TWI710855B - Photosensitive resin composition and photo-cured pattern prepared from the same - Google Patents

Abstract

The present invention provides a photosensitive resin composition with improved chemical resistance and developability to solvents and a photocurable pattern produced therefrom. The present invention relates to a photosensitive resin composition and a photocurable pattern produced therefrom. In more detail, it relates to a photosensitive resin composition and a photocurable pattern produced therefrom, by making the photosensitive resin composition contain an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, wherein the polymerizable The compound includes a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2, so that chemical resistance to solvents and developability are improved at the same time.

Description

Photosensitive resin composition and photocurable pattern produced therefrom

The present invention relates to a photosensitive resin composition and a photocurable pattern produced therefrom. In more detail, it relates to a negative photosensitive resin composition with improved chemical properties and a photocurable pattern produced therefrom.

In the display field, photosensitive resin compositions are used in order to form various photocurable patterns such as photoresist, insulating film, protective film, black matrix, and columnar spacer. Specifically, the photosensitive resin composition is selectively exposed and developed through a photolithography process to form a desired photocurable pattern. In this process, in order to increase the yield of the process and improve the physical properties of the application object, it is necessary High-sensitivity photosensitive resin composition.

The pattern formation of the photosensitive resin composition is performed by, for example, a photolithography process including a change in the polarity of a polymer caused by a photoreaction and a crosslinking reaction. After exposure, the change characteristics of the solubility with respect to a developer such as an alkaline aqueous solution can be used.

According to the solubility of the photosensitive part for development, the pattern formation system using the photosensitive resin composition is classified into a positive type and a negative type. The positive photoresist is a method in which the exposed part is dissolved in a developing solution to form a pattern, and the negative photoresist is a method in which the exposed part is insoluble in the developing solution and the unexposed part is dissolved to form a pattern. The positive type and the negative type are different from each other depending on the binder resin, crosslinking agent, etc. used.

In recent years, the use of touch screens with touch panels has increased dramatically, and recently, flexible touch screens have received a lot of attention. Therefore, various substrates and other materials used in touch screens have been required for flexibility. Therefore, the usable raw materials are limited to flexible polymer raw materials, and the manufacturing process is also required to be carried out under milder conditions.

Therefore, the curing conditions of the photosensitive resin composition also require low-temperature curing rather than conventional high-temperature curing. However, low-temperature curing has the problem of reduced reactivity and reduced durability of the formed pattern.

Korean Patent No. 1302508 discloses a photosensitive resin composition, which contains a copolymer polymerized using a cyclohexenyl acrylate monomer, which has excellent heat resistance and light resistance and can improve sensitivity. However, the composition does not meet the required durability under low-temperature curing conditions.

Prior art literature

Patent literature

Patent Document 1: Korean Patent No. 1302508

The object of the present invention is to provide a photosensitive resin composition that can be cured at a low temperature, has excellent reactivity, and has excellent durability such as chemical resistance of the formed pattern.

In addition, an object of the present invention is to provide a photosensitive resin composition which has excellent pattern forming ability in a photolithography process.

Furthermore, an object of the present invention is to provide a photocurable pattern formed using the above-mentioned photosensitive resin composition.

1. A photosensitive resin composition including an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, the polymerizable compound including a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2.

(化學式1中，R¹和R²各自獨立地為氫或者碳數1至6的直鏈型或分支型的烷基，m為4至12的整數。)

(In Chemical Formula 1, R ¹ and R ² are each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, and m is an integer of 4 to 12.)

(化學式2中，R₃為碳數1至6的飽和烴基或者含雜原子的飽和烴基，R₄相互獨立地為氫、丙烯醯氧基、琥珀酸酯基或者碳數1至5的直鏈型或分支型的烷基，條件是至少二個R₄係丙烯醯氧基，n為3至8的整數。)

(In Chemical Formula 2, R ₃ is a saturated hydrocarbon group with 1 to 6 carbons or a saturated hydrocarbon group containing heteroatoms, and R _{4 is} independently hydrogen, an acryloxy group, a succinate group or a straight chain with 1 to 5 carbons. Type or branched alkyl, provided that at least two R ₄ are propylene oxy groups, and n is an integer from 3 to 8.)

2. The photosensitive resin composition according to the first point, wherein R ¹ and R ² in the compound of Chemical Formula 1 are each independently hydrogen.

