Alkali-soluble resin, photosensitive resin composition and application thereof

Abstract

The invention provides alkali-soluble resin, a photosensitive resin composition and application thereof. The alkali-soluble resin comprises a combination of Cardo-series resin and epoxy resin, the Cardo resin comprises a thiobenzene structure and a phenol structure, and the epoxy resin comprises a triazine structure. According to the alkali-soluble resin and the photosensitive resin composition containing the alkali-soluble resin, through design and mutual compounding of the Cardo-series resin and the epoxy resin with specific structures, the problems that a conventional black matrix has many residues and is difficult to develop cleanly are effectively solved, so that the alkali-soluble resin and the photosensitive resin composition containing the alkali-soluble resin are excellent in developing performance, low in cost and excellent in stability; and the formed cured product / colored film is low in residue, good in chemical resistance, high in adhesive force with a substrate and excellent in heat resistance and mechanical property, and fully meets the use requirements of a high-performance display device.

Description

Technical Field

[0001] This invention belongs to the field of display materials technology, specifically relating to an alkali-soluble resin, a photosensitive resin composition, and its applications. Background Technology

[0002] In display technologies such as liquid crystal displays and organic electroluminescence (EL) displays, a light-shielding film known as a black matrix is ​​typically placed on a transparent substrate such as glass or plastic to prevent the degradation of display characteristics caused by light leakage between red, green, and blue pixels. Conventionally, black matrices are made of vapor-deposited films using metals or metal compounds such as chromium, nickel, and aluminum. For example, black matrices formed using multilayer films containing zirconium compounds have been proposed as examples of black matrices using metal compounds.

[0003] With the development of display technology, vapor-deposited films of metals or metal compounds are no longer sufficient to meet the performance requirements of black matrices. In recent years, considering excellent dimensional accuracy, excellent positional accuracy, and ease of pattern formation, photosensitive coloring resin compositions containing light-shielding materials are commonly used to form black matrices using photolithography. For example, black resin compositions containing acrylic polymers, acrylic polyfunctional monomers or oligomers, photoinitiators, solvents, and light-shielding materials are widely used as coloring resin compositions with negative photosensitivity. As light-shielding materials, carbon black, titanium black such as titanium oxynitride and titanium nitride, metal oxides such as iron oxide, and other organic pigment mixtures are used.

[0004] Although the performance of black matrices formed by photolithography using photosensitive coloring resin compositions has been significantly improved compared to metal-based vapor-deposited films, currently used black matrices still suffer from drawbacks such as high residue levels, poor adhesion, and poor heat resistance. Furthermore, black matrices used in flexible displays require superior mechanical properties, which existing photosensitive coloring resin compositions struggle to meet. Therefore, developing black matrix materials with low residue, excellent adhesion, heat resistance, and superior mechanical properties is a pressing issue in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an alkali-soluble resin, a photosensitive resin composition, and its application. By compounding Cardo-based resins and epoxy resins with specific structures, the alkali-soluble resin and the photosensitive resin composition containing it exhibit excellent developability, and the cured colored film possesses excellent heat resistance, adhesion, and mechanical properties.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides an alkali-soluble resin, which comprises a combination of a Cardo resin and an epoxy resin; the Cardo resin contains a thio-benzene structure and a phenol structure, and the epoxy resin contains a triazine structure.

[0008] In the present invention, the Cardo resin contains a thio-benzene structure and a phenol structure. The sulfur atom in the thio-benzene structure has a relatively high electronegativity and a small atomic radius, enabling it to effectively form relatively tight bonds with other atoms. The lone pair electrons of the sulfur atom can also form coordination bonds such as hydrogen bonds or ionic bonds with other atoms or ions. Such coordination bonds generally have strong binding ability and high stability. The phenol structure can enhance the alkali solubility of the resin, strengthen the development performance, and help reduce residues. The epoxy resin contains a triazine structure, which can improve the heat resistance of the cured product and its adhesion to the substrate. Through the design and mutual compounding of the Cardo resin and the epoxy resin with specific structures, the present invention makes the alkali-soluble resin and the photosensitive resin composition containing the same have excellent development performance, effectively solving the problems of a large amount of residue and difficult development of conventional black matrices. The cured product / colored film formed by the photosensitive resin composition has less residue, good chemical resistance, high adhesion to the substrate, excellent heat resistance and mechanical properties, fully meeting the use requirements of high-performance display devices.

[0009] The following are preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved.

[0010] In the present invention, for the expression of chemical elements, unless otherwise specified, the concept of isotopes with the same chemical properties is included. For example, hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C, 13 C, etc.

