Positive photosensitive resin composition and display element using the same

Abstract

The present invention relates to a positive photosensitive resin composition that contains a siloxane copolymer of two types of reactive silane compounds with a specific structure that minimizes residual impurities such as unreacted monomers and catalysts, as well as a UV absorber having an alkoxy group and at least one phenolic hydroxyl group that can undergo a crosslinking reaction unlike conventional benzotriazole-based compounds. This allows the composition to not only exhibit excellent performance in terms of sensitivity, resolution, and flatness, but also excellent weather resistance and UV absorption rate, ensuring panel reliability.

Description

Technical Field

[0001] [Cross - Reference to Related Applications] This application claims the benefit of priority based on Korean Patent Application No. 10 - 2019 - 0126256 filed on October 11, 2019, and all the contents disclosed in the literature of the Korean patent application are incorporated herein by reference in their entirety.

[0002] The present invention relates to a positive photosensitive resin composition, and more particularly, to a positive photosensitive resin composition capable of realizing high resolution together with insulation and heat resistance of an organic light - emitting diode (hereinafter, OLED) display device, forming a pattern having excellent light resistance and heat resistance characteristics and environmental resistance, and reducing pattern defects due to development residues that may occur during development and differences in solubility occurring at the boundary between exposed and unexposed portions.

Background Art

[0003] Recently, in the display industry, organic light - emitting diode (OLED) devices that display images through an organic layer that emits light autonomously without a backlight unit (hereinafter, BLU) in a liquid - crystal display device (hereinafter, LCD) where images are displayed through a separate light source such as a BLU have been growing. In particular, the OLED display device is applied and used from small electronic devices such as smartphones to large electronic devices such as televisions. In addition, since the OLED display device can realize a panel on which an organic light - emitting layer is vapor - deposited in a flexible manner, it can be bent and applied to various forms of display devices such as outdoor advertisements and automobiles.

[0004] The OLED display includes a Pixel Defining Layer (hereinafter referred to as PDL) layer that separates the boundaries between the self-emitting red, green, and blue pixels and insulates each of them, and an interlayer insulating film having both insulating properties and electrode flattening properties below the PDL layer. At this time, the PDL layer is precisely patterned by a photo-etching process, and a photosensitive resin composition containing a polyamic acid compound has been widely used as a material for forming the PDL layer.

[0005] However, the photosensitive resin composition containing the polyamic acid and polyimide generally has insufficient sensitivity, a high film thickness change rate during the process, and low productivity compared to the photosensitive resin composition containing a siloxane resin. The ability to uniformly form red, green, and blue pixels of different sizes, which is the main role of the PDL layer, that is, the resolution is insufficient, affecting the quality of the panel of the final display device. In addition, the insoluble property of the polyimide resin can induce development residues generated during development.

[0006] In addition, as the popularity of OLED display element panels spreads for displays exposed to sunlight conditions and various climates such as large advertisements or automobiles, it is necessary to develop display elements improved in terms of weatherability.

Summary of the Invention

Problems to be Solved by the Invention

[0007] In order to solve such problems of the prior art, the present invention not only has excellent performance such as sensitivity, resolution, and flatness, but also has excellent weatherability, ensuring the reliability of excellent panels, and thereby can be usefully applied to interlayer insulating films, planarization films, or PDLs in various OLED displays. A positive photosensitive resin composition, a method for forming a pattern of a display element using the same, and a positive photosensitive siloxane resin composition are provided.

Means for Solving the Problems

[0008] The present invention a) A siloxane copolymer; b) A 1,2 - quinonediazide compound; c) One or more UV absorbers represented by the following Chemical Formula 1; and d) A solvent; provided is a positive - type photosensitive resin composition characterized by containing them: [Chemical Formula 1] JPEG0007701350000001.jpg65170 In the above Chemical Formula 1, R1 is one functional group selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, a substituted or unsubstituted hemi - acetal having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloheteroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroalkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroalkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroacetal having 1 to 30 carbon atoms, and a substituted or unsubstituted heterohemi - acetal having 1 to 30 carbon atoms;

[0009] R2 to R5 are each independently the same as or different from each other, and are hydrogen, hydroxy, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, a substituted or unsubstituted hemiacetal having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloheteroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroalkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroalkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroacetal having 1 to 30 carbon atoms, and a substituted or unsubstituted heterohemiacetal having 1 to 30 carbon atoms, and is a functional group selected from the group consisting of these.

[0010] Further, according to another embodiment of the present invention, a cured film containing a cured product of the positive photosensitive resin composition is provided. Further, according to still another embodiment of the present invention, a display element containing a cured product of the positive photosensitive resin composition is provided.

Effects of the Invention

[0011] The positive photosensitive resin composition containing the siloxane copolymer according to the present invention minimizes the content of unreacted monomers and catalysts, and uses a UV absorber with a specific structure to exhibit excellent insulating properties, which are the properties of siloxane, heat resistance that can maintain a stable form up to about 350 °C, and a low moisture absorption rate with poor moisture absorption. Therefore, the present invention can provide a PDL layer that separates the boundaries between pixels of display elements such as OLEDs and insulates them, and an interlayer insulating film having both insulating properties and electrode flattening properties below the PDL layer, so that the defect rate due to moisture that affects the reliability of OLED panel operation can be significantly reduced.

Brief Description of Drawings

[0012]

Figure 1

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the present invention will be described more specifically. Terms and words used in this specification and the claims should not be construed as limited to their ordinary or dictionary meanings, and the inventor himself should interpret them as meanings and concepts that conform to the technical idea of the present invention based on the principle that he can appropriately define the concept of the terms in order to explain the invention in the best way.

[0014] In addition, the meaning of the term "comprising" used in the specification does not exclude the presence or addition of other characteristics, regions, integers, steps, operations, elements and / or components while embodying specific characteristics, regions, integers, steps, operations, elements and / or components.

[0015] According to an embodiment of the present invention, a positive photosensitive resin composition characterized by containing a) a siloxane copolymer; b) a 1,2 - quinonediazide compound; c) one or more UV absorbers represented by the following Chemical Formula 1; and d) a solvent can be provided. [Chemical Formula 1] In Chemical Formula 1,

[0016] R1 is one functional group selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, a substituted or unsubstituted hemiacetal having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloheteroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroalkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroalkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroacetal having 1 to 30 carbon atoms, and a substituted or unsubstituted heterohemiacetal having 1 to 30 carbon atoms,

[0017] R2 to R5 are each independently the same as or different from one another, and are hydrogen, hydroxy, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, a substituted or unsubstituted hemiacetal having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloheteroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroalkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroalkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroacetal having 1 to 30 carbon atoms, and a substituted or unsubstituted heterohemiacetal having 1 to 30 carbon atoms, and is a functional group selected from the group consisting of these.

[0018] The positive photosensitive resin composition of the present invention contains one or more phenolic hydroxyl groups capable of undergoing a crosslinking reaction, which is different from conventional benzotriazole-based ones, and contains a UV absorber having an alkoxy group. As a result, not only is it excellent in performance such as sensitivity, resolution, and flatness, but it also has excellent weather resistance and can ensure the reliability of a panel with excellent ultraviolet absorption rate.

[0019] In addition, the positive photosensitive siloxane composition of the present invention contains a siloxane resin for forming an insulating film capable of achieving high resolution together with the insulation and heat resistance of an organic light-emitting diode (hereinafter, OLED) display device.

[0020] More specifically, the photosensitive resin composition according to the present invention uses a siloxane copolymer of two reactive silane compounds having a specific structure with minimized residual impurities such as unreacted monomers and catalysts, and can form a pattern excellent in light resistance and heat resistance properties and having environmental resistance. Further, it can exhibit the effect of reducing development residues that may occur during development and pattern defects due to differences in solubility occurring at the boundary between the exposed portion and the non-exposed portion.

[0021] The present invention also includes a cured body formed from the positive photosensitive resin composition and a display element having the cured body. Hereinafter, the siloxane copolymer, 1,2-quinonediazide compound, UV absorber, and solvent used as the positive photosensitive resin composition of the present invention will be sequentially described in detail.

[0022] a) Siloxane copolymer The siloxane copolymer according to the present invention is used in the photosensitive resin composition, and not only has excellent performance such as sensitivity and resolution, but also contributes to ensuring excellent panel reliability by maintaining a low water absorption rate.

[0023] Such a siloxane copolymer is obtained by hydrolyzing and condensation-polymerizing i) a silane compound represented by the following Chemical Formula 2 and ii) a silane compound represented by the following Chemical Formula 3 as a condensation polymer and removing impurities such as unreacted monomers.

[0024] According to one embodiment of the present invention, the siloxane copolymer can be obtained by hydrolyzing and condensation-polymerizing 10 to 90 parts by weight of i) a silane compound represented by the following Chemical Formula 2 and 10 to 90 parts by weight of ii) a silane compound represented by the following Chemical Formula 3 with respect to 100 parts by weight of the total monomers. [Chemical Formula 2] (R6) n Si(R7) 4-n In the above Chemical Formula 2, Each R6 is independently the same as or different from each other, and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Each R7 is independently the same as or different from each other, and is a hydrogen atom, an alkoxy group, or a chloro group. n is an integer from 1 to 3. [Chemical Formula 3] Si(OR8)4 In the above Chemical Formula 3, Each R8 is independently the same as or different from each other, and is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group.

