A resin, its preparation and use

Abstract

The present application relates to a resin, a preparation method and application thereof, the resin comprising at least one heat-resistant structural unit, at least one heat-latent structural unit with formula I and at least one structural unit containing an acid group. The resin provided by the present application is used in a photosensitive resin composition, which can improve the curing rate, adhesion, chemical resistance, heat resistance and light resistance of the cured film under the premise of high resolution, and can reduce the emission of small molecule gas of the photosensitive resin composition.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a resin, its preparation method, and its application. Background Technology

[0002] In recent years, the use of touch panels has surged, especially in the application of organic light-emitting elements, such as organic light-emitting diode (OLED) displays, leading to a proliferation of new technologies and applications. Organic EL (electroluminescence) display devices using OLEDs and similar technologies do not require a backlight. Compared to liquid crystal displays, they offer advantages such as lighter weight, thinner profiles, faster response times, higher contrast ratios, and higher image quality. They are also energy-efficient and flexible, making them widely used in mobile phones, portable information terminals, televisions, and other fields. Because the organic light-emitting layer used in organic EL display devices typically has low heat resistance, the photosensitive resin composition used to form the filters in these devices requires low-temperature curing (below 130°C).

[0003] The technology of removing polarizers from OLED screens, also known as COE (color filter on encapsulation) technology, improves the contrast of OLED displays by blocking reflected light from the electrodes as much as possible through the color filter. Simultaneously, removing the polarizer increases screen brightness and significantly reduces thickness. In the manufacturing process of OLED panels, manufacturing is carried out directly on the top of the panel, therefore a low-temperature curing process (below 100°C) is necessary to avoid affecting the lifespan of OLED components. Furthermore, flexible touchscreens are also gaining attention. For the various substrate materials used in flexible touchscreens, polymer materials are required due to flexibility requirements, and the manufacturing process also requires low-temperature conditions (below 130°C).

[0004] CN116149137A discloses a curable resin composition capable of forming a light-diffusing cured film, which exhibits excellent low-temperature curing properties and chemical resistance, and is used to solve the problem of unevenness caused by external light reflection in image display devices such as organic electroluminescent (EL) displays. As a resin capable of forming a cured film with excellent solvent resistance, it contains: a constitutive unit having an α,β-unsaturated carbonyl group, a constitutive unit having an active methylene or active methine group, and a constitutive unit having an acid group.

[0005] CN110997740B discloses a photosensitive composition with good developability and storage stability, and excellent solvent resistance even after low-temperature curing. The composition comprises a copolymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D), and a colorant (E), wherein the copolymer (A) contains: a structural unit (a) having a capped isocyanate group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group.

[0006] CN111123648A discloses a low-temperature curable photosensitive resin composition, comprising quantum dots, an alkali-soluble resin, a photopolymerizable monomer, a dispersing resin, a photoinitiator, a leveling agent, a solvent, and scattering particles. The alkali-soluble resin comprises a silicone resin having a silane group and at least one other resin; the silicone resin is present in a weight percentage of 20-50 wt% relative to the alkali-soluble resin.

[0007] The above photosensitive resin compositions still retain double bonds after exposure, requiring baking at 200-250℃ for approximately 10-60 minutes to promote double bond conversion and improve the curing film's durability. However, the post-baking temperatures of low-temperature curing negative photosensitive resin compositions for OLEDs are all below 130℃, making it difficult to achieve complete double bond conversion. High double bond residue and insufficient photoresist crosslinking density can lead to abnormal chemical and photothermal resistance of the cured film. Therefore, there is an urgent need for a novel resin that, when used in photosensitive resin compositions, can improve the curing rate of the photosensitive resin composition while maintaining resolution, reduce double bond residue, enhance the adhesion, chemical resistance, heat resistance, and light resistance of the cured film, and reduce the emission of small molecule gases. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide a resin, its preparation method, and its application. Through the design of the resin structure, it can be used in photosensitive resin compositions to improve the curing rate of the photosensitive resin composition while ensuring resolution, reduce the residue of double bonds, improve the adhesion, chemical resistance, heat resistance, and light resistance of the cured film, and reduce the emission of small molecule gases.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a resin comprising at least one heat-resistant structural unit, at least one heat-latent structural unit having as shown in Formula I, and at least one structural unit containing an acidic group.

[0011]

[0012] in, The connection point represents the structural unit.

[0013] R1 is selected from any one of C1-C5 straight-chain or branched alkylene groups; when multiple (at least two) R1s are present, R1s may be the same or different.

[0014] R3 is selected from any one of C3-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 cycloalkenyl, C2-C10 alkenyl, substituted or unsubstituted C6-C20 aryl; when multiple (at least two) R3s are present, R3s may be the same or different.

[0015] The substituents described in R3 are each independently selected from at least one of C1-C6 straight-chain or branched alkyl groups.

[0016] R2 has the structure shown in equation a. When there are multiple (at least two) R2s, they can be the same or different.

