Negative photosensitive insulating film composition and insulating film using the same

Abstract

A negative photosensitive insulating film composition comprising: an alkali-soluble acrylic resin blend containing a first alkali-soluble acrylic resin having a 9,9-bis(4-hydroxyphenyl)fluorene-derived structural unit and a second alkali-soluble acrylic resin having a tetra(4-hydroxyphenyl)ethane-derived structural unit, a cross-linkable acrylic monomer having two or more acrylic double bonds, a photopolymerization initiator; and a silicon coupling agent having an epoxy group or an amine group. Thereby, an insulating film pattern having excellent photosensitivity and a high-resolution pattern can be formed.

Description

Technical Field

[0001] Embodiments of the present invention relate to a photosensitive insulating film composition. More specifically, embodiments of the present invention relate to a negative photosensitive insulating film composition that simultaneously satisfies the requirements of forming high-resolution patterns, high heat resistance, excellent insulating properties, and plasma resistance. Background Technology

[0002] With the development of high-resolution display technologies such as Organic Light-Emitting Diode (OLED), Oxide Thin-Film Transistor (Oxide TFT), and Touch Panel, insulating films need to possess additional properties beyond their simple insulating function. These include high-temperature processing stability, high aspect ratio pattern retention, low shrinkage, excellent insulation properties, and long-term reliability.

[0003] Traditional mononuclear acrylic negative photosensitive resins suffer from problems such as limited transition temperature (Tg), pattern shrinkage, plasma damage, and increased leakage current.

[0004] In particular, in the OLED pixel define layer (PDL) process, problems such as bank deformation, edge rounding, and outgassing occur during the deposition process, while in the interlayer dielectric (ILD) for oxide TFTs, problems such as leakage and reduced bias stress stability occur.

[0005] Therefore, there is a need for a novel photosensitive insulating film composition that can maintain photosensitivity and developability while incorporating a high-rigidity aromatic framework. Summary of the Invention

[0006] Technical problems to be solved

[0007] Embodiments of the present invention provide a negative-type photosensitive insulating film composition that simultaneously meets the following requirements: First, excellent photosensitivity and ability to form high-resolution patterns; second, high glass transition temperature (Tg) and thermal stability; third, excellent adhesion to metal wiring and substrates; and fourth, excellent insulation properties, plasma resistance, and crack suppression properties.

[0008] In addition, embodiments of the present invention provide an insulating film formed using the above-described composition.

[0009] Technical solution

[0010] A negative photosensitive insulating film composition according to an embodiment of the present invention comprises the following components.

[0011] According to an embodiment of the present invention, a negative photosensitive insulating film composition comprises: an alkali-soluble acrylic resin blend containing a first alkali-soluble acrylic resin having a 9,9-bis(4-hydroxyphenyl)fluorene-derived structural unit and a second alkali-soluble acrylic resin having a tetra(4-hydroxyphenyl)ethane-derived structural unit, a crosslinked acrylic monomer having two or more acrylic double bonds, a photopolymerization initiator, and a silicone coupling agent having epoxy or amine groups.

[0012] In one embodiment of the present invention, the mixture may contain: 5 to 50% by weight of the above-mentioned alkali-soluble acrylic resin blend, 5 to 30% by weight of the above-mentioned crosslinking acrylic monomer, 0.1 to 10% by weight of the above-mentioned photopolymerization initiator, 0.1 to 5% by weight of the above-mentioned silicone coupling agent, and the balance being a solvent.

[0013] In one embodiment of the present invention, the solid component content may be 10 to 30% by weight.

[0014] In one embodiment of the present invention, based on tetrahydrofuran, the first alkali-soluble acrylic resin and the second alkali-soluble acrylic resin may each have a weight-average molecular weight in the range of 2000 to 20000 g / mol.

[0015] In one embodiment of the present invention, the weight ratio between the first alkali-soluble acrylic resin and the second alkali-soluble acrylic resin may be from 30:70 to 70:30.

