Resin composition, resin film and display device

Abstract

According to the present invention, a resin composition can be provided, comprising at least three components (a), (b) and (c); wherein the component (a) is a polymer having a structure represented by the following formula (1), the component (b) comprises a thermal crosslinking agent (b1) and a thermal crosslinking agent (b2), and the component (c) is a photosensitizer, wherein R 1 , R 2 Independently selected from at least one atom other than hydrogen; R 3 , R 4 They are independently selected from organic groups having 1 to 20 hydrogen atoms or carbon atoms, and n is selected from integers of 1 to 10. The resin composition of the present invention can obtain better flatness and bending recovery performance.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 202110851447.X, with the invention title of "Resin Composition, Resin Film and Display Device", filed on July 27, 2021. Technical Field

[0002] The present invention relates to a resin composition, a resin film formed from the resin composition, and a display device formed from the resin composition and / or the resin film. Background Art

[0003] In recent years, organic electroluminescent (hereinafter referred to as "organic EL") display devices have been widely used in many electronic devices. Generally, an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and emits light by applying a voltage between the oppositely disposed first electrode and second electrode or by current flow. Among them, as the material for the planarization layer and the insulating layer, a photosensitive resin composition capable of being patterned by ultraviolet irradiation is usually used.

[0004] With the miniaturization, high functionality, and high integration of electronic devices, the performance requirements for the electronic components used in these electronic devices are also continuously increasing. Resins such as polyimide, polybenzoxazole, and polyamideimide have excellent properties in terms of heat resistance, electrical insulation, etc., and photosensitive resin compositions containing such resins are suitable as materials for the insulating layer or planarization layer of organic EL display devices.

[0005] On the other hand, in a flexible organic EL display device including a bent portion, the material for the insulating layer or planarization layer is required to have good flatness and bending properties. Therefore, it is also of great significance to improve the flatness and bending properties of the photosensitive resin composition.

[0006] Currently, it is known that a phenolic hydroxyl compound can be introduced into a polyimide precursor to solve the problem of being unable to be developed in a short time, thereby improving the resolution of fine patterns. However, there are problems such as compound scattering and thermal shrinkage during the curing process (Patent Document 1). In addition, it is known that introducing a thermal crosslinking agent into a photosensitive resin precursor composition can reduce the thermal shrinkage rate. However, the obtained photosensitive resin precursor composition has problems such as poor bending resistance and easy formation of printing creases (Patent Document 2).

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: CN1246389C

[0010] Patent Document 2: CN100362429C SUMMARY OF THE INVENTION

[0011] When the photosensitive resin precursor composition described in the above patent document is used in an organic EL display device, there are many problems such as insufficient long-term reliability, poor flexibility, and poor flatness. Therefore, the technical solution of the present invention mainly aims to solve the above-mentioned problems.

[0012] According to an embodiment of the present invention, a resin composition can be provided, which contains at least three components (a), (b), and (c); wherein, the component (a) is a polymer having a structure represented by the following formula (1), the component (b) contains a thermal crosslinking agent (b1) and a thermal crosslinking agent (b2), and the component (c) is a photosensitizer.

[0013]

[0014] Wherein, R 1 and R 2 are independently selected from at least one atom other than hydrogen; R 3 and R 4 are independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms, and n is selected from an integer of 1 to 10.

[0015] In another embodiment of the present invention, the thermal crosslinking agent (b1) is an aromatic ester-based thermal crosslinking agent, and the thermal crosslinking agent (b2) is a thermal crosslinking agent containing an unsaturated bond.

[0016] In another embodiment of the present invention, the thermal crosslinking agent (b1) is selected from low-temperature thermal crosslinking compounds with a thermal crosslinking temperature of 120 to 180 °C, and more specifically, is selected from the structure represented by the following formula (2).

[0017]

[0018] Wherein, R 8 is selected from an organic group having 2 to 30 carbon atoms; R 9 is selected from an organic group having 1 to 10 carbon atoms; s is selected from an integer of 1 to 4, p is selected from an integer of 1 to 16, and s + p > 2.

[0019] In another embodiment of the present invention, the thermal crosslinking agent (b2) is selected from thermal crosslinking compounds with a thermal crosslinking temperature of 180 to 400 °C, and more specifically, is selected from one or more of the structures represented by the following formula (3) and / or formula (4).

[0020]

[0021] Wherein, R 6 and R 7Independently selected from organic groups having at least 2 to 30 carbon atoms; y and q are independently selected from integers of 1 to 10.

[0022] In another embodiment of the present invention, wherein the structure represented by the formula (3) contains an acrylic structure, and more specifically, is selected from one or more of the structures represented by the following formula (5),

[0023]

[0024] wherein, R 10 is selected from organic groups having 2 to 25 carbon atoms, and z is selected from integers of 1 to 10.

[0025] In another embodiment of the present invention, wherein the component (a) is a polymer having a structure represented by the following formula (6),

[0026]

[0027] wherein, R 1 , R 2 are independently selected from at least containing an atom other than hydrogen; R 3 , R 4 are independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R 5 is selected from halogen and / or halogenated hydrocarbon group and / or an organic group having 1 to 10 carbon atoms; n and m are independently selected from integers of 1 to 10.

[0028] In another embodiment of the present invention, it may further contain one or more of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, or their copolymers.

[0029] In another embodiment of the present invention, wherein the photosensitizer of the component (c) is a photoacid generator.

[0030] In another embodiment of the present invention, it further contains a phenolic hydroxyl compound.

[0031] According to another embodiment of the present invention, a resin film can be provided, which is prepared from the photosensitive resin composition of the present invention.

[0032] According to another embodiment of the present invention, a display device can be provided, which is prepared from the resin composition of the present invention or contains the resin film of the present invention.

[0033] In another embodiment of the present invention, it may further contain a component (a1), and the component (a1) contains an aliphatic group having a siloxane structure; preferably, the component (a1) has a structure represented by the formula (7),

[0034]

[0035] Among them, R 11 is an organic group containing at least 1 to 20 Si-O repeating units and also contains an aliphatic group.

[0036] In another embodiment of the present invention, among them, R 11 is selected from one or more of the structures represented by the following:

[0037] In another embodiment of the present invention, among them, the weight ratio of the (a1) component to the (a) component is 0.01 to 10 wt%.

[0038] In another embodiment of the present invention, among them, the residue containing R 1 can be selected from one or more of the structures represented by the following:

[0039] -O-, -SO 2 -, -NH-, -CO-, -Si-O-,

[0040]

[0041]

[0042] In another embodiment of the present invention, among them, the residue containing R 1 can be further selected from one or more of the structures represented by the following:

[0043] -O-, -SO 2 -, -NH-, -CO-, -Si-O-,

[0044] In another embodiment of the present invention, among them, the residue containing R 2 can be selected from one or more of the structures represented by the following:

[0045]

[0046] Considering the degree of graphic refinement, the residue containing R 2 preferably has the structure represented by the following:

[0047]

[0048] In another embodiment of the present invention, the thermal crosslinking agent (b1) can specifically be selected from one or more of the following compounds:

[0049]

[0050]

[0051] In another embodiment of the present invention, the thermal crosslinking agent (b1) can more specifically be selected from one or more of the following compounds:

[0052]

[0053] In another embodiment of the present invention, the thermal crosslinking agent (b2) can specifically be selected from one or more of the following compounds:

[0054]

[0055]

[0056]

[0057] After in-depth research, the inventors of the present invention found that by using the resin composition of the present invention, an organic EL display device with better flatness and bending recovery performance, and good luminous efficiency and flexibility can be obtained. Detailed implementation manners

[0058] In order to make the purpose and advantages of the present invention clearer, the technical solutions of the present invention will be further clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, which are used to help those skilled in the art further understand the present invention, but do not limit the present invention in any form. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0059] <Resin composition>

[0060] The resin composition of the present invention can at least contain three components (a), (b), and (c), wherein the component (a) is a polymer having the structure represented by formula (1), the component (b) contains a thermal crosslinking agent (b1) and a thermal crosslinking agent (b2), and the component (c) is a photosensitizer.