[0017]

[0018] Here, -* represents the linking site of a group.

[0019] R 11 It is selected from any one of C1-C10 straight-chain or branched alkylene groups.

[0020] R 12 Selected from hydrogen atoms or methyl groups.

[0021] In this invention, the heat-resistant structural unit refers to a structural unit containing cyclic groups such as benzene rings, aliphatic rings, aliphatic heterocyclic rings, or heteroaromatic rings, and may also refer to a structural unit formed by monomers such as methyl methacrylate, ethyl methacrylate, and propyl methacrylate; the acidic group includes a carboxyl group.

[0022] 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.

[0023] The resin provided by this invention contains at least one thermally latent structural unit, which contains a double bond and a sterically hindered group R3. When the resin provided by this invention is used in a photosensitive resin composition, during the post-baking process at 85-130°C, the thermally latent structural unit in the resin decomposes to contain isocyanate groups. The isocyanate groups can undergo cross-linking reactions with the polyfunctional monomers in the photosensitive resin composition, thereby enhancing the chemical resistance, heat resistance, and light resistance of the photosensitive resin composition. At the same time, the double bonds contained in the thermally latent structural unit participate in photocuring, preventing the generation of small molecule substances and resulting in high levels of small molecule spillage, thereby improving the conversion rate of the double bonds.

[0024] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0025] In this invention, the expression Ca-Cb represents that the group has ab carbon atoms. Unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms of the substituents.

[0026] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0027] In this invention, C1-C5 can all be C2, C3 or C4.

[0028] C3-C10 can all be C4, C5, C6, C7, C8 or C9.

[0029] C3-C20 can all be C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19.

[0030] C2-C10 can all be C3, C4, C5, C6, C7, C8, C9, etc.

[0031] C6-20 can all be C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19.

[0032] C1-C6 can all be C2, C3, C4, C5, etc.

[0033] C1-C10 can all be C2, C3, C4, C5, C6, C7, C8, C9, etc.

[0034] In this invention, the C1-C5 straight-chain or branched alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, 2-methylbutylene, n-pentylene, isopentylene, or neopentylene, etc.

[0035] The C3-C10 straight-chain or branched alkyl groups include n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, 2-ethylhexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0036] The C3-C20 cycloalkyl group, preferably C3-C10 cycloalkyl group, includes monocycloalkyl or polycycloalkyl groups. Monocycloalkyl refers to an alkyl group containing a single ring structure, while polycycloalkyl refers to a structure formed by two or more cycloalkyl groups sharing one or more carbon atoms on a ring; exemplary examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl.

[0037] The C3-C20 cycloalkenyl group, preferably C3-C10 cycloalkenyl group, refers to a group containing a double bond in the cyclic structure of the above-mentioned cycloalkyl group, including but not limited to: cyclohexenyl, norbornenyl, cyclopentadienyl, etc.

[0038] The C2-C10 alkenyl group refers to a straight-chain alkenyl or branched alkenyl group containing at least one carbon-carbon double bond, including but not limited to: vinyl, propenyl, allyl, etc.

[0039] The C6-20 aryl group includes monocyclic aryl and fused-ring aryl groups; a monocyclic aryl group means that the group contains at least one phenyl group, and when it contains at least two phenyl groups, the phenyl groups are linked by single bonds, including but not limited to: phenyl, biphenyl, terphenyl, etc.; a fused-ring aryl group means that the group contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms fused together, including but not limited to: naphthyl, anthraceneyl, phenanthryl, indene, fluorenyl, fluoranyl, triphenylene, pyrene, perylene, etc. Aryl, tetraphenyl, acenaphthene, benzo[a]acenaphthene, etc. It should be noted that monocyclic aryl and fused-ring aryl groups linked by single bonds also fall under the aryl group category, such as phenylnaphthyl, naphthylphenyl, naphthylnaphthyl, etc.

[0040] As a preferred technical solution, the heat-resistant structural unit is derived from a heat-resistant monomer having a structure as shown in Formula II-1 and / or Formula II-2:

[0041]

[0042] Among them, R 21 Selected from hydrogen atoms or methyl groups.

[0043] R22 It is selected from any one of substituted or unsubstituted C1-C3 (e.g., C1, C2, C3) straight-chain or branched alkyl groups, substituted or unsubstituted C3-C10 (e.g., C4, C5, C6, C7, C8, or C9) cycloalkyl groups, and substituted or unsubstituted C3-C10 (e.g., C4, C5, C6, C7, C8, or C9) cycloalkenyl groups; at least one of the C1-C3 straight-chain or branched alkyl groups is substituted or not substituted with O.

[0044] In this invention, at least one -CH2- in the C1-C3 straight-chain or branched alkyl group is replaced by O. For example, replacing one -CH2- in -CH2-CH2-CH3 with O yields -O-CH2-CH3 or -CH2-O-CH3.

