Cured film, photosensitive resin composition for forming same, and display device

Abstract

Provided is a cured film which derives new parameters and improves the reliability of a device. One embodiment of the present invention provides a cured film obtained by curing a photosensitive resin composition, the photosensitive resin composition comprising: an alkali-soluble resin; and a photoactive compound (PAC), at a temperature of 250 DEG C, by means of a purge and trap (Purge, Purge, Purge, Purge, Purge, Purge, Purge, Purge, Purge; the cured film has a phenol-based gas content of 30% (v / v) or less in the total outgasses as measured by Trap analysis for 60 minutes, and is characterized in that the phenol-based gas content in the total outgasses is 30% (v / v) or less.

Description

Technical Field

[0001] The present invention relates to a cured film, a photosensitive resin composition for forming the cured film, and a display device. Background Art

[0002] Photosensitive resin compositions are representative functional polymer materials that are put into practical use in the production of various precision electronic industry products. Currently, they are used in cutting-edge technology industries, especially in the production of semiconductors and displays. Generally, a photosensitive resin composition means a composition that undergoes chemical changes in its molecular structure in a short period of time through light irradiation, resulting in changes in physical properties such as solubility in specific solvents, coloring, and curing. Photosensitive resin compositions can be used for fine precision processing, which can greatly save energy and raw materials compared to thermal reaction processes, and can perform work quickly and accurately in a small setting space. They are widely used in various precision electronic industry fields such as cutting-edge printing, semiconductor production, display production, and photocurable surface coating materials.

[0003] Such photosensitive resin compositions can be roughly divided into negative type and positive type. Negative type photosensitive resin compositions are types in which the light-irradiated portion is insoluble in a developer, while positive type photosensitive resin compositions are types in which the light-irradiated portion is soluble in a developer. Recently, with the high integration and fine patterning of electronic devices, positive type photosensitive resin compositions are mainly used, which can minimize the defective rate and improve the processing efficiency and resolution.

[0004] In particular, organic light emitting display (OLED) has attracted much attention in the display industry due to its excellent resolution. OLED has the characteristic of emitting light from the device itself, and therefore, unlike liquid crystal display (LCD), it does not require a backlight. Therefore, OLED has the characteristics of being thin-filmable, lightweight, providing clear readability in the wild, and having excellent light-dark contrast and color reproduction. On the other hand, a partition wall (pixel defining layer, PDL) can be configured on the side wall of the light-emitting layer forming such an OLED device, and such a partition wall can be defined as a cured film (or insulating film) made of a photosensitive resin composition, for example. When the above-mentioned photosensitive resin composition includes a phenolic additive that improves the sensitivity to the developer, the phenolic gas released from the cured film causes the above-mentioned light-emitting layer to be affected, causing the OLED device to become black, and there is a problem of reduced reliability of the OLED. Summary of the invention

[0005] Problem that the invention aims to solve

[0006] An object of the present invention is to provide a cured film which has excellent sensitivity to a developer and leaves no residue after development.

[0007] Still another object of the present invention is to provide a cured film having excellent adhesion to a substrate, outstanding chemical resistance, and excellent device reliability.

[0008] Another object of the present invention is to provide new parameters related to outgassing of a cured film to achieve the above-mentioned properties.

[0009] Another object of the present invention is to provide a photosensitive resin composition that forms the above-mentioned cured film.

[0010] Another object of the present invention is to provide a display device including the above-mentioned cured film.

[0011] The purpose of the present invention is not limited to the above-mentioned purpose. Other purposes and advantages of the present invention that are not mentioned can be understood through the following description and can be more clearly understood through the embodiments of the present invention. In addition, it can be easily seen that the purposes and advantages of the present invention can be achieved through the schemes and combinations thereof that appear in the claims.

[0012] Means used to solve problems

[0013] According to a first embodiment of the present invention for achieving the above-mentioned purpose, the following cured film is provided, which is formed by curing a photosensitive resin composition, and the content of phenolic gas in the total outgas of the cured film measured by a purge & trap analysis method at 250° C. for 60 minutes is less than 30% (v / v).

[0014] According to a second embodiment of the present invention, in the first embodiment, in the cured film measured by the purge & trap analysis method, the content of the phenolic gas in the total outgas may be 0.1 to 10% (v / v).

[0015] According to a third embodiment of the present invention, in the first or second embodiment, the photosensitive resin composition may include: an alkali-soluble resin; and a photoactive compound (PAC).

[0016] According to a fourth embodiment of the present invention, in the third embodiment, the alkali-soluble resin may be one selected from the group consisting of polyimide resins, polyamic acid, polyamide ester, polyhydroxystyrene, and copolymers thereof.

[0017] According to a fifth embodiment of the present invention, in the fourth embodiment, the imidization index of the polyimide-based resin may be 50 to 100%.

[0018] According to a sixth embodiment of the present invention, in the fourth or fifth embodiment, the polyimide-based resin may include a structure induced from a diamine containing a hydroxyl group.

[0019] According to a seventh embodiment of the present invention, in one of the third to sixth embodiments, the photoactive compound may be generated by a reaction between a phenolic compound and a quinonediazide compound.

[0020] According to an eighth embodiment of the present invention, in one of the first to seventh embodiments, the content of the unreacted phenol monomer in the total weight of the photosensitive resin composition may be less than 1.0 weight percent.

[0021] According to the ninth embodiment of the present invention, in one of the first to eighth embodiments, the content of unreacted phenolic compounds in the total weight of the photosensitive resin composition may be less than 1.0 weight percent, and the unreacted phenolic compounds include a phenol structure as a matrix (ballast).