[0061] The component (a) is a polymer having the structure represented by formula (1), containing alkali-soluble groups such as hydroxyl groups, and can be called an alkali-soluble polymer.

[0062]

[0063] Among them, R 1 and R 2 are independently selected from those containing at least one other atom except hydrogen; R 3 and R 4 are independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms, and n is selected from an integer of 1 to 10.

[0064] For the other atoms except hydrogen contained in R 1 and R 2 , they are independently preferably selected from one or more of O, S, N, P, B, Si1 to Si20, and C1 to 30; considering from the flexibility of the polymer, R 1 is further preferably a group that does not contain an aromatic hydrocarbon group but contains one or more of O, S, N, and C atoms. Considering from the heat resistance of the polymer, R 2 is further preferably a group containing an aromatic group and / or a heteroaromatic group, and more preferably the aromatic group and / or the heteroaromatic group in R 2 is on the polymer main chain; considering from the solubility of the polymer, R 2 is still further preferably that a hydroxyl group is directly linked to the aromatic group and / or the heteroaromatic group; the polymer (a) may further contain a polymer having a structure represented by formula (6), wherein R 2 may further be linked with R 5 ; among them, R 5 may be selected from a halogen and / or a halogenated hydrocarbon group and / or an organic group having 1 to 10 carbon atoms; considering from the fineness degree of the formed pattern, R 5 is preferably a halogen and / or a halogenated hydrocarbon group having an electron-withdrawing group; n and m are independently selected from an integer of 1 to 10.

[0065]

[0066] The polymers having the structures represented by formula (1) and / or formula (6) provided by the present invention can be obtained by polymerizing, for example, an acid dianhydride and a diamine, and for example, a method of reacting an acid dianhydride with a diamine compound in a solvent can be cited.

[0067] As the residue of the acid dianhydride containing R 1 used in the polymer (a), the following represented structures can be specifically cited:

[0068] -O-, -SO 2 -, -NH-, -CO-, -Si-O-,

[0069]

[0070]

[0071] In terms of obtaining the flexibility of the polymer, R 1 preferably has the following group structure with less steric hindrance:

[0072] -O-, -SO 2 -, -NH-, -CO-, -Si-O-,

[0073] As the acid dianhydride containing R 1 the following compounds can be specifically listed:

[0074]

[0075] As the residue of the diamine containing R 2 used in the (a) polymer, the following structures can be specifically listed:

[0076]

[0077]

[0078] In terms of the degree of pattern refinement, the diamine residue containing the R 2 structure preferably has the following structure: ,

[0079] As the diamine containing R 2 the following compounds can be specifically listed:

[0080]

[0081]

[0082] In another embodiment of the present invention, in terms of controlling the molecular weight and its distribution of the polymer, the molar ratio of the acid dianhydride to the diamine is preferably 35:65 to 65:35, more preferably 40:60 to 60:40, and even more preferably 45:55 to 55:45.

[0083] In another embodiment of the present invention, the resin composition may further contain one or more of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, or their copolymers.

[0084] In the present invention, the acid dianhydride and the diamine can be used alone or in combination, and can be synthesized by known methods without special instructions.

[0085] In addition, for the purpose of further increasing the flexibility of the resin composition, a component (a1) containing an aliphatic group having a siloxane structure may be introduced into the resin composition. The compound containing an aliphatic group having a siloxane structure used is not particularly limited; considering the dispersibility effect after addition and the effect of improving flexibility, it is preferably selected from those containing the structure represented by the formula (7):

[0086]

[0087] wherein, R 11 is an organic group containing at least 1 to 20 Si-O repeating units; in addition, R 11 may also contain an aliphatic group, and the aliphatic group is copolymerized and linked with the siloxane; preferably, the aliphatic group has 1 to 30 carbon atoms. Considering the warpage performance of the polymer, the weight molecular weight range of R 11 is from 10 to 5000.

[0088] Specifically, R 11 may be exemplified by one or more of the structures represented below:

[0089]

[0090]

[0091] wherein, R 11 preferably has the structure represented by

[0092] represented.

[0093] The structure represented by the formula (7) contained in the component (a1) may be derived from a compound having a diamine at the end. Specifically, the following compounds may be exemplified:

[0094]

[0095]

[0096] The structure represented by the formula (7) contained in the component (a1) may be derived from a compound having a diamine at the end, and its addition method is not particularly limited. It may be directly mixed into the polymer (a), or introduced into the main chain and / or side chain of the polymer (a) through a polymerization reaction, that is, used as a raw material of a diamine to participate in the polymerization reaction, thereby being introduced into the macromolecular chain of the polymer (a).

[0097] For the purpose of further increasing the flexibility of the resin composition, preferably, the addition amount of the compound containing an aliphatic group having a siloxane structure accounts for 0.01 to 10 wt% of the total polymer by weight.

[0098] (b) Thermal crosslinking agent

[0099] The resin composition of the present invention contains component (b) as (b1) aromatic ester thermal crosslinking agent and (b2) unsaturated bond-containing thermal crosslinking agent. Generally, crosslinking agents can enhance the heat resistance and chemical resistance of the cured film formed from the resin composition; it should be noted in the present invention that thermal crosslinking agents are used to improve the flatness performance of the cured film in order to obtain better performance and higher yield when manufacturing devices.

[0100] In the present invention, the aromatic ester thermal crosslinking agent of thermal crosslinking agent (b1) is preferably selected from low-temperature thermal crosslinking compounds with a thermal crosslinking temperature of 120 - 180 °C. Specifically, it can be a compound represented by the following formula (2).

[0101]

[0102] In formula (2), R 8 is selected from organic groups containing 2 - 30 carbon atoms; R 9 is selected from organic groups containing 1 - 10 carbon atoms; s is an integer selected from 1 - 4, p is an integer selected from 1 - 16, and s + p > 2. In order to achieve a better thermal crosslinking effect, formula (2) can be further preferably limited. Preferably, s is an integer of 2 - 4; preferably, p is an integer of 2 - 6; preferably, R 8 has an aromatic group or heteroaromatic group structure. In addition, the phenolic hydroxyl group mentioned in formula (2) can be esterified and protected, which does not affect the thermal crosslinking performance and also belongs to a part of the present invention.

[0103] Specifically, the aromatic ester thermal crosslinking agent of thermal crosslinking agent (b1) can be listed as one or more of the following compounds:

[0104]

[0105] Among them, the aromatic ester thermal crosslinking agent of thermal crosslinking agent (b1) is preferably selected from one or more of the compounds with the following structures:

[0106]

[0107] In the present invention, the unsaturated bond-containing thermal crosslinking agent of thermal crosslinking agent (b2) is preferably selected from thermal crosslinking compounds with a thermal crosslinking temperature of 180 - 400 °C. Specifically, it can be selected from one or more of the compounds represented by the following formula (3) and / or formula (4):

[0108]

[0109] Among them, R 6 、R 7Independently selected from organic groups containing 2 to 30 carbon atoms; y and q are independently selected from integers of 1 to 10. Among them, R 6 In addition to carbon atoms, may also contain other heteroatoms, such as heteroatoms such as O and N; Preferably, the compound represented by formula (3) contains an acrylic acid structure, specifically represented as one or more of the compounds represented by the following formula (5):

[0110]

[0111] Among them, R 10 Is selected from organic groups containing 2 to 25 carbon atoms, and z is selected from integers of 1 to 10. Considering the thermal crosslinking effect, z is further preferably selected from integers of 2 to 8; In addition, R 10 May contain an aromatic group structure or may not contain an aromatic group structure, and both have good thermal crosslinking properties.