[0016] In embodiments of the present invention, the crosslinkable acrylic monomer may be selected from:

[0017] One or more of the group consisting of 1,4-butanediol diacrylate, 1,3-butenediol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivatives, trimethylolpropane triacrylate, dipentaerythritol polyacrylate, and their methacrylate derivatives.

[0018] In embodiments of the present invention, the above-mentioned photopolymerization initiator can be a triazine compound, a benzoin compound, an acetophenone compound, a xanthonone compound, or an imidazole compound, etc. Specifically, it can be selected from triazine compounds such as 2,4-bis(trichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bis(trichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine; benzoin compounds such as benzophenone and p-(diethylamino)benzophenone; 2,2-dichloro-4-phenoxyacetophenone, 2 The group consisting of one or more compounds from the following groups: 2-diethoxyacetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, etc.; xanthoxanone compounds such as xanthoxanone, thioxanthoxanone, 2-methylthioxanthoxanone, 2-isobutylthioxanthoxanone, 2-dodecylthioxanthoxanone, 2,4-dimethylthioxanthoxanone, 2,4-diethylthioxanthoxanone, etc.; and 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-bisimidazole, 2,2-bis(2,4,6-tricyanophenyl)-4,4,5,5-tetraphenyl-1,2-bisimidazole.

[0019] In embodiments of the present invention, the aforementioned silicon coupling agent (silicon-based compound) may be selected from:

[0020] One or more of the group consisting of (3-glycidyl etheroxypropyl)trimethoxysilane, (3-glycidyl etheroxypropyl)triethoxysilane, (3-glycidyl etheroxypropyl)methyldimethoxysilane, (3-glycidyl etheroxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and aminopropyltrimethoxysilane.

[0021] Technical effect

[0022] The compositions of the present invention comprise an alkali-soluble acrylic resin blend containing a first alkali-soluble acrylic resin having a 9,9-bis(4-hydroxyphenyl)fluorene-derived structural unit and a second alkali-soluble acrylic resin having a tetra(4-hydroxyphenyl)ethane-derived structural unit. This allows for the formation of high-resolution patterns, achieving high heat resistance and thermal stability, excellent insulation properties, improved plasma resistance, excellent substrate adhesion, improved process margin, and excellent crack suppression characteristics. In particular, the combination of a rigid aromatic central structure and photosensitive acrylic groups simultaneously ensures high heat resistance and photosensitivity.

[0023] The above description only illustrates specific examples of the present invention. However, it is obvious to those skilled in the art that various modifications and variations can be made within the scope of the technical concept of the present invention, and such modifications and variations fall within the scope of the appended claims. Detailed Implementation

[0024] The embodiments of the present invention will now be described in detail. However, the present invention is not necessarily configured as limited to the embodiments described below, but can be embodied in various forms different from there. The following embodiments are provided to enable the present invention to be carried out completely. Furthermore, they are provided to fully convey the scope of the present invention to those skilled in the art.

[0025] In embodiments of the present invention, it should be understood that when describing a component configured or connected to another component, this includes not only the case where the component is configured to directly form or directly contact the other component, but also the case where one or more intermediate layers, intermediate elements, or dielectric structures are provided therebetween. That is, the above description is not limited to direct physical contact or bonding, but also includes all indirect configurations or connections where other layers, films, patterns, adhesive layers, interface layers, or functional layers required for process or structure are provided.

[0026] The technical terms used in the embodiments of this invention are for describing specific embodiments only and are not intended to limit the invention. Furthermore, unless otherwise specified, all terms, including technical and scientific terms, have the same meaning as would be understood by one of ordinary skill in the art to which this invention pertains. The foregoing terms, having the same definition in a conventional dictionary, are interpreted in the context of the relevant art and the description of this invention as they have in a conventional dictionary, and should not be interpreted ideally or through excessive external intuition unless expressly specified otherwise.