[0022] According to a tenth embodiment of the present invention, in one of the first to ninth embodiments, the photosensitive resin composition may not include a phenolic additive.

[0023] According to the eleventh embodiment of the present invention, in one of the first to tenth embodiments, in the above-mentioned cured film measured by the above-mentioned purge and trap (Purge & Trap) analysis method, the content of alcohol gas in the total outgas can be less than 20% (v / v), and the above-mentioned alcohol gas is formed by methanol and ethanol.

[0024] According to a twelfth embodiment of the present invention, in one of the third to eleventh embodiments, the photosensitive resin composition may further include a thermal crosslinking agent.

[0025] According to a thirteenth embodiment of the present invention, in the twelfth embodiment, the thermal crosslinking agent may include: a first thermal crosslinkable compound; and a second thermal crosslinkable compound different from the first thermal crosslinkable compound.

[0026] According to the fourteenth embodiment of the present invention, in the thirteenth embodiment, the first thermally crosslinkable compound may include 1 to 2 functional groups represented by the following chemical formula 1-1, and the second thermally crosslinkable compound may include 3 to 5 functional groups represented by the following chemical formula 1-1.

[0027] According to a fifteenth embodiment of the present invention, a photosensitive resin composition forming a cured film according to one of the first to fourteenth embodiments described above may be provided.

[0028] According to a sixteenth embodiment of the present invention, a display device including the cured film according to one of the first to fourteenth embodiments described above may be provided.

[0029] The solutions to the above problems do not list all the features of the present invention. The various features of the present invention and the advantages and effects based thereon will be understood in more detail with reference to the following specific embodiments.

[0030] Effects of the Invention

[0031] According to several embodiments of the present invention, by proposing parameters related to the content of phenolic gas in the total outgassing of the above-mentioned cured film, it is possible to achieve a cured film with excellent sensitivity to the developer and no residue after development, a cured film with excellent adhesion to the substrate, outstanding chemical resistance, and excellent device reliability.

[0032] In addition to the above-mentioned effects, specific effects of the present invention will be described together with the explanation of specific contents for implementing the invention below. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 FIG. 1 is a top view of an OLED according to an embodiment of the present invention. DETAILED DESCRIPTION

[0034] The following describes various structures of the present invention in more detail so that ordinary technicians in the technical field to which the present invention belongs can easily implement it, but it is only an example, and the scope of rights of the present invention is not limited to the following content.

[0035] One embodiment of the present invention provides a cured film formed by curing a photosensitive resin composition, wherein the content of phenolic gas in the total outgas of the cured film measured by purge & trap at 250° C. for 60 minutes is 30% (v / v) or less. According to one embodiment of the present invention, by providing parameters related to the content of phenolic gas in the total outgas of the cured film, a cured film having excellent sensitivity to a developer and no residue after development can be achieved, and a cured film having excellent adhesion to a substrate, outstanding chemical resistance, and excellent device reliability can be achieved.

[0036] Hereinafter, the structure of the present invention will be described in more detail.

[0037] 1. Cured film and photosensitive resin composition forming the same

[0038] One embodiment of the present invention provides a cured film made of a photosensitive resin composition, and the photosensitive resin composition according to the present invention may include an alkali-soluble resin that is soluble in alkali. Specifically, the alkali-soluble resin may be one selected from the group consisting of polyimide resins, polyamic acid, polyamide ester, polyhydroxystyrene, and copolymers thereof, and specifically, may be a polyimide resin generated by a polycondensation reaction of an anhydride and a diamine compound.

[0039] According to one embodiment of the present invention, the imidization index of the polyimide resin can be 50 to 100%, specifically, 60 to 98%, and more specifically, 60 to 90%. The imidization index of the polyimide resin can be adjusted by changing the synthesis temperature and synthesis time during the synthesis of the polyimide resin. For example, the synthesis temperature and synthesis time of the polyimide resin can be 2 to 6 hours under the conditions of 100 to 180°C. When the imidization index of the polyimide resin exceeds the above numerical range, the heat resistance becomes excellent, and the source of induced gas can be controlled, but there may be a problem of precipitation due to the lower sensitivity to the developer and the lower solubility. When the imidization index of the polyimide resin is less than the above numerical range, the solubility becomes relatively high, and there may be no precipitation problem, but there may be a problem of lower heat resistance and the source of induced gas cannot be controlled. The imidization index of the polyimide-based resin can be measured by confirming the peak of the polyimide-based resin using Fourier transform infrared spectroscopy (FTIR, Bruker IFS-66 / S).

[0040] The monomers for synthesizing the polyimide resin according to the present invention may include a diamine containing a hydroxyl group that improves sensitivity to a developer and improves solubility. For example, the diamine containing the above hydroxyl group may be 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (2,2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, bis-APAF (bis-APAF)). That is, the polyimide resin according to the present invention may include repeating units induced from a diamine containing a hydroxyl group. In addition, the above polyimide resin may also include repeating units induced from a variety of dianhydrides commonly used in the technical field. For example, the dianhydride may include one or more selected from the group consisting of 4,4'-oxydiphthalic anhydride (ODPA), 1,4-bis(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P6FDA), 4,4-phthalic anhydride (BPDA), and 4,4-hexafluoroisopropylidenediphthalic dianhydride (6FDA).