[0112] Considering the thermal crosslinking effect, in the compound represented by formula (4), q is preferably selected from integers of 1 to 6, and R 7 Is preferably selected from those containing an aromatic ring structure.

[0113] Specifically, among the thermal crosslinking agents containing unsaturated bonds in the thermal crosslinking agent (b2), the compounds represented by formula (3) and / or formula (4) can be specifically exemplified as one or more of the following compounds:

[0114]

[0115]

[0116]

[0117] The present invention does not particularly limit the synthesis method of the thermal crosslinking agent. Without special instructions, known methods can be applied for synthesis.

[0118] The content of the thermal crosslinking agent is not particularly limited. Relative to 100 parts by mass of the total amount of component (a) in the resin composition, the thermal crosslinking agent is preferably 10 to 40 parts by mass, more preferably 12 - 35 parts by mass, further preferably 14 - 30 parts by mass, and particularly preferably 16 - 26 parts by mass. The mass ratio of (b1) to (b2) is preferably 25:1 to 5:1, more preferably 22:1 to 8:1, and further preferably 20:1 to 10:1.

[0119] (c) Photosensitizer

[0120] The (c) photosensitizer contained in the resin composition of the present invention is not particularly limited. As the photosensitizer, a photopolymerization initiator and / or a photoacid generator that generates free radicals by absorbing a specific wavelength and decomposing can be used. In the present invention, a photoacid generator is preferably used.

[0121] Examples of the photoacid generator as the photosensitizer of the resin composition include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, etc. From the viewpoint of the long-term reliability of the organic EL device, etc., a photoacid generator containing a quinone diazide compound is preferably used.

[0122] Examples of the quinone diazide compound include a compound obtained by bonding a sulfonic acid of quinone diazide to a polyhydroxy compound in an ester manner; a compound obtained by bonding a sulfonic acid of quinone diazide to a polyamine compound in a sulfonamide manner; a compound obtained by bonding a sulfonic acid of quinone diazide to a polyhydroxy polyamine compound in an ester manner and / or a sulfonamide manner, etc. All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds may not be completely substituted by quinone diazide, but preferably 40 mol% or more of the entire functional groups are substituted by quinone diazide on average. By containing such a quinone diazide compound, the affinity of the quinone diazide compound for an alkaline aqueous solution is reduced, the ratio of the dissolution rate of the exposed part to the unexposed part of the composition increases, a pattern can be obtained with high resolution, and a positive photosensitive resin precursor composition that is sensitive to i-ray (wavelength 365 nm), h-ray (wavelength 405 nm), and g-ray (wavelength 436 nm) of a mercury lamp as ordinary ultraviolet rays can be obtained.

[0123] The present invention does not particularly limit the type and synthesis method of the quinone diazide compound as the photosensitizer. Unless otherwise specified, known quinone diazide compounds and synthesis methods can be adopted. The quinone diazide compound can be used alone or in combination of multiple kinds. Thereby, the ratio of the dissolution rate of the exposed part to the unexposed part can be further increased, and a photosensitive resin precursor composition with high sensitivity can be obtained.

[0124] The content of the photosensitizer is not particularly limited. Relative to 100 parts by mass of the total amount of the (a) component in the resin composition, it is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass. By setting the content of the photosensitizer within this range, high sensitivity can be achieved, and a sensitizer, etc. can be further contained as needed.

[0125] In addition to the (a) polymer, (b) thermal crosslinking agent, and (c) photosensitizer, the resin composition of the present invention may further contain the following additives.

[0126] (d) Solvent

[0127] The resin composition of the present invention may further include an organic solvent. By adding a solvent, components (a), (b), and (c) can be more fully and uniformly dispersed, and each component can be dissolved in the solvent to form a varnish-like state, further improving the coating properties and other properties of the resin composition.

[0128] There is no particular limitation on the organic solvent of the resin composition, and compounds such as ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, or alcohols can be cited. More specifically, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monon-propyl ether, ethylene glycol monon-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monon-propyl ether, diethylene glycol monon-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monon-propyl ether, propylene glycol monon-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monon-propyl ether, dipropylene glycol monon-butyl ether, tripropylene glycol monomethyl ether, tripropylene ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, methyl 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-propyl valerate, n-butyl butyrate, ethyl butyrate, n-propyl butyrate, isobutyric acid butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, aromatic compounds (such as toluene and / or xylene), amides (for example, one or more of alkyl, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide). One or several of them can be contained.

[0129] The content of the solvent is not particularly limited. In order to dissolve the composition, relative to 100 parts by mass of the total amount of component (a) in the resin composition excluding the solvent, it is preferably 100 to 2000 parts by mass, more preferably 300 to 1700 parts by mass, further preferably 400 to 1200 parts by mass, and particularly preferably 600 to 1100 parts by mass. Also, according to the needs of the coating process, resin composition solutions with different viscosities can be prepared by adjusting the content of the polymer, and a resin film with excellent performance can be obtained better; preferably, the viscosity range of the resin composition solution is 0.1 to 12000 cP, more preferably 0.5 to 10000 cP, and even more preferably 1 to 8000 cP.

[0130] (e) End-capping agent

[0131] For the resin composition, in order to adjust the molecular weight to the preferred range, the two ends can be capped using an end-capping agent. As the end-capping agent that reacts with the acid dianhydride compound, monoamines, monohydric alcohols, etc. can be cited. In addition, as the end-capping agent that reacts with the diamine compound, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonate compounds, vinyl ether compounds, etc. can be cited. Considering the end-capping effect and heat resistance, preferably, the end-capping agent contains an aromatic group functional group. In addition, by obtaining other good effects, various functional organic groups can also be introduced into the end-capping agent as terminal groups. For example, introducing alkali-soluble functional groups such as hydroxyl groups and carboxyl groups can improve its alkali-soluble performance; introducing unsaturated bonds can improve its thermal cross-linking performance, etc. Further preferably, the various functional organic groups introduced are connected to the aromatic ring in the end-capping agent to obtain better performance.

[0132] The content of the end-capping agent is not particularly limited. Relative to 100 parts by mass of the total amount of component (a) in the resin composition, it is preferably 0.1 to 20 parts by mass, more preferably 0.8 to 15 parts by mass, and even more preferably 1.0 to 10. By setting the content of the end-capping agent within this range, a good end-capping effect can be obtained, and at the same time, not too much organic matter will remain in the resin composition.

[0133] (f) Phenolic hydroxyl compound

[0134] As an additive to the resin composition of the present invention, a compound having a phenolic hydroxyl group can also be contained. By containing a compound having a phenolic hydroxyl group, the alkali-soluble performance of the polymer can be improved better, thereby shortening the development time. Specifically, the resin composition obtained by containing a compound having a phenolic hydroxyl group is basically insoluble in the alkaline developer before exposure, but easily dissolves in the alkaline developer after exposure and is easily developed in a short time. Therefore, the film loss caused by development is small. Therefore, a finer concavo-convex pattern can be obtained.