[0025] The silane compound represented by the above Chemical Formula 2 is a reactive silane. For example, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, dimethyldiphenylmethoxysilane, 1-naphthyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, etc. can be used, and these can be used alone or in a mixture of two or more.

[0026] The reactive silane represented by the above Chemical Formula 2 can be used in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total monomer. When the content of the reactive silane compound of Chemical Formula 2 is less than 10 parts by weight, cracks may occur during the curing of the cured body. When the content exceeds 90 parts by weight, it is difficult to achieve high resolution due to the pattern sag phenomenon.

[0027] Also, the compound represented by the above Chemical Formula 3 used in the present invention is a tetrafunctional reactive silane. For example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. can be used, and these can be used alone or in a mixture of two or more.

[0028] The reactive silane represented by the chemical formula 3 can be used in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total monomer. When the content of the reactive silane of the chemical formula 3 is less than 10 parts by weight, the dissolution rate in the developer is very slow, which is disadvantageous in terms of sensitivity. When the content exceeds 90 parts by weight, precipitation may occur because the solubility in the solvent used in the composition is low.

[0029] The hydrolysis and condensation polymerization reaction conditions for producing the siloxane copolymer are not particularly limited and can be carried out according to what is known in this field. For example, the polymerization reaction can be carried out at a temperature of 50 to 100 °C for 4 to 24 hours. Further, the reaction is carried out under an inert atmosphere.

[0030] Also, an acid or base catalyst can be further used during the hydrolysis and condensation polymerization. The acid catalyst used in the method can be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, propionic acid, butanoic acid, pentanoic acid, and the base catalyst can be sodium hydroxide, potassium hydroxide, ammonia and organic amines, alkylammonium hydroxide salts, and can be used alone or in combination of two or more simultaneously or stepwise. Also, after the condensation polymerization reaction is completed, an extraction process of water and an organic solvent can be passed through to remove unreacted monomers and the catalyst.

[0031] The siloxane copolymer provided by such a method may include a copolymer having an unreacted monomer content of less than 10% by weight and a residual catalyst content of less than 2,000 ppm. The siloxane copolymer from which the unreacted monomer and the catalyst have been removed has improved storage stability and improved developability residues due to side reactions during the cured film process of the photosensitive resin composition. At this time, when the catalyst content is 2000 ppm or more, the sensitivity due to the residual catalyst may become slow, or corrosion of the lower or upper metal wiring may occur due to diffusion. Therefore, when using the siloxane copolymer, the desired effect cannot be achieved unless a product purified with a catalyst content within a specific range as in the method of the present invention is used.

[0032] Also, the finally obtained siloxane copolymer may have a polystyrene-reduced weight average molecular weight (Mw) of 1,000 g / mol to 30,000 g / mol. The polystyrene-reduced weight average molecular weight (Mw) may be measured using the standard analysis method of a gel permeation chromatography (GPC) system used in the e2695 Alliance Separation Module manufactured by Waters.

[0033] When the polystyrene-reduced weight average molecular weight (Mw) of the siloxane copolymer is less than 1,000 g / mol, the residual film rate during the development process in the evaluation of the positive-type photosensitive resin composition decreases, or the heat resistance decreases, and the moisture absorption rate of moisture is vulnerable. Also, when the reduced weight average molecular weight (Mw) exceeds 30,000 g / mol, the sensitivity and developability of the positive-type photosensitive resin composition decrease.

[0034] b) 1,2-quinonediazide compound The photosensitive resin composition containing the 1,2-quinonediazide compound according to the present invention forms a positive-type pattern in which the exposed portion is soluble in an alkaline developer and is removed by the development process.

[0035] The 1,2-quinonediazide compound in the present invention has a structure in which a Ballast having a phenolic hydroxyl group and naphthoquinonediazide sulfonic acid form an ester bond.

[0036] As the naphthoquinonediazide sulfonic acid, 4-naphthoquinonediazide sulfonic acid halide or 5-naphthoquinonediazide sulfonic acid halide can be used. The ester compound obtained from the 4-naphthoquinonediazide sulfonic acid halide has absorption in the i-line (wavelength 365 nm) region and is suitable for i-line exposure. In addition, since the ester compound obtained from the 5-naphthoquinonediazide sulfonic acid halide has absorption in a wide wavelength region, it is suitable for exposure at a wide range of wavelengths. The 4- or 5-naphthoquinonediazide sulfonic acid compound can be selected or mixed and used depending on the exposure wavelength.

[0037] In addition, the content of the 1,2-quinonediazide compound varies depending on the esterification rate of the naphthoquinonediazide sulfonic acid, the physical properties of the siloxane copolymer used, the required sensitivity, and the contrast due to the difference in solubility between the exposed and unexposed parts. Specifically, the 1,2-quinonediazide compound may be contained in an amount of 5 to 50 parts by weight or 10 to 35 parts by weight based on 100 parts by weight of the siloxane copolymer. When the 1,2-quinonediazide compound is contained in the photosensitive resin composition in an amount of 5 to 50 parts by weight, the patterning characteristics are improved due to the difference in solubility between the exposed and unexposed parts.

[0038] At this time, when the content of the 1,2-quinonediazide compound is less than 5 parts by weight, the dissolution contrast between the exposed and unexposed parts decreases and it does not have photosensitive characteristics. In addition, when the amount of the 1,2-quinonediazide compound used is 50 parts by weight or more, the compatibility decreases, turbidity occurs in the cured film, the insulation characteristics of the cured product decrease due to the decomposition of the quinonediazide compound that may occur during the thermosetting process, or the gas components of the decomposition products may cause problems in the subsequent process.

[0039] c) UV absorber The composition of the present invention contains a UV absorber represented by the following specific Chemical Formula 1. [Chemical Formula 1] JPEG0007701350000003.jpg65170 In the Chemical Formula 1,

[0040] R1 is a functional group selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, a substituted or unsubstituted hemiacetal having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloheteroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroalkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroalkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroacetal having 1 to 30 carbon atoms, and a substituted or unsubstituted heterohemiacetal having 1 to 30 carbon atoms,

[0041] R2 to R5 are each independently the same as or different from one another and are each a functional group selected from the group consisting of hydrogen, hydroxy, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, a substituted or unsubstituted hemiacetal having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloheteroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroalkylaryl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted heteroalkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroacetal having 1 to 30 carbon atoms, and a substituted or unsubstituted heterohemiacetal having 1 to 30 carbon atoms.

[0042] At this time, the alkyl group, cycloalkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group which is the functional group of R1 to R5 may be substituted with a hydroxy group, a halogen atom, an alkyl or alkoxy group having 1 to 12 carbon atoms.

[0043] Also, the alkyl group, cycloalkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group which is the functional group of R1 to R5 may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. Also, the substitution and interruption by the respective substituents of the functional groups of R1 to R5 may be combined. Furthermore, in the present invention, the alkyl group means a linear or branched alkyl group.

[0044] In the above chemical formula 1, R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R2 to R4 are each independently or simultaneously one kind of functional group selected from hydrogen and substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, and R5 may be a hydroxy group.

[0045] In the above chemical formula 1, R1 is one kind of functional group selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, and a substituted or unsubstituted hemiacetal having 1 to 30 carbon atoms, and R2 to R5 may each independently or simultaneously be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The alkyl group which is the functional group of R1 may each independently or simultaneously be substituted with a hydroxy group or an alkyl or alkoxy group having 1 to 12 carbon atoms, or may be interrupted by an oxygen atom, a carbonyl group, or an ester group.

[0046] In the above chemical formula 1, R1 is one kind of functional group selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted acetal having 1 to 30 carbon atoms, and a substituted or unsubstituted hemiacetal having 1 to 30 carbon atoms, R2 and R3 are each independently hydrogen, and R4 and R5 may each independently or simultaneously be one kind of functional group selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 18 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 18 carbon atoms. The alkyl group which is the functional group of R1 may each independently or simultaneously be substituted with a hydroxy group or an alkyl or alkoxy group having 1 to 12 carbon atoms, or may be interrupted by an oxygen atom, a carbonyl group, or an ester group. Further, it is more preferable that R4 and R5 are each independently or simultaneously a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.

[0047] In Chemical Formula 1, R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and each of R2 to R5 can be independently or simultaneously one kind of functional group selected from hydrogen and substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0048] The cured film obtained by using the photosensitive resin composition containing the UV absorber having such a definition is excellent in sensitivity, resolution, transmittance, and lightfast discoloration resistance. Not only can cracks not be observed, but also the reliability of the OLED can be improved. Further, when the photosensitive resin composition is used, it has excellent solubility and does not cause precipitation and cloudiness, and the coating property can be improved.

[0049] Specifically, in the case of a conventional positive photosensitive composition, a composition composed of an alkali-soluble resin and a 1,2-quinonediazide compound is thermally decomposed during post-exposure baking after exposure and development. Therefore, when the light transmittance in the visible light region decreases, or the cured film is exposed to heat at a certain temperature or higher, or absorbs light with a short wavelength of high energy such as ultraviolet rays, some components of the cured film are decomposed and discoloration occurs or impurities are generated, resulting in problems with the reliability of the organic EL element.