3. The photosensitive resin composition according to the first point, wherein the compound of Chemical Formula 2 is represented by Chemical Formula 3 or 4 below.

4. The photosensitive resin composition according to the first point, wherein the content of the compound of Chemical Formula 1 is 3 to 12 parts by weight relative to 100 parts by weight of the composition in total, and is relative to 100 parts by weight of the composition in total The content of the compound of Chemical Formula 2 is 3 to 15 parts by weight.

5. The photosensitive resin composition according to the fourth point, wherein the mixing ratio of the compound of Chemical Formula 1 and the compound of Chemical Formula 2 is 1:4 to 3:1 based on the weight ratio.

6. The photosensitive resin composition according to point 5, wherein the mixing ratio of the compound of Chemical Formula 1 to the compound of Chemical Formula 2 is 1:2 to 1:1 based on the weight ratio.

7. The photosensitive resin composition according to the first point, wherein the alkali-soluble resin includes a binder resin represented by the following chemical formula 7.

(化學式7中，a、b、c和d各自表示莫耳百分比，a為5至50莫耳%，b為5至70莫耳%，c為10至70莫耳%，d為5至70莫耳%。)

(In Chemical Formula 7, a, b, c, and d each represent molar percentage, a is 5 to 50 mol%, b is 5 to 70 mol%, c is 10 to 70 mol%, and d is 5 to 70 Mole%.)

8. The photosensitive resin composition according to the first point, wherein the weight average molecular weight of the alkali-soluble resin is 5,000 to 35,000.

9. A photocurable pattern made from the photosensitive resin composition described in any one of points 1 to 7.

10. The photocurable pattern according to point 9, wherein the photocurable pattern is selected from the following group: array planarization film pattern, protective film pattern, insulating film pattern, photoresist pattern, black matrix pattern, and column spacer pattern.

11. An image display device having the photocurable pattern as described in point 9.

If the photosensitive resin composition of the present invention is used, it is possible to form a photocurable film or a photocurable pattern having excellent adhesion to a substrate, chemical resistance, and durability. In addition, the photocurable pattern can be formed with improved reactivity and developability. The above-mentioned photocurable pattern has excellent chemical resistance and durability, and therefore can be suitably used as various patterns of image display devices.

Figure 1a is an image showing the evaluation criteria of developability according to an experimental example.

Figure 1b is an image showing the evaluation criteria of developability according to the experimental example.

Figure 1c is an image showing the evaluation criteria of developability according to an experimental example.

Figure 2a is an image showing the evaluation criteria of chemical resistance based on an experimental example.

Figure 2b is an image showing the evaluation criteria of chemical resistance based on the experimental example.

Figure 2c is an image showing the evaluation criteria of chemical resistance based on the experimental example.

Figure 2d is an image showing the evaluation criteria of chemical resistance based on the experimental example.

Figure 2e is an image showing the evaluation criteria of chemical resistance based on the experimental example.

Figure 2f is an image showing the evaluation criteria of chemical resistance based on an experimental example.

The present invention relates to a photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent. The polymerizable compound has improved physical properties by including the compounds of Chemical Formula 1 and Chemical Formula 2 described later. Stability and chemical stability, and improve reactivity such as developability.

The following describes the implementation aspects of the present invention in detail. In this specification, when the repeating unit, compound, or resin represented by each chemical formula has an isomer, the chemical formula representing the repeating unit, compound, or resin means that the representative chemical formula also includes the isomer.

In the present invention, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid" or both.

In the present invention, each repeating unit should not be interpreted as limited to the situation shown, and can exist freely at any position of the chain within a range that limits the molar% of the sub-repeat unit in parentheses. That is, the parentheses of each repeating unit are represented by one block in order to indicate mole %, but each sub repeating unit may exist as a block or separate from each other without limitation as long as it is in the resin.

<Photosensitive resin composition>

Polymeric compound

The polymerizable compound used in the photosensitive resin composition of the embodiment of the present invention is a compound that can be polymerized or crosslinked under the action of a photopolymerization initiator described later, which can increase the crosslink density in the manufacturing process and enhance the photocuring The mechanical properties of the pattern.

The aforementioned polymerizable compound includes a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2.