[0011] In the present invention, the expression of Ca-Cb represents that the group has a carbon atom number of a-b. Unless otherwise specified, the carbon atom number does not include the carbon atom number of substituents.

[0012] In the present invention, "independently of each other" means that when its subject has multiple ones, they can be the same or different from each other.

[0013] In the present invention, the expression of a ring structure crossed by "-" indicates that the connection site is at any position on the ring structure where bonding can occur.

[0014] In the present invention, the dotted lines of "-*", "*", "-#", and "#" all represent the connection sites of groups.

[0015] In this invention, the Cardo-based resin contains a Cardo structure. Thiobenzene structure and phenol structure The Cardo-based resin has a molecular structure in which the number of thiobenzene structures is ≥1, for example, 1, 2, 3, 4, 5, 6, etc.; the Cardo-based resin has a molecular structure in which the number of phenol structures is ≥1, for example, 1, 2, 3, 4, 5, 6, etc.

[0016] Preferably, the Cardo-based resin comprises at least one structural unit of Formula I, at least one structural unit of Formula II, at least one structural unit of Formula III, and at least one structural unit of Formula IV:

[0017]

[0018] Wherein, R1 is selected from any one of the substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkylene groups, and C2-C10 (e.g., C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkenyl groups; the substituents in R1 are selected from any one of the C2-C10 (e.g., C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkenyl groups.

[0019] R2 is selected from any one of the following: straight-chain or branched alkylene groups of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) or straight-chain or branched alkenyl groups of C2-C10 (e.g., C3, C4, C5, C6, C7, C8, C9, etc.).

[0020] R3, R4, and R6 are each independently selected from hydrogen and any one of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl groups.

[0021] R5 is selected from hydrogen, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl groups, phenyl groups, phenolic groups (… Any one of them.

[0022] In this invention, the C1-C10 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10, and exemplary include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, straight-chain hexyl, branched hexyl, straight-chain octyl, branched octyl, straight-chain heptyl, branched heptyl, straight-chain nonyl, branched nonyl, straight-chain decyl, branched decyl, etc.

[0023] A specific example of the C1-C10 straight-chain or branched alkylene groups is a divalent group formed by the aforementioned straight-chain or branched alkyl group losing one hydrogen atom.

[0024] The C2-C10 straight-chain or branched alkenyl groups can be straight-chain or branched alkenyl groups of C2, C3, C4, C5, C6, C7, C8, C9, and C10, containing at least one C=C, and exemplary including but not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0025] A specific example of the C2-C10 straight-chain or branched alkenyl group is a divalent group formed by the aforementioned straight-chain or branched alkenyl group losing one hydrogen atom.

[0026] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents (at least two), they can be the same or different substituents. The same expression used below has the same meaning.

[0027] Preferably, R1 is selected from any one of unsubstituted or vinyl-substituted C2-C8 straight-chain or branched alkylene groups, or C2-C8 straight-chain or branched alkenyl groups; more preferably... Any of the following, where -* represents the linking site of the group.

[0028] Preferably, R2 is selected from any one of C2-C8 straight-chain or branched alkylene groups, and more preferably... Any of the following, where -* represents the linking site of the group.

[0029] Preferably, R3, R4, and R6 are each independently selected from hydrogen or methyl.

[0030] Preferably, R5 is selected from hydrogen, methyl, or phenol.

[0031] Preferably, the weight-average molecular weight of the Cardo resin is 2500-4000, for example, it can be 2200, 2500, 2800, 3000, 3200, 3500 or 3800, and more preferably 3000-3800.

[0032] Preferably, the Cardo resin has an acid value of 30-100 mg KOH / g, such as 40 mg KOH / g, 45 mg KOH / g, 50 mg KOH / g, 55 mg KOH / g, 60 mg KOH / g, 65 mg KOH / g, 70 mg KOH / g, 75 mg KOH / g, 80 mg KOH / g, 85 mg KOH / g, or 90 mg KOH / g, and more preferably 40-60 mg KOH / g.

[0033] In this invention, the Cardo-based resin has a polymer chain segment structure, including at least one (preferably multiple) structural unit represented by Formula I, at least one (preferably multiple) structural unit represented by Formula II, at least one (preferably multiple) structural unit represented by Formula III, and at least one structural unit represented by Formula IV; this invention does not limit the connection order of the above structural units, and any connection order / connection method feasible in chemistry is within the scope of this invention.

[0034] For example, the Cardo resin is obtained by copolymerization of a first monomer with the structure shown in Formula IA, a second monomer with the structure shown in Formula IIA, a third monomer with the structure shown in Formula IIIA, and a fourth monomer with the structure shown in Formula IVA.