[0050] Also, usually, a benzotriazole-based compound is used as a UV absorber in a conventional photosensitive composition, but there are limitations in preventing discoloration of the cured film, and there are problems such as resolution and cloudiness.

[0051] Therefore, the present invention can prevent the problem of discoloration of the cured film by using, as a UV absorber, a substance having a triazine skeleton of Chemical Formula 1 and containing one or more specific phenolic hydroxyl groups and alkoxy groups as functional groups, and can provide excellent light resistance and good heat resistance effects.

[0052] In addition, the UV absorber of the present invention has a higher molar extinction coefficient than the conventionally used benzotriazole-based compounds, and when the same content is used, the UV absorption characteristics are enhanced. Further, the UV absorber of Chemical Formula 3 has a functional group of an alkoxy group together with one or more phenolic hydroxyl groups, and thus undergoes a cross-linking reaction during heat treatment with a compound having an alkoxy such as a siloxane resin. Due to such a cross-linking reaction, it may stably exist during additional heat treatment, long-term storage of the cured film, visible light exposure, etc. Further, the UV absorber exhibits good heat resistance characteristics.

[0053] Such a UV absorber may be contained in an amount of 0.1 to 10 parts by weight or 5 to 10 parts by weight with respect to 100 parts by weight of the siloxane-based copolymer. When the content of the UV absorber is less than 0.1 part by weight, the light resistance is not sufficient, and when it exceeds 10 parts by weight, there is a problem that the sensitivity decreases and it becomes difficult to embody the pattern.

[0054] The UV absorber and the 1,2-quinonediazide compound are contained in a weight ratio of 1:1 to 1:20. When the ratio of the above content is deviated, there may be a problem that the light resistance is not sufficient or the sensitivity decreases, and the contents can be adjusted and used at an appropriate ratio.

[0055] Further, the UV absorber may have an absorption region at 400 nm or less or 280 nm to 380 nm. Specifically, when the photosensitive resin contains 0.1 to 10 parts by weight of the UV absorber, it may have an absorption region at 400 nm or less or 280 nm to 380 nm.

[0056] As an example of such a UV absorber, it may be any one or more selected from the compounds represented by the following Chemical Formula 4 to Chemical Formula 5, Chemical Formula 6-1, Chemical Formula 6-2, Chemical Formula 7 to Chemical Formula 12, but it is not limited to the type as long as it is included in the definition of Chemical Formula 1 described above. [Chemical Formula 4] JPEG0007701350000004.jpg60170

[0057] In Chemical Formula 4, in Chemical Formula 1, R1 is propyl, R2, R3, and R4 are each independently buthoxy, R5 has a hydroxyl structure, and it has a maximum absorption wavelength at 350 nm. [Chemical Formula 5] JPEG0007701350000005.jpg44170

[0058] In Chemical Formula 5, in Chemical Formula 1, R1 is 4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyl], R2, R3, R4, and R5 each independently have a methyl structure, and it has a maximum absorption wavelength at 295 nm. [Chemical Formula 6] JPEG0007701350000006.jpg46170

[0059] In Chemical Formula 6, in Chemical Formula 1, it includes the case where R1 is 4-[2-Hydroxy-3-tridecyloxypropyl] and 4-[2-hydroxy-3-dodecyloxypropyl], R2, R3, R4, and R5 each independently have a methyl structure, and it has a maximum absorption wavelength at 295 nm.

[0060] That is, Chemical Formula 6 means that it consists of a mixture of the following Chemical Formula 6-1 and Chemical Formula 6-2. The mixing ratio of these mixtures of Chemical Formula 6-1 and Chemical Formula 6-2 is not particularly limited and can be, for example, a weight ratio of 1:99 to 99:1. [Chemical Formula 6-1] JPEG0007701350000007.jpg46170[Chemical Formula 6-2] JPEG0007701350000008.jpg46170[Chemical Formula 7] JPEG0007701350000009.jpg60170

[0061] In Chemical Formula 7, in Chemical Formula 1, R1 is Isooctylpropanoate, R2 and R3 are each independently Hydrogen, R4 and R5 are each independently of the structure of Phenyl, and it has a maximum absorption wavelength at 322 nm. [Chemical Formula 8] JPEG0007701350000010.jpg46170

[0062] In Chemical Formula 8, in Chemical Formula 1, R1 is Octyl, R2, R3, R4 and R5 are each independently of the structure of methyl, and it has a maximum absorption wavelength at 287 nm. [Chemical Formula 9] JPEG0007701350000011.jpg53170

[0063] In Chemical Formula 9, in Chemical Formula 1, R1 is 2-(2-ethylhexanoyloxy)ethyl, R2, R3, R4 and R5 are each independently of the structure of hydrogen, and it has a maximum absorption wavelength at 287 nm. [Chemical Formula 10] JPEG0007701350000012.jpg67170

[0064] In Chemical Formula 10, in Chemical Formula 1, R1 is 2-ethylhexyl, R2 is hydrogen, R3 is Methoxy, R4 is 2-ethylhexyloxy, R5 is of the structure of hydroxyl, and it has a maximum absorption wavelength at 340 nm. [Chemical Formula 11] JPEG0007701350000013.jpg51170

[0065] In Chemical Formula 11, in Chemical Formula 1, R1 is 2-ethylhexyl, R2 and R3 are each independently Hydrogen, R4 and R5 are each independently a Phenyl structure, and it has a maximum absorption wavelength at 370 nm. [Chemical Formula 12] JPEG0007701350000014.jpg42170

[0066] In Chemical Formula 12, in Chemical Formula 1, R1 is methyl, R2, R3, R4 and R5 are each independently a Hydrogen structure, and it has a maximum absorption wavelength at 290 nm.

[0067] For the UV absorber, a mixture of two types can be used. As specific examples, i) one selected from the group consisting of a mixture of Chemical Formula 4, Chemical Formula 5, Chemical Formula 6-1 and Chemical Formula 6-2, and Chemical Formula 8; and ii) a mixture of one selected from the group consisting of Chemical Formula 7, Chemical Formula 9 and Chemical Formula 10 can be used.

[0068] As still other examples, for the UV absorber, iii) one selected from the group consisting of Chemical Formula 9 and Chemical Formula 10; and iv) a mixture of one selected from the group consisting of Chemical Formula 11 and Chemical Formula 12 can be used.

[0069] Also, when using the two types of UV absorbers, the mixing ratio of i) and ii) or iii) and iv) can be used at a weight percentage ratio of 25 - 75:75 - 25 based on the total amount of the total UV absorber used.

[0070] d) Solvent In the positive photosensitive resin composition of the present invention, the solvent can be used so as to be 10 - 90% by weight of the solid content of the entire resin composition. Therefore, the solvent content can be appropriately adjusted and used within the range that satisfies the range of the solid content.

[0071] As the solvent in d) above, one or more can be selected from the group consisting of methanol, ethanol, benzyl alcohol, hexyl alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl 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, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether for use.

[0072] e) Other additives The positive photosensitive resin composition according to the present invention may further contain a surfactant within a range that does not damage the effects of the present invention in order to improve coating properties. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and other surfactants.

[0073] In addition, in order to improve the chemical resistance and film adhesion of the composition of the present invention without damaging the effects of the present invention, a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a thermal acid or thermal base generator, a photoacid or photobase generator, a dissolution promoter, a dissolution inhibitor, a stabilizer, an antifoaming agent, etc. that crosslink with a hydroxyl group as necessary can be contained. In addition, the contents of the surfactant and the additive are not particularly limited and can be used as is well known in this field.

[0074] Therefore, as a specific example, the positive photosensitive resin composition of the present invention contains a) a siloxane copolymer, b) a 1,2-quinonediazide compound, (c) a UV absorber, and (d) a solvent, and can further contain one or more of a surfactant and other additives for improving coating properties.

[0075] In the present invention, after mixing the above-described respective components, it is preferable to use the composition after filtering the solution of the positive photosensitive resin composition using a filter having a pore size of 0.1 μm level or the like.

[0076] When a cured film is formed using such a photosensitive resin composition of the present invention, a cured film having a transmittance of 80% or more and less than 95% can be formed based on a film thickness of 3 μm at 400 nm. Method for forming a pattern of a display element and a display element using the same On the other hand, according to another embodiment of the present invention, a cured film containing a cured product of the positive photosensitive resin composition is provided. In addition, a display element containing a cured product of the positive photosensitive resin composition is provided. At this time, according to the present invention, it is also possible to provide a method for forming a pattern of a display element using the positive photosensitive resin composition.

[0077] The OLED display includes a Pixel Defining Layer (hereinafter referred to as PDL) layer that separates the boundaries between self-emitting red, green, and blue pixels and insulates each of them, and an interlayer insulating film having both insulating properties and electrode planarization properties below the PDL layer. At this time, the PDL layer is precisely patterned by a photo-etching process, and a photosensitive resin composition containing a polyamic acid compound has been widely used as a material for forming the PDL layer.

[0078] Therefore, in the present invention, it is possible to provide various display elements including a cured film containing a cured body of a positive photosensitive resin composition having the above-described specific composition, and including a pattern of such a cured film.

[0079] Specifically, the positive photosensitive resin composition is applied on a semiconductor substrate with a certain thickness, pre-dried in a vacuum chamber, and then pre-baked on a hot plate or in an oven, etc., to form a cured film containing a cured body obtained by curing the resin composition.