[0041] According to one embodiment of the present invention, by using the diamine containing the above-mentioned hydroxyl group as a monomer of the polyimide-based resin, it is possible to effectively prevent the problem of precipitation caused by the lower sensitivity or solubility to the developer as the imidization index of the polyimide-based resin increases. The content of the diamine containing the above-mentioned hydroxyl group can be 10 to 95 mol% based on 100 mol% of the total monomers, specifically, it can be 30 to 95 mol%. Specifically, the molar ratio of the repeating unit induced from the diamine containing the above-mentioned hydroxyl group to the repeating unit induced from the above-mentioned dianhydride can be 10:90 to 95:5 or 30:70 to 95:5. When the content of the diamine containing the above-mentioned hydroxyl group or the molar percentage of the repeating unit meets the above-mentioned numerical range, the sensitivity and solubility to the best developer can be achieved.

[0042] The photosensitive resin composition according to the present invention may include a photoactive compound (PAC) activated by light irradiation. Specifically, the photoactive compound may generate an acid by photoreaction to improve the solubility of the light-irradiated portion to an alkaline developer. The photoactive compound may be generated by the reaction of a phenolic compound and a quinone diazide compound. The phenolic compound may be selected from the group consisting of 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylene)bisphenol, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, bisphenol-A, methyl gallate and propyl gallate. The quinone diazide compound may be, for example, 5-naphthoquinone diazide sulfonic acid chloride. The photoactive compound is synthesized using a phenolic compound, so the content of the phenolic gas in the total outgassing of the cured film may be different depending on the degree of decomposition of the photoactive compound.

[0043] According to another embodiment of the present invention, in the total weight of the above-mentioned photosensitive resin composition, the content of the unreacted phenolic compound may be less than 1.0 weight percent, specifically, less than 0.5 weight percent. The above-mentioned unreacted phenolic compound is a compound that does not react with the quinone diazide compound used to synthesize the photoactive compound and remains in the cured film, and is a compound including at least one hydroxyl group (-OH) directly bonded to the benzene ring. When the content of the above-mentioned unreacted phenolic compound meets the above-mentioned numerical range, the content of the phenolic gas in the total outgassing is properly adjusted, and excellent sensitivity to the developer can be achieved. After development, there is no residue in the cured film, and excellent adhesion to the substrate can be achieved. The chemical resistance is outstanding, and the reliability of the device is also excellent. The content of the above-mentioned unreacted phenolic compound is properly adjusted by the synthesis process of the photoactive compound, the content of the photoactive compound, etc., and the source of the phenolic outgassing can be effectively controlled. The above-mentioned unreacted phenolic compound can be, for example, a structure including a phenol structure as a matrix (ballast). The above-mentioned matrix can, for example, include one or more of the compounds represented by the following chemical formulas 1 to 9.

[0044] Chemical formula 1

[0045]

[0046] Chemical formula 2

[0047]

[0048] Chemical formula 3 Chemical formula 4

[0049]

[0050] Chemical formula 5

[0051]

[0052] Chemical formula 6

[0053]

[0054] Chemical formula 7

[0055]

[0056] Chemical formula 8

[0057]

[0058] Chemical formula 9

[0059]

[0060] In the above chemical formulas 1 to 9, R4, R6, R8 to R 13 can be independently a hydrogen atom (H) or an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. In each chemical formula, when R4, R6, R8 to R 13 If all of them are hydrogen atoms (H), there may be problems with chemical resistance and reliability. 13 Preferably, at least one alkyl group or alkenyl group may be included. Specifically, the above chemical formulas 1 to 9 may respectively include one or more alkyl groups having 1 to 4 carbon atoms or alkenyl groups having 2 to 4 carbon atoms. Furthermore, R5 and R7 are independently hydrogen atoms (H) or alkyl groups having 1 to 4 carbon atoms.

[0061] According to another embodiment of the present invention, in the total weight of the above-mentioned photosensitive resin composition, the content of unreacted phenol monomers may be less than 1.0 weight percent, specifically, less than 0.5 weight percent. The above-mentioned unreacted phenol monomers are monomers including a phenol structure that can be used to synthesize alkali-soluble resins. When such unreacted phenol monomers exist, they may become the cause of phenol-based outgassing. When the content of the above-mentioned unreacted phenol monomers meets the above-mentioned numerical range, the content of phenol-based gas in the total outgassing is properly adjusted, and a cured film with excellent sensitivity to the developer and no residue after development can be achieved, and a cured film with excellent adhesion to the substrate, outstanding chemical resistance, and excellent device reliability can be achieved. The content of the above-mentioned unreacted phenol monomers is appropriately adjusted within the above-mentioned numerical range by the conditions (monomer content, temperature conditions, etc.) when synthesizing the alkali-soluble resin, and the source of phenol-based outgassing can be effectively controlled.

[0062] The content of the photoactive compound may be greater than 20 and less than 35 parts by weight based on 100 parts by weight of the alkali-soluble resin, specifically, 20 to 30 parts by weight, 21 to 29 parts by weight, 22 to 28 parts by weight, 23 to 27 parts by weight, 24 to 26 parts by weight, or 25 to 26 parts by weight. When the content of the photoactive compound is less than the above numerical range, the adhesion of the cured film to the substrate may be reduced or the chemical resistance may be reduced. When the content exceeds the above numerical range, the reliability of the device may be reduced.

[0063] The photosensitive resin composition according to the present invention may not include a phenolic additive for improving sensitivity to a developer. Specifically, the phenolic additive may be one selected from a mixture consisting of compounds represented by the following chemical formula A or T and combinations thereof.