[0035]

[0036] Among them, R1, R2, R3, R4, R5, and R6 have the same definitions as those mentioned above.

[0037] Preferably, the first monomer comprises any one or a combination of at least two of the following compounds:

[0038]

[0039] Preferably, the fourth monomer includes and / or

[0040] Preferably, the molar ratio of the first monomer, the second monomer, the third monomer, and the fourth monomer is 1:(0.5-1.5):(0.5-1.5):(0.5-1.5), and more preferably 1:(0.8-1.3):(0.8-1.3):(0.8-1.3); wherein each "0.5-1.5" can independently be 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, etc.

[0041] In this invention, the epoxy resin contains an epoxy structure. and triazine structure The epoxy resin has a molecular structure in which the number of epoxy structures is ≥1, for example, 1, 2, 3, 4, 5, 6, etc.; the epoxy resin has a molecular structure in which the number of triazine structures is ≥1, for example, 1, 2, 3, etc. The connection method between the epoxy and triazine structures in the epoxy resin is not particularly limited; any resin / compound containing both epoxy and triazine structures is applicable to this invention.

[0042] Preferably, the epoxy resin comprises any one, two, or a combination of three of the following compounds:

[0043]

[0044]

[0045] Preferably, the mass ratio of Cardo resin to epoxy resin is (0.1-9):1, for example, it can be 0.2:1, 0.5:1, 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1 or 8.5:1, etc., and more preferably (1-6):1.

[0046] In a second aspect, the present invention provides a photosensitive resin composition comprising a combination of an alkali-soluble resin, a polymerizable monomer, a photoinitiator, and a colorant as described in the first aspect.

[0047] Preferably, the mass percentage of alkali-soluble resin in the photosensitive resin composition is 1%-30%, for example, it can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, etc.

[0048] In this invention, the polymerizable monomer is a compound containing polymerizable groups, preferably a compound containing at least one (e.g., 1, 2, 3, 4, 5, 6, etc.) C=C group, and more preferably a compound containing at least one (e.g., 1, 2, 3, 4, 5, 6, etc.) (meth)acrylate group.

[0049] It should be noted that the (meth)acrylate is an acrylate ( ) and / or methacrylates ( ).

[0050] Preferably, the polymerizable monomer includes any one or a combination of at least two of the following: polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, phenoxyethyl methacrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, neopentyl glycol (meth)acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and acryloyloxypropyl cage-like polysilsesquioxane monomer.

[0051] Preferably, the mass percentage of polymerizable monomers in the photosensitive resin composition is 1%-20%, for example, it can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc.

[0052] Preferably, the photoinitiator comprises any one or a combination of at least two of the following: dialkoxyacetophenone photoinitiators, α-hydroxyalkylphenyl ketone photoinitiators, α-aminoalkylphenyl ketone photoinitiators, acylphosphine oxide photoinitiators, oxime ester photoinitiators, benzoyl photoinitiators, benzoin photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, anthraquinone photoinitiators, coumarone photoinitiators, camphorquinone, triethanolamine, and N-methyldiethanolamine.

[0053] Preferably, the photoinitiator in the photosensitive resin composition has a mass percentage content of 0.2%-2%, for example, it can be 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, etc.

[0054] Preferably, the colorant is a black colorant, and more preferably carbon black and / or organic black.

[0055] In this invention, the organic black can be any one or a combination of at least two black organic colorants, including but not limited to: aniline black, perylene black, and lactam black. Any one or at least two of the following:

[0056] Preferably, the colorant in the photosensitive resin composition has a mass percentage content of 3%-30%, for example, it can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, etc.

[0057] Preferably, the photosensitive resin composition also includes a solvent, which facilitates subsequent application and coating.

[0058] In this invention, the solvent is a solvent commonly used in the art, and exemplary includes, but is not limited to, any one or at least a combination of two of the following: 3-methoxybutyl acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether acetate, dipropylene glycol propyl ether, dipropylene glycol butyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, ethyl acetate, propyl acetate, cyclohexanone, ethylene glycol ethyl ether, γ-butyrolactone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether formate, ethyl lactate, butyl lactate, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0059] Preferably, the solvent content in the photosensitive resin composition is 50%-95% by mass, for example, it can be 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 94%, etc.

[0060] In a preferred embodiment, the photosensitive resin composition comprises the following components by weight percentage:

[0061]

[0062] It should be noted that the photosensitive resin composition provided by the present invention may also include any other additives that are motivated to be added in the art.

[0063] For example, the other additives include, but are not limited to, any one or a combination of at least two of the following: dispersants, photosensitizing agents, leveling agents, coupling agents, and surfactants.