[0080] Examples of the semiconductor substrate include a silicon substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, and an ITO substrate. Examples of the coating method that can be used include spin coating, slit coating, spin coating after slitting, and inkjet coating. The heat treatment conditions employ, for example, an optimal heating temperature and heating time selected within the range of a temperature of 70°C to 150°C and a time of 0.5 minutes to 30 minutes.

[0081] Also, the thickness of the cured film formed from the positive photosensitive resin composition is, for example, 0.1 μm to 20 μm. The cured film may have a transmittance of 80% or more and less than 95% based on a film thickness of 3 μm at a wavelength of 400 nm.

[0082] The cured film of the present invention is formed from a photosensitive resin composition containing a UV absorber, has a transmittance of less than 95% at a short wavelength of 400 nm, and can prevent the problem of damage to materials such as elements when showing an excessively high transmittance.

[0083] Further, the present invention can form a pattern applicable to a display element using the cured film. That is, the present invention provides a method for forming a pattern of a display element using the positive photosensitive resin composition.

[0084] When the positive photosensitive cured film formed using the positive photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, or KrF using a mask having a predetermined pattern, the 1,2 - quinonediazide derivative contained in the positive photosensitive resin film is carboxylated and oxidized, and the exposed portion becomes soluble in an alkaline developer.

[0085] Thereafter, when development of the exposed portion is performed using an alkaline developer, the exposed portion in the cured film formed of the positive photosensitive resin is removed, and a pattern in the form of a mask is formed. Also, as the developing method, any of a dipping method, a rocking immersion method, etc. can be used. At this time, the developing time is usually 20 seconds to 180 seconds.

[0086] After the alkali development, the positive photosensitive resin cured film is washed with running water for, for example, 20 seconds to 120 seconds, and then dried by compressed air or compressed nitrogen or a rotation method to remove moisture on the substrate, and a film with a formed pattern can be obtained.

[0087] Next, post - baking is performed on the pattern - forming film for thermosetting. Specifically, heating is performed using a hot plate or an oven to obtain a cured film having excellent heat resistance, planarization property, low water absorption, etc. and with a good pattern formed.

[0088] The post-baking is usually carried out at a heating temperature selected within the range of 130°C to 300°C for 5 to 30 minutes in the case of a hot plate or for 20 minutes to 90 minutes in the case of an oven.

[0089] As described above, the cured film formed by the positive photosensitive resin composition of the present invention is not only excellent in performance such as resolution and flatness, but also excellent in weather resistance, so that it is possible to ensure the reliability of an excellent panel, and thus it can be suitably used for applications such as an interlayer insulating film, a planarizing film, or a PDL in various OLED displays.

[0090] That is, the positive photosensitive resin composition can be used for pattern formation for application to an interlayer insulating film of a TFT-LCD, an interlayer insulating film of an OLED, or an interlayer insulating film of an O-TFT; a protective insulating film of a TFT-LCD, a protective insulating film of an OLED, or a protective insulating film of an O-TFT; a gate insulating film of a TFT-LCD, a gate insulating film of an OLED, or a gate insulating film of an O-TFT; a planarizing film of a TFT-LCD, a planarizing film of an OLED, or a planarizing film of an O-TFT; or a pixel define layer of an OLED. A display element including a cured film having such a pattern exhibits excellent insulating properties, heat resistance capable of maintaining a stable form up to about 350°C, can improve the defect rate with respect to moisture, and can also provide excellent effects in light resistance and weather resistance. In addition, the reliability of the display element can be improved.

[0091] Hereinafter, embodiments are presented to assist in the understanding of the present invention. However, the following embodiments are merely examples of the present invention, and the present invention is not limited thereto.

[0092] <Examples and Comparative Examples> A silane copolymer was synthesized using the reactive silane monomers shown in Table 1 below, and the molecular weights of the synthesized silane copolymers are as shown in Table 2. Hereinafter, each synthesis example will be described in detail.

[0093]

Table 1

[0094]

Table 2

[0095] <Examples and Comparative Examples> [Synthesis Example 1]: Production of Siloxane Copolymer (1-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 30 parts by weight of phenyltrimethoxysilane, 30 parts by weight of propyltrimethoxysilane, and 40 parts by weight of tetramethoxysilane were respectively placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% acetic acid aqueous solution was added dropwise, and then the temperature was raised to 60 °C at 5 °C per minute. After maintaining this temperature for 12 hours for condensation polymerization, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (1-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 6,500 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of a gel permeation chromatography (GPC) System using an e2695 Alliance Separation Module manufactured by Waters.

[0096] [Synthesis Example 2]: Production of siloxane copolymer (2-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 20 parts by weight of diphenyldimethoxysilane, 40 parts by weight of methyltrimethoxysilane, and 40 parts by weight of tetraethoxysilane were respectively placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% ammonia aqueous solution was added dropwise, and then the temperature was raised to 60 °C at 5 °C per minute. After maintaining this temperature for 12 hours for condensation polymerization, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (2-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 12,000 (g / mol). At this time, the weight average molecular weight is the polystyrene-equivalent weight average molecular weight measured using GPC.

[0097] [Synthesis Example 3]: Production of Siloxane Copolymer (3-a) Into a 2 L three-necked flask equipped with a thermometer, a condenser, and a stirrer, as reactive silanes, 30 parts by weight of dimethyldimethoxysilane, 40 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 30 parts by weight of tetramethoxysilane were placed, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. After maintaining this temperature for 12 hours for condensation polymerization, the reaction was terminated by cooling to room temperature. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto, and the mixture was distilled under reduced pressure to produce a siloxane copolymer (3-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 13,500 (g / mol). At this time, the weight average molecular weight was the polystyrene-converted weight average molecular weight measured using GPC.

[0098] [Synthesis Example 4]: Production of Siloxane Copolymer (4-a) Into a 2 L three-necked flask equipped with a thermometer, a condenser, and a stirrer, as reactive silanes, 35 parts by weight of dimethyldimethoxysilane, 35 parts by weight of methyltrimethoxysilane, and 30 parts by weight of tetramethoxysilane were placed, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous ammonia solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. After maintaining this temperature for 12 hours for condensation polymerization, the reaction was terminated by cooling to room temperature. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto, and the mixture was distilled under reduced pressure to produce a siloxane copolymer (4-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 8,300 (g / mol). At this time, the weight average molecular weight was the polystyrene-converted weight average molecular weight measured using GPC.

[0099] [Synthesis Example 5]: Production of Siloxane Copolymer (5-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 30 parts by weight of diphenyldimethoxysilane, 30 parts by weight of propyltrimethoxysilane, and 40 parts by weight of tetramethoxysilane were placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. The temperature was maintained for 12 hours for condensation polymerization, and then cooled to room temperature to terminate the reaction. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (5-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 5,500 (g / mol). At this time, the weight average molecular weight was the weight average molecular weight in terms of polystyrene measured using GPC.

[0100] [Synthesis Example 6]: Production of siloxane copolymer (6-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 50 parts by weight of phenyltrimethoxysilane, 40 parts by weight of dimethyldimethoxysilane, and 10 parts by weight of tetraethoxysilane were placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. The temperature was maintained for 12 hours for condensation polymerization, and then cooled to room temperature to terminate the reaction. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (6-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 3,100 (g / mol). At this time, the weight average molecular weight was the weight average molecular weight in terms of polystyrene measured using GPC.

[0101] [Synthesis Example 7]: Production of siloxane copolymer (7-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 25 parts by weight of phenyltrimethoxysilane, 25 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 50 parts by weight of tetramethoxysilane were placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, the reaction was terminated by cooling to room temperature. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (7-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 17,500 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0102] [Synthesis Example 8]: Production of siloxane copolymer (8-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 30 parts by weight of diphenyldimethoxysilane, 10 parts by weight of dimethyldimethoxysilane, 20 parts by weight of propyltrimethoxysilane, and 40 parts by weight of tetraethoxysilane were placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous ammonia solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, the reaction was terminated by cooling to room temperature. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (8-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 7,800 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0103] [Synthesis Example 9]: Production of siloxane copolymer (9-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 70 parts by weight of dimethyldimethoxysilane, 10 parts by weight of methyltrimethoxysilane, and 20 parts by weight of tetraethoxysilane were placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. After maintaining this temperature for 12 hours for condensation polymerization, the reaction was terminated by cooling to room temperature. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (9-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 4,800 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0104] [Synthesis Example 10]: Production of Siloxane Copolymer (10-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 20 parts by weight of methyltrimethoxysilane, 40 parts by weight of dimethyldimethoxysilane, and 40 parts by weight of tetramethoxysilane were placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. After maintaining this temperature for 12 hours for condensation polymerization, the reaction was terminated by cooling to room temperature. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (10-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 11,000 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0105] [Synthesis Example 11]: Production of Siloxane Copolymer (11-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 30 parts by weight of diphenyldimethoxysilane, 30 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 40 parts by weight of tetrapropoxysilane were placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% acetic acid aqueous solution was added dropwise, and then the temperature was raised to 60 °C at a rate of 5 °C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (11-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 3,500 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0106] [Synthesis Example 12]: Production of Siloxane Copolymer (12-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 40 parts by weight of diphenyldimethoxysilane, 45 parts by weight of methyltrimethoxysilane, and 15 parts by weight of tetramethoxysilane were placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% aqueous ammonia solution was added dropwise, and then the temperature was raised to 60 °C at a rate of 5 °C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (12-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 9,200 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0107] [Synthesis Example 13]: Production of Siloxane Copolymer (13-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 35 parts by weight of phenyltrimethoxysilane, 15 parts by weight of methyltrimethoxysilane, and 50 parts by weight of tetraethoxysilane were respectively placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% acetic acid aqueous solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (13-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 22,000 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0108] [Synthesis Example 14]: Production of Siloxane Copolymer (14-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 40 parts by weight of diphenyldimethoxysilane, 15 parts by weight of propyltrimethoxysilane, and 45 parts by weight of tetramethoxysilane were respectively placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% acetic acid aqueous solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (14-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 19,000 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0109] [Synthesis Example 15]: Production of Siloxane Copolymer (15-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 40 parts by weight of phenyltrimethoxysilane, 10 parts by weight of propyltrimethoxysilane, and 50 parts by weight of tetraethoxysilane were placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% acetic acid aqueous solution was added dropwise, and then the temperature was raised to 60 °C at a rate of 5 °C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (15-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 25,000 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0110] [Synthesis Example 16]: Production of siloxane copolymer (16-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 25 parts by weight of diphenyldimethoxysilane, 35 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 40 parts by weight of tetraethoxysilane were placed as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% ammonia aqueous solution was added dropwise, and then the temperature was raised to 60 °C at a rate of 5 °C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (16-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 18,900 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0111] [Synthesis Example 17]: Production of siloxane copolymer (17-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 80 parts by weight of diphenyldimethoxysilane and 20 parts by weight of tetramethoxysilane were each placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous ammonia solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, the reaction was terminated by cooling to room temperature. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (17-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 5,400 (g / mol). At this time, the weight average molecular weight was the weight average molecular weight in terms of polystyrene measured using GPC.