[0135] As these phenolic hydroxyl compounds, in addition to the types of compounds containing phenolic hydroxyl groups mentioned above, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTPB-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTPB-CP, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPG-26X, BisPC-OCHP, Bis26X-OCHP, BisPG-26X, BisOCHP-OC, Bis236T-OCHP, BisRS-26X, BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, BIR-BIPC-F, TEP-BIP-A, etc. can also be cited; preferably Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F. One or several of them can be contained. In the present invention, other structures or substances with phenolic hydroxyl groups mentioned can also exist as a phenolic hydroxyl compound.

[0136] From the viewpoint of the heat resistance of the phenolic hydroxyl compound, bisphenols are preferred. The content of the phenolic hydroxyl compound is preferably 1 to 50 parts by mass relative to 100 parts by mass of the total amount of the resin composition. Thereby, the alkali developability of the photosensitive resin precursor composition can be improved while maintaining high heat resistance.

[0137] The resin composition of the present invention may further include at least one or more of polyamide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, or their copolymers.

[0138] <Preparation of Resin Composition>

[0139] The first step is the synthesis of the polymer. First, the diamine and acid dianhydride required by the present invention are respectively added into a solvent, and under the condition of -20 to 150 °C, stirring reaction is carried out for 1 to 10 hours for polymerization reaction. A capping agent is added during the reaction to form the polymer (a) with the target molecular weight. Then, an esterifying agent is added to the solution system for reaction for 1 minute to 3 hours. Finally, the polymer is put into water to obtain the target polymer.

[0140] Considering the dissolution uniformity, the molecular weight range of the polymer (a) is preferably 5000 to 500000, more preferably 8000 to 350000, and even more preferably 10000 to 250000.

[0141] As the diamine and / or acid dianhydride of the present invention, in addition to the above-mentioned diamine and / or acid dianhydride, other common diamines and / or acid dianhydrides can also be used in combination, and the purpose is to adjust the performance of the polymer to obtain a resin film with more excellent performance.

[0142] As the esterifying agent, there is no particular limitation. If not otherwise specified, known methods can be used for synthesis. Specific examples can be listed as follows:

[0143]

[0144] Considering the esterification effect and the performance of the formed resin film, an esterifying agent with a smaller molecular weight is preferred to form a small molecular weight esterification protecting group. Among them, the esterifying agent is preferably selected from compounds with the following structures:

[0145]

[0146] As the solvent used in the polymerization process, there is no particular limitation as long as it can dissolve the acid dianhydride and diamine as raw material monomers. Specifically, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropanamide, etc. can be listed; cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc.; carbonates such as ethylene carbonate, propylene carbonate, etc.; diols such as triethylene glycol, etc.; phenols such as m-cresol, p-cresol, etc.; acetophenone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, ethyl lactate, etc.

[0147] The second step is the preparation of the varnish. First, the obtained target polymer is added to a solvent for dissolution, and then (b) a thermal crosslinking agent and (c) a photosensitizer are added to the solution system. According to other functional requirements, some other additives can also be added. For example, a phenolic hydroxyl compound is added to improve alkali solubility, etc. Finally, a varnish is obtained, which is also called a resin composition. Considering the stability of the varnish, the preferred content is 5-55%, more preferably 6-35%, still more preferably 7-25%, and even more preferably 8-15%. Considering the coating performance, preferably, the viscosity range of the resin composition solution is 0.1-12000 cP, more preferably 0.5-10000 cP, still more preferably 1-8000 cP.

[0148] <Resin film>

[0149] The resin film of the present invention can be prepared from the above resin composition. Specifically, the resin composition can be coated on a substrate, and then dried, exposed, developed, and heat-treated for curing to obtain a resin film with a fixed pattern, which is called a photosensitive resin film. It is also possible not to perform the exposure and development processes, but directly obtain an ordinary resin film. If this ordinary resin film is further laminated, a protective film can be formed.

[0150] As the substrate, a silicon wafer, ceramics, gallium arsenide, an organic circuit board, an inorganic circuit board, and a substrate obtained by disposing a circuit constituent material on these substrates, etc. can be used, but are not limited to these.

[0151] The coating method can include a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc.; preferably, it is a slit coating method.

[0152] The drying method can be one or a combination of using an oven, a hot plate, or an infrared method. The heating temperature is preferably 50°C to 180°C, and the heating time is preferably greater than 30 seconds.

[0153] The exposure method is to cover the dried resin composition with a mask having a desired pattern and irradiate chemical rays for exposure. As the chemical rays used for exposure, there are ultraviolet rays, visible light rays, electron rays, X-rays, etc. The present invention preferably uses the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. In order to form a pattern of a heat-resistant resin, the exposed part is removed with a developer after exposure. After development, a photosensitive resin film can be obtained by heat curing. The developer can be a generally known developer, and the development method can also be a generally known method.

[0154] The heat treatment curing method can be a method that uses one or a combination of an oven, a hot plate, and infrared rays; considering the planarization degree, the heat treatment stage is divided into a first stage and a second stage; during the heat treatment curing in the first stage, the curing temperature is 120 to 180 °C, and the curing time is 2 minutes to 4 hours; during this heat treatment curing stage, the thermal crosslinking agent (b1), an aromatic ester-based thermal crosslinking agent, starts to undergo the main crosslinking reaction; through the heat treatment curing in the first stage, the resin film can be pre-crosslinked to a controllable degree, reducing the deformation of the resin film caused by the crosslinking reaction; then, during the heat treatment curing in the second stage, the curing temperature is 180 to 400 °C, and the curing time is 2 minutes to 4 hours; during this heat treatment curing stage, the thermal crosslinking agent (b2), a thermal crosslinking agent containing unsaturated bonds, starts to undergo the main crosslinking reaction; through the heat treatment curing in the second stage, the resin film can be further crosslinked and cured to form a stable resin film; because of the crosslinking reaction in the first stage, the crosslinking reaction in the second stage will not be very intense, thus effectively controlling the huge deformation of the resin film after development due to heat treatment curing, and therefore better controlling the planarization degree of the photosensitive resin film after heat treatment curing. Considering the planarization degree of the obtained photosensitive resin film, in the heat treatment curing conditions of the second stage, the maximum temperature is preferably below 380 °C, more preferably below 350 °C; also preferably, in the heating program, it is preferred to increase the temperature gently in multiple stages.

[0155] The resin film of the present invention includes a photosensitive resin film, a general resin film, and a protective film, and can be applied not only to organic EL display devices but also to electronic components such as semiconductor devices and multilayer wiring boards. To obtain good device performance, the thickness of the resin film is preferably 0.4 to 25 μm, more preferably 1.0 - 18 μm, and further preferably 1.5 to 12 μm.

[0156] <Display device>

[0157] The present invention also provides a display device; specifically, it includes a general resin film and / or a photosensitive resin film and / or a protective film obtained from the resin composition of the present invention, and can be used for the planarization layer and / or the insulating layer in an organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate. To obtain an organic EL display device with long-term reliability and excellent bending recovery performance.

[0158] The display device of the present invention can be bent and folded in a suitable manner. For example, it can be bent at the central part of the photosensitive device or at the end of the photosensitive device; according to the specific use and basic configuration, it can be bent multiple times at a specific part of the display device and maintain long-term effective display characteristics.

[0159] <Example>

[0160] The following are examples for explaining the present invention, but the present invention is not limited to these examples. First, the abbreviations corresponding to some monomers involved in the examples are explained.