[0064]

[0065]

[0066] <Chemical formula T>

[0067]

[0068] A partition wall may be arranged on the side wall of the light-emitting layer forming the OLED device, and such a partition wall may be defined as a cured film made of a photosensitive resin composition, for example. When the photosensitive resin composition forming the cured film includes the above-mentioned phenolic additive for improving the sensitivity to the developer, the phenolic gas released from the cured film causes the above-mentioned light-emitting layer to be affected, resulting in the problem of reduced reliability of the OLED. The photosensitive resin composition according to one embodiment of the present invention can reduce the content of the phenolic gas in the total outgassing discharged from the cured film by not including the above-mentioned phenolic additive. As a result, the content of the phenolic gas that affects the light-emitting layer forming the OLED device is significantly reduced, and ultimately, the reliability of the OLED can be significantly improved.

[0069] According to one embodiment of the present invention, in the above-mentioned cured film measured by the purge & trap analysis method, the content of phenolic gas in the total outgas may be 30% (v / v) or less, specifically, 0.1 to 30% (v / v), more specifically, 0.1 to 20% (v / v), and more specifically, 0.1 to 10% (v / v). When the content of phenolic gas in the total outgas in the above-mentioned cured film exceeds the above-mentioned numerical range, the phenolic gas released from the cured film affects the light-emitting layer of the OLED, causing the OLED device to become black, thereby reducing the reliability of the OLED.

[0070] According to another embodiment of the present invention, in the above-mentioned cured film measured by the above-mentioned purge & trap analysis method, the content of alcohol-based gas in the total outgas may be less than 20% (v / v), specifically, it may be 0.1 to 15% (v / v). When the content of the above-mentioned alcohol-based gas in the total outgas in the above-mentioned cured film exceeds the above-mentioned numerical range, the reliability of the OLED may decrease like the phenol-based gas. Specifically, the above-mentioned alcohol-based gas may be formed by methanol and ethanol, and the above-mentioned alcohol-based gas may be generated in the process of imidization. The content of the above-mentioned alcohol-based gas may be less because the imidization index of the above-mentioned polyimide resin satisfies more than 50%.

[0071] The purge & trap analysis method according to the present invention may be a method of analyzing the cured film at 180 to 250° C. for 30 to 120 minutes, and specifically, may be a method of analyzing the cured film at 250° C. for 60 minutes. Specifically, in the step of realizing the pattern film using the photosensitive resin composition, the purge & trap analysis method may be performed in a hard bake process.

[0072] The photosensitive resin composition according to another embodiment of the present invention may further include a solvent. Specifically, the solvent may be, for example, one selected from the group consisting of gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl 3-methoxypropionate (MMP), propylene glycol monomethyl ether (PGME), diethylene glycol ethyl methyl ether (MEDG), diethylene glycol butyl methyl ether (MBDG), diethylene glycol dimethyl ether (DMDG), diethylene glycol diethyl ether (DEDG) and mixtures thereof. For example, the content of the solvent may be 50 to 95 weight percent based on the total weight of the photosensitive resin composition.

[0073] The photosensitive resin composition according to the present invention may further include additives as required. The additives may be one selected from the group consisting of a thermal crosslinking agent, a thermal acid generator, an ultraviolet (UV) absorber, and a combination thereof.

[0074] According to another embodiment of the present invention, the photosensitive resin composition may further include a thermal crosslinking agent that reacts with the alkali-soluble resin by heat, thereby effectively preventing the cured film from being unable to maintain the original pattern due to heat and sliding off.

[0075] The thermal crosslinking agent included in the photosensitive resin composition of the present invention may include two or more thermal crosslinking compounds having different numbers of functional groups, that is, the thermal crosslinking agent may include a first thermal crosslinking compound and a second thermal crosslinking compound different from the first thermal crosslinking compound.

[0076] Specifically, the thermal crosslinking agent may include: a first thermal crosslinking compound including 1 to 2 functional groups represented by the following Chemical Formula 1-1; and a second thermal crosslinking compound including 3 to 5 functional groups represented by the following Chemical Formula 1-1.

[0077] Chemical formula 1-1

[0078]

[0079] Chemical formula 2-1

[0080]

[0081] In the above chemical formula 1-1, R 1 are independently hydrogen, a substituent represented by the above chemical formula 2-1, or an organic group having 1 to 30 carbon atoms, R 1 At least one of them is a substituent represented by the above chemical formula 2-1, R 2 Each independently represents hydrogen, hydroxyl or an organic group having 1 to 30 carbon atoms.

[0082] In the above chemical formula 2-1, m is an integer from 1 to 27, R 3 It is an alkyl group having 1 to 3 carbon atoms.

[0083] In the above chemical formula 1-1, R 1 At least one of the substituents is a substituent represented by the above Chemical Formula 2-1, which means that 1 to 2 substituents of Chemical Formula 2-1 are substituted in Chemical Formula 1-1. In addition, when m of Chemical Formula 2-1 is 1 to 2, the curing rate of the photosensitive resin composition may be excellent. In particular, when m of Chemical Formula 2-1 is 1 to 2, R 3 When R in Chemical Formula 2-1 is methyl, excellent curing rate can be achieved. 3When the position includes 90 mol % or more of methyl groups, the curing rate of the photosensitive resin composition may be particularly excellent, and 100 mol % may be the most ideal.