(化學式1中，R¹和R²各自獨立地為氫或者碳數1至6的直鏈型或分支型的烷基，括弧表示主鏈內的重複單元，m為4至12的整數。)

(In Chemical Formula 1, R ¹ and R ² are each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbons, parentheses indicate repeating units in the main chain, and m is an integer of 4 to 12.)

(化學式2中，R₃為碳數1至6的飽和烴基或者含雜原子的飽和烴基，R₄相互獨立地為氫、丙烯醯氧基、琥珀酸酯基或者碳數1至5的直鏈型或分支型的烷基，條件是至少二個R₄係丙烯醯氧基，n為3至8的整數。)

(In Chemical Formula 2, R ₃ is a saturated hydrocarbon group with 1 to 6 carbons or a saturated hydrocarbon group containing heteroatoms, and R _{4 is} independently hydrogen, an acryloxy group, a succinate group or a straight chain with 1 to 5 carbons. Type or branched alkyl, provided that at least two R ₄ are propylene oxy groups, and n is an integer from 3 to 8.)

The above-mentioned polymerizable compound can include a mixture or blend of the compound of Chemical Formula 1 and the compound of Chemical Formula 2. With the compound of Formula 1 having a larger molecular weight or molecular size, chemical resistance such as solvent resistance after photocrosslinking is increased, and a photocurable pattern with improved adhesion to the substrate can be formed. In addition, the carboxyl group-containing compound of Chemical Formula 2 improves the reactivity such as developability and can form, for example, a hole pattern having a target size with high resolution.

In Chemical Formula 1, for example, R ¹ and R ² are each independently hydrogen. If m in the chemical formula 1 is less than 4, the residual film rate and chemical resistance may deteriorate, and if it exceeds 12, the developability may decrease. From this viewpoint, m may preferably be an integer of 4-10, and more preferably may be an integer of 4-8.

In an embodiment of the present invention, the compound of Chemical Formula 1 can be contained in an amount of 0.1 to 25 parts by weight with respect to 100 parts by weight of the photosensitive resin composition in total. If the content of the compound of Chemical Formula 1 is less than 0.1 parts by weight, the chemical resistance of the coating film formed from the above-mentioned composition is reduced, and the photoresist coating film of the target physical properties may not be formed. If the content of the compound of Chemical Formula 1 exceeds 25 parts by weight, the developability is significantly reduced, and a residual film may remain in the non-exposed area. If the above-mentioned chemical resistance and developability are considered at the same time, the content of the compound of Chemical Formula 1 may preferably be 3 to 12 parts by weight.

In Chemical Formula 2, R ₄ is n functional groups bonded to R ₃ via methylene (-CH ₂ -), and each of the n functional groups can be independently selected from hydrogen, acryloxy group, succinate group or carbon number 1 to 5 in a linear or branched alkyl group.

R ₃ represents, for example, a methylene group, and the compound of the above chemical formula 2 can be represented by the following chemical formula 3.

R _{3 is} represented by the following general formula 1 ("*" represents a bonding end), for example, and the compound of the aforementioned chemical formula 2 can be represented by the following chemical formula 4.

In an embodiment of the present invention, the compound of Chemical Formula 2 can be contained in 3 to 50 parts by weight with respect to 100 parts by weight in total of the photosensitive resin composition. If the content of the compound of Chemical Formula 2 is less than 3 parts by weight, the amount of the photopolymerizable monomer is insufficient, and the development cannot be effectively carried out. Sometimes a residual film is generated in the non-exposed area. If it exceeds 50 parts by weight, the coating film will develop It will be excessive and sometimes the chemical resistance will be excessively reduced. If the above chemical resistance and developability are considered at the same time, the content of the compound of Chemical Formula 2 may preferably be 3 to 40 parts by weight, more preferably 3 to 15 parts by weight.

In a specific example, the mixing ratio of the compound of Chemical Formula 1 and the compound of Chemical Formula 2 can be adjusted to a range of about 1:4 to about 3:1 based on the weight ratio.

Within the above-mentioned mixing ratio range, it is possible to simultaneously achieve better chemical resistance and developability of the coating film or photocurable pattern formed from the photosensitive resin composition. From the viewpoint of simultaneously achieving chemical resistance and developability, it is preferable that the above-mentioned mixing ratio can be adjusted to a range of about 1:2 to about 1:1.

In addition, the polymerizable compound can further include a monofunctional monomer, a difunctional monomer, and other polyfunctional monomers.