[0045] R 22 The substituents described herein are each independently selected from at least one of the following: C1-C5 (e.g., C2, C3, C4) straight-chain or branched alkyl groups, unsubstituted or R'-substituted C3-C6 (e.g., C4 or C5) cycloalkyl groups, C3-C6 (e.g., C4 or C5) heterocyclic alkyl groups, and C3-C10 (e.g., C4, C5, C6, C7, C8, or C9) cycloalkenyl groups.

[0046] R' is selected from at least one of hydroxylated C1-C3 straight-chain or branched alkyl groups.

[0047] R 23 Selected from C6-C10 (e.g., C7, C8, or C9) aryl, C6-C12 (e.g., C7, C8, C9, C11) heteroaryl, Any one of them; -* represents the linking site of the group.

[0048] The heat-resistant structural units contained in the resin provided by the present invention may originate from the same heat-resistant monomer or from two or more heat-resistant monomers. When they originate from two or more heat-resistant monomers, the heat-resistant monomers from which the same heat-resistant structural unit originates may be the same or different.

[0049] The heteroatoms in the C6-C12 heteroaryl group are selected from N, O, S, P, B, Si, or Se, preferably N, O, or S. The C6-C12 heteroaryl group includes monocyclic heteroaryl or fused-ring heteroaryl. A monocyclic heteroaryl means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: bipyridyl, phenylpyridyl, pyridylphenyl, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), with the two sharing two adjacent atoms fused together in a group. Exemplary examples include, but are not limited to: quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, isobenzothiopheneyl, indolyl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl, phenothiazinyl, phenothiazinyl, etc. It should be noted that heteroaryl groups linked by single bonds, and aryl groups linked by single bonds, also fall within the scope of heteroaryl groups, such as phenylpyridinyl and phenylpyrimidinyl.

[0050] The heteroatom in the C3-C6 heterocyclic alkyl group is selected from O, N or S, and is a group obtained by replacing at least one carbon atom in the above-mentioned cycloalkyl group with a heteroatom, including but not limited to tetrahydrofuranyl, morpholinyl, piperazineyl, piperidinyl or tetrahydropyrroleyl.

[0051] Preferably, the heat-resistant structural unit is derived from cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, ethylcyclohexyl methacrylate, 1,4-cyclohexanediol mono(meth)acrylate, rosin (meth)acrylate, norborneol methacrylate, 5-methylnorborneol methacrylate, 5-ethylnorborneol methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, and isoborneol methacrylate. The formulation comprises any one or a combination of at least two of the following: methacrylate, adamantane acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, α-styrene, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmaleimide, or N-benzylmaleimide, more preferably dicyclopentyl methacrylate, methyl methacrylate, N-vinylmaleimide, or N-benzylmaleimide, and more preferably dicyclopentyl methacrylate and / or N-benzylmaleimide.

[0052] Preferably, the structural unit containing the acidic group is derived from any one or a combination of at least two of the following: a monomer containing an acidic group having the structure shown in Formula III, propynic acid, or unsaturated acid anhydride.

[0053]

[0054]

[0055] R 31 It is selected from any one of the following: hydrogen atom, carboxyl-substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9) straight-chain or branched alkyl, halogen, cyano group.

[0056] The halogen can be fluorine, chlorine, bromine or iodine.

[0057] R 32 R 33 Each is independently selected from any one of hydrogen atom, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9) straight-chain or branched alkyl, C6-C15 (e.g., C9, C10, C12, C14, etc.) aryl, C4-C15 (C5, C6, C7, C8, C9, C10, C12, C14, etc.) heteroaryl, carboxyl, L-OOC-; L is selected from any one of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9) straight-chain or branched alkyl.

[0058] Preferably, the unsaturated anhydride includes any one or a combination of at least two of maleic anhydride, itaconic anhydride, or citraconic anhydride.

[0059] Preferably, the structural unit containing the acidic group is derived from a monomer and / or propynic acid having an acidic group having a structure as shown in Formula III.

[0060] The structural units containing acidic groups in the resin provided by the present invention may originate from the same monomer containing acidic groups, or from two or more monomers containing acidic groups. When originating from two or more monomers containing acidic groups, the monomers containing acidic groups from which the structural units containing the same acidic group originate may be the same or different.

[0061] Preferably, the structural unit containing the acidic group is derived from any one or a combination of at least two of (meth)acrylic acid, α-bromoacrylic acid, β-furanyl(meth)acrylic acid, crotonic acid, propynic acid, cinnamic acid, α-cyanocinonic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, or citraconic acid, and more preferably (meth)acrylic acid.

[0062] Preferably, the R 11 It is selected from any one of C1-C6 (e.g., C2, C3, C4, C5) straight-chain or branched alkylene groups.

[0063] Preferably, R3 is selected from any one of isopropyl, tert-butyl, 2-ethylhexyl, cyclohexyl, norbornenyl, isobornel, 4-tert-butylcyclohexyl or biphenyl, and more preferably tert-butyl.