[0064] Thirdly, the present invention provides a coloring film prepared by means of a photosensitive resin composition as described in the second aspect.

[0065] Fourthly, the present invention provides a decorative substrate, wherein the decorative substrate includes a coloring film as described in the third aspect.

[0066] Fifthly, the present invention provides a touch panel, the touch panel including the decorative substrate as described in the fourth aspect.

[0067] In a sixth aspect, the present invention provides an organic electroluminescent (EL) display device, wherein the organic electroluminescent display device includes a coloring film as described in the third aspect.

[0068] Preferably, the coloring film is used as a planarization layer on the driving circuit of an organic EL display device, an insulating layer on the first electrode, a pixel defining layer (PDL), etc.

[0069] Preferably, the photosensitive resin composition can form a colored film after coating, pre-baking, photolithography, development and curing, which remains in organic EL display devices, touch panels and decorative substrates. The colored film has excellent heat resistance, adhesion, chemical resistance and mechanical properties, and can be used in flexible display devices.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] The alkali-soluble resin provided by this invention, through the design and mutual compounding of Cardo-based resin and epoxy resin with specific structures, effectively solves the problems of excessive residue and difficulty in clear development of conventional black matrices. This results in the alkali-soluble resin and the photosensitive resin composition containing it having excellent development performance, low cost, and excellent stability. The cured / colored film formed has low residue, good chemical resistance, high adhesion to the substrate, and excellent heat resistance and mechanical properties, fully meeting the usage requirements of high-performance display devices. Attached Figure Description

[0072] Figure 1 The residual condition test diagram of the photosensitive resin composition provided in Example 1;

[0073] Figure 2 The residual condition test diagram of the photosensitive resin composition provided in Example 2;

[0074] Figure 3 The residual condition test diagram of the photosensitive resin composition provided in Example 3;

[0075] Figure 4 The residual condition test diagram of the photosensitive resin composition provided in Example 4;

[0076] Figure 5 The residual condition test diagram of the photosensitive resin composition provided in Comparative Example 5 is shown. Detailed Implementation

[0077] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0078] In one specific embodiment, the Cardo-based resin comprises at least one structural unit of Formula I, at least one structural unit of Formula II, at least one structural unit of Formula III, and at least one structural unit of Formula IV, and can be prepared by the following preparation method: copolymerizing a first monomer, a second monomer, a third monomer, and a fourth monomer to obtain the Cardo-based resin;

[0079] The first monomer is The second monomer is The third monomer is The fourth monomer is R1, R2, R3, R4, R5, and R6 have the same definitions as described above.

[0080] In one specific embodiment, the copolymerization reaction is carried out in the presence of a free radical initiator.

[0081] The specific preparation method of the Cardo-based resin of the present invention will be described in detail below using synthetic examples, but the preparation method of the Cardo-based resin is not limited to these synthetic examples.

[0082] In the following specific embodiments of the present invention, compounds not mentioned in the synthesis method are all raw material products obtained through commercial means.

[0083] Synthesis example 1

[0084] Cardo-based resin A1 comprises at least one structural unit shown in Formula I, at least one structural unit shown in Formula II, at least one structural unit shown in Formula III, and at least one structural unit shown in Formula IV, and is obtained through a first monomer ( CAS: 203174-59-8, source: AldrichCPR), second monomer, third monomer, and fourth monomer ( CAS: 1557975-30-0, source: Aurora Building Blocks 2) Obtained by copolymerization reaction, the specific method is as follows:

[0085] The synthesis method is as follows:

[0086] 17.8 g of the first monomer, 41.8 g of the second monomer, 37.4 g of the third monomer, 17.6 g of the fourth monomer, 240 g of propylene glycol methyl ether acetate, and 0.3 mL of molecular weight regulator (dodecyl mercaptan) were added to a 500 mL three-necked flask. Under nitrogen protection, the system was heated to 80 °C. Under stirring, a solution of 17 g of propylene glycol methyl ether acetate containing 1.0 g of azobisisobutyronitrile was added dropwise to the three-necked flask over 30 min using a constant pressure dropping funnel. The reaction was then stirred at a constant temperature for 3 h. The temperature was then lowered to room temperature, and the solvent was removed to obtain the final product, Cardo resin A1, with a weight-average molecular weight of 3612 and an acid value of 46 mg KOH / g.

[0087] Structural characterization: Infrared spectroscopy revealed characteristic peaks of thiobenzene and phenol structures, indicating that it possesses the target structure.