[0084] According to another embodiment of the present invention, the weight ratio of the first thermal crosslinkable compound to the second thermal crosslinkable compound (first thermal crosslinkable compound: second thermal crosslinkable compound) can be 5:95 to 80:20. Within the above weight ratio range, the photosensitive resin composition achieves excellent sensitivity and low residual film rate, and can also achieve excellent adhesion, chemical resistance, heat resistance, sunlight resistance and driving reliability. As a thermal crosslinkable compound, the weight ratio of the first thermal crosslinkable compound to the second thermal crosslinkable compound can be more finely adjusted to greatly improve the sunlight resistance, hygroscopicity and driving reliability of the photosensitive resin composition. Specifically, the weight ratio of the first thermal crosslinkable compound to the second thermal crosslinkable compound can be a weight ratio of 30:70 to 60:40.

[0085] The thermal crosslinking agent according to the present invention may be included in 100 parts by weight of the alkali-soluble resin in an amount of 5 to 50 parts by weight, specifically, 10 to 30 parts by weight. When the content of the thermal crosslinking agent is less than the above numerical range, the alkali-soluble resin may not be sufficiently thermally crosslinked, and when it exceeds the above numerical range, the hygroscopicity and driving reliability may be reduced.

[0086] The first heat-crosslinkable compound is a compound including 1 to 2 functional groups represented by the above Chemical Formula 1-1, and may include, for example, one or more of the compounds represented by the following Chemical Formulas 3-1 to 15-1.

[0087]

[0088] In addition, the second heat-crosslinkable compound is a compound including 3 to 5 functional groups represented by the above Chemical Formula 1-1, and for example, may include one or more of the compounds represented by the following Chemical Formulas 16-1 to 24-1.

[0089]

[0090]

[0091] In the above chemical formulae 3-1 to 24-1, R 4 are independently a substituent represented by the above chemical formula 2-1, an alkyl group having 2 to 30 carbon atoms, or hydrogen, and at least one R in each chemical formula is 4 is a substituent represented by the above Chemical Formula 2-1.

[0092] The ratio of the substituents included in the heat-crosslinkable compound may affect the crosslinkability of the resin composition. Specifically, it is preferable that the first heat-crosslinkable compound and the second heat-crosslinkable compound each include 1 to 2 substituents represented by the above chemical formula 2-1 in the phenolic hydroxyl structure of the above chemical formula 1-1. The substituent of the alkoxyalkyl structure represented by the chemical formula 2-1 is located at R in the substituent represented by the above chemical formula 1-1. 1 , which is preferable, but the substituent represented by Chemical Formula 2-1 may not necessarily be included in Chemical Formula 1. In the heat-crosslinkable compound, the number of the substituent represented by Chemical Formula 2-1 in the structure of Chemical Formula 1-1 having the above-mentioned phenolic hydroxyl group is in the range of 1 to 2, the crosslinking reaction is excellent, and an excellent chemical resistance effect can be achieved, and the content of phenol gas and / or alcohol gas in the outgas may be reduced.

[0093] According to another embodiment of the present invention, the sensitivity of the cured film can be 120 mJ / cm 2 Specifically, the factors affecting the sensitivity of the cured film may be the presence or absence of phenolic additives and the content of the photoactive compound. For example, only when the photosensitive resin composition forming the cured film does not include phenolic additives and the content of the photoactive compound meets the appropriate level range, the sensitivity performance of the cured film can be excellent.

[0094] Another embodiment of the present invention can provide a photosensitive resin composition for forming the above-mentioned cured film. The description overlapping with the above-mentioned parts is omitted.

[0095] 2. Display device

[0096] Yet another embodiment of the present invention may provide a display device including the above-mentioned cured film.

[0097] The display device according to the present invention may be, for example, an OLED. The cured film forming the display device may be a partition wall (or an insulating film) disposed on the side wall of the light-emitting layer. According to one embodiment of the present invention, by patterning the partition wall using the cured film made from the photosensitive resin composition, the content of the phenolic gas that affects the light-emitting layer of the OLED device can be significantly reduced, thereby significantly improving the reliability of the OLED.

[0098] The following describes the embodiments of the present invention in detail so that those skilled in the art can easily implement the embodiments. However, the embodiments are only examples, and the scope of the present invention is not limited to the following contents.

[0099] Synthesis Example 1: Synthesis of polyamic acid

[0100] Under a dry nitrogen stream, 2,2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (bis-APAF, 0.2 mol) and 1,3-Bis(3-aminophenoxy)benzene (APB, 0.02 mol) as diamines were dissolved in γ-butyrolactone, and the mixture was stirred. 4,4'-oxydiphthalic anhydride (ODPA, 0.1 mol) was added to the stirred mixture to dissolve it, and then stirred at 70°C for 4 hours. Then, phthalic anhydride (PA, 0.1 mol) was added to the stirred result, and then stirred at 70°C for 2 hours to terminate the reaction and synthesize polyamic acid.

[0101] Synthesis Example 2: Synthesis of polyimide

[0102] After synthesizing a polyamic acid in the same manner as in Synthesis Example 1, the mixture was additionally stirred at 100° C. for 4 hours to synthesize a polyimide (imidization index: 60%).

[0103] Synthesis Example 3: Synthesis of polyimide

[0104] Polyimide was synthesized in the same manner as in Synthesis Example 2, except that the synthesized polyamic acid was stirred at 120° C. for 4 hours instead of at 100° C. for 4 hours (imidization index: 70%).

[0105] Synthesis Example 4: Synthesis of polyimide

[0106] Polyimide was synthesized in the same manner as in Synthesis Example 2, except that the synthesized polyamic acid was stirred at 130° C. for 4 hours instead of at 100° C. for 4 hours (imidization index: 75%).