[0161] Compound 1: Diamine 5 (3,3'-dihydroxybenzidine, CAS No.: 2373-98-0)

[0162]

[0163] Compound 2: Acid dianhydride 1 (4,4'-oxybisphthalic anhydride, CAS No.: 1823-59-2)

[0164]

[0165] Compound 3: Acid dianhydride 2 (hexafluorodiacid anhydride, CAS No.: 1107-00-2)

[0166]

[0167] Compound 4: Acid dianhydride 3 (p-phenylene-bis(trimellitic anhydride), CAS No.: 2770-49-2)

[0168]

[0169] Compound 5: Acid dianhydride 4 (3,3,4,4-diphenylsulfone tetracarboxylic dianhydride, CAS No.: 2540-99-0)

[0170]

[0171] Compound 6: Acid dianhydride 5 (4,4'-p-phenylenedioxybisphthalic anhydride, CAS No.: 17828-53-4)

[0172]

[0173] Compound 7: Acid dianhydride 6 (3,3',4,4'-biphenyltetracarboxylic dianhydride, CAS No.: 2420-87-3)

[0174]

[0175] Compound 8: Thermal crosslinking agent (b1)-1 (4,4',4''-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol), CAS No.: 672926-26-0)

[0176]

[0177] Compound 9: Thermal crosslinking agent (b2)-1 (pentaerythritol dipentaerythritol hexaacrylate, CAS No.: 29570-58-9)

[0178]

[0179] Compound 10: Thermal crosslinking agent (b2)-2 ((methyl-1,3-phenylene)bis[iminocarbonyl-oxy[2,2-bis[[(1-oxoallyl)oxy]methyl]]-3,1-propanediyl] diacrylate, CAS No.: 51160-64-6)

[0180]

[0181] Compound 11: Thermal crosslinking agent (b2)-3 (4-(triisopropylsilylethynyl)phenylacetylene, CAS No.: 75345-90-1)

[0182]

[0183] Compound 12: Siloxane compound 1 (SiDA, CAS No.: 2469-55-8)

[0184]

[0185] Compound 13: Siloxane compound 2 (2,2′-(1,1-diethyl-3,3-dimethyldisiloxane-1,3-diyl)bis(ethan-1-amine), CAS No.: 2152657-68-4)

[0186]

[0187] Compound 14: Esterifying agent 1 (N,N-dimethylformamide diethyl acetal, CAS No.: 1188-33-6)

[0188]

[0189] Compound 15: Capping agent 1 (MAP, CAS No.: 591-27-5)

[0190]

[0191] Compound 16: Capping agent 2 (4-ethynylaniline, CAS No.: 14235-81-5)

[0192]

[0193] Compound 17: Solvent 1 (NMP, CAS No.: 872-50-4)

[0194] Compound 18: Solvent 2 (GBL, CAS No.: 96-48-0)

[0195] Synthesis Example 1

[0196] Diamine 1: N,N′-((Perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide)

[0197]

[0198] Step 1: In a 1 L reaction flask, add 22 g (0.06 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 20.91 g (0.36 mol) of propylene oxide, and 120 mL of acetone. Stir at room temperature until completely dissolved, and cool the reaction system to -15°C. Then, add 120 ml of an acetone solution containing 24.49 g (0.132 mol) of m-nitrobenzoyl chloride dropwise. After the addition is complete, stir at -15°C for 5 hours, and then allow to warm to room temperature naturally. Filter the resulting reaction solution under reduced pressure to obtain an off-white solid. Dry the solid in a vacuum oven at 60°C for 20 hours.

[0199] Step 2: Add 20 g (0.03 mol) of the obtained off-white solid, 2.58 g of 5% palladium on carbon, and 170 mL of ethylene glycol methyl ether to a 500 mL high-pressure reaction kettle, displace the hydrogen, and pressurize with hydrogen to make the pressure in the kettle reach 10 kgf / cm 2 , and stir at 35°C for 2 hours. Then, slowly release the pressure, filter the reaction solution under reduced pressure to obtain a transparent solution. Add ethanol and petroleum ether to the solution, stir for 6 hours, and then filter to obtain a white solid. Dry the solid in a vacuum oven at 50°C for 20 hours to obtain Diamine 1, that is, N,N′-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide).

[0200] Synthesis Example 2

[0201] Diamine 2: N,N′-((Perfluoropropane-2,2-diyl)bis(5-hydroxy-3,1-phenylene))bis(3-aminobenzamide)

[0202]

[0203] Step 1: In a 1 L reaction flask, add 22 g (0.06 mol) of 2,2-bis(3-amino-5-hydroxyphenyl)hexafluoropropane, 20.91 g (0.36 mol) of propylene oxide, and 120 ml of acetone. Stir at room temperature until completely dissolved, and cool the reaction system to -15°C. Then, slowly add dropwise a solution of 24.49 g (0.132 mol) of 3-nitrobenzoyl chloride in acetone (120 ml). After the addition is complete, stir at -15°C for 5 hours, and then let it warm to room temperature naturally. Filter the resulting reaction solution under reduced pressure to obtain an off-white solid, and dry the solid in a vacuum oven at 60°C for 20 hours.

[0204] Step 2: Add 20 g (0.03 mol) of the obtained off-white solid, 2.58 g of 5% palladium on carbon, and 170 ml of ethylene glycol methyl ether to a 500 ml high-pressure reaction kettle, displace the hydrogen, and pressurize with hydrogen to make the pressure in the kettle reach 10 kgf / cm2. Stir at 35°C for 2 hours. Then, slowly release the pressure, filter the reaction solution under reduced pressure to obtain a transparent solution. Add ethanol and petroleum ether to this solution, stir for 6 hours to precipitate a solid, filter to obtain a white solid, and dry the solid in a vacuum oven at 50°C for 20 hours to obtain diamine 2, namely N,N′-((perfluoropropane-2,2-diyl)bis(5-hydroxy-3,1-phenylene)bis(3-aminobenzamide)).

[0205] Synthesis Example 3

[0206] Diamine 3: N,N′-(oxybis(6-hydroxy-5-(trifluoromethyl)-3,1-phenylene)bis(3-aminobenzamide)

[0207]

[0208] Step 1: In a 1 L reaction flask, add 22.1 g (0.06 mol) of bis(3-trifluoromethyl-4-hydroxy-5-amino)phenyl ether, 20.91 g (0.36 mol) of propylene oxide, and 120 ml of acetone. Stir at room temperature until completely dissolved, and cool the reaction system to -15°C. Then, slowly add dropwise a solution of 24.49 g (0.132 mol) of 3-nitrobenzoyl chloride in acetone (120 ml). After the addition is complete, stir at -15°C for 5 hours, and then let it warm to room temperature naturally. Filter the resulting reaction solution under reduced pressure to obtain an off-white solid, and dry the solid in a vacuum oven at 60°C for 20 hours.

[0209] Step 2: Add 20 g (0.03 mol) of the obtained off-white solid, 2.58 g of 5% palladium-carbon, and 170 ml of ethylene glycol methyl ether into a 500 ml high-pressure reactor, displace the hydrogen, pressurize with hydrogen to make the pressure in the reactor reach 10 kgf / cm2, and stir at 35 °C for 2 hours. Then, slowly release the pressure, filter the reaction solution under reduced pressure to obtain a transparent solution. Add ethanol and petroleum ether to this solution, stir for 6 hours to precipitate a solid, filter to obtain a white solid, and dry the solid in a vacuum oven at 50 °C for 20 hours to obtain diamine 3, namely N,N′-(oxybis(6-hydroxy-5-(trifluoromethyl)-3,1-phenylene))bis(3-aminobenzamide).