[0088] Synthesis example 2

[0089] Cardo-based resin A2, comprising at least one structural unit of formula I, at least one structural unit of formula II, at least one structural unit of formula III, and at least one structural unit of formula IV, wherein the resin is obtained by means of a first monomer ( ), second monomer, third monomer and fourth monomer ( CAS: 39011-86-4, sourced from Angene International Limited) obtained through copolymerization reaction, the specific method of which is as follows:

[0090] 17.8 g of the first monomer, 41.8 g of the second monomer, 37.4 g of the third monomer, 26.8 g of the fourth monomer, 240 g of propylene glycol methyl ether acetate, and 0.3 mL of molecular weight regulator (dodecyl mercaptan) were added to a 500 mL three-necked flask. Under nitrogen protection, the system was heated to 80 °C. Under stirring, a solution of 17 g of propylene glycol methyl ether acetate containing 1.0 g of azobisisobutyronitrile was added dropwise to the three-necked flask over 30 min using a constant pressure dropping funnel. The reaction was then stirred at a constant temperature for 3 h. The temperature was then lowered to room temperature, and the solvent was removed to obtain the final product, Cardo resin A2, with a weight-average molecular weight of 3780 and an acid value of 44.5 mg KOH / g.

[0091] Structural characterization: Infrared spectroscopy revealed characteristic peaks of thiobenzene and phenol structures.

[0092] Synthesis example 3

[0093] Cardo-based resin A3 comprises at least one structural unit shown in Formula I, at least one structural unit shown in Formula II, at least one structural unit shown in Formula III, and at least one structural unit shown in Formula IV, and is obtained through a first monomer ( CAS: 121410-49-9, source: Aurora Building Blocks 11), second monomer, third monomer, and fourth monomer ( It is obtained through copolymerization, and the specific method is as follows:

[0094] 24.8 g of the first monomer, 41.8 g of the second monomer, 37.4 g of the third monomer, 17.6 g of the fourth monomer, 240 g of propylene glycol methyl ether acetate, and 0.3 mL of molecular weight regulator (dodecyl mercaptan) were added to a 500 mL three-necked flask. Under nitrogen protection, the system was heated to 80 °C. Under stirring, a solution of 17 g of propylene glycol methyl ether acetate containing 1.0 g of azobisisobutyronitrile was added dropwise to the three-necked flask over 30 min using a constant pressure dropping funnel. The reaction was then stirred at a constant temperature for 3 h. The temperature was then lowered to room temperature, and the solvent was removed to obtain the final product, Cardo resin A3, with a weight-average molecular weight of 3802 and an acid value of 44.5 mg KOH / g.

[0095] Synthesis example 4

[0096] Cardo-based resin A4 comprises at least one structural unit shown in Formula I, at least one structural unit shown in Formula II, at least one structural unit shown in Formula III, and at least one structural unit shown in Formula IV, and is obtained through a first monomer ( CAS: 83577-62-2, source: Aurora Building Blocks 11), second monomer, third monomer, and fourth monomer ( It is obtained through copolymerization, and the specific method is as follows:

[0097] 19.2 g of the first monomer, 41.8 g of the second monomer, 37.4 g of the third monomer, 17.6 g of the fourth monomer, 240 g of propylene glycol methyl ether acetate, and 0.3 mL of molecular weight regulator (dodecyl mercaptan) were added to a 500 mL three-necked flask. Under nitrogen protection, the system was heated to 80 °C. Under stirring, a solution of 17 g of propylene glycol methyl ether acetate containing 1.0 g of azobisisobutyronitrile was added dropwise to the three-necked flask over 30 min using a constant pressure dropping funnel. The reaction was then stirred at a constant temperature for 3 h. The temperature was then lowered to room temperature, and the solvent was removed to obtain the final product, Cardo resin A4, with a weight-average molecular weight of 3653 and an acid value of 46 mg KOH / g.

[0098] Comparative Synthesis Example 1

[0099] Cardo-based resin B1 is prepared as follows:

[0100] The first single unit Second single unit and the third monomer A polymerization reaction was carried out to prepare Cardo-based resin B1, wherein the amount of each monomer and the reaction conditions were the same as those in synthesis example 1. The weight-average molecular weight of Cardo-based resin B1 was 2896 and the acid value was 46.1 mg KOH / g.

[0101] Comparative Synthesis Example 2

[0102] Cardo-based resin B2 is prepared as follows:

[0103] The second monomer Third single and the fourth monomer A polymerization reaction was carried out to prepare Cardo-based resin B2, wherein the amount of each monomer and the reaction conditions were the same as those in synthesis example 1. The weight-average molecular weight of Cardo-based resin B2 was 2868 and the acid value was 58.7 mg KOH / g.