[0027] The negative photosensitive insulating film composition according to an embodiment of the present invention comprises: an alkali-soluble acrylic resin blend containing a first alkali-soluble acrylic resin having a 9,9-bis(4-hydroxyphenyl)fluorene-derived structural unit and a second alkali-soluble acrylic resin having a tetra(4-hydroxyphenyl)ethane-derived structural unit, a crosslinked acrylic monomer having at least two acrylic double bonds, a photopolymerization initiator, a silicon compound containing epoxy or amine groups, and a solvent.

[0028] The first alkali-soluble acrylic resin mentioned above can be represented by the following chemical formula 1.

[0029] [Chemical Formula 1]

[0030]

[0031] Where n is a natural number in the range of 1 to 10.

[0032] On the other hand, the aforementioned second alkali-soluble acrylic resin can be represented by the following chemical formula 2.

[0033] [Chemical Formula 2]

[0034]

[0035] Where n is a natural number in the range of 1 to 10.

[0036] In addition, R1 and R2 are each independently epoxy groups.

[0037] In particular, the alkali-soluble acrylic resin blend comprises a first alkali-soluble acrylic resin having a 9,9-bis(4-hydroxyphenyl)fluorene derivatized structural unit and a second alkali-soluble acrylic resin having a tetrakis(4-hydroxyphenyl)ethane derivatized structural unit. Therefore, the alkali-soluble acrylic resin blend comprising both 9,9-bis(4-hydroxyphenyl)fluorene (BPF) and tetrakis(4-hydroxyphenyl)ethane (THPE) derivatized structural units can improve the balance of physical properties based on the complementarity of their molecular structures.

[0038] Specifically, BPF-derived structures, due to their relatively rigid fluorene framework, can impart high glass transition temperature (Tg), excellent heat resistance, and high refractive index. On the other hand, THPE-derived structures, due to their multifunctional phenolic structure, can achieve precise control of crosslinking density and contribute to improved mechanical strength.

[0039] Therefore, when the two resins are mixed, the rigid thermal and optical properties and the mechanical stability based on the cross-linked structure complement each other, thereby ensuring a balance between rigidity and flexibility.

[0040] In addition, the resin blends with two different structures have differences in the configuration of phenolic hydroxyl groups (OH) and acidity (pKa). Therefore, in the alkaline development process, the penetration rate of alkali and the dissolution rate of resin can be controlled in stages. Thus, compared with simple physical blends, it can more stably ensure development margin and improve the reproducibility and stability of pattern outlines.

[0041] Furthermore, by mixing resin blends with two different structures, based on similar acrylic backbones, the different aromatic core structures may enhance intermolecular interactions such as π-π interactions and hydrogen bonds, thereby suppressing microphase separation within the composition and improving pattern uniformity and dimensional stability.

[0042] Furthermore, the fluorene structure (BPF) imparts relatively high refractive index properties, while the THPE structure helps maintain transparency and ensure uniform light response, thus enabling the simultaneous achievement of high refractive properties and high transparency in low-temperature overcoat (OC) or photosensitive insulating film compositions.

[0043] In addition, THPE-derived resins with multiple phenol groups can enhance reactivity with crosslinking agents, thereby increasing crosslinking density. BPF-derived resins, through their large-volume spatial bulk structure, can suppress excessive shrinkage during the curing process. Therefore, they ultimately reduce curing shrinkage and suppress cracking, thereby improving the reliability of the film.

[0044] The first and second alkali-soluble acrylic resins described above have a weight-average molecular weight in the range of 2000 to 20000 g / mol, more preferably 5000 to 10000 g / mol. When the weight-average molecular weights of the first and second alkali-soluble acrylic resins are each within the above range, the development time is shortened, and improved high resolution and residual film removal rate are achieved.