[0107] Synthesis Example 5: Synthesis of polyimide

[0108] Polyimide was synthesized in the same manner as in Synthesis Example 2, except that the synthesized polyamic acid was stirred at 140° C. for 4 hours instead of at 100° C. for 4 hours (imidization index: 80%).

[0109] Synthesis Example 6: Synthesis of polyimide

[0110] Polyimide was synthesized in the same manner as in Synthesis Example 2, except that the synthesized polyamic acid was stirred at 150° C. for 4 hours instead of at 100° C. for 4 hours (imidization index: 87%).

[0111] Synthesis Example 7: Synthesis of polyimide

[0112] Polyimide was synthesized by the same method as in Synthesis Example 2, except that 4,4'-oxydianiline (ODA, 0.02 mol) was used instead of 1,3-bis(3-aminophenoxy)benzene (APB, 0.02 mol). The synthesized polyamic acid was stirred at 160°C for 4 hours instead of at 100°C for 4 hours (imidization index: 90%).

[0113] Synthesis Example 8: Synthesis of polyimide

[0114] Polyimide was synthesized in the same manner as in Synthesis Example 7, except that 1,3-Bis(4-aminophenoxy)benzene (TPE-R, 0.02 mol) was used instead of 4,4'-oxydianiline (ODA, 0.02 mol) (imidization index: 90%).

[0115] Synthesis Example 9: Synthesis of polyimide

[0116] Polyimide was synthesized in the same manner as in Synthesis Example 2, except that the synthesized polyamic acid was stirred at 160° C. for 4 hours instead of at 100° C. for 4 hours (imidization index: 90%).

[0117] Synthesis Example 10: Synthesis of polyimide

[0118] Polyimide was synthesized in the same manner as in Synthesis Example 7, except that 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenylether (6FODA, 0.02 mol) was used instead of 4,4'-oxydianiline (ODA, 0.02 mol) (imidization index: 90%).

[0119] Synthesis Example 11: Synthesis of polyimide

[0120] A polyimide was synthesized in the same manner as in Synthesis Example 10, except that the content of phthalic anhydride (PA, 0.1 mol) was changed to 0.2 mol (imidization index: 90%).

[0121] Synthesis Example 12: Synthesis of polyimide

[0122] Polyimide was synthesized in the same manner as in Synthesis Example 9, except that 1,4-bis(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P6FDA, 0.1 mol) was used instead of the above-mentioned 4,4'-phthalic anhydride (4,4'-oxydiphthalic anhydride, ODPA, 0.1 mol) (imidization index: 90%).

[0123] Synthesis Example 13: Synthesis of polyimide

[0124] Polyimide was synthesized in the same manner as in Synthesis Example 9, except that 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA, 0.1 mol) was used instead of 4,4'-phthalic anhydride (ODPA, 0.1 mol) (imidization index: 90%).

[0125] Synthesis Example 14: Synthesis of polyimide

[0126] Polyimide was synthesized in the same manner as in Synthesis Example 2, except that the synthesized polyamic acid was stirred at 170° C. for 4 hours instead of at 100° C. for 4 hours (imidization index: 93%).

[0127] Synthesis Example 15: Synthesis of polyimide

[0128] Polyimide was synthesized in the same manner as in Synthesis Example 2, except that the synthesized polyamic acid was stirred at 180° C. for 4 hours instead of at 100° C. for 4 hours (imidization index: 95%).

[0129] Synthesis Example 16: Synthesis of polyimide using bis-APHP as diamine

[0130] Polyimide was synthesized by the same method as in Synthesis Example 9, using 2,2-bis(3-aminophenyl)hexafluoropropane (bis-APHP, 0.2 mol) instead of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (bis-APAF, 0.2 mol) (imidization index: 90%).

[0131] Synthesis Example 17: Synthesis of Photoactive Compounds

[0132] Under dry nitrogen (N2), 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1 mol) and 5-naphthoquinonediazidesulfonic acid chloride (2 mol) as ballast are dissolved in 1,4-dioxane at room temperature. Triethylamine is added dropwise to prevent the mixture from reaching 35°C or above, and then the added mixture is stirred at 40°C for 2 hours. After filtering the triethylamine salt, the remaining (waste liquid) after filtration is added to water. After filtering the precipitate, it is washed in hydrochloric acid water (1% HCl (aq)). After that, it is washed in water 3 times and then dried in a vacuum dryer to synthesize a quinonediazide compound.

[0133] Production Example 1: Production of a photosensitive resin composition

[0134] The photosensitive resin composition was prepared according to the following Tables 1 to 5. In the following Tables 1 to 5, polyimide was synthesized by the method according to the above synthesis example using diamine, dianhydride and anhydride as monomers. And, in Comparative Examples 2 to 25, the compounds represented by the above chemical formulas A to S (phenolic additives) were used as additives. The quinone diazide compound synthesized by the above synthesis example 17 was used as PAC, and 100 parts by weight of the alkali-soluble resin according to the above synthesis example was used as a reference, 1000 parts by weight of a mixed solvent of propylene glycol monomethyl ether (PGME) and gamma-butyrolactone (GBL) (mixing weight ratio of 5:5) was used as a solvent, and 15 parts by weight of two thermal crosslinking agents were used.

[0135] As the above-mentioned two thermal crosslinking agents, a first thermal crosslinking compound represented by the following chemical formula A-1 and a second thermal crosslinking compound represented by the following chemical formula B-1 are used. Specifically, a thermal crosslinking agent in which the above-mentioned first thermal crosslinking compound and the second thermal crosslinking compound are mixed in a weight ratio of 1:2 is used.

