60 50 3 ○ ○ ◎ ○ ○ Example 61 50 3 ○ ○ ◎ ○ ○ Example 62 50 3 ○ ○ ◎ ○ ○ Example 63 50 3 ○ ○ ◎ ○ ○ Example 64 50 3 ○ ○ ◎ ○ ○ Example 65 50 3 ○ ○ ◎ ◎ ○ Example 66 50 3 ○ ○ ◎ ◎ ○ Example 67 50 3 ○ ○ ◎ ◎ ○ Example 68 50 3 ○ ○ ○ ◎ ○ Example 69 50 3 ○ ○ ○ ◎ ○ Example 70 50 3 ○ ○ ○ ◎ ○ Example 71 50 3 ○ ○ ○ ◎ ○ Example 72 50 3 ◎ ◎ ○ ○ ○ Example 73 50 3 ◎ ◎ ○ ○ ○ Example 74 50 3 ◎ ◎ ○ ○ ○ Example 75 50 3 ◎ ◎ ◎ ◎ ○ Comparative example 1 200 10 ○ ○ X ○ ○ Comparative example 2 250 8 X X X X X Comparative example 3 200 8 ○ ○ X X X Comparative example 4 60 5 ○ ○ X X X Reference example 1 200 10 ○ ○ X X X Reference example 2 120 8 ○ ○ X X X Reference example 3 120 5 X X X X X Reference example 4 120 5 X X X X X Reference example 5 120 5 X X X X X Reference example 6 130 5 X X X X X Reference example 7 135 5 X X X X X Reference example 8 140 5 X X X X X

As shown in Table 3 above, the insulating film containing the cured product of the positive photosensitive resin composition of Examples 1 to 75 of the present application showed a sensitivity of 50 mJ and a resolution of 3 μm, which can confirm that it has excellent sensitivity and Resolution. Not only that, it also shows a transmittance of 95% or more, a thermal discoloration resistance of less than 3%, and a CD change rate of less than 5%, which can confirm that it has excellent transmittance, thermal discoloration resistance, and lithography process margin. In addition, adhesion can be ensured at a low temperature of 95°C or higher, and the temperature at which 5 wt% is lost is greater than 300°C, and it can be confirmed that excellent adhesion and heat resistance are achieved. That is, the insulating film prepared from the positive photosensitive resin composition of the embodiment of the present application has excellent sensitivity, resolution, transmittance, heat discoloration resistance, lithography process margin, adhesion, and heat resistance.

In particular, since the positive photosensitive resin composition of Examples 52 to 67 and Example 75 further contains a basic compound, it can be confirmed that the cured product containing the positive photosensitive resin composition of Examples 52 to 67 and Example 75 The insulating film exhibits very excellent heat discoloration resistance with a transmittance change rate of less than 1%.

In addition, since the positive photosensitive resin composition of Examples 65 to 71 and Example 75 further contains an adhesion promoter, it can be confirmed that the cured product of the positive photosensitive resin composition of Examples 65 to 71 and Example 75 is The insulating film has a very excellent adhesion to ensure the adhesion at a pre-baking temperature of 90°C or more.

In addition, since the positive photosensitive resin composition of Examples 72 to 75 further contains an antioxidant, it can be confirmed that the insulating film containing the cured product of the positive photosensitive resin composition of Examples 72 to 75 shows 97% or more Very excellent transmittance and transmittance change rate of less than 1%, very excellent heat discoloration resistance.

In contrast, the positive photosensitivity of Comparative Example 1 of the present application is composed of the first copolymer Q of Comparative Synthesis Example 1 described above, which contains no ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group as a monomer. The insulating film obtained from the resin composition shows a sensitivity of 200 mJ and a resolution of 10 μm. Compared with the examples of this application, it not only shows a significantly poorer sensitivity and resolution, but also shows a CD change rate greater than or equal to 10% , It can be confirmed that the lithography process margin is also very poor.

In addition, the positive photoreceptor of Comparative Example 2 of the present application is composed of the first copolymer R of Comparative Synthesis Example 2 described above, which is copolymerized by adding more than 50 mol% of the terminal hydroxyl group protected by an acid-decomposable protective group. The insulating film obtained from the flexible resin composition shows a sensitivity of 250mJ and a resolution of 8μm. Compared with the examples of this application, it not only shows a significantly poorer sensitivity and resolution, but also shows a transmittance of less than 90%. With a thermal discoloration resistance of 5% or more and a CD change rate of 10% or more, it can be confirmed that it exhibits significantly poor transmittance, thermal discoloration resistance, and lithography process margin. In addition, the loss of the pattern leads to poor adhesion, and a 5 wt% loss occurs at a temperature of less than 280°C. It can be confirmed that the heat resistance at 300°C is also poor.