[0210] Synthesis Example 4

[0211] Diamine 4: 5,5′-(perfluoropropane-2,2-diyl)bis(2-(4-aminophenoxy)phenol)

[0212]

[0213] Step 1: In a 1 L reaction flask, add 15.5 g (0.06 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)-dimethylpropane, 20.91 g (0.36 mol) of propylene oxide, and 140 ml of acetone, stir at room temperature until completely dissolved, and cool the reaction system to -15 °C. Then, slowly dropwise add a solution of 24.49 g (0.132 mol) of m-nitrobenzoyl chloride in 140 ml of acetone. After the addition is complete, stir at -15 °C for 5 hours, and then naturally rise to room temperature. Filter the obtained reaction solution under reduced pressure to obtain a white solid, and dry the solid in a vacuum oven at 60 °C for 20 hours.

[0214] Step 2: Add 14.9 g (0.03 mol) of the obtained white solid, 2.58 g of 5% palladium-carbon, and 170 ml of ethylene glycol methyl ether into a 500 ml high-pressure reactor, displace the hydrogen, pressurize with hydrogen to make the pressure in the reactor reach 10 kgf / cm2, and stir at 40 °C for 2 hours. Then, slowly release the pressure, filter the reaction solution under reduced pressure to obtain a transparent solution. Add ethanol and petroleum ether to the solution, stir for 6 hours to precipitate a solid, filter to obtain a white solid, and dry the solid in a vacuum oven at 50 °C for 20 hours to obtain diamine 4, namely 5,5′-(perfluoropropane-2,2-diyl)bis(2-(4-aminophenoxy)phenol).

[0215] Synthesis Example 5

[0216] Photosensitizer 1: Diazonaphthoquinone compound

[0217]

[0218] Under a nitrogen protection system, 30.6 g of 1,1,1-tris(4-hydroxyphenyl)ethane and 80.5 g of a solution of 5-diazidonaphthoquinone sulfonyl chloride in 1,4-dioxane were placed. The reaction system was heated to 30 °C, and a mixed solution of 100 g of 1,4-dioxane and 13.3 g of triethylamine was added dropwise. The temperature of the system was maintained at 30 °C, and the mixture was stirred for 3 hours. The reaction solution was filtered to remove the triethylamine salt. The filtrate was added dropwise to pure water, and a solid precipitated. The solution was filtered, and the precipitated solid was collected and dried in a vacuum oven to obtain photosensitizer 1, that is, a diazidonaphthoquinone compound.

[0219] Synthesis of Resin (a-1) in Synthesis Example 6

[0220] Under a nitrogen protection system, 0.09 mol of 5,5′-(perfluoropropane-2,2-diyl)bis(2-(4-aminophenoxy)phenol) (diamine 4) obtained in Synthesis Example 4 and 0.05 mol of MAP (capping agent 1) were dissolved in 500 mL of NMP. After stirring and dissolving, an oil bath heating at 60 °C was carried out. 0.1 mol of 4,4′-oxybisphthalic anhydride (acid dianhydride 1) was added to the oil bath of the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of N,N-dimethylformamide diethyl acetal as an esterifying agent was added, and the mixture was stirred for 3 hours. Then it was poured into 2 L of water, filtered, and washed 3 times. It was dried at 50 °C for 72 hours using a vacuum dryer to obtain resin (a-1).

[0221] Synthesis of Resin (a-2) in Synthesis Example 7

[0222] Under a nitrogen protection system, 0.085 mol of N,N′-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide) (diamine 1) obtained in Synthesis Example 1, 0.005 mol of SiDA, and 0.05 mol of MAP (capping agent 1) were dissolved in 500 mL of NMP. After stirring and dissolving, an oil bath heating at 60 °C was carried out. 0.1 mol of 4,4′-oxybisphthalic anhydride (acid dianhydride 1) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of N,N-dimethylformamide diethyl acetal as an esterifying agent was added, and the mixture was stirred for 3 hours. Then it was poured into 2 L of water, filtered, and washed 3 times. It was dried at 50 °C for 72 hours using a vacuum dryer to obtain resin (a-2).

[0223] Synthesis of Resin (a-3) in Synthesis Example 8

[0224] Under a nitrogen protection system, 0.085 mol of N,N′-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide) (diamine 1) obtained in Synthesis Example 1, 0.005 mol of SiDA, and 0.05 mol of MAP (capping agent 1) were dissolved in 500 mL of NMP. After stirring to dissolve, an oil bath heating was carried out at 60 °C. 0.1 mol of hexafluorodiacid anhydride (acid dianhydride 2) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of N,N-dimethylformamide diethyl acetal as an esterifying agent was added, and the mixture was stirred for 3 hours, then poured into 2 L of water, filtered, and washed 3 times. It was dried in a vacuum dryer at 50 °C for 72 hours to obtain resin (a-3).

[0225] Synthesis of resin (a-4) in Synthesis Example 9

[0226] Under a nitrogen protection system, 0.085 mol of N,N′-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide) (diamine 1) obtained in Synthesis Example 1, 0.005 mol of SiDA, and 0.05 mol of MAP (capping agent 1) were dissolved in 500 mL of NMP. After stirring to dissolve, an oil bath heating was carried out at 60 °C. 0.1 mol of p-phenylene-bis(trimellitic anhydride) (acid dianhydride 3) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of N,N-dimethylformamide diethyl acetal as an esterifying agent was added, and the mixture was stirred for 3 hours, then poured into 2 L of water, filtered, and washed 3 times. It was dried in a vacuum dryer at 50 °C for 72 hours to obtain resin (a-4).

[0227] Synthesis of resin (a-5) in Synthesis Example 10

[0228] Under a nitrogen protection system, 0.085 mol of N,N′-((perfluoropropane-2,2-diyl)bis(5-hydroxy-3,1-phenylene))bis(3-aminobenzamide) (diamine 2) obtained in Synthesis Example 2, 0.005 mol of SiDA, and 0.05 mol of capping agent MAP (capping agent 1) were dissolved in 500 mL of NMP. After stirring to dissolve, an oil bath heating was carried out at 60 °C. 0.1 mol of 3,3,4,4-diphenylsulfone tetracarboxylic dianhydride (acid dianhydride 4) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of N,N-dimethylformamide diethyl acetal as an esterifying agent was added, and the mixture was stirred for 3 hours, then poured into 2 L of water, filtered, and washed 3 times. It was dried in a vacuum dryer at 50 °C for 72 hours to obtain resin (a-5).

[0229] Synthesis of resin (a-6) in Synthesis Example 11

[0230] Under a nitrogen protection system, 0.085 mol of N,N′-(oxybis(6-hydroxy-5-(trifluoromethyl)-3,1-phenylene))bis(3-aminobenzamide) (diamine 3) obtained in Synthesis Example 3, 0.005 mol of SiDA, and 0.05 mol of capping agent MAP were dissolved in 500 mL of NMP. After stirring to dissolve, an oil bath heating was carried out at 60 °C. 0.1 mol of 4,4′-phenylenedioxydiphthalic anhydride (acid dianhydride 5) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of esterifying agent N,N-dimethylformamide diethyl acetal was added, and the mixture was stirred for 3 hours. Then it was poured into 2 L of water, filtered, and washed 3 times. It was dried at 50 °C for 72 hours using a vacuum dryer to obtain resin (a-6).