[0064] Preferably, the thermal latency structural unit is selected from any one of the following structural units:

[0065]

[0066] in, The connection point represents the structural unit.

[0067] Preferably, the resin comprises at least one heat-resistant structural unit as shown in Formula IV-1, at least one heat-latent structural unit as shown in Formula IV-2, and at least one structural unit containing an acidic group as shown in Formula IV-3.

[0068]

[0069] in, The connection points represent structural units; R1, R2, and R3 have the same range as in Equation I.

[0070] In this invention, the way the ring structure is represented by "—" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0071] Preferably, R3 is selected from any one of isopropyl, tert-butyl, 2-ethylhexyl, cyclohexyl, norbornenyl, isobornel, 4-tert-butylcyclohexyl or biphenyl, and more preferably tert-butyl.

[0072] Preferably, the molar percentage of the heat-resistant structural unit in the resin is 55-65% (e.g., 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, etc.), the molar percentage of the heat-latent structural unit is 10-30% (e.g., 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc.), and the molar percentage of the structural unit containing acidic groups is 5-15% (e.g., 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, etc.).

[0073] Preferably, the acid value of the resin is 34-61 mgKOH / g, for example, it can be 36 mgKOH / g, 38 mgKOH / g, 40 mgKOH / g, 42 mgKOH / g, 44 mgKOH / g, 46 mgKOH / g, 48 mgKOH / g, 50 mgKOH / g, 52 mgKOH / g, 54 mgKOH / g, 56 mgKOH / g, 58 mgKOH / g, 60 mgKOH / g, etc.

[0074] Preferably, the weight-average molecular weight of the resin is 9600-13200, for example, it can be 9800, 10000, 10200, 10400, 10600, 10800, 11000, 11200, 11400, 11600, 11800, 12000, 12200, 12400, 12600, 12800, 13000, etc.

[0075] In a second aspect, the present invention provides a method for preparing the resin as described in the first aspect, the method comprising the following steps:

[0076] (1) A heat-resistant monomer, a monomer containing an acidic group, and monomer A react to obtain a first copolymer;

[0077] (2) The first copolymer reacts with monomer B to obtain the resin.

[0078] The monomer A has the structure shown in Formula I-1, and the monomer B has the structure shown in Formula I-2;

[0079]

[0080] Among them, R1, R2, and R3 have the same range as in Equation I.

[0081] The resin provided by this invention first copolymerizes NCO-containing monomer A onto the polymer backbone, and then grafts secondary amine-containing monomer B onto the structural unit formed by monomer A, thereby obtaining the heat-latent structural unit; in addition, the heat-latent structural unit will decompose to generate secondary amine during post-baking. Since R3 is a sterically hindered group, the reaction between the secondary amine of monomer B and the active group in the photosensitive resin composition can be avoided, thus preventing the problem of abnormal storage stability caused by the reaction between the secondary amine of monomer B and the active group in the photosensitive resin composition.

[0082] Preferably, monomer A comprises ethyl isocyanate methacrylate.

[0083] Preferably, monomer B comprises at least one selected from tert-butylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, 1,4-tert-butylcyclohexylaminoethyl methacrylate, 2-ethylhexylaminoethyl methacrylate, or isobornylaminoethyl methacrylate, and more preferably tert-butylaminoethyl methacrylate; the structure of monomer B is shown below:

[0084]

[0085] Preferably, the reaction time in step (1) is 2-4 hours, for example, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, etc.

[0086] Preferably, the reaction temperature in step (1) is 60-85℃, for example, it can be 62℃, 64℃, 66℃, 68℃, 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, 82℃, 84℃, etc.

[0087] Preferably, the reaction in step (1) is carried out in the presence of an initiator.

[0088] Preferably, the mass of the initiator is 0.5-5% based on the total mass of the heat-resistant monomer, the monomer containing the acidic group, monomer A and monomer B as 100%, for example, it can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.

[0089] Preferably, the initiator includes any one or a combination of at least two of azobisisobutyronitrile, azobisisobutyronitrile, or azobisisovalerate.

[0090] Preferably, the reaction in step (1) is carried out in the presence of the first solvent.

[0091] Preferably, the first solvent comprises propylene glycol monomethyl ether acetate and / or propylene glycol monomethyl ether.

[0092] Preferably, with the total mass of the heat-resistant monomer, the monomer containing the acidic group, monomer A and monomer B being 100%, the mass of the first solvent is 200-500%, for example, it can be 220%, 240%, 260%, 280%, 300%, 320%, 340%, 360%, 380%, 400%, 420%, 440%, 460%, 480%, etc.

[0093] Preferably, the reaction time in step (2) is 3-5 hours, for example, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, etc.

[0094] Preferably, the reaction temperature in step (2) is 50-70℃, for example, it can be 52℃, 54℃, 56℃, 58℃, 60℃, 62℃, 64℃, 66℃, 68℃, etc.