Specific examples of monofunctional monomers include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy acrylate Ethyl ester, N-vinylpyrrolidone, etc.

As specific examples of difunctional monomers, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

As specific examples of other multifunctional monomers, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trihydroxyl Methyl propane tri (meth) acrylate, neopentyl erythritol tri (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, ethoxylate Alkylated dineopentaerythritol hexa(meth)acrylate, propoxylated dineopentaerythritol hexa(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc. Among them, it is preferable to use a polyfunctional monomer having two or more functions.

Alkali soluble resin

The alkali-soluble resin of the photosensitive resin composition of the embodiment of the present invention is a component that imparts solubility to the alkali developer used in the development process, and at the same time imparts adhesion to the substrate, thereby making it possible to form a coating film. For example, alkali-soluble resin can function as a binder resin of a photosensitive resin composition.

The type of the alkali-soluble resin mentioned above is a type generally used in the technical field, such as the field of negative photosensitive resin compositions. As long as it does not deviate from the purpose of the present invention, it is not particularly limited and may be The polymer of monomers or copolymers of two or more monomers commonly used in the art has no particular limitation on the polymerization steps and arrangement of the monomers.

For example, the above-mentioned alkali-soluble resin contains a repeating unit represented by the following chemical formula 5.

(化學式5中，R₅為氫或者甲基，R₆為直接鍵合或者碳數1至5的伸烷基，R₇為碳數1至4的直鏈或分支鏈的烷基或者烯基。)

(In chemical formula 5, R ₅ is hydrogen or methyl, R ₆ is a direct bond or an alkylene group having 1 to 5 carbons, and R ₇ is a straight or branched alkyl or alkenyl group having 1 to 4 carbons. .)

The alkali-soluble resin is cured by including a resin having a repeating unit of the chemical formula 5, in the heat treatment stage, by a ring opening reaction caused by heat and polymerization generated therefrom, for example, based on etching The etching resistance of the agent can improve the adhesion and chemical resistance.

In addition to the repeating unit represented by Chemical Formula 5, the alkali-soluble resin can further have repeating units derived from other monomers known in this field.

The above-mentioned other monomers are not particularly limited, and examples include monomers selected from carboxylic acids, dicarboxylic acids, and anhydrides thereof; aromatic vinyl compounds; vinyl cyanide compounds; and polymers having carboxyl groups and hydroxyl groups at both ends. (Meth) acrylic esters; (meth) acrylic acid alkyl esters; cycloaliphatic (meth) acrylic acid esters; (meth) acrylic acid aryl esters; using cycloalkanes or bicyclic hydrocarbons with 4 to 16 carbon atoms One or two or more of (meth)acrylates substituted with alkane ring; unsaturated oxetane compounds; unsaturated oxirane compounds. More preferably, (meth)acrylic monomers can be used.

The repeating unit derived from the above-mentioned (meth)acrylic monomer can be represented by the following Chemical Formula 6, for example.

(化學式6中，R₈為氫或者甲基，R₉為碳數1至6的烷基或者碳 數3至6的環烷基。)

(In Chemical Formula 6, R ₈ is hydrogen or methyl, and R ₉ is an alkyl group having 1 to 6 carbons or a cycloalkyl group having 3 to 6 carbons.)

For example, the aforementioned alkali-soluble resin can include a binder resin represented by Chemical Formula 7 below.

(化學式7中，a、b、c和d各自表示莫耳百分比，a為5至50莫耳%，b為5至70莫耳%，c為10至70莫耳%，d為5至70莫耳%。)

(In Chemical Formula 7, a, b, c, and d each represent molar percentage, a is 5 to 50 mol%, b is 5 to 70 mol%, c is 10 to 70 mol%, and d is 5 to 70 Mole%.)

In Chemical Formula 7, each repeating unit in parentheses can freely exist in any position of the chain within a limited molar percentage range. That is, each parenthesis in Chemical Formula 7 is represented by one block in order to show the molar percentage, but each repeating unit may exist in blocks or separate from each other without limitation as long as it is in the resin.

The weight average molecular weight of the alkali-soluble resin is not particularly limited, but from the viewpoint of improving adhesion and developability, it may be in the range of about 5,000 to 35,000.