[0112] [Synthesis Example 18]: Production of Siloxane Copolymer (18-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 60 parts by weight of phenyltrimethoxysilane and 40 parts by weight of tetraethoxysilane were each placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, the reaction was terminated by cooling to room temperature. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (18-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 8,700 (g / mol). At this time, the weight average molecular weight was the weight average molecular weight in terms of polystyrene measured using GPC.

[0113] [Synthesis Example 19]: Production of 1,2-Quinonediazide Compound (A) 1 mol of a phenol compound represented by the following chemical formula G was reacted with 2 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride to produce a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound having an esterification degree of 67%. [Chemical formula G] TIFF0007701350000017.tif47170

[0114] [Comparative Synthesis Example 1]: Production of siloxane copolymer (20-a) Into a 2 L three-necked flask equipped with a thermometer, a condenser, and a stirrer, 95 parts by weight of phenyltrimethoxysilane and 5 parts by weight of tetraethoxysilane were placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous ammonia solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. The temperature was maintained for 12 hours for condensation polymerization, and then the reaction was terminated by cooling to room temperature. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto, and the mixture was distilled under reduced pressure to produce a siloxane copolymer (20-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 1,900 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0115] [Comparative Synthesis Example 2]: Production of siloxane copolymer (21-a) Into a 2 L three-necked flask equipped with a thermometer, a condenser, and a stirrer, 95 parts by weight of methyltrimethoxysilane and 5 parts by weight of tetramethoxysilane were placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute. The temperature was maintained for 12 hours for condensation polymerization, and then the reaction was terminated by cooling to room temperature. Thereafter, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto, and the mixture was distilled under reduced pressure to produce a siloxane copolymer (21-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 980 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0116] [Comparative Synthesis Example 3]: Production of siloxane copolymer (22-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 93 parts by weight of 3-glycidoxypropyltrimethoxysilane and 7 parts by weight of tetrapropoxysilane were put as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% acetic acid aqueous solution was added dropwise, and then the temperature was raised to 60 °C at 5 °C per minute. After maintaining this temperature for 12 hours for condensation polymerization, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (22-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 38,000 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0117] [Comparative Synthesis Example 4]: Production of Siloxane Copolymer (23-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 4 parts by weight of diphenyldimethoxysilane, 4 parts by weight of dimethyldimethoxysilane, and 92 parts by weight of tetramethoxysilane were put as reactive silanes, and they were slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10 °C, 30 parts by weight of a 5% acetic acid aqueous solution was added dropwise, and then the temperature was raised to 60 °C at 5 °C per minute. After maintaining this temperature for 12 hours for condensation polymerization, it was cooled to room temperature to terminate the reaction. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto and distilled under reduced pressure to produce a siloxane copolymer (23-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 8,800 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0118] [Comparative Synthesis Example 5]: Production of Siloxane Copolymer (24-a) Into a 2 L three-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 5 parts by weight of diphenyldimethoxysilane, 4 parts by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 91 parts by weight of tetramethoxysilane were placed as reactive silanes, and the mixture was slowly stirred at room temperature for 1 hour under a nitrogen atmosphere. After cooling the reaction solution to 10°C, 30 parts by weight of a 5% aqueous acetic acid solution was added dropwise, and then the temperature was raised to 60°C at a rate of 5°C per minute and maintained at that temperature for 12 hours for condensation polymerization. After that, the reaction was terminated by cooling to room temperature. Then, the catalyst and unreacted monomers were removed by a water washing and extraction process. 30 parts by weight of PGMEA was added thereto, and distillation under reduced pressure was performed to produce a siloxane copolymer (24-a) having a solid content of 40%. The weight average molecular weight of the siloxane copolymer was 31,000 (g / mol). At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0119] [Reference Synthesis Example 1]: Production of Siloxane Copolymer (1-b) The procedure was carried out in the same manner as in Synthesis Example 1 except for the process of removing the catalyst and unreacted monomers by a water washing and extraction process. At this time, the weight average molecular weight was 6,800 (g / mol) which was the polystyrene-equivalent weight average molecular weight measured using GPC. At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0120] [Reference Synthesis Example 2]: Production of Siloxane Copolymer (6-b) The procedure was carried out in the same manner as in Synthesis Example 6 except for the process of removing the catalyst and unreacted monomers by a water washing and extraction process. At this time, the weight average molecular weight was 2,900 (g / mol) which was the polystyrene-equivalent weight average molecular weight measured using GPC. At this time, the weight average molecular weight was the polystyrene-equivalent weight average molecular weight measured using GPC.

[0121] [Reference Synthesis Example 3]: Production of Siloxane Copolymer (8-b) Except for the process of removing the catalyst and unreacted monomers by washing with water and extraction in Synthesis Example 8, it was carried out in the same manner. At this time, the weight-average molecular weight was 7,600 (g / mol) in terms of polystyrene weight-average molecular weight measured using GPC. At this time, the weight-average molecular weight is the polystyrene weight-average molecular weight measured using GPC.

[0122] [Reference Synthesis Example 4]: Production of siloxane copolymer (11-b) Except for the process of removing the catalyst and unreacted monomers by washing with water and extraction in Synthesis Example 11, it was carried out in the same manner. At this time, the weight-average molecular weight was 3,800 (g / mol) in terms of polystyrene weight-average molecular weight measured using GPC. At this time, the weight-average molecular weight is the polystyrene weight-average molecular weight measured using GPC.

[0123] [Reference Synthesis Example 5]: Production of siloxane copolymer (12-b) Except for the process of removing the catalyst and unreacted monomers by washing with water and extraction in Synthesis Example 12, it was carried out in the same manner. At this time, the weight-average molecular weight was 9,700 (g / mol) in terms of polystyrene weight-average molecular weight measured using GPC. At this time, the weight-average molecular weight is the polystyrene weight-average molecular weight measured using GPC.

[0124] [UV Absorbent] The UV absorbents used in the following Examples, Comparative Examples, and Reference Examples are as follows. [Chemical Formula 4] JPEG0007701350000018.jpg60170

[0125] In Chemical Formula 4 above, in Chemical Formula 1, R1 is propyl, R2, R3, and R4 are each independently buthoxy, R5 has a hydroxyl structure, and has a maximum absorption wavelength at 350 nm. [Chemical Formula 5] JPEG0007701350000019.jpg44170

[0126] In Chemical Formula 5, in Chemical Formula 1, R1 is 4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyl], R2, R3, R4, and R5 are each independently of the structure of methyl, and it has a maximum absorption wavelength at 295 nm. [Chemical Formula 6] JPEG0007701350000020.jpg46170

[0127] In Chemical Formula 6, in Chemical Formula 1, R1 includes the cases where it is 4-[2-Hydroxy-3-tridecyloxypropyl] and 4-[2-hydroxy-3-dodecyloxypropyl], R2, R3, R4, and R5 are each independently of the structure of methyl, and it has a maximum absorption wavelength at 295 nm.