[0095] Preferably, both the reaction in step (1) and the reaction in step (2) are carried out under a nitrogen atmosphere.

[0096] Thirdly, the present invention provides a photosensitive resin composition, wherein the components of the photosensitive resin composition include the resin as described in the first aspect.

[0097] Preferably, the photosensitive resin composition further includes a multifunctional monomer.

[0098] The multifunctional monomer (or photosensitive monomer) contains multiple (at least two) reactive functional groups in its molecule. Adding the multifunctional monomer can achieve technical effects such as forming clear pixel patterns in the exposed area and preventing development and mold detachment.

[0099] Preferably, the multifunctional monomer includes any one or a combination of at least two of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(hydroxyethyl) isocyanurate di(meth)acrylate, or tri(hydroxyethyl) isocyanurate tri(meth)acrylate.

[0100] Preferably, the mass ratio of the resin to the multifunctional monomer is 1:(0.3-1), for example, it can be 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, etc.

[0101] Preferably, the photosensitive resin composition further includes any one or a combination of at least two of the following: a photoinitiator, a co-initiator, an additive, an organic solvent, or a colorant.

[0102] Preferably, the photoinitiator comprises any one or a combination of at least two of the following: benzoin photoinitiators, benzoyl photoinitiators, alkyl benzophenone photoinitiators, acyl phosphooxide photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, oxime photoinitiators, diaryl iodonium salts, triaryl iodonium salts, alkyl iodonium salts, or cumeneferrocene hexafluorophosphate.

[0103] Preferably, the alkyl phenyl ketone photoinitiator includes any one or a combination of at least two of the oligomers of diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, or 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, more preferably 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one.

[0104] Preferably, the benzophenone photoinitiator includes any one or a combination of at least two of benzophenone, methyl phthalobenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, or 2,4,6-trimethylbenzophenone.

[0105] Preferably, the thioxanthone photoinitiator includes any one or a combination of at least two of thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, or 2-chlorothioxanthone.

[0106] Preferably, the oxime photoinitiator comprises any one or a combination of at least two of the following: O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone, or O-ethoxycarbonyl-α-oxoamino-1-phenylprop-1-one.

[0107] Preferably, the O-acyl oxime compound includes any one or a combination of at least two of the following: 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylthiophenyl)-but-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one-oxime-O-acetate, or 1-(4-phenylthiophenyl)-but-1-one-oxime-O-acetate.

[0108] Preferably, the co-initiator includes at least one of aliphatic tertiary amines, ethanolamine tertiary amines, tertiary amine benzoates, or active amines.

[0109] When the photoinitiator is a hydrogen-abstracting photoinitiator, it needs to be used in conjunction with the co-initiator.

[0110] Preferably, the mass ratio of the photoinitiator to the co-initiator is 1:(0.001-1.1), for example, it can be 1:0.005, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, etc.

[0111] Preferably, the additive includes any one or a combination of at least two of the following: leveling agent, polymerization inhibitor, or adhesion promoter.

[0112] Preferably, the leveling agent comprises silicone-based surfactants and / or fluorinated surfactants.

[0113] The silicone surfactants mentioned can be, by way of example, purchased from, but not limited to, BYK-310, 313, 315N, 320, 322, 331, 333, 342, 346, 348, 370, 378, 3455, 3510, 3570 manufactured by BYK Chemical Co., Ltd., and KF-351A, KF-354L, KF-945, KF-640, KF-642, KF-643, KF-6004, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0114] The fluorinated surfactants can be, by way of example, purchased from, but not limited to, Megafac F-477, 551, 552, 558, 560, 575, 576, R-41, RS-72-K, DS-21, etc., manufactured by D.E.S.

[0115] Preferably, the polymerization inhibitor includes any one or a combination of at least two of the following: p-hydroxyanisole, alkyl catechol compounds, alkyl resorcinol compounds, alkyl hydroquinone compounds, or organophosphorus compounds.

[0116] Preferably, the alkyl catechol compound includes 3,5-di-tert-butylcatechol.

[0117] Preferably, the alkyl resorcinol compounds are any one or a combination of at least two of the following: 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, or 4-tert-butylresorcinol.

[0118] Preferably, the alkyl hydroquinone compound includes any one or a combination of at least two of methyl hydroquinone, ethyl hydroquinone, propionic hydroquinone, tert-butyl hydroquinone, or 2,5-di-tert-butyl hydroquinone.

[0119] Preferably, the organophosphorus compound includes any one or a combination of at least two of tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, or triphenylphosphine oxide.

[0120] Preferably, the adhesion promoter comprises any one or a combination of at least two of the following: vinyl silane compounds, silane compounds containing (meth)acrylate groups, epoxy silane compounds, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.

[0121] Preferably, the vinyl silane compounds include vinyltrimethoxysilane and / or vinyltriethoxysilane.

[0122] Preferably, the silane compound containing (meth)acrylate groups includes any one or a combination of at least two of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, or 3-acryloxypropyltrimethoxysilane.