[0045] Crosslinkable acrylic monomers containing at least two of the above-mentioned double bonds may include 1,4-butanediol diacrylate, 1,3-butenediol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivatives, trimethylolpropane triacrylate, dipentaerythritol polyacrylate, and their methacrylate derivatives, etc.

[0046] The crosslinked acrylic monomer containing at least two double bonds is preferably contained in 5 to 30% by weight in the photosensitive insulating film composition.

[0047] When its content is less than 5% by weight, there is a problem that the curing degree of the negative photosensitive insulating film composition cannot be achieved. When it exceeds 30% by weight, there is a problem that the developability and adhesion may be reduced.

[0048] The aforementioned photopolymerization initiators can be triazine compounds, benzoin compounds, acetophenone compounds, xanthone compounds, or imidazole compounds, etc. Specifically, triazine compounds such as 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-6-triazine, and 2,4-trichloromethyl-4-methylnaphthyl-6-triazine can be used; benzoin compounds such as benzophenone and p-(diethylamino)benzophenone can be used; 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethylamino)benzophenone, etc. can be used. Acetophenone compounds such as oxyacetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, and p-tert-butyltrichloroacetophenone; xanthone compounds such as xanthone, thioxanthone, 2-methylthioxanthone, 2-isobutylthioxanthone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; or imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-bisimidazole and 2,2-bis(2,4,6-tricyanophenyl)-4,4,5,5-tetraphenyl-1,2-bisimidazole, etc.

[0049] The aforementioned photopolymerization initiator is preferably contained in the photosensitive insulating film composition at 0.1 to 5% by weight, more preferably at 1 to 2% by weight. When its content is less than 0.1% by weight, the degree of curing decreases, and there is a problem that it is difficult to achieve a normal insulating film shape due to low photosensitivity, and it is also detrimental to the straightness of the pattern. If it is greater than 5% by weight, there may be problems with storage stability, and there may be a problem that the resolution may decrease due to high degree of curing, and residual film is easily generated in the areas outside the formed pattern.

[0050] Silicon compounds containing the above-mentioned epoxy or amino groups may use one or more selected from the group consisting of (3-glycidyl etheroxypropyl)trimethoxysilane, (3-glycidyl etheroxypropyl)triethoxysilane, (3-glycidyl etheroxypropyl)methyldimethoxysilane, (3-glycidyl etheroxypropyl)trimethoxysilane, (3-glycidyl etheroxypropyl)dimethylethoxysilane, (3-glycidyl etheroxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and aminopropyltrimethoxysilane.

[0051] The silicon-based compound containing the aforementioned epoxy or amine groups is preferably contained in the photosensitive insulating film composition at a concentration of 0.1 to 5% by weight, more preferably 0.1 to 1% by weight. When its content is less than 0.1% by weight, the adhesive strength decreases, and the insulating film may peel off due to the decreased adhesive strength. If it is greater than 5% by weight, storage stability may be problematic, and the insulating film may peel off due to excessive use.

[0052] The solvents mentioned above are selected based on their solubility, coatability, etc. Specifically, propylene glycol monoethyl ether acetate, ethyl ethoxypropionate, butyl acetate, methyl 3-methoxypropionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, ethyl 3-methoxypropionate, or methyl 3-ethoxypropionate are preferred, with propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether being particularly preferred.

[0053] The content of the solvent can be varied according to the viscosity or the total solid content in the composition. It can of course be included in the remaining amount other than the solid content used in the negative photosensitive insulating film composition of the present invention. In particular, 50 to 100% by weight of propylene glycol monoethyl ether acetate is preferred relative to the total amount of solvent used. When the solvent is not included in the above range, there is a problem that the uniformity of the negative photosensitive insulating film composition is reduced because the thickness deviation cannot be overcome.

[0054] The solvents mentioned above are selected based on their solubility, coatability, etc. Specifically, propylene glycol monoethyl ether acetate, ethyl ethoxypropionate, butyl acetate, methyl 3-methoxypropionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, ethyl 3-methoxypropionate, or methyl 3-ethoxypropionate are preferred, with propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether being particularly preferred.