[0128] Chemical Formula 6 means that it consists of a mixture of the following Chemical Formula 6-1 and Chemical Formula 6-2. In the following Examples, Comparative Examples, and Reference Examples, TINUVIN 400 (product name) corresponding to Chemical Formula 6 was used. [Chemical Formula 6-1] JPEG0007701350000021.jpg46170[Chemical Formula 6-2] JPEG0007701350000022.jpg46170[Chemical Formula 7] JPEG0007701350000023.jpg60170

[0129] In Chemical Formula 7, in Chemical Formula 1, R1 is Isooctylpropanoate, R2 and R3 are each independently Hydrogen, R4 and R5 are each independently of the structure of Phenyl, and it has a maximum absorption wavelength at 322 nm. [Chemical Formula 8] JPEG0007701350000024.jpg46170

[0130] In Chemical Formula 8, in Chemical Formula 1, R1 is octyl, R2, R3, R4, and R5 are each independently of the methyl structure, and it has a maximum absorption wavelength at 287 nm. [Chemical Formula 9] JPEG0007701350000025.jpg53170

[0131] In Chemical Formula 9, in Chemical Formula 1, R1 is 2-(2-ethylhexanoyloxy)ethyl, R2, R3, R4, and R5 are each independently of the hydrogen structure, and it has a maximum absorption wavelength at 287 nm. [Chemical Formula 10] JPEG0007701350000026.jpg67170

[0132] In Chemical Formula 10, in Chemical Formula 1, R1 is 2-ethylhexyl, R2 is hydrogen, R3 is methoxy, R4 is 2-ethylhexyloxy, R5 is of the hydroxyl structure, and it has a maximum absorption wavelength at 340 nm. [Chemical Formula 11] JPEG0007701350000027.jpg51170

[0133] In Chemical Formula 11, in Chemical Formula 1, R1 is 2-ethylhexyl, R2 and R3 are each independently of hydrogen, R4 and R5 are each independently of the phenyl structure, and it has a maximum absorption wavelength at 370 nm. [Chemical Formula 12] JPEG0007701350000028.jpg42170

[0134] In Chemical Formula 12, in Chemical Formula 1, R1 is methyl, R2, R3, R4, and R5 are each independently in the structure of hydrogen, and it has a maximum absorption wavelength at 290 nm. [Chemical Formula 13] JPEG0007701350000029.jpg88170 The structure is CAS No. 116244-12-3, Uvinul® T150, and it has a maximum absorption wavelength at 310 nm. [Chemical Formula 14] JPEG0007701350000030.jpg59170

[0135] The structure is CAS No. 31274-51-8, Tris-biphenyl triazine (TBPT), and it has a maximum absorption wavelength at 305 nm. [Chemical Formula 15] JPEG0007701350000031.jpg28170 The structure is CAS No. 127519-17-9, TINUVIN® 384-2, and it has a maximum absorption wavelength at 345 nm. [Chemical Formula 16] JPEG0007701350000032.jpg31170 The structure is CAS No. 102577-46-8, TINUVIN® 1130, and it has a maximum absorption wavelength at 348 nm. [Chemical Formula 17] JPEG0007701350000033.jpg49170 The structure is CAS No. 70321-86-7, TINUVIN® 900, and it has a maximum absorption wavelength at 348 nm. Manufacture of Positive Photoresist Composition

[0136] [Example 1] To 100 parts by weight of the siloxane copolymer (1-a) produced in Synthesis Example 1, 23 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 and 8 parts by weight of the compound of Chemical Formula 4 as a UV absorber were mixed, and the mixture was dissolved in propylene glycol methyl ether acetate so that the solid content of the mixture became 30 parts by weight, and then filtered through a 0.1-μm Millipore filter to produce a positive photosensitive resin composition.

[0137] [Example 2] A photosensitive resin composition was produced in the same manner as in Example 1, except that the compound of Chemical Formula 5 was used instead of the compound of Chemical Formula 4 as the UV absorber in Example 1.

[0138] [Example 3] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (2-a) of Synthesis Example 2 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 and the compound of Chemical Formula 6 was used instead of the compound of Chemical Formula 4 in Example 1.

[0139] [Example 4] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (2-a) of Synthesis Example 2 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 and the compound of Chemical Formula 8 was used instead of the compound of Chemical Formula 4 in Example 1.

[0140] [Example 5] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (3-a) of Synthesis Example 3 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 and the compound of Chemical Formula 10 was used instead of the compound of Chemical Formula 4 in Example 1.

[0141] [Example 6] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (3-a) of Synthesis Example 3 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 12 was used instead of Chemical Formula 4.

[0142] [Example 7] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (4-a) of Synthesis Example 4 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 9 was used instead of Chemical Formula 4.

[0143] [Example 8] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (4-a) of Synthesis Example 4 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 11 was used instead of Chemical Formula 4.

[0144] [Example 9] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (5-a) of Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 7 was used instead of Chemical Formula 4.

[0145] [Example 10] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (5-a) of Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1.

[0146] [Example 11] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (6-a) of Synthesis Example 6 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 5 was used instead of Chemical Formula 4.

[0147] [Example 12] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (6-a) of Synthesis Example 6 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 6 was used instead of Chemical Formula 4.

[0148] [Example 13] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (7-a) of Synthesis Example 7 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 8 was used instead of Chemical Formula 4.

[0149] [Example 14] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (7-a) of Synthesis Example 7 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 10 was used instead of Chemical Formula 4.

[0150] [Example 15] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (8-a) of Synthesis Example 8 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 12 was used instead of Chemical Formula 4.

[0151] [Example 16] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (8-a) of Synthesis Example 8 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 9 was used instead of Chemical Formula 4.

[0152] [Example 17] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (9-a) of Synthesis Example 9 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 11 was used instead of Chemical Formula 4.

[0153] [Example 18] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (9-a) of Synthesis Example 9 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 7 was used instead of Chemical Formula 4.

[0154] [Example 19] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (10-a) of Synthesis Example 10 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1.

[0155] [Example 20] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (10-a) of Synthesis Example 10 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 5 was used instead of Chemical Formula 4.

[0156] [Example 21] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (11-a) of Synthesis Example 11 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 6 was used instead of Chemical Formula 4.

[0157] [Example 22] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (11-a) of Synthesis Example 11 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 6 was used instead of Chemical Formula 4.

[0158] [Example 23] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (12-a) of Synthesis Example 12 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 10 was used instead of Chemical Formula 4.

[0159] [Example 24] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (12-a) of Synthesis Example 12 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 12 was used instead of Chemical Formula 4.

[0160] [Example 25] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (13-a) of Synthesis Example 13 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 9 was used instead of Chemical Formula 4.

[0161] [Example 26] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (13-a) of Synthesis Example 13 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 11 was used instead of Chemical Formula 4.

[0162] [Example 27] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (14-a) of Synthesis Example 14 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 7 was used instead of Chemical Formula 4.

[0163] [Example 28] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (14-a) of Synthesis Example 14 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1.

[0164] [Example 29] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (15-a) of Synthesis Example 15 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 5 was used instead of Chemical Formula 4.

[0165] [Example 30] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (15-a) of Synthesis Example 15 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 6 was used instead of Chemical Formula 4.

[0166] [Example 31] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (16-a) of Synthesis Example 16 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 8 was used instead of Chemical Formula 4.

[0167] [Example 32] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (16-a) of Synthesis Example 16 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 10 was used instead of Chemical Formula 4.

[0168] [Example 33] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (17-a) of Synthesis Example 17 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 12 was used instead of Chemical Formula 4.

[0169] [Example 34] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (17-a) of Synthesis Example 17 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 9 was used instead of Chemical Formula 4.

[0170] [Example 35] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (18-a) of Synthesis Example 18 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 11 was used instead of Chemical Formula 4.

[0171] [Example 36] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (18-a) of Synthesis Example 18 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and Chemical Formula 7 was used instead of Chemical Formula 4.

[0172] [Example 37] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (2-a) of Synthesis Example 2 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 4 parts by weight of Chemical Formula 6 and 4 parts by weight of Chemical Formula 12 were used instead of 8 parts by weight of Chemical Formula 4.

[0173] [Example 38] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (2-a) of Synthesis Example 2 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 4 parts by weight of Chemical Formula 8 and 4 parts by weight of Chemical Formula 9 were used in admixture instead of 8 parts by weight of Chemical Formula 4.

[0174] [Example 39] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (3-a) of Synthesis Example 3 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 6 parts by weight of Chemical Formula 10 and 2 parts by weight of Chemical Formula 12 were used in admixture instead of 8 parts by weight of Chemical Formula 4.

[0175] [Example 40] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (3-a) of Synthesis Example 3 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 6 parts by weight of Chemical Formula 9 and 2 parts by weight of Chemical Formula 11 were used in admixture instead of 8 parts by weight of Chemical Formula 4.

[0176] [Example 41] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (4-a) of Synthesis Example 4 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 2 parts by weight of Chemical Formula 4 and 6 parts by weight of Chemical Formula 7 were used in admixture instead of 8 parts by weight of Chemical Formula 4.

[0177] [Example 42] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (4-a) of Synthesis Example 4 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 6 parts by weight of Chemical Formula 5 and 2 parts by weight of Chemical Formula 10 were used in admixture instead of 8 parts by weight of Chemical Formula 4.

[0178] [Example 43] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 0.5 part by weight was used instead of 8 parts by weight of Chemical Formula 4.

[0179] [Example 44] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 8 parts by weight was used instead of 23 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19, and 8 parts by weight of Chemical Formula 12 was used instead of 8 parts by weight of Chemical Formula 4.

[0180] [Example 45] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 8 parts by weight was used instead of 23 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19, and 0.5 part by weight of Chemical Formula 8 was used instead of 8 parts by weight of Chemical Formula 4.