Regarding the content of the alkali-soluble resin, it can be appropriately adjusted in consideration of the resolution of the photocurable pattern formed therefrom and the uniformity of the pattern. As a specific example, the content of the alkali-soluble resin may be in the range of 10 to 50 parts by weight relative to 100 parts by weight of the photosensitive resin composition in total.

Photopolymerization initiator

The photopolymerization initiator of the present invention can be used without particular limitation as long as it can polymerize the above-mentioned polymerizable compound. For example, it can be selected from acetophenone-based compounds, benzophenone-based compounds, and triazine-based compounds. A compound of at least one of a biimidazole-based compound, a thioxanthone-based compound, and an oxime ester-based compound, preferably a biimidazole-based compound and/or an oxime ester-based compound can be used.

Moreover, in order to improve the sensitivity of the photosensitive resin composition of this invention, the said photoinitiator may further contain a photoinitiation assistant. When the photosensitive resin composition of the present invention contains a photopolymerization initiation assistant, the sensitivity is further improved and productivity can be improved.

Examples of the photopolymerization initiation aid include one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organosulfur compounds having a thiol group.

The content of the photopolymerization initiator is not particularly limited. For example, it can be 0.1 to 10 parts by weight, preferably 0.1 to 7 parts by weight, relative to 100 parts by weight of the photosensitive resin composition in total.

Within the above content range, the durability of the photocurable pattern will not be hindered, and the sensitivity and resolution of the exposure process can be improved.

additive

The photosensitive resin composition of the present invention may further contain additives such as fillers, other polymer compounds, curing agents, adhesion promoters, antioxidants, surfactants, ultraviolet absorbers, anti-agglomeration agents, and chain transfer agents as necessary.

The above additives may be used alone or in combination of two or more.

The content of the above additives is not particularly limited. For example, it may be 0.001 to 2 parts by weight with respect to 100 parts by weight of the photosensitive resin composition in total.

Solvent

The solvent is not particularly limited, as long as it can dissolve the above-mentioned components, has an appropriate drying speed, and can form a uniform and smooth coating film after evaporation of the solvent, it can be used.

As the above solvent, if coating properties and drying properties are considered, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers can be preferably used. Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. More preferably, diethylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, 3- Ethyl ethoxypropionate, methyl 3-methoxypropionate, etc.

The content of the above-mentioned solvent may be 30 to 70 parts by weight with respect to 100 parts by weight of the photosensitive resin composition in total. If the above range is met, spin coaters, slit and spin coaters, slit coaters (also sometimes called "die coaters", "curtain flow coaters"), inkjet coaters are used The coating property during coating by a coating device becomes good, so it is preferable.

Light curing pattern and image display device

The object of the present invention is to provide a photocurable pattern manufactured using the above-mentioned photosensitive resin composition and an image display device having the photocurable pattern.

The photocurable pattern produced from the photosensitive resin composition is excellent in low-temperature curability, and excellent in chemical resistance, heat resistance, and the like. This can be used in various patterns in image display devices such as adhesive layers, array planarization films, protective films, insulating film patterns, etc., as well as photoresist, black matrix, columnar spacer patterns, black columnar patterns, etc. Although it is used for a spacer pattern etc., it is not limited to these, It is especially suitable as an insulating film pattern.

Examples of image display devices having such a photocurable pattern or using the above-mentioned pattern in the manufacturing process include liquid crystal display devices, OLEDs, flexible displays, etc., but are not limited to these, and can be listed All image display devices known in this field.

The photocurable pattern can be produced by coating the above-mentioned photosensitive resin composition of the present invention on a substrate, and forming a photocurable pattern after undergoing a development process as necessary.

In order to facilitate the understanding of the present invention, preferred embodiments are given below, but these embodiments are only examples of the present invention and are not limited to the scope of the attached patent application. It is obvious to those skilled in the art that, within the scope of the present invention and the scope of the technical idea, various changes and modifications can be made to these embodiments, and these changes and modifications of course also belong to the scope of the attached patent application.

Production example: Synthesis of alkali-soluble resin (A) (Chemical formula 7)

In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was introduced at 0.02 liter/min to create a nitrogen atmosphere, and 250 g of propylene glycol monomethyl ether acetate was added. Then, it was heated at 100°C and contained 32.4 g (0.45 mol) of acrylic acid, 82.9 g (0.45 mol) of methyl methacrylate (3-ethyl-3-oxetanyl), and vinyl In a mixture of 11.8 g (0.10 mol) of toluene and 150 g of propylene glycol monomethyl ether acetate, 2,2'-azobis(2,4-dimethylpentane) is added using a dropping funnel for 2 hours. Nitrile) 3.6 g of the solution was dropped into the flask, and the stirring was continued for 5 hours at 100°C.