[0231] Synthesis of resin (a-7) in Synthesis Example 12

[0232] Under a nitrogen protection system, 0.085 mol of 5,5′-(perfluoropropane-2,2-diyl)bis(2-(4-aminophenoxy)phenol) (diamine 4) obtained in Synthesis Example 4, 0.005 mol of SiDA, and 0.05 mol of capping agent MAP were dissolved in 500 mL of NMP. After stirring to dissolve, an oil bath heating was carried out at 60 °C. 0.1 mol of 4,4′-phenylenedioxydiphthalic anhydride (acid dianhydride 5) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of esterifying agent N,N-dimethylformamide diethyl acetal was added, and the mixture was stirred for 3 hours. Then it was poured into 2 L of water, filtered, and washed 3 times. It was dried at 50 °C for 72 hours using a vacuum dryer to obtain resin (a-7).

[0233] Synthesis of resin (a-8) in Synthesis Example 13

[0234] Under a nitrogen protection system, 0.085 mol of N,N′-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide) (diamine 1) obtained in Synthesis Example 1, 0.005 mol of SiDA, and 0.05 mol of 4-ethynylaniline (capping agent 2) were dissolved in 500 mL of NMP. After stirring to dissolve, an oil bath heating was carried out at 60 °C. 0.1 mol of 4,4′-oxydiphthalic anhydride (acid dianhydride 1) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of esterifying agent N,N-dimethylformamide diethyl acetal was added, and the mixture was stirred for 3 hours. Then it was poured into 2 L of water, filtered, and washed 3 times. It was dried at 50 °C for 72 hours using a vacuum dryer to obtain resin (a-8).

[0235] Synthesis of resin (a-9) in Synthesis Example 14

[0236] Under a nitrogen protection system, 0.085 mol of N,N′-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-aminobenzamide) (diamine 1) obtained in Synthesis Example 1, 0.005 mol of 2,2′-(1,1-diethyl-3,3-dimethyldisiloxane-1,3-diyl)bis(ethan-1-amine) (siloxane compound 2), and 0.05 mol of capping agent MAP were dissolved in 500 mL of NMP. After stirring and dissolving, an oil bath heating was carried out at 60 °C. 0.1 mol of 4,4′-oxybisphthalic anhydride (acid dianhydride 1) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of N,N-dimethylformamide diethyl acetal as an esterifying agent was added, and the mixture was stirred for 3 hours. Then, it was poured into 2 L of water, filtered, and washed 3 times. Drying was carried out at 50 °C for 72 hours using a vacuum dryer to obtain resin (a-9).

[0237] Synthesis of resin (a-10) in Synthesis Example 15

[0238] Under a nitrogen protection system, 0.085 mol of 3,3′-dihydroxybenzidine (diamine 5) and 0.05 mol of capping agent MAP were dissolved in 500 mL of NMP. After stirring and dissolving, an oil bath heating was carried out at 60 °C. 0.1 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (acid dianhydride 6) was added to the reaction solution, and the reaction was carried out for 2 hours. Subsequently, 5.0 mol of N,N-dimethylformamide diethyl acetal as an esterifying agent was added, and the mixture was stirred for 3 hours. Then, it was poured into 2 L of water, filtered, and washed 3 times. Drying was carried out at 50 °C for 72 hours using a vacuum dryer to obtain resin (a-10).

[0239] The synthesis ratios of polymer (a) in Synthesis Examples 6 to 15 are shown in Table 1.

[0240] [Table 1]

[0241]

[0242]

[0243] Example 1

[0244] Weigh 10 g of resin (a-1) obtained in Synthesis Example 6 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1), 0.11 g of polydipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 1. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0245] Example 2

[0246] Weigh 10 g of the resin (a-2) obtained in Synthesis Example 7 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1), 0.11 g of polydipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 2. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0247] Example 3

[0248] Weigh 10 g of the alkali-soluble resin (a-2) obtained in Synthesis Example 7 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1) and 0.11 g of (methyl-1,3-phenylene)bis[iminocarbonyloxy[2,2-bis[[(1-oxoallyl)oxy]methyl]]-3,1-propanediyl] diacrylate (thermal crosslinking agent (b2)-2), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 3. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0249] Example 4

[0250] Weigh 10 g of the resin (a-3) obtained in Synthesis Example 8 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1), 0.11 g of polydipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 4. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0251] Example 5

[0252] Weigh 10 g of the resin (a-4) obtained in Synthesis Example 9 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1), 0.11 g of polydipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 5. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0253] Example 6

[0254] Weigh 10 g of the resin (a-5) obtained in Synthesis Example 10 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1) and 0.11 g of (methyl-1,3-phenylene)bis[carbamoyloxy[2,2-bis[[(1-oxoallyl)oxy]methyl]]-3,1-propanediyl] diacrylate (thermal crosslinking agent (b2)-2), as well as 3 g of a quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 6. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0255] Example 7

[0256] Weigh 10 g of the resin (a-6) obtained in Synthesis Example 11 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1) and 0.11 g of polydipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1), as well as 3 g of a quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 7. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0257] Example 8

[0258] Weigh 10 g of the resin (a-7) obtained in Synthesis Example 12 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1) and 0.11 g of (methyl-1,3-phenylene)bis[carbamoyloxy[2,2-bis[[(1-oxoallyl)oxy]methyl]]-3,1-propanediyl] diacrylate (thermal crosslinking agent (b2)-2), as well as 3 g of a quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 8. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0259] Example 9

[0260] Weigh 10 g of the resin (a-7) obtained in Synthesis Example 12 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1) and 0.11 g of polydipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1), as well as 3 g of a quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 9. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0261] Example 10

[0262] Weigh 10 g of the resin (a-8) obtained in Synthesis Example 13 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1), 0.11 g of 4-(triisopropylsilylethynyl)phenylacetylene (thermal crosslinking agent (b2)-3), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 10. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0263] Example 11

[0264] Weigh 10 g of the resin (a-9) obtained in Synthesis Example 14 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1), 0.11 g of 4-(triisopropylsilylethynyl)phenylacetylene (thermal crosslinking agent (b2)-3), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 11. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0265] Comparative Example 1

[0266] Weigh 10 g of the resin (a-10) obtained in Synthesis Example 15 above, add it to 150 g of GBL solvent, and then add 2 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1) and 0.11 g of polydipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 12. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0267] Comparative Example 2

[0268] Weigh 10 g of the resin (a-2) obtained in Synthesis Example 7 above, add it to 150 g of GBL solvent, and then add 2.11 g of 4,4′,4″-(ethane-1,1,1-triyl)tris(2,6-bis(methoxymethyl)phenol) (thermal crosslinking agent (b1)-1), and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 13. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0269] Comparative Example 3

[0270] Weigh 10 g of the alkali-soluble resin (a-2) obtained in Synthesis Example 7 above, add it to 150 g of GBL solvent, then add 2.11 g of dipentaerythritol hexaacrylate (thermal crosslinking agent (b2)-1) and 3 g of quinone diazide compound photosensitizer, and stir for 1 hour to obtain Slurry 14. The obtained slurry was subjected to effect evaluation, and the results are shown in Table 3.

[0271] The synthesis ratios of the slurries in Examples 1 to 11 and Comparative Examples 1 to 3 are shown in Table 2.

[0272] [Table 2]

[0273]

[0274]

[0275] Performance Test Method

[0276] In the examples, the molecular weight of the resin composition can be tested by ordinary GPC, the viscosity can be tested by an E-type viscometer, and the film thickness can be tested by an ordinary film thickness meter; the evaluation of the resin film formed from the resin composition is carried out according to the following method.