[0181] [Example 46] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 48 parts by weight was used instead of 23 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19, and 8 parts by weight of Chemical Formula 9 was used instead of 8 parts by weight of Chemical Formula 4.

[0182] [Example 47] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 48 parts by weight was used instead of 23 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19, and 0.5 part by weight of Chemical Formula 6 was used instead of 8 parts by weight of Chemical Formula 4.

[0183] [Comparative Example] 1) Production of a siloxane copolymer without using the UV absorber of the present invention In order to compare the physical properties when the UV absorber of the present invention is not used, photosensitive resin compositions of Comparative Examples 1 to 11 were produced. [Comparative Example 1] A photosensitive resin composition was produced in the same manner as in Example 1, except that Chemical Formula 13 was used instead of Chemical Formula 4 in Example 1. [Comparative Example 2] A photosensitive resin composition was produced in the same manner as in Example 1, except that Chemical Formula 14 was used instead of Chemical Formula 4 in Example 1. [Comparative Example 3] A photosensitive resin composition was produced in the same manner as in Example 1, except that Chemical Formula 16 was used instead of Chemical Formula 4 in Example 1. [Comparative Example 4] A photosensitive resin composition was produced in the same manner as in Example 1, except that Chemical Formula 17 was used instead of Chemical Formula 4 in Example 1. [Comparative Example 5] A photosensitive resin composition was produced in the same manner as in Example 1, except that Chemical Formula 15 was used instead of Chemical Formula 4 in Example 1.

[0184] [Comparative Example 6] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (5-a) of Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 in Example 1, and Chemical Formula 13 was used instead of Chemical Formula 4. [Comparative Example 7] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (5-a) of Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 in Example 1, and Chemical Formula 14 was used instead of Chemical Formula 4. [Comparative Example 8] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (5-a) of Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 in Example 1, and Chemical Formula 16 was used instead of Chemical Formula 4. [Comparative Example 9] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (5-a) of Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 in Example 1, and Chemical Formula 17 was used instead of Chemical Formula 4. [Comparative Example 10] A photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (5-a) of Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1 in Example 1, and Chemical Formula 15 was used instead of Chemical Formula 4.

[0185] [Comparative Example 11] A photosensitive resin composition was produced in the same manner as in Example 1, except that no UV absorber was used in Example 1. 2) Production of Siloxane Copolymer with Changed Content of Quinonediazide or Type of UV Absorber Unlike Example 1 of the present invention, in order to compare the physical properties when the content of quinonediazide is different and no UV absorber of the present invention is used, or when different types of UV absorbers from the present invention are mixed together, photosensitive resin compositions of Comparative Examples 12 to 18 were produced. [Comparative Example 12] A photosensitive resin composition was produced in the same manner as in Example 1, except that 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and no UV absorber was used. [Comparative Example 13] A photosensitive resin composition was produced in the same manner as in Example 1, except that 3 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight in Example 1, and no UV absorber was used. [Comparative Example 14] A photosensitive resin composition was produced in the same manner as in Example 1, except that 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight in Example 1, and 4 parts by weight of Chemical Formula 13 and 4 parts by weight were used instead of 8 parts by weight of Chemical Formula 4 as the UV absorber. [Comparative Example 15] In Example 1, 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 4 parts by weight of the compound of Chemical Formula 5 and 4 parts by weight of the compound of Chemical Formula 14 were used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. A photosensitive resin composition was produced in the same manner as in Example 1, except for the above.

[0186] [Comparative Example 16] In Example 1, 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 9 parts by weight of the compound of Chemical Formula 10 and 1 part by weight of the compound of Chemical Formula 15 were used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. A photosensitive resin composition was produced in the same manner as in Example 1, except for the above. [Comparative Example 17] In Example 1, 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 9 parts by weight of the compound of Chemical Formula 6 and 1 part by weight of the compound of Chemical Formula 17 were used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. A photosensitive resin composition was produced in the same manner as in Example 1, except for the above. [Comparative Example 18] In Example 1, 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 9 parts by weight and 1 part by weight of the compound of Chemical Formula 16 were used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. A photosensitive resin composition was produced in the same manner as in Example 1, except for the above.

[0187] [Reference Example] 1) Production of a siloxane copolymer with a modified siloxane copolymer In order to compare the physical properties in the cases of Comparative Synthesis Examples 1 to 10 produced by changing the reactive silane monomer instead of the siloxane copolymer of Synthesis Example 1 used in the present invention, photosensitive resin compositions of Reference Examples 1 to 10 were produced. [Reference Example 1] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (20-a) of Comparative Synthesis Example 1 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1. [Reference Example 2] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (21-a) of Comparative Synthesis Example 2 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 6 was used instead of 8 parts by weight of Chemical Formula 4. [Reference Example 3] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (22-a) of Comparative Synthesis Example 3 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 10 was used instead of 8 parts by weight of Chemical Formula 4. [Reference Example 4] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (23-a) of Comparative Synthesis Example 4 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 9 was used instead of 8 parts by weight of Chemical Formula 4. [Reference Example 5] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (24-a) of Comparative Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 7 was used instead of 8 parts by weight of Chemical Formula 4.

[0188] [Reference Example 6] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (1-b) of Reference Synthesis Example 1 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 11 was used instead of 8 parts by weight of Chemical Formula 4. [Reference Example 7] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (6-b) of Reference Synthesis Example 2 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 12 was used instead of 8 parts by weight of Chemical Formula 4. [Reference Example 8] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (8-b) of Reference Synthesis Example 3 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 8 was used instead of 8 parts by weight of Chemical Formula 4. [Reference Example 9] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (11-b) of Reference Synthesis Example 4 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 8 parts by weight of Chemical Formula 5 was used instead of 8 parts by weight of Chemical Formula 4. [Reference Example 10] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that the siloxane copolymer (12-b) of Reference Synthesis Example 5 was used instead of the siloxane copolymer (1-a) of Synthesis Example 1, and 4 parts by weight of Chemical Formula 4 and 4 parts by weight of Chemical Formula 10 were used instead of 8 parts by weight of Chemical Formula 4.

[0189] 2) Production of Siloxane Copolymer with Altered Content of Quinonediazide and / or UV Absorbent Unlike Example 1 of the present invention, photosensitive resin compositions of Reference Examples 11 to 18 were produced to compare the physical properties when the content of quinonediazide and / or UV absorbent was outside the scope of the present invention.

[0190] [Reference Example 11] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 8 parts by weight of Chemical Formula 6 was used as the UV absorbent. [Reference Example 12] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 54 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 12 parts by weight of the compound of Chemical Formula 7 was used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. [Reference Example 13] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 12 parts by weight of the compound of Chemical Formula 6 was used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. [Reference Example 14] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 3 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 8 parts by weight of the compound of Chemical Formula 10 was used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. [Reference Example 15] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 3 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 12 parts by weight of the compound of Chemical Formula 12 was used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber.

[0191] [Reference Example 16] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 12 parts by weight of the compound of Chemical Formula 9 was used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. [Reference Example 17] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 12 parts by weight of the compound of Chemical Formula 7 was used instead of 8 parts by weight of the compound of Chemical Formula 4 as the UV absorber. [Reference Example 18] In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1, except that 3 parts by weight of the 1,2-naphthoquinonediazide compound (A) produced in Synthesis Example 19 was used instead of 23 parts by weight, and 6 parts by weight of the compound of Chemical Formula 11 and 6 parts by weight of the compound of Chemical Formula 4 were used instead of 8 parts by weight as the UV absorber.

[0192] [Experimental Example] For each of the above Examples, Reference Examples, and Comparative Examples, sensitivity, resolution, transmittance, lightfast discoloration, crack, precipitation, clouding, and the reliability of the OLED were measured and shown in Tables 1 and 2 below.

[0193] i) Sensitivity Using a predetermined pattern mask on the film formed as described above, ultraviolet light with an intensity of 20 mW / cm 2 at 435 nm was irradiated with a Dose amount based on a CD of 15 μm line&Space 1:1. After that, it was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23°C for 1 minute and then washed with ultrapure water for 1 minute. Thereafter, it was cured in an oven at 250°C for 60 minutes to obtain a pattern cured film with a thickness of 3 μm.

[0194] ii) Resolution Measure the minimum size at which a pattern is normally formed in the pattern cured film formed during the sensitivity measurement in i) above. When the minimum size is less than 3 μm, it is indicated as O, when it is less than 3 - 5 μm, it is indicated as β, and when it is 5 μm or more, it is indicated as ×.

[0195] iii) Transmittance and lightfast discoloration For the evaluation of transmittance and lightfast discoloration, the transmittance of the pattern film at 400 nm was measured using a spectrophotometer for the pattern cured film formed during the sensitivity measurement in i) above. Also, in order to measure the lightfast discoloration, after irradiating with 500 J of energy using a Metal Halide Lamp, the transmittance change rate was measured. When the transmittance change rate is 10% or more, it is indicated as ×, when it is less than 5 - 10%, it is indicated as β, and when it is less than 5%, it is indicated as ○.

[0196] iv) Crack The evaluation of cracks was carried out by visually inspecting the transparency evaluation substrate and observing it under a microscope at 100 times magnification. When cracks were observed, it was marked as ×; when cracks were observed only in the coating frame, it was marked as β; when no cracks were observed, it was marked as ○.