[0104] Example 1

[0105] This embodiment provides an alkali-soluble resin, which is a Cardo-based resin A1 (synthesis example 1) and an epoxy resin ( The composition (source: Qiangli Advanced Electronic Materials Co., Ltd.) has a Cardo resin A1 and epoxy resin mass ratio of 4:1.

[0106] This embodiment provides a photosensitive resin composition comprising the aforementioned alkali-soluble resin, which, by weight percentage, includes the following components: 9.75% alkali-soluble resin, 1.5% polymerizable monomer (acryloyloxypropyl cage-like polysilsesquioxane monomer), 0.75% photoinitiator (benzoyl), and organic black pigment (lactam black). 3%, solvent (propylene glycol monomethyl ether acetate, PGMEA) 85%.

[0107] The photosensitive resin composition is prepared as follows: all components are mixed and fully dissolved according to the formula to obtain the photosensitive resin composition.

[0108] Example 2

[0109] This embodiment provides an alkali-soluble resin, which is a Cardo-based resin A2 (synthesis example 2) and an epoxy resin ( The composition is from Qiangli Advanced Electronic Materials Co., Ltd., in which the mass ratio of Cardo resin A2 to epoxy resin is 7:3.

[0110] This embodiment provides a photosensitive resin composition comprising the aforementioned alkali-soluble resin, comprising the following components by weight percentage: 13% alkali-soluble resin, 2% polymerizable monomer (acryloyloxypropyl cage polysilsesquioxane monomer), 1% photoinitiator (benzoyl), 4% organic black pigment (lactam black), and 80% PGMEA solvent.

[0111] The photosensitive resin composition is prepared as follows: all components are mixed and fully dissolved according to the formula to obtain the photosensitive resin composition.

[0112] Example 3

[0113] This embodiment provides an alkali-soluble resin, which is a Cardo-based resin A1 (synthesis example 1) and an epoxy resin ( The composition (source: Qiangli Advanced Electronic Materials Co., Ltd.) has a Cardo resin A1 and epoxy resin mass ratio of 4:1.

[0114] This embodiment provides a photosensitive resin composition comprising the aforementioned alkali-soluble resin, comprising the following components by weight percentage: 10.2% alkali-soluble resin, 4% polymerizable monomer (acryloyloxypropyl cage polysilsesquioxane monomer), 0.8% photoinitiator (benzoyl), 5% organic black pigment (lactam black), and 80% PGMEA solvent.

[0115] The photosensitive resin composition is prepared as follows: all components are mixed and fully dissolved according to the formula to obtain the photosensitive resin composition.

[0116] Example 4

[0117] This embodiment provides an alkali-soluble resin, which is a Cardo-based resin A2 (synthesis example 2) and an epoxy resin ( The composition of Cardo resin A2 and epoxy resin has a mass ratio of 7:3.

[0118] This embodiment provides a photosensitive resin composition comprising the aforementioned alkali-soluble resin, comprising the following components by weight percentage: 7.3% alkali-soluble resin, 4% polymerizable monomer (acryloyloxypropyl cage polysilsesquioxane monomer), 0.7% photoinitiator (benzoyl), 3% organic black pigment (lactam black), and 85% PGMEA solvent.

[0119] The photosensitive resin composition is prepared as follows: all components are mixed and fully dissolved according to the formula to obtain the photosensitive resin composition.

[0120] Example 5

[0121] This embodiment provides an alkali-soluble resin, which is a Cardo-based resin A3 (synthesis example 3) and an epoxy resin ( The composition (source: Qiangli Advanced Electronic Materials Co., Ltd.) has a Cardo resin A3 and epoxy resin mass ratio of 4:1.

[0122] This embodiment provides a photosensitive resin composition comprising the aforementioned alkali-soluble resin, comprising the following components by weight percentage: 10.2% alkali-soluble resin, 4% polymerizable monomer (acryloyloxypropyl cage polysilsesquioxane monomer), 0.8% photoinitiator (benzoyl), 5% organic black pigment (lactam black), and 80% PGMEA solvent.

[0123] The photosensitive resin composition is prepared as follows: all components are mixed and fully dissolved according to the formula to obtain the photosensitive resin composition.

[0124] Example 6

[0125] This embodiment provides an alkali-soluble resin, which is a Cardo-based resin A4 (synthesis example 4) and an epoxy resin ( The composition (source: Qiangli Advanced Electronic Materials Co., Ltd.) has a Cardo resin A4 and epoxy resin mass ratio of 4:1.