[0055] The content of the solvent can be varied according to the viscosity or the total solid content in the composition. It can of course be included in the remaining amount other than the solid content used in the negative photosensitive insulating film composition of the present invention. In particular, it is preferable to use 50 to 100% by weight of propylene glycol monoethyl ether acetate relative to the total amount of solvent used, and more preferably 50 to 80% by weight of propylene glycol monoethyl ether acetate. When the solvent is not included in the above range, there is a problem that the uniformity of the negative photosensitive insulating film composition is reduced because the thickness deviation cannot be overcome.

[0056] Furthermore, the negative-type photosensitive insulating film composition of the present invention may further include additives such as surfactants, curing accelerators, and pigments as needed. In particular, the aforementioned surfactants may be silicone-based or acrylic surfactants.

[0057] The additives mentioned above are preferably contained in a maximum of 2% by weight in the photosensitive insulating film composition. When the content is greater than 2% by weight, there is a possibility of residual film or reduced stability, and the phenomenon of ions and impurities dissolving into the liquid crystal.

[0058] Furthermore, the present invention relates to a method for forming an insulating film characterized by using a negative photosensitive insulating film composition comprising the components described above. The method for forming the insulating film by the above method is as follows:

[0059] First, the negative photosensitive insulating film composition of the present invention is coated onto the substrate surface using methods such as spin coating, fine application system (FAS, slit & spin) coating, or slit coating. After removing the solvent in a vacuum process, residual solvent is removed by pre-baking, thereby forming a coated film. Preferably, the pre-baking is performed at a temperature of 80-120°C for 1-3 minutes.

[0060] Then, according to the pre-prepared pattern, the coating film formed above is irradiated with light of a composite wavelength of g, h, and I lines, and developed using a developer to remove unnecessary parts, thereby forming the predetermined pattern.

[0061] The developer solution is preferably an alkaline aqueous solution. Specifically, it can be an aqueous solution of inorganic bases such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, etc.; alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine, etc.; or an aqueous solution of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, etc.

[0062] At this point, the above-mentioned developer solution is used with the alkaline compound dissolved at a concentration of 0.01~10% by weight, and an appropriate amount of surfactant may also be added.

[0063] In addition, after developing with the developer solution described above, rinse with ultrapure water for 30 to 90 seconds to remove unnecessary parts and form a pattern. Then, heat the pattern at a temperature of 80 to 250°C for 30 to 120 minutes using a heating device such as an oven to obtain the final pattern.

[0064] The negative photosensitive insulating film composition according to the present invention can simultaneously achieve high-resolution patterning, high heat resistance, excellent insulation properties, and plasma resistance. Furthermore, the negative photosensitive insulating film composition according to embodiments of the present invention exhibits excellent heat stability, excellent adhesion to customer substrates, and excellent developability and process margin characteristics.

[0065] The following preferred embodiments are provided for the purpose of understanding the present invention. However, the following embodiments are only used to illustrate the present invention, and the scope of the present invention is not limited to the following embodiments.

[0066] Synthesis example

[0067] [Synthesis example 1]