[0197] e) Precipitation For the evaluation of precipitation, after applying a positive photosensitive resin composition manufactured using a spin coater on a Glass substrate, pre-baking was performed on a hot plate at 110 °C for 2 minutes to form a film with a thickness of 3.2 μm. Then, visual inspection and observation under a microscope at 100 times magnification were carried out to observe whether precipitation occurred due to insufficient solubility. When no precipitation occurred, it was marked as ○; when precipitation occurred, it was marked as ×.

[0198] f) Cloudiness For the evaluation of cloudiness, after applying a positive photosensitive resin composition manufactured using a spin coater on a Glass substrate, pre-baking was performed on a hot plate at 110 °C for 2 minutes to form a film with a thickness of 3.2 μm. Then, it was measured with a Haze meter. When the value was less than 0 to 0.5, it was marked as ○; when the value was between 0.5 and less than 1, it was marked as β; when the value was 1 or more, it was marked as ×.

[0199] g) Reliability of OLED In the same manner as the measurement of sensitivity in item a) above, a pattern film was formed on a patterned ITO substrate as shown in Fig. 1, and EL was deposited. Al was deposited on the top with a Cathod electrode, and an encapsulation process was performed. The time T when the luminance dropped by 3% with the device turned on under the conditions of 85 °C and 85% RH was evaluated. 97 When it was ensured for 1000 hours or more, it was marked as ○; when it was less than 1000 hours, it was marked as ×.

[0200] <Experimental Example 1> Comparison of physical properties depending on the type of UV absorber The physical properties of Examples 1 to 36 and Comparative Examples 1 to 12 without using the UV absorber of the present invention were compared, and the results are shown in Tables 3, 4, and 5, respectively.

[0201]

Table 3

[0202]

Table 4

[0203]

Table 5

[0204] From Table 3, Table 4, and Table 5 above, it can be seen that the positive photosensitive resin compositions manufactured in Examples 1 to 36 according to the present invention, by using a specific UV absorber of Chemical Formula 1 together with a siloxane copolymer and a quinonediazide compound, are not only excellent in performance such as sensitivity and resolution overall compared to Comparative Examples 1 to 11, but also excellent in weather resistance, that is, lightfastness discoloration resistance. Thus, excellent panel reliability is ensured, and it has been confirmed that it can be usefully applied to an interlayer insulating film, a planarizing film, or a PDL, etc. in various OLED displays.

[0205] On the other hand, in the case of Comparative Examples 1 to 10, they contain a benzotriazole-based or benzotriazine-based UV absorber different from the present invention. Even if any one of the physical properties such as sensitivity, transmittance, lightfastness discoloration, cracking, and clouding is excellent, the remaining physical properties are poor, resulting in a decrease in the reliability of the OLED. Also, in Comparative Example 11, since the UV absorber according to the present invention is not used together, the lightfastness discoloration resistance and the reliability of the OLED have decreased.

[0206] <Experimental Example 2> Comparison of Physical Properties Depending on the Type of Siloxane Copolymer The physical properties of Comparative Examples 12 to 18, in which the content of quinonediazide is outside the scope of the present invention, or the UV absorber of the present invention is not used, or a different type of UV absorber from the present invention is mixed together, were compared with those of Example 1 above. The results are shown in Table 6.

[0207]

Table 6

[0208] According to Table 6 above, compared with Example 1 according to the present invention, in Comparative Examples 12 and 13, the content of quinonediazide was outside the scope of the present invention, resulting in poor resolution. In particular, since no UV absorber was used, the lightfast discoloration resistance was also poor, and generally the reliability of the panel was poor. Also, in Comparative Examples 14 to 18, even when the absorber of the present invention was used, a benzotriazole-based or benzotriazine-based UV absorber different from the present invention was included, and the content of the quinonediazide compound was also relatively excessively used. Even if any one of the physical properties such as sensitivity, transmittance, lightfast discoloration, cracking, and clouding was excellent, the remaining physical properties were poor, and the reliability of the OLED decreased.

[0209] <Experimental Example 3> Comparison of Physical Properties Depending on the Type of Siloxane Copolymer The physical properties were compared for Reference Examples 1 to 10 using a siloxane copolymer different from that of Example 1, and the results are shown in Table 7.

[0210]

Table 7

[0211] As can be seen from Table 7 above, when different types of siloxane copolymers are included compared with Example 1, even if the UV absorber is the same as that of the present invention, it can be seen that some characteristics of the physical properties such as sensitivity, transmittance, lightfast discoloration, cracking, and clouding are insufficient. Thus, it was found that the characteristics can be further improved when using a siloxane copolymer having a specific structure.

[0212] <Experimental Example 4> Comparison of Physical Properties Depending on the Type of Siloxane Copolymer The physical properties of Example 1 and Reference Examples 11 to 18 in which the content of quinonediazide and / or UV absorber is outside the scope of the present invention were compared, and the results are shown in Table 8.

[0213]

Table 8

[0214] As can be seen from Table 8 above, compared with Example 1, in Comparative Examples 11 and 12, the content of the quinonediazide compound was too high, resulting in poor resolution and a decrease in the reliability of the OLED. In particular, in Comparative Example 12, the content of the UV absorber was too high, resulting in a clouding phenomenon.

[0215] Also, in the case of Comparative Examples 13 to 18, it was found that the content of the quinonediazide compound was too low or the content of the UV absorber was too high, and all physical properties such as sensitivity, transmittance, lightfast discoloration, cracking, and clouding could not be satisfied.

[0216] <Experimental Example 5> Comparison of Physical Properties According to Content Ratio of UV Absorber In order to compare the physical properties according to the content ratio of the quinonediazide and the UV absorber, physical property evaluations were performed with the compositions as shown in the following table, and the results are shown in Table 9.

[0217]

Table 9

[0218] As can be seen from Table 9 above, it was found that depending on the content ratio of the UV absorber and the quinonediazide compound, the sensitivity decreased slightly or the lightfast discoloration effect tended to decrease.

Claims

1. a) A siloxane copolymer; b) A 1,2-quinonediazide compound; c) One or more UV absorbers; and d) A solvent; The positive photosensitive resin composition containing the UV absorber is any one or more selected from the compounds represented by the following Chemical Formula 4, Chemical Formula 5, Chemical Formula 6-1, Chemical Formula 6-2, Chemical Formula 7 to Chemical Formula 12: [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6-1] [Chemical Formula 6-2] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] 。

2. a) 100 parts by weight of the siloxane copolymer; b) 5 to 50 parts by weight of the 1,2-quinonediazide compound; and c) 0.1 to 10 parts by weight of the UV absorber; The positive photosensitive resin composition according to Claim 1, wherein d) The solvent is contained so as to be 10 to 90% by weight of the solid content of the entire resin composition.

3. The siloxane copolymer is obtained by hydrolyzing and condensation polymerizing i) 10 to 90 parts by weight of a silane compound represented by the following Chemical Formula 2 and ii) 10 to 90 parts by weight of a silane compound represented by the following Chemical Formula 3 with respect to 100 parts by weight of the total monomers. The positive photosensitive resin composition according to Claim 1. [Chemical Formula 2] (R ６ ) ｎ Si(R ７ ) ４－ｎ In the Chemical Formula 2, R ６ are each independently the same as or different from one another and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ７ are each independently the same as or different from one another and are a hydrogen atom, an alkoxy or chloro group, n is an integer of 1 to 3, [Chemical Formula 3] Si(OR ８ ) ４ In the Chemical Formula 3, R ８ are each independently the same as or different from one another and are a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group.

4. The positive photosensitive resin composition according to Claim 1, wherein the siloxane copolymer contains a copolymer having a content of unreacted monomers of less than 10% by weight and a residual catalyst content of less than 2,000 ppm.

5. The positive photosensitive resin composition according to Claim 1, wherein the siloxane copolymer has a polystyrene-equivalent weight average molecular weight of 1,000 g / mol to 30,000 g / mol.

6. The positive photosensitive resin composition according to Claim 1, wherein the 1,2-quinonediazide compound is one or more selected from the group consisting of 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester.

7. The UV absorber is i) One selected from the group consisting of a mixture of Chemical Formula 4, Chemical Formula 5, Chemical Formula 6-1 and Chemical Formula 6-2, and Chemical Formula 8; and ii) A mixture of one selected from the group consisting of Chemical Formula 7, Chemical Formula 9 and Chemical Formula 10; or iii) One selected from the group consisting of Chemical Formula 9 and Chemical Formula 10; and iv) A positive photosensitive resin composition according to claim 1, which is two kinds of mixtures containing one kind of mixture selected from the group consisting of Chemical Formula 11 and Chemical Formula 12.

8. As the solvent in d), one or more are selected from the group consisting of methanol, ethanol, benzyl alcohol, hexyl alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl 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, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether. The positive photosensitive resin composition according to claim 1.

9. The positive photosensitive resin composition according to claim 1, which contains a UV absorber and a 1,2-quinonediazide compound in a weight ratio of 1:1 to 1:

20.

10. A cured film containing a cured product of the positive photosensitive resin composition according to any one of claims 1 to 9.

11. The cured film according to claim 10, wherein the transmittance at a wavelength of 400 nm and a film thickness of 3 μm is 80% or more and less than 95%.

12. A display element containing a cured product of the positive photosensitive resin composition according to any one of claims 1 to 9.

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