[0277] 1. Evaluation method for thermal crosslinking and other groups:

[0278] In the present invention, the glass transition temperature T is tested using thermomechanical analysis (TMA) g (Equipment model of Netzsch: DSC3500); in addition, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and other methods can also be used for testing. The specific method is as follows: After the prepared varnish is subjected to spin coating, drying, exposure, development, and heat treatment curing processes, a photosensitive resin film is obtained, and its film thickness is 5 μm ± 0.1 μm; then the photosensitive resin film is prepared into a sample for thermomechanical analysis test, and after testing, the T g value can be obtained. T g represents the movement performance of the molecular chain segments. The larger the T g value, the smaller the movement performance of the molecular chain segments, that is, the better the degree of thermal crosslinking. When T g ≧335 °C, the degree of thermal crosslinking is excellent, and it is rated as ○; when T g is 325 - 335 °C, the degree of thermal crosslinking is good, and it is rated as △; when T g ≦325 °C, the degree of thermal crosslinking is poor, and it is rated as ×.

[0279] 2. Evaluation method for flatness index:

[0280] The flatness index of the present invention is tested using a CD-SEM (equipment of Hitachi-Hightechnology Corporation, model: SU3500). The specific method is as follows: The prepared varnish is spin-coated and pre-baked to make the film thickness 4 μm ± 0.1 μm; then after the exposure and development processes, the film thickness is measured as h 1 , and after the heat treatment and curing process, the film thickness is measured as h 2 ; Use CD-SEM to measure h 1 , h 2 . Calculate the flatness index (%) according to the following formula (1). The larger the flatness index, the greater the shrinkage deformation of the film during heat treatment and curing, and the worse the planarization degree; the smaller the flatness index, the smaller the shrinkage deformation of the film during heat treatment and curing, and the better the planarization degree. The planarization degree ultimately affects the performance of the device, such as efficiency, yield, and lifespan. When the flatness index ≤ 25%, it is rated as excellent and marked as ○; when the flatness index is between 25% and 35%, it is rated as good and marked as △; when the flatness index ≥ 35%, it is rated as poor and marked as ×.

[0281] Flatness index (%) = (h 1 - h 2 ) / h 1 × 100% Formula (1)

[0282] 3. Flexibility index evaluation:

[0283] The mechanical properties of the film were tested using a tensile testing machine (equipment model: RTG1210 of Tensilon). The specific method is as follows: After the prepared varnish is subjected to spin coating, drying, and heat treatment curing processes, an ordinary resin film is obtained, and the film thickness is 5 μm ± 0.1 μm; then the ordinary resin film is made into a specimen for tensile testing to obtain data on tensile strength, elongation, and Young's modulus. Tensile strength characterizes the degree of easy breakage during stress deformation, so the greater the tensile strength, the better; elongation characterizes the degree of elongation movement of molecular chains during stress deformation. When the elongation is too small, the elongation movement of molecular chains is extremely small / extremely difficult, that is, it is difficult to undergo elastic deformation. When the elongation is too large, plastic deformation is likely to occur, and it is difficult to recover during stress deformation. Therefore, elongation within a certain range is beneficial to bending recovery; Young's modulus characterizes the rigidity of the material. That is, when the rigidity is too large, it is difficult to undergo stress deformation. When the rigidity is too small, plastic deformation is likely to occur, making it difficult to recover after deformation. Therefore, Young's modulus within a certain range is beneficial to bending recovery; that is, the quality of the flexibility index also reflects the quality of the bending recovery performance. When the tensile strength ≥ 120 MPa, the elongation range is 5 - 28%, and the Young's modulus range is 0.5 - 9.0 GPa, the flexibility index is excellent and is rated as ◎; when the tensile strength range is 90 - 120 MPa, the elongation range is 5 - 28%, and the Young's modulus range is 0.5 - 9.0 GPa, the flexibility index is good and is rated as ○; when the tensile strength ≥ 90 MPa, the elongation ≥ 28% or the elongation ≤ 2%, the Young's modulus ≥ 9.0 GPa or the Young's modulus ≤ 0.5 GPa, the flexibility index is average and is rated as △; when the tensile strength ≤ 90 MPa, the flexibility index is poor and is rated as ×.

[0284] The evaluation results of Examples 1 - 11 and Comparative Examples 1 - 3 are shown in Table 3.

[0285] [Table 3]

[0286]

[0287]

[0288] According to the evaluation results of Examples 1 - 11 and Comparative Examples 1 - 3 in Table 3 above, Examples 2 - 4 and Example 6 have excellent levels of thermal crosslinking degree, flatness index, and flexibility index. That is to say, the resin compositions in Examples 2 - 4 and Example 6 can obtain better flatness and bending recovery performance, which is ideal.

[0289] The degree of thermal crosslinking of Examples 1, 5, 7 to 9 is excellent, the flatness index level is excellent or good, and the flexibility index evaluation is good. In terms of both the flatness index level performance and the flexibility index, they are slightly inferior to the ideal Examples 2 to 4 and Example 6. The degree of thermal crosslinking of Examples 10 and 11 is good, the flatness index level is excellent, and the flexibility index evaluation is superior. It is inferior to the ideal Examples 1 to 9 in terms of the degree of thermal crosslinking, but maintains a superior flexibility index. Therefore, compared with Examples 2 to 4 and Example 6, Examples 1, 5, 7 to 11 are sub-ideal.

[0290] The degree of thermal crosslinking of Comparative Examples 1 to 3 is evaluated as good or poor, the flat elasticity index level is evaluated as good or poor, and the flexibility index evaluation is average. Compared with Examples 1 to 11, the comprehensive performance is poor and they are not ideal.

Claims

1. A photosensitive resin composition comprising at least three components (a), (b) and (c); wherein: The component (a) is a polymer having a structure represented by the following formula (1) as a structural unit, the component (b) contains a thermal crosslinking agent (b1) and a thermal crosslinking agent (b2), and the component (c) is a photosensitizer. Among them, R 1 , R 2 are independently selected from a group containing at least one atom other than hydrogen; R 3 , R 4 independently selected from hydrogen atoms or organic groups having 1 to 20 carbon atoms, wherein n is selected from an integer of 1 to 10; The thermal crosslinking agent (b1) is selected from low-temperature thermal crosslinking compounds having a thermal crosslinking temperature of 120 to 180° C., and is selected from the structure represented by the following formula (2): Among them, R 8 is selected from organic groups containing 2 to 30 carbon atoms; R 9 is selected from an organic group containing 1 to 10 carbon atoms; s is selected from an integer of 1 to 4, p is selected from an integer of 1 to 16, and s+p>2; The thermal crosslinking agent (b2) is a thermal crosslinking agent containing an unsaturated bond, and the thermal crosslinking agent (b2) is selected from thermal crosslinking compounds having a thermal crosslinking temperature of 180 to 400° C., and is selected from one or more structures represented by the following formula (3), Among them, R 7 is selected from an organic group containing 2 to 25 carbon atoms, and q is selected from an integer of 1 to 10; The photosensitizer of the component (c) is a photoacid generator.

2. The photosensitive resin composition according to claim 1, wherein The component (a) is a polymer having a structure represented by the following formula (4) as a structural unit, Among them, R 1 , R 2 are independently selected from a group containing at least one atom other than hydrogen; R 3 , R 4 independently selected from hydrogen atoms or organic groups having 1 to 20 carbon atoms, R 5 Selected from halogen and / or halogenated hydrocarbon group and / or organic group of 1 to 10 carbon atoms; n and m are independently selected from integers of 1 to 10.

3. The photosensitive resin composition according to claim 1 or 2, wherein: It also contains one or more of polyamide, polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.

4. The photosensitive resin composition according to claim 1 or 2, wherein: It also contains compounds having phenolic hydroxyl groups.

5. A photosensitive resin film, formed from the photosensitive resin composition according to any one of claims 1 to 4.

6. A display device comprising the photosensitive resin film according to claim 5.

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