[0126] This embodiment provides a photosensitive resin composition comprising the aforementioned alkali-soluble resin, comprising the following components by weight percentage: 10.2% alkali-soluble resin, 4% polymerizable monomer (acryloyloxypropyl cage polysilsesquioxane monomer), 0.8% photoinitiator (benzoyl), 5% organic black pigment (lactam black), and 80% PGMEA solvent.

[0127] The photosensitive resin composition is prepared as follows: all components are mixed and fully dissolved according to the formula to obtain the photosensitive resin composition.

[0128] Comparative Example 1

[0129] This comparative example provides a photosensitive resin composition whose components and proportions are the same as in Example 1, except that the alkali-soluble resin used is Cardo-based resin A1 (Synthesis Example 1) and epoxy resin ( The composition (from Adico Corporation) has a Cardo resin A1 to epoxy resin mass ratio of 4:1; other components are the same as in Example 1, and the preparation method is the same as in Example 1.

[0130] Comparative Example 2

[0131] This comparative example provides a photosensitive resin composition whose components and proportions are the same as those in Example 1. The only difference is that the alkali-soluble resin used is only Cardo-based resin A1 (synthesis example 1), and its amount is the same as that of the alkali-soluble resin composition used in Example 1. The preparation method is the same as that in Example 1.

[0132] Comparative Example 3

[0133] This comparative example provides a photosensitive resin composition, which differs from Example 1 only in that the alkali-soluble resin is Cardo-based resin B1 (Comparative Synthesis Example 1) and epoxy resin. The composition has a Cardo resin B1 to epoxy resin mass ratio of 4:1; the types and amounts of other components are the same as in Example 1.

[0134] Comparative Example 4

[0135] This comparative example provides a photosensitive resin composition, which differs from Example 1 only in that the alkali-soluble resin used is Cardo-based resin B2 (Comparative Synthesis Example 2) and epoxy resin. The composition has a Cardo resin B2 to epoxy resin mass ratio of 4:1; the types and amounts of other components are the same as in Example 1.

[0136] Comparative Example 5

[0137] This comparative example uses commercially available black PDL photoresist (Toray Corporation).

[0138] The aforementioned photosensitive resin composition was subjected to a photolithography process: the photosensitive resin composition to be tested was coated to form a wet film, preheated at 120°C for 120 seconds, exposed using a 365nm wavelength light source, then developed with an alkaline solution (tetramethylammonium hydroxide TMAH solution), and baked at 250°C for 1 hour to obtain a black pixel coloring film, and the following performance tests were performed:

[0139] (1) Thermodynamic properties

[0140] Thermogravimetric analysis (TGA) was used for testing. The temperature was raised to 50℃ and held for 40 min, then raised to 250℃ and held for 1 h, followed by raising to 270℃ and holding for 1 h, and then cooled. The residual mass ratio was then observed based on the test curve.

[0141] The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC). The DSC instrument is heated to 400℃ at a rate of 10℃ / min, and then cooled down. The temperature at which the endothermic peak is located is observed to obtain Tg.

[0142] (2) Mechanical properties

[0143] Tensile strength: Tensile strength of 10μm thick film was tested using a tensile testing machine;

[0144] Elongation: For a 10μm thick film, the elongation was tested using a tensile testing machine;

[0145] Young's modulus: 10μm thick film, tested using UTM-100 electronic tensile testing machine;

[0146] Nanoindentation hardness: 2μm film, directly tested using Nano-Indenter nanomechanical probe.

[0147] (3) Residual status

[0148] Sample preparation method: Cut the sample piece, retain the area with the round hole, and spray gold using a gold sprayer.

[0149] The residue was tested using a scanning electron microscope (SEM, Hitachi SU8000). The residue test images for the photosensitive resin compositions of Examples 1-4 and Comparative Example 5 are shown below. Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 As shown in the comparison, it can be seen that the residual coloring film formed by the photosensitive resin composition provided in Examples 1-4 of the present invention has significantly lower residue compared with Comparative Example 5.

[0150] The test results of thermodynamic and mechanical properties are shown in Table 1:

[0151] Table 1

[0152]

[0153]

[0154] According to the performance data in Table 1, compared with the PDL (pixel-defined layer) formed by the photosensitive resin composition using the sulfur-free benzene and phenol-based Cardo resins in Comparative Example 1, the black pixel coloring film prepared by the photosensitive resin composition provided in Examples 1-6 of this invention has a lower mass change rate and a higher glass transition temperature at 250°C and 270°C, indicating that the coloring film prepared in Examples 1-6 has better thermal stability and effectively improved heat resistance. At the same time, the coloring film obtained in Examples 1-6 has higher tensile strength and elongation, lower Young's modulus, and excellent mechanical properties such as flexibility, which can fully meet the performance requirements of flexible display devices.