In addition, an insulating film obtained from the positive photosensitive resin composition of Comparative Example 3 of the present application containing the first copolymer S of Comparative Synthesis Example 3 in which an ethylenic unsaturated compound was added in excess of 70 mol% or more and copolymerized It shows a sensitivity of 200mJ and a resolution of 8μm. Compared with the examples of this application, it not only shows a significantly poorer sensitivity and resolution, but also shows a CD change rate greater than or equal to 10%. It can be confirmed that the display is significantly poorer. Lithography process margin. In addition, the loss of the pattern leads to poor adhesion, and a 5 wt% loss occurs at a temperature of less than 280°C. It can be confirmed that the heat resistance at 300°C is also poor.

On the other hand, an insulating film obtained from the positive photosensitive resin composition of Comparative Example 4 of the present application containing the first copolymer T of Comparative Synthesis Example 4 described above by adding more than 40 mol% of an unsaturated carboxylic acid compound to copolymerize It shows a sensitivity of 60mJ and a resolution of 5μm. Compared with the examples of this application, it not only shows inferior sensitivity and resolution, but also shows a CD change rate greater than or equal to 10%. It can be confirmed that the display is obviously poor. Lithography process margin. In addition, the loss of the pattern leads to poor adhesion, and a 5 wt% loss occurs at a temperature of less than 280°C. It can be confirmed that the heat resistance at 300°C is also very poor.

In addition, the positive type of Reference Examples 1 and 2 of the present application comprising the first copolymers U and V of the above-mentioned Comparative Synthesis Examples 5 and 6 which are copolymerized by adding less than 2 parts by weight or more than 24 parts by weight of a radical polymerization initiator The insulating film obtained from the photosensitive resin composition shows a CD change rate of 10% or more, and it can be confirmed that it shows a relatively poor lithography process margin. In addition, it can be confirmed that the characteristics of adhesion and heat resistance have also decreased.

In particular, the insulating film obtained from the positive photosensitive resin composition of Reference Example 1 of the present application containing the first copolymer U of the above-mentioned Comparative Synthesis Example 5 showed a sensitivity of 200 mJ and a resolution of 10 μm. Compared with the example, the sensitivity and resolution are decreased. The insulating film obtained from the positive photosensitive resin composition of Reference Example 2 of the present application containing the first copolymer V of Comparative Synthesis Example 6 was also measured. The sensitivity is 120 mJ, and the resolution is 8 μm. Compared with the embodiment of the present application, it can be confirmed that the sensitivity and resolution have decreased.

On the other hand, the insulating film obtained from the positive photosensitive resin composition of Reference Examples 3 to 5 of the present application which does not contain the olefinic copolymer peculiar to the present invention shows a sensitivity of 120 mJ and a resolution of 5 μm, which is comparable to the present invention. Compared with the application examples, it not only shows relatively poor sensitivity and resolution, but also shows a transmittance of less than 90%, a heat discoloration resistance of 5% or more, and a CD change rate of 10% or more, which can confirm the transmission There are also some inferior characteristics in terms of temperature, thermal discoloration resistance and lithography process margin. In addition, it can be confirmed that the characteristics of adhesion and heat resistance have also decreased.

On the other hand, relative to the total 100 parts by weight of the first copolymer and the second copolymer, the positive photosensitive resin composition of Reference Examples 6 to 8 of the present application contains more than 50 parts by weight of the second copolymer. The insulating film obtained from the positive photosensitive resin composition of 6 to 8 shows a sensitivity of 130 mJ or more and a resolution of 5 μm. Compared with the examples of the present application, it not only shows relatively poor sensitivity and resolution, but also shows With a transmittance of less than 90%, a thermal discoloration resistance of 5% or more, and a CD change rate of 10% or more, it can be confirmed that the transmittance, thermal discoloration resistance, and lithography process margin characteristics are also somewhat poor. In addition, it can be confirmed that the characteristics of adhesiveness and heat resistance have also decreased.

no.

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Claims (16)

A positive photosensitive resin composition comprising: a) a first copolymer comprising i) a repeating unit derived from an ethylenically unsaturated compound protected by an acid-decomposable protective group for a terminal hydroxyl group; ii) derived from A repeating unit of an unsaturated carboxylic acid compound and iii) a repeating unit derived from an ethylenically unsaturated compound; b) a second copolymer in which at least a part of the terminal hydroxyl group is protected by an acid-decomposable protective group; c) a light An acid generator; and d) a solvent, the second copolymer including a repeating unit represented by the following chemical formula 1 and a chemical formula 2, [chemical formula 1]

[Chemical formula 2]