The atmosphere in the flask was changed from nitrogen to air, and 49.8 g (0.35 mol (relative to the acrylic acid used in this reaction, 78 mol%) of glycidyl methacrylate) was put into the flask and kept at 110°C React for 6 hours. Thus, an unsaturated group-containing alkali-soluble resin having a solid acid value of 44 mg KOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 17,500, and the molecular weight distribution (Mw/Mn) was 2.20.

Examples and comparative examples

The photosensitive resin compositions of Examples and Comparative Examples were prepared with the compositions and contents (unit: parts by weight) of Table 1 and Table 2 below.

The components used in Table 1 and Table 2 are as follows.

A: Alkali-soluble resin produced in the production example (Chemical formula 7)

B-1: Dineopentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.)

B-2:

B-3:

C-1: Biimidazole series initiator

C-2: Oxime ester series initiator

D: Antioxidant

E-1: Diethylene glycol methyl ethyl ether

E-2: Propylene glycol monomethyl ether acetate

Experimental example

A 2-inch square glass substrate (EAGLE 2000, manufactured by Corning Incorporated) was washed with neutral detergent, water, and alcohol in this order, and then dried. On this glass substrate, after spin-coating the photosensitive resin composition prepared in the said Example and the comparative example, respectively, using a hot plate, it prebaked at 90 degreeC for 125 second.

After cooling the prebaked substrate to normal temperature, use an exposure machine (UX-1100SM, manufactured by Ushio Co., Ltd.) to expose at 50 millijoules/cm² (mJ/cm ² ) The amount (365nm standard) irradiates the entire coating film with light. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25° C. for 60 seconds, developed and washed with water. Then, in an oven, post-baking was performed at 130°C for 60 minutes. The thickness of the obtained coating film was 3.0 micrometers. For the cured film obtained in this way, the following physical property evaluation was performed, and the result is shown in the following Table 3 and Table 4.

(1) Evaluation of developability

The photosensitive resin compositions of the foregoing Examples and Comparative Examples were spin-coated on a glass substrate, and then prebaked. After cooling the prebaked substrate to room temperature, it was immersed in a 0.04% KOH-based aqueous solution, and the dissolution process of the coating film was observed for 60 seconds. The observation results were evaluated according to the following criteria, and the material with the soluble type was judged as the most suitable material.

<Evaluation Criteria>

Dissolution type: As shown in Figure 1a, the coating film is dissolved within 30 seconds from the moment the coating film is immersed in the developer solution.

Weak peeling type: As shown in Figure 1b, almost all the coating film is dissolved, but undissolved fine particles remain

Peeling type: As shown in Figure 1c, the coating film is peeled off as a whole as shown in the photo until it dissolves slowly over time, which takes 60 seconds

Undeveloped: The peeling or dissolution of the coating film itself in the state of being immersed in the developer is not completed even after 60 seconds or more

(2) Evaluation of chemical resistance

On a 2-inch square glass substrate (EAGLE 2000, manufactured by Corning Incorporated), the photosensitive resin compositions prepared in the Examples and Comparative Examples were spin-coated, respectively, and prebaked at 80°C for 125 seconds using a hot plate. After cooling the pre-baked substrate to room temperature, use an exposure machine (UX-1100SM, manufactured by UZW Co., Ltd.) to expose the entire surface without a mask at an exposure of 50 mJ/cm² (365 nm standard) Perform light irradiation. For the exposed coating film, immerse the above-mentioned coating film in a 2.38% tetramethylammonium hydroxide aqueous solution at 25°C for 60 seconds. After developing, washing and drying, use a clean oven at 100°C for 60 minutes. Baking.

The coating film with a film thickness of 1.5 micrometers formed as described above was immersed in an NMP solution and treated at 50°C for 3 minutes. Then, based on the conditions of the ASTM D-3359-08 standard test, the coating film was cut with a cutter, and then a tape was attached to the surface and peeled off. The chemical resistance was confirmed by this method. In the dicing/tape test after the chemical solution treatment, the degree of peeling of the coating film was defined as 0B to 5B based on the standard test method, and the coating film with the most excellent performance was set to 5B.