[0068] In a 1L jacketed reactor equipped with a cooling pipe and a stirrer, 50:50 parts by weight of 4,4'-(9H-fluorene-9-ylidene)bisphenol [Sigma-Aldrich]:4,4'-phthalic anhydride [Sigma-Aldrich] were added, along with 1% by weight of V-65 [Sigma-Aldrich] as a photopolymerization initiator and 2% by weight of tert-butylhydroquinone [Sigma-Aldrich] as a polymerization inhibitor. Propylene glycol methyl ether acetate was added as a solvent, using 70% by weight of the solvent. After nitrogen purging, stirring was initiated. The stirring speed was preferably 80 rpm. The reaction solution was heated to 60°C and maintained at this temperature for 6 hours, then cooled to 25°C to recover the primary intermediate (ester bond). Additionally, 80:20 parts by weight of the primary intermediate (ester bond): methacrylic acid was added, along with 1% by weight of V-65 [Sigma-Aldrich] as a photopolymerization initiator and 1% by weight of tert-butylhydroquinone [Sigma-Aldrich] as a polymerization inhibitor. After nitrogen purging, stirring was initiated. The stirring speed was preferably 80 rpm. Furthermore, the reaction solution was heated to 60°C and maintained at this temperature for 10 hours, then cooled to 25°C to obtain the polymer resin of Formula 1, which serves as the first alkali-soluble acrylic resin.

[0069] [Synthesis example 2]

[0070] The same method as in Synthesis Example 1 above was used, but 1,1,2,2-tetra(p-hydroxyphenyl)ethane was used instead of 4,4'-(9H-fluorene-9-ylidene)bisphenol. The reaction was carried out under the same conditions to obtain the second alkali-soluble acrylic resin of Formula 2.

[0071] Example

[0072] [Example]

[0073] As an alkali-soluble acrylic resin, the alkali-soluble acrylic resins having chemical formulas 1 and 2 obtained in Synthesis Example 1 and Synthesis Example 2 above were mixed, and a negative photosensitive insulating film composition was prepared by using 5 to 20% by weight of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol polyacrylate as crosslinking monomers having at least two or more acrylic double bonds, 0.5% by weight of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and aminopropyltrimethoxysilane as silicon compounds containing epoxy or amino groups, 1% by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, and 1.0% by weight of 4,4-bis(diethylamino)benzophenone, with the balance being propylene glycol methyl ether acetate as a solvent.

[0074] At this time, the combination of Example 1 and Example 2 is shown in Table 1 below.

[0075] [Comparative Example]

[0076] In Comparative Example 1, the preparation was the same as in Example 1, except that 30% by weight of the alkali-soluble acrylic resin of Formula 1 and 20% by weight of the ordinary acrylic resin were mixed. In Comparative Example 2, the preparation was the same as in Example 1, except that 30% by weight of the alkali-soluble acrylic resin of Formula 2 and 20% by weight of the ordinary acrylic resin were mixed. Cardoresin (model name PR-RM-013™, Alfa Chemistry) was used as the ordinary acrylic resin. The mixing ratios of Comparative Example 1 and Comparative Example 2 are shown in Table 1 below.

[0077] [Table 1] Comparison of composition (weight %) of the Examples and Comparative Examples

[0078]

[0079] [Table 2] Comparison of physical properties and process characteristics

[0080]

[0081] Using the negative-type photosensitive insulating film compositions manufactured in Examples 1 to 2 and Comparative Examples 1 to 2 above, the following evaluations were conducted on minimum resolution, Tg, insulation breakdown voltage, leakage current, plasma etching rate, adhesion, cracking after 230°C, and high-temperature reliability peeling characteristics.

[0082] 1. Minimum Pattern Resolution Evaluation

[0083] The photosensitive insulating film composition was spin-coated onto a glass substrate at 3000 rpm for 30 seconds to form a film with a thickness of approximately 2.0 μm.

[0084] After pre-baking at 100℃ for 2 minutes, exposure was performed using a g, h, i-line exposure machine in the range of 30 mJ / cm².

[0085] The image was developed using a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with ultrapure water for 60 seconds, and cured in an oven at 230°C for 30 minutes. The resolution was then defined as the minimum linewidth (based on line and space) that did not cause pattern collapse and maintained linewidth using an optical microscope and a scanning electron microscope (SEM).

[0086] 2. Measure the glass transition temperature (Tg).

[0087] After heat-treating the cured film at 230°C for 30 minutes, it is peeled off to produce test pieces.