[0136] Chemical formula A-1

[0137]

[0138] Chemical formula B-1

[0139]

[0140] Table 1

[0141]

[0142]

[0143] Table 2

[0144]

[0145] Table 3

[0146]

[0147]

[0148] Table 4

[0149]

[0150]

[0151] Table 5

[0152]

[0153] Experimental example: Physical property evaluation

[0154] After applying the photosensitive resin composition according to the above-mentioned manufacturing example 1 on a glass substrate using a slit coater, a vacuum drying process was performed at a pressure of 40 Pa, and then pre-baked on a hot plate at 120° C. for 2 minutes to form a pre-cured film with a thickness of 3.0 μm. The pre-cured film was irradiated with an intensity of 20 mW / cm2 using a predetermined pattern mask. 2After irradiation with ultraviolet light (2.5μm contact hole critical dimension reference Dose), the film was developed with tetramethylammonium hydroxide aqueous solution (N(CH3)4+OH-, 2.38 weight percent) at 23°C for 1 minute and cleaned with ultrapure water for 1 minute. After that, the cleaned product was cured in an oven at 250°C for 60 minutes to form a pattern film (or cured film) with a thickness of 3.0μm.

[0155] 1) Analysis of phenol and alcohol in the exhaust gas

[0156] For the pattern film, the outgassing analysis was performed at 250°C for 60 minutes using a Purge & Trap device (JTD-505III of JAI). When the content of phenol gas was 10% (v / v) or less based on the total volume of outgassing, it was marked as "◎", when it was greater than 10% and less than 20% (v / v), it was marked as "O", when it was greater than 20% and less than 30% (v / v), it was marked as "△", when it was greater than 30% (v / v), it was marked as "X", when the content of alcohol gas (methanol + ethanol) was less than 20% (v / v), it was marked as "O", otherwise it was marked as "X", as shown in the following Tables 6 to 8.

[0157] 2) Sensitivity

[0158] For the above pattern film, when the sensitivity is 120mJ / cm 2 The following are marked with "O" when necessary and "X" otherwise, as shown in the following Tables 6 to 8.

[0159] 3) Scum (residue)

[0160] The inside of the pattern film was observed using a scanning electron microscope (SEM), and the presence of scum (residue) after development was marked with "X", and the absence of scum was marked with "O", as shown in Tables 6 to 8 below.

[0161] 4) Adhesion

[0162] In order to evaluate the adhesion of the pattern film to the substrate, the adhesion was compared based on the minimum critical dimension of the dot pattern. Specifically, in the Dot pattern CD 5μm, "O" was marked when the adhesion of the pattern film to the substrate was ensured, and "X" was marked when the adhesion was insufficient and peeling occurred, as shown in Tables 6 to 8 below.

[0163] 5) Chemical resistance

[0164] The pattern film was immersed in N-methylpyrrolidone (NMP) at 60°C for 120 seconds, and the thickness change rate of the pattern film before and after the immersion was measured. The thickness change rate is When it is less than 0, it is marked as "O", and when it is greater than The time is marked with "X" and shown in the following Tables 6 to 8.

[0165] 6) OLED reliability

[0166] Figure 1 FIG. 1 is a top view of an OLED according to an embodiment of the present invention.

[0167] like Figure 1 As shown, after forming a pattern film (insulating film) on an indium tin oxide (ITO) substrate (anode electrode) in the same manner as the above sensitivity analysis method, an organic light-emitting layer (EL, light-emitting substance, TADF) is deposited. After forming an aluminum film (Al) on the upper part using a cathode electrode, an encapsulation process is performed to manufacture an OLED device. The time (T97) for the OLED device to reduce its brightness by 3% in the On state is evaluated based on 85°C and 85% RH. When it is ensured to be more than 1000 hours, it is marked as "O", when it is more than 800 hours and less than 1000 hours, it is marked as "△", and when it is less than 800 hours, it is marked as "X", as shown in the following Tables 6 to 8.

[0168] Table 6

[0169] phenol alcohol Sensitivity scum Adhesion Chemical resistance OLED Reliability Example 1 △ O O O O O O Example 2 △ O O O O O O Example 3 △ O O O O O O Example 4 O O O O O O O Example 5 O O O O O O O Example 6 ◎ O O O O O O Example 7 ◎ O O O O O O Example 8 ◎ O O O O O O Example 9 ◎ O O O O O O Example 10 ◎ O O O O O O Embodiment 11 ◎ O O O O O O Example 12 ◎ O O O O O O Embodiment 13 ◎ O O O O O O Embodiment 14 ◎ O O O O O O Embodiment 15 ◎ O O O O O O Example 16 ◎ O O O O O O Embodiment 17 ◎ O O O O O O Embodiment 18 ◎ O O O O O O

[0170] Table 7

[0171]

[0172]

[0173] Table 8

[0174] phenol alcohol Sensitivity scum Adhesion Chemical resistance OLED Reliability Comparative Example 19 X X O O O X X Comparative Example 20 X X O O O X X Comparative Example 21 X X O O O X X Comparative Example 22 X X O O O X X Comparative Example 23 X X O O O X X Comparative Example 24 X X O O O X X Comparative Example 25 X X O O O X X Comparative Example 26 O O X O X X O Comparative Example 27 O O X O X X O Comparative Example 28 O O X O X X O Comparative Example 29 X X O O O O X Comparative Example 30 X X X X O O X Comparative Example 31 O O X X O O O Reference Example 1 △ O O O O O △ Reference Example 2 X X O O O X △ Reference Example 3 ◎ O O O O O △ Reference Example 4 ◎ O O O O O △