5B: 0% peeling (refer to figure 2a)

4B: Less than 5% peeling (refer to Figure 2b)

3B: 5% or more but less than 15% peeling (refer to Figure 2c)

2B: 15% or more but less than 35% peeling (refer to Figure 2d)

1B: 35% or more but less than 65% peeling (refer to Figure 2e)

0B: 65% or more peeling (refer to Figure 2f)

(3) Measurement of hole pattern size

The pore pattern size at the film thickness of 1.5 micrometers of the coating film obtained above was measured by SEM, and the pore size of the coating film when the mask pattern size was 10 micrometers is shown in the following table. In addition, when the hole and the glass substrate did not meet and a residual film was formed, it was shown that the size could not be measured (see Fig. 3).

As shown in the above Table 3 and Table 4, in the case of the examples containing both the polymerizable compounds of the above chemical formula 1 and the chemical formula 2, the overall developability was evaluated as dissolution compared with the comparative example, and the pores were confirmed Large size and improved chemical resistance. In addition, in the case of Examples 1 to 7 in which the mixing ratio of the polymerizable compound of Chemical Formula 1 and Chemical Formula 2 was in the range of 1:2 to 2:1, results that were excellent in both chemical resistance and developability were obtained. In the case of Example 10 in which the photopolymerizable monomer (B-1) was omitted, compared with Examples 1 to 7, the pore size was formed slightly smaller.

In the case of Comparative Example 6, the chemical resistance was relatively excellent, but the coating film was not developed, and a residual film was formed so that the pore size could not be measured. In the case of Comparative Example 7, it can be confirmed that the developability is "dissolution", while the pore size is large, and the chemical resistance is the worst.

Claims (10)

A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent. The polymerizable compound contains a compound represented by the following chemical formula 1 and a compound represented by the chemical formula 2, relative to a total of 100 Parts by weight of the composition, the content of the compound of chemical formula 1 is 0.1 to 25 parts by weight; and relative to 100 parts by weight of the composition in total, the content of the compound of chemical formula 2 is 3 to 50 parts by weight,

In Chemical Formula 1, R ¹ and R ² are each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, and m is an integer from 4 to 12,

In the chemical formula 2, R ₃ is a saturated hydrocarbon group with 1 to 6 carbons or a saturated hydrocarbon group containing heteroatoms, and R _{4 is} independently hydrogen, an acryloxy group, a succinate group or a straight chain type with 1 to 5 carbons. Or a branched alkyl group, provided that at least two R ₄ are propylene oxy groups, and n is an integer from 3 to 8. The photosensitive resin composition according to claim 1, wherein R ¹ and R ² of the compound of Chemical Formula 1 are each independently hydrogen. The photosensitive resin composition according to claim 1, wherein the compound of Chemical Formula 2 is represented by the following Chemical Formula 3 or 4:

The photosensitive resin composition according to claim 1, wherein the content of the compound of Chemical Formula 1 is 3 to 12 parts by weight relative to 100 parts by weight in total of the composition The content of the compound of Chemical Formula 2 is 3 to 15 parts by weight relative to 100 parts by weight of the composition in total. The photosensitive resin composition according to claim 4, wherein the mixing ratio of the compound of Chemical Formula 1 and the compound of Chemical Formula 2 is 1:4 to 3:1 based on the weight ratio. The photosensitive resin composition according to claim 5, wherein the mixing ratio of the compound of Chemical Formula 1 to the compound of Chemical Formula 2 is 1:2 to 1:1 based on the weight ratio. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin includes a binder resin represented by the following chemical formula 7:

In Chemical Formula 7, a, b, c, and d each represent mole percentage, a is 5 to 50 mole%, b is 5 to 70 mole%, c is 10 to 70 mole%, and d is 5 to 70 mole%. ear%. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the alkali-soluble resin is 5,000 to 35,000. A product made from the photosensitive resin composition according to any one of claims 1 to 7 The light-cured pattern made. The photocurable pattern according to claim 9, wherein the photocurable pattern is selected from the following group: array planarization film pattern, protective film pattern, insulating film pattern, photoresist pattern, black matrix pattern, and column spacer pattern.

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