[0123] Preferably, the epoxy silane compound includes any one or a combination of at least two of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, or 3-glycidoxypropyltriethoxysilane.

[0124] Preferably, the mass ratio of the resin to the photoinitiator is 1:(0.001-0.1), for example, it can be 1:0.005, 1:0.01, 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, 1:0.05, 1:0.055, 1:0.06, 1:0.065, 1:0.07, 1:0.075, 1:0.08, 1:0.085, 1:0.09, 1:0.095, etc.

[0125] Preferably, the mass ratio of the resin to the additive is 1:(0.001-0.1), for example, it can be 1:0.005, 1:0.01, 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, 1:0.05, 1:0.055, 1:0.06, 1:0.065, 1:0.07, 1:0.075, 1:0.08, 1:0.085, 1:0.09, 1:0.095, etc.

[0126] Preferably, the mass ratio of the resin to the organic solvent is 1:(1-8), for example, it can be 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, etc.

[0127] Preferably, the mass ratio of the resin to the colorant is 1:(2-5), for example, it can be 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, 1:4, 1:4.2, 1:4.6, 1:4.8, etc.

[0128] Preferably, the organic solvent includes any one or a combination of at least two of the following: cyclohexane, isopropanol, ether organic solvents, ester organic solvents, ketone organic solvents, aromatic hydrocarbon organic solvents, or amide organic solvents.

[0129] Preferably, the ether organic solvent includes any one or a combination of at least two of the following: (poly)alkylene glycol monoalkyl ether organic solvents, (poly)alkylene glycol monoalkyl ether acetate organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether acetate, or tetrahydrofuran.

[0130] Preferably, the (poly)alkylene glycol monoalkyl ether organic solvent includes any one or a combination of at least two of the following: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol monomethyl ether, or tripropylene glycol monoethyl ether.

[0131] Preferably, the (poly)alkylene glycol monoalkyl ether acetates include any one or a combination of at least two of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate.

[0132] Preferably, the ester organic solvent includes any one or a combination of at least two of the following: lactic acid alkyl ester organic solvents, diethylene glycol diethyl ether acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxyacetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methyl-3-methoxybutylacetate, methyl 3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-acetoacetate, or ethyl lactate.

[0133] Preferably, the lactic acid alkyl ester organic solvent includes methyl 2-hydroxypropionate and / or ethyl 2-hydroxypropionate.

[0134] Preferably, the ketone organic solvent includes any one or a combination of at least two of butanone, cyclohexanone, 2-heptanone, or 3-heptanone.

[0135] Preferably, the aromatic hydrocarbon organic solvent includes toluene and / or xylene.

[0136] Preferably, the amide organic solvent includes any one or a combination of at least two of N-methylpyrrolidone, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0137] Considering environmental protection requirements, membrane surface smoothness, and processability, the organic solvents include high-boiling-point solvents with a boiling point of 150-200℃ and low-boiling-point solvents with a boiling point below 150℃.

[0138] Preferably, the mass ratio of the high-boiling-point solvent to the low-boiling-point solvent is 1:(1-9), for example, it can be 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, 1:8.5, etc.

[0139] Preferably, the high-boiling-point solvent includes at least one of dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether acetate, ethyl 3-ethoxypropionate, butyl 3-methoxyacetate, or ethyl lactate.

[0140] Preferably, the low-boiling-point solvent includes at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, or isopropanol.

[0141] From the perspective of solubility and dispersibility, the organic solvent includes at least one of propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate, and more preferably propylene glycol monomethyl ether acetate and / or 3-methoxybutyl acetate.

[0142] Preferably, the colorant comprises any one or a combination of at least two of dyes, pigments, or color pastes; the color paste is formed by dispersing the pigment and / or the dye in a second solvent.

[0143] Preferably, the solid content of the pigment is 5-50%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.

[0144] Preferably, the pigment includes organic pigments and / or inorganic pigments.

[0145] Preferably, the pigment includes any one or a combination of at least two of the following: red pigment, green pigment, blue pigment, yellow pigment, orange pigment, brown pigment, or purple pigment.

[0146] Preferably, the yellow pigment includes any one or a combination of at least two of CI pigment yellow 1, CI pigment yellow 3, CI pigment yellow 12, CI pigment yellow 13, CI pigment yellow 14, CI pigment yellow 15, CI pigment yellow 16, CI pigment yellow 17, CI pigment yellow 20, CI pigment yellow 24, CI pigment yellow 31, CI pigment yellow 53, CI pigment yellow 83, CI pigment yellow 86, CI pigment yellow 93, CI pigment yellow 94, CI pigment yellow 109, CI pigment yellow 110, CI pigment yellow 117, CI pigment yellow 125, CI pigment yellow 128, CI pigment yellow 137, CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 147, CI pigment yellow 148, CI pigment yellow 150, CI pigment yellow 153, CI pigment yellow 154, CI pigment yellow 166, CI pigment yellow 173, CI pigment yellow 194, or CI pigment yellow 214.