[0088] The temperature range of 30℃ to 300℃ was measured using a differential scanning calorimeter (DSC) under a nitrogen atmosphere at a heating rate of 10℃ / min.

[0089] The midpoint of the change in heat capacity is defined as Tg.

[0090] 3. Measure the insulation breakdown voltage

[0091] A 2.0 μm thick film was formed on a Si wafer and cured at 230 °C for 30 minutes.

[0092] An Al electrode with a diameter of 1 mm is deposited on the upper part.

[0093] Record the voltage at which insulation breakdown occurs when a voltage rise rate of 0.1 MV / cm·sec is applied.

[0094] Divide it by the film thickness to convert it to MV / cm.

[0095] 4. Measure leakage current

[0096] After forming a metal-insulator-metal (MIM) structure, an electric field of 1 MV / cm is applied.

[0097] Using a Keithley source meter, measure the current value after 60 seconds of stabilization.

[0098] Convert it to the current value per unit area (A / cm²).

[0099] 5. Measurement of plasma etching rate

[0100] O2 plasma conditions:

[0101] • Radio Frequency Power (RF Power): 300W

[0102] • Pressure: 100mTorr

[0103] O2 flow rate: 50 sccm

[0104] The initial thickness and the thickness after 5 minutes of processing were measured using an ellipsometer.

[0105] Divide the reduced thickness by time and calculate in nm / min.

[0106] 6. Adhesion strength assessment (Cross-cut test)

[0107] According to ASTM D3359, 100 grids are formed with 1 mm intervals.

[0108] After applying 3M 600 tape, peel it off in a 180° direction.

[0109] Evaluation is based on the grid retention status, ranging from 0B to 5B.

[0110] 7. Crack occurrence assessment

[0111] After heat treatment at 230°C for 30 minutes, the sample was cooled to room temperature.

[0112] Use an optical microscope (200x) to observe whether there are surface cracks.

[0113] When three or more cracks with a length of 10 μm or more are confirmed, it is judged that "cracks have occurred".

[0114] 8. High-Temperature Reliability Assessment

[0115] Store at 85℃ / 85% relative humidity (RH) for 500 hours.

[0116] Afterwards, the adhesion and peeling were reassessed.

[0117] When the edge peeling length reaches 1mm or more, it is determined that "peeling has occurred".

Claims

1. A negative-type photosensitive insulating film composition, characterized in that, Include: Alkali-soluble acrylic resin blends comprising a first alkali-soluble acrylic resin having a 9,9-bis(4-hydroxyphenyl)fluorene-derived structural unit and a second alkali-soluble acrylic resin having a tetra(4-hydroxyphenyl)ethane-derived structural unit; Crosslinked acrylic monomers, which have two or more acrylic double bonds; Photopolymerization initiator; as well as Silicon coupling agents, which have epoxy or amine groups.

2. The negative-type photosensitive insulating film composition according to claim 1, characterized in that, It comprises 5 to 50% by weight of the alkali-soluble acrylic resin blend, 5 to 30% by weight of the crosslinking acrylic monomer, 0.1 to 10% by weight of the photopolymerization initiator, 0.1 to 5% by weight of the silicone coupling agent, and the balance being a solvent.

3. The negative photosensitive insulating film composition according to claim 1, characterized in that, The solid content is 10 to 30% by weight.

4. The negative photosensitive insulating film composition according to claim 1, characterized in that, Based on tetrahydrofuran, the first alkali-soluble acrylic resin and the second alkali-soluble acrylic resin each have a weight-average molecular weight in the range of 2000 to 20000 g / mol.

5. The negative photosensitive insulating film composition according to claim 1, characterized in that, The weight ratio between the first alkali-soluble acrylic resin and the second alkali-soluble acrylic resin is 30:70 to 70:

30.

6. A cured insulating film, characterized in that, It is formed by coating a substrate with the composition of any one of claims 1 to 5 and then exposing and developing it.

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