[0175] In the above Tables 6 to 8, by comparing Comparative Example 1 using polyamic acid as a binder resin and an embodiment using a polyimide resin as a binder resin, it can be inferred that by using a polyimide resin as a binder resin, chemical resistance and reliability of OLED are improved. By comparing Comparative Examples 2 to 25 using a phenolic additive to improve sensitivity to a developer and an embodiment not including a phenolic additive, it can be inferred that the embodiment can reduce the content of phenolic gas released from the cured film by not using a phenolic additive to improve sensitivity, thereby improving the reliability and chemical resistance of OLED. Moreover, by comparing Comparative Examples 26 to 30 with the embodiment, when the content of the photoactive compound (PAC) is greater than 20 and less than 35 parts by weight based on 100 parts by weight of the alkali-soluble resin, the adhesion of the cured film to the substrate, chemical resistance, sensitivity to the developer, and reliability of OLED can all be improved. By comparing Comparative Example 31 with the embodiment, it can be inferred that in order to synthesize a polyimide resin used as a binder resin, by using a diamine monomer containing a hydroxyl group (bis-APAF), the imidization index of the polyimide resin can be increased, thereby effectively preventing the sensitivity to the developer from decreasing or the solubility from decreasing, resulting in precipitation.

[0176] In the above Tables 6 and 8, by comparing Example 8 with Reference Examples 1 and 2, it can be confirmed that when the content of unreacted phenol monomers equivalent to monomers including phenol structures that can be used when synthesizing alkali-soluble resins is less than 1 weight percent based on the total weight of the photosensitive resin composition, or the content of unreacted phenolic compounds that have not reacted with quinonediazide compounds is less than 1.0 weight percent, the content of phenolic gas in the total outgas is appropriately adjusted, and a cured film with excellent sensitivity to the developer and no residue after development can be achieved, and a cured film with excellent adhesion to the substrate, outstanding chemical resistance, and excellent device reliability can be achieved.

[0177] The preferred embodiments of the present invention are described in detail above, but the scope of rights of the present invention is not limited thereto. Various modifications and improvements made by ordinary technicians in the technical field of the present invention using the basic concepts of the present invention defined in the following claims also fall within the scope of rights of the present invention.

Claims

1. A cured film formed by curing a photosensitive resin composition, characterized in that: In the cured film measured by purge and trap analysis at 250° C. for 60 minutes, the content of phenolic gas in the total outgas was 30% (v / v) or less.

2. The cured film according to claim 1, characterized in that In the cured film measured by the purge and trap analysis method, the content of the phenolic gas in the total outgas is 0.1 to 10% (v / v).

3. The cured film according to claim 1, characterized in that The photosensitive resin composition comprises: Alkali soluble resin; and Photoactive compounds.

4. The cured film according to claim 3, characterized in that The alkali-soluble resin is one selected from the group consisting of polyimide resins, polyamic acid, polyamide ester, polyhydroxystyrene, and copolymers thereof.

5. The cured film according to claim 4, characterized in that The imidization index of the polyimide resin is 50 to 100%.

6. The cured film according to claim 4, characterized in that The polyimide-based resin includes repeating units induced from a diamine containing a hydroxyl group.

7. The cured film according to claim 3, characterized in that The photoactive compound is produced by the reaction of a phenolic compound and a quinonediazide compound.

8. The cured film according to claim 1, characterized in that In the total weight of the photosensitive resin composition, the content of the unreacted phenol monomer is less than 1.0 weight percent.

9. The cured film according to claim 1, characterized in that In the total weight of the photosensitive resin composition, the content of the unreacted phenolic compound is less than 1.0 weight percent. The unreacted phenolic compound includes a phenol structure as a matrix, that is, a ballast.

10. The cured film according to claim 1, characterized in that The photosensitive resin composition does not include a phenolic additive.

11. The cured film according to claim 1, characterized in that In the cured film, the content of alcohol gas in the total outgas measured by the purge and trap analysis method is 20% (v / v) or less, The alcohol gas is composed of methanol and ethanol.

12. The cured film according to claim 1, characterized in that The photosensitive resin composition further includes a thermal crosslinking agent.

13. The cured film according to claim 12, characterized in that The above-mentioned thermal crosslinking agent includes: a first thermally crosslinkable compound; and A second thermally crosslinkable compound different from the first thermally crosslinkable compound.

14. The cured film according to claim 13, characterized in that The first heat-crosslinkable compound includes 1 to 2 functional groups represented by the following chemical formula 1-1: The second heat-crosslinkable compound includes 3 to 5 functional groups represented by the following chemical formula 1-1: Chemical formula 1-1 Chemical formula 2-1 In the above chemical formula 1-1, R 1 are independently hydrogen, a substituent represented by the above chemical formula 2-1, or an organic group having 1 to 30 carbon atoms, R 1 At least one of them is a substituent represented by the above chemical formula 2-1, R 2 are independently hydrogen, hydroxyl or an organic group having 1 to 30 carbon atoms, In the above chemical formula 2-1, m is an integer from 1 to 27, R 3 It is an alkyl group having 1 to 3 carbon atoms.

15. A photosensitive resin composition, characterized in that: A cured film according to any one of claims 1 to 14 is formed.

16. A display device, characterized in that: The cured film according to any one of claims 1 to 14 is included.

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