[0147] Preferably, the orange pigment includes any one or a combination of at least two of CI Pigment Orange 13, CI Pigment Orange 31, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 42, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 65, CI Pigment Orange 71, or CI Pigment Orange 73.

[0148] Preferably, the red pigment includes any one or a combination of at least two of CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 265, or CI Pigment Red 291.

[0149] Preferably, the blue pigment includes any one or a combination of at least two of CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, or CI Pigment Blue 60.

[0150] Preferably, the purple pigment includes any one or a combination of at least two of CI pigment purple 1, CI pigment purple 19, CI pigment purple 23, CI pigment purple 29, CI pigment purple 32, CI pigment purple 36 or CI pigment purple 38.

[0151] Preferably, the green pigment includes any one or a combination of at least two of CI Pigment Green 7, CI Pigment Green 36, or CI Pigment Green 58.

[0152] Preferably, the brown pigment includes CI pigment brown 23 and / or CI pigment brown 25.

[0153] Preferably, the pigment includes any one or a combination of at least two of CI pigments: Yellow 138, Yellow 139, Yellow 150, Red 177, Red 209, Red 254, Violet 23, Blue 15:6, or Green 36.

[0154] The organic and inorganic pigments can be used individually or in combination; for example, when forming a red pixel, it is preferable to contain CI pigment red 254 and CI pigment yellow 139; when forming a green pixel, it is preferable to contain CI pigment green 58, CI pigment yellow 150 or CI pigment yellow 138; when forming a blue pixel, it is preferable to contain CI pigment blue 15:6.

[0155] The photosensitive resin composition provided by the present invention is coated on a substrate, and then subjected to pre-baking, exposure, development and post-baking processes to obtain a pattern of a specific shape, thereby forming a pixel.

[0156] Fourthly, the present invention provides the use of the photosensitive resin composition as described in the third aspect in a display device or a semiconductor device.

[0157] Compared with the prior art, the present invention has the following beneficial effects:

[0158] The resin provided by this invention contains at least one heat-resistant structural unit, at least one heat-latent structural unit, and at least one structural unit containing an acidic group. Using the resin provided by this invention in a photosensitive resin composition can improve the curing rate, adhesion, chemical resistance, heat resistance, and light resistance of the cured film while maintaining high resolution, and can also reduce the emission of small molecule gases from the photosensitive resin composition. The photosensitive resin composition using the resin provided by this invention achieves a curing rate of 93-95%, a small molecule efflux content of 0.58-0.86% by mass, and an adhesion of 5B for the cured film. Detailed Implementation

[0159] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0160] The sources of some components in the examples and comparative examples are as follows:

[0161] (1) Cyclohexylaminoethyl methacrylate: purchased from Aladdin Reagent;

[0162] (2) 1,4-tert-butylcyclohexylaminoethyl methacrylate: purchased from Aladdin Reagent;

[0163] (3) 2-Ethylhexylaminoethyl methacrylate: purchased from Aladdin Reagent;

[0164] (4) Isoborneol aminoethyl methacrylate: purchased from Aladdin Reagent;

[0165] (5) Diethyl-2-[2-(methacryloyloxy)ethylcarbamoyl]malonate: purchased from Resonac Corporation;

[0166] (6) 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate: purchased from Resonac Corporation.

[0167] Example 1

[0168] A resin A1 contains structural units, wherein the values ​​57, 30 and 13 in each structural unit represent the molar percentages of each structural unit in resin A1 as 57%, 30% and 13%, respectively.

[0169]

[0170] The preparation method of the resin A1 includes:

[0171] Add 139.51g of propylene glycol monomethyl ether acetate to a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube. Dissolve 9.42g of azobisisobutyronitrile in 400g of propylene glycol monomethyl ether acetate and transfer the solution to constant pressure dropping funnel A. Mix 27.93g of ethyl isocyanate methacrylate, 147.61g of dicyclopentyl methacrylate, and 12.91g of methacrylic acid thoroughly and then add the mixture to constant pressure dropping funnel B. The air atmosphere in the flask was replaced with nitrogen, and the temperature of the flask was raised to 80°C while stirring. Then, the initiator and monomer were added dropwise from dropping funnels A and B, with the addition time controlled at 1 hour, while the temperature was maintained at 80±3°C. After the addition was completed, the reaction was continued at 80°C for 2 hours. After the double bonds were completely eliminated by infrared detection, the reaction temperature was lowered to 60°C, and 33.35 g of tert-butylaminoethyl methacrylate was added dropwise to the reaction system, with the addition time controlled at 1 hour. After the addition was completed, the reaction was kept at the temperature for 3 hours. After the NCO was completely eliminated by infrared detection, alkali-soluble resin A1 with an acid value of 36.4 mg KOH / g and a solid content of 30% was obtained.

[0172] Acid value was tested by titration.