In this chemical formula 2, R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuran group, and 2 , 3-Propylene carbonate group, methoxyethoxyethyl group or ethoxyethoxyethyl group. The positive photosensitive resin composition according to claim 1, wherein Relative to the total monomers used to synthesize the first copolymer 100 mol%, The content of the ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group is 1 to 50 mol%, The content of the unsaturated carboxylic acid compound is 5 to 40 mol%, The content of the ethylenically unsaturated compound is greater than or equal to 10 mol% and less than 70 mol%. The positive photosensitive resin composition according to 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, citraconic acid, meconic acid, itaconic acid, and anhydrides of unsaturated dicarboxylic acids. One kind. The positive photosensitive resin composition according to claim 1, wherein The ethylenically unsaturated compound comprises selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate , Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentyl acrylate, dicyclopentenyl methacrylate, dicyclopentyl methacrylate, acrylic acid 1-adamantyl ester, 1-adamantyl methacrylate, dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, bicyclic acrylate Pentoxyethyl, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, o-methyl styrene, m-methyl styrene, p Methyl styrene, vinyl toluene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, glycidyl acrylate, methyl Glycidyl acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, β-methyl glycidyl acrylate, β-methacrylic acid -Methyl glycidyl ester, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxy methacrylate Butyl ester, acrylate-6,7-epoxyheptyl ester, methacrylate-6,7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether , M-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4 acrylic acid -Epoxycyclohexyl ester, 3,4-epoxycyclohexyl methyl acrylate, 3-ethyl-3-oxetanate methacrylate, 3-ethyl-3-oxetanate acrylate, methyl methacrylate 3-butyl-3-oxetanyl acrylate, 3-butyl-3-oxetanate acrylate, 3-propyl-3-oxetanyl methacrylate, 3-propyl acrylate -3-oxetanate, 3-oxetanate methacrylate, 3-oxetanate acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, At least one of the group consisting of hydroxyethyl acrylate, hydroxybutyl acrylate, and hydroxypropyl acrylate. The positive photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protective group includes any of the compounds represented by the following one chemical formula 3 or one chemical formula 4 One kind, [Chemical formula 3]

In the chemical formula 3, R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuran group, 2 , One of 3-propylene carbonate group, methoxyethoxyethyl group or acetoxyethoxyethyl group, [Chemical formula 4]

In the chemical formula 4, R ₂ is hydrogen or a C1 to C10 alkyl group, and R ₃ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, 2-tetrahydropyran One of a group, a vinyl ether group, a 2-tetrahydrofuran 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 according to claim 1, wherein the second copolymer contains any one of the main chains represented by the following chemical formula 5, chemical formula 6, and chemical formula 7, [chemical formula 5]

In the chemical formula 5, a+b=100, a is 50 to 99, b is 1 to 50, and R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, One of 2-tetrahydropyranyl, vinyl ether, 2-tetrahydrofuran, 2,3-propylene carbonate, methoxyethoxyethyl or acetoxyethoxyethyl, [Chemical formula 6 ]

In the chemical formula 6, a+b+c+d=100, b+d is 1 to 50, and R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, One of 2-tetrahydropyranyl, vinyl ether, 2-tetrahydrofuran, 2,3-propylene carbonate, methoxyethoxyethyl or acetoxyethoxyethyl, R ₂ is Hydrogen or C1 to C10 alkyl group, n is an integer of 0 to 4, [Chemical formula 7]

In the chemical formula 7, a+b+c+d=100, b+d is 1 to 50, and R ₁ is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a silanoxy group, One of 2-tetrahydropyranyl, vinyl ether, 2-tetrahydrofuran, 2,3-propylene carbonate, methoxyethoxyethyl or acetoxyethoxyethyl, R ₂ is Hydrogen or a C1 to C10 alkyl group, n is an integer of 0 to 4. The positive photosensitive resin composition according to claim 1, wherein Relative to the entire repeating unit, the second copolymer includes 0.01 mol% or more and 50 mol% or more of the repeating unit in which the terminal hydroxyl group is protected by an acid-decomposable protective group. The positive photosensitive resin composition according to claim 1, wherein Relative to 100 parts by weight of the total weight of monomers used to synthesize the first copolymer, The first copolymer is polymerized in the presence of a radical polymerization initiator of 2 parts by weight or more and 24 parts by weight or less. The positive photosensitive resin composition according to claim 1, wherein Relative to the total 100 parts by weight of the first copolymer and the second copolymer, 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. The positive photosensitive resin composition according to claim 1, wherein Relative to the total 100 parts by weight of the first copolymer and the second copolymer, 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 photosensitive resin composition according to claim 1, which further comprises: e) a basic compound, f) an adhesion promoter, g) an antioxidant, and h) at least one additive in a photosensitizer. The positive photosensitive resin composition according to claim 11, wherein: Relative to the total 100 parts by weight of the first copolymer and the second copolymer, The positive photosensitive resin composition includes 0.01 parts by weight or more and 3 parts by weight of the basic compound, 0.5 parts by weight or more and 10 parts by weight of the adhesion assistant, and 0.1 parts by weight or more and less than At least one of 10 parts by weight of the antioxidant and 0.1 parts by weight or more and 10 parts by weight or less of the photosensitizer. The positive photosensitive resin composition according to claim 1, wherein The weight average molecular weight (Mw) of the first copolymer in terms of polystyrene is 3,000 to 30,000. The positive photosensitive resin composition according to claim 1, wherein The weight average molecular weight (Mw) of the first copolymer in terms of polystyrene is 3,000 to 30,000, The weight average molecular weight (Mw) of the second copolymer in terms of polystyrene is 3,000 to 30,000. A photosensitive resin film comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 14. A display device comprising the photosensitive resin film according to claim 15.