[0155] Comparing Example 1 with Comparative Examples 1-5, it can be seen that Examples 1-6 of the present invention, by using a combination of Cardo-based resin with a specific structure and epoxy resin containing a triazine structure, enable the black pixel coloring film formed by the photosensitive resin composition to have better thermal and mechanical properties and better residual performance.

[0156] The applicant declares that the present invention illustrates the alkali-soluble resin, photosensitive resin composition, and their applications through the above embodiments. However, the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials used in the present invention, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An alkali-soluble resin, characterized in that, The alkali-soluble resin comprises a combination of Cardo-based resin and epoxy resin; the Cardo-based resin contains a thiobenzene structure and a phenol structure, and the epoxy resin contains a triazine structure.

2. The alkali-soluble resin according to claim 1, characterized in that, The Cardo-based resin comprises at least one structural unit of Formula I, at least one structural unit of Formula II, at least one structural unit of Formula III, and at least one structural unit of Formula IV: Wherein, R1 is selected from any one of substituted or unsubstituted C1-C10 straight-chain or branched alkylene groups and C2-C10 straight-chain or branched alkenyl groups; the substituents in R1 are selected from any one of C2-C10 straight-chain or branched alkenyl groups. R2 is selected from any one of C1-C10 straight-chain or branched alkylene groups and C2-C10 straight-chain or branched alkenyl groups; R3, R4, and R6 are each independently selected from hydrogen, C1-C10 straight-chain or branched alkyl groups; R5 is selected from any one of hydrogen, C1-C10 straight-chain or branched alkyl, phenyl, and phenolic groups; The Cardo resin has a weight-average molecular weight of 2000-4000 and an acid value of 30-100 mgKOH / g. Preferably, R1 is selected from any one of unsubstituted or vinyl-substituted C2-C8 straight-chain or branched alkylene groups, or C2-C8 straight-chain or branched alkenyl groups; more preferably... Any one of them, -* represents the linking site of the group; Preferably, R2 is selected from any one of C2-C8 straight-chain or branched alkylene groups, and more preferably... Any one of them, -* represents the linking site of the group; Preferably, R3, R4, and R6 are each independently selected from hydrogen or methyl; Preferably, R5 is selected from hydrogen, methyl, or phenolic groups; Preferably, the weight-average molecular weight of the Cardo resin is 3000-3800; Preferably, the Cardo resin has an acid value of 40-60 mg KOH / g.

3. The alkali-soluble resin according to claim 1, characterized in that, The epoxy resin comprises any one, two, or a combination of three of the following compounds:

4. The alkali-soluble resin according to claim 1, characterized in that, The mass ratio of Cardo resin to epoxy resin is (0.1-9):1, preferably (1-6):

1.

5. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises a combination of an alkali-soluble resin as described in any one of claims 1-4, a polymerizable monomer, a photoinitiator, and a colorant.

6. The photosensitive resin composition according to claim 5, characterized in that, The polymerizable monomers include any one or a combination of at least two of the following: polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, phenoxyethyl methacrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, neopentyl glycol (meth)acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and acryloyloxypropyl cage-like polysilsesquioxane monomers.

7. The photosensitive resin composition according to claim 5, characterized in that, The photoinitiator includes any one or a combination of at least two of the following: dialkoxyacetophenone photoinitiators, α-hydroxyalkylphenyl ketone photoinitiators, α-aminoalkylphenyl ketone photoinitiators, acylphosphine oxide photoinitiators, oxime ester photoinitiators, benzoyl photoinitiators, benzoin photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, anthraquinone photoinitiators, coumarone photoinitiators, and camphorquinone.

8. The photosensitive resin composition according to claim 5, characterized in that, The colorant is a black colorant, preferably carbon black and / or organic black.

9. The photosensitive resin composition according to any one of claims 5-8, characterized in that, The photosensitive resin composition contains 1%-20% by mass of polymerizable monomers, 0.2%-2% by mass of photoinitiator, and 3%-30% by mass of colorant.

10. The photosensitive resin composition according to claim 5, characterized in that, The photosensitive resin composition also includes a solvent; Preferably, the solvent in the photosensitive resin composition has a mass percentage content of 50%-95%.

11. A colored film, characterized in that, The coloring film is prepared by the photosensitive resin composition as described in any one of claims 5-10.

12. A decorative substrate, characterized in that, The decorative substrate includes the coloring film as described in claim 11.

13. A touch panel, characterized in that, The touch panel includes the decorative substrate as described in claim 12.

14. An organic electroluminescent display device, characterized in that, The organic electroluminescent display device includes the coloring film as described in claim 11.

Images