[0173] The determination was performed by gel permeation chromatography (GPC, Waters Alliance e2695) at a detector temperature of 40°C, using tetrahydrofuran solution as the mobile phase and a flow rate of 1.0 mL / min. The weight-average molecular weight of the resin A1, converted relative to the polystyrene standard, was 11,000.

[0174] Examples 2-7, Comparative Example 2

[0175] A resin and its preparation method are disclosed, which differ from Example 1 only in the raw materials and / or the amount of raw materials (g). All other process parameters and steps are the same as in Example 1. The characterization data of the raw materials and the target product are shown in Tables 1 and 2.

[0176] Comparative Example 1

[0177] A resin, the raw materials, amounts, and target product characterization data of which are shown in Table 2, and the preparation method of the resin includes:

[0178] 132.63 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube. 10.87 g of azobisisobutyronitrile was dissolved in 400 g of propylene glycol monomethyl ether acetate and transferred to constant-pressure dropping funnel A. 56.88 g of diethyl-2-[2-(methacryloyloxy)ethylcarbamoyl]malonate, 147.61 g of dicyclopentyl methacrylate, and 12.91 g of methacrylic acid were mixed thoroughly and added to constant-pressure dropping funnel B. The air atmosphere in the flask was replaced with nitrogen, and the temperature of the flask was raised to 60°C while stirring. Subsequently, the initiator and monomer were added dropwise from dropping funnels A and B, with the addition time controlled at 1 h, while maintaining the temperature at 60 ± 3°C. After the addition was completed, the reaction was continued at 60°C for 4 h. The resin was obtained after the double bonds were completely disappeared, as detected by infrared spectroscopy.

[0179] Table 1

[0180]

[0181]

[0182] Table 2

[0183]

[0184] The sources of some components in the application examples and comparative application examples are as follows:

[0185] The red MB composition is composed of 10.8g of R254 dispersion, 11.5g of R291 dispersion, 11.2g of R177 dispersion and 0.86g of G58 dispersion; the solid content of the red MB composition is 20.9%; wherein the R254 dispersion, R291 dispersion, R177 dispersion and G58 dispersion were all purchased from Artience Co., Ltd.

[0186] Application Example 1

[0187] A photosensitive resin composition comprising 10.32 parts by weight of resin A1 provided in Example 1, 5 parts by weight of dipentaerythritol hexaacrylate (DPHA), 0.5 parts by weight of photoinitiator OXE01, 0.01 parts by weight of p-hydroxyanisole, 0.01 parts by weight of leveling agent RS-72-K (Dearson), 34.16 parts by weight of red MB composition, 17 parts by weight of EEP and 33 parts by weight of PMA;

[0188] The preparation method of the photosensitive resin composition includes:

[0189] The photosensitive resin composition is obtained by thoroughly dissolving and mixing resin A1, DPHA, photoinitiator OXE01, p-hydroxyanisole, leveling agent RS-72-K, red MB composition, EEP and PMA.

[0190] Application Example 2-7, Comparison with Application Example 1-2

[0191] A photosensitive resin composition differs from Application Example 1 only in that the resin provided in Example 1 is replaced in equal amounts with the resins provided in Examples 2, 3, 4, 5, 6, 7, Comparative Example 1, and Comparative Example 2, while the remaining components and amounts are the same as in Application Example 1.

[0192] Performance testing

[0193] The photosensitive resin compositions provided in the application examples and comparative application examples were coated onto the surface of a glass substrate with a diameter of 6 inches and a thickness of 1.12 mm to form a thin film coating with a thickness of 3 μm. The coated glass substrate was then pre-baked in a dryer at 85°C for 2 minutes to remove solvents. A mask was then applied, and the coating underwent photopolymerization under ultraviolet light irradiation at an intensity of 60 mJ / cm². 2 The developing method is selected at 23±2℃, and the spray developing time is 50 seconds. The unexposed photosensitive resin composition is washed away with 0.04% KOH developing solution to obtain the desired image. The post-baking process is carried out in an oven at 85℃ for about 60 minutes.

[0194] The obtained pattern was tested as follows, and the test results are shown in Table 3.

[0195] (1) Resolution evaluation

[0196] After development and baking, the minimum linewidth that basically meets the mask size and has a clear image without residual film is taken as the optimal resolution.

[0197] (2) Evaluation of curing rate

[0198] The double bond content of the photosensitive resin composition and cured film before and after the process was tested using FTIR (Thermo Fisher Scientific, Nicolet iS20) at 1480 cm⁻¹. -1 The peak for the CH vibration of the double bond is 1720 cm⁻¹. -1 The peak value is C=O vibrational. Using the C=O bond as an internal standard, the curing rate is calculated as follows: Curing rate = (AU value of the photosensitive resin composition before exposure - AU value of the cured film after exposure) / AU value of the photosensitive resin composition before exposure, AU = 1480 cm⁻¹ -1Peak area / 1720cm -1 Peak area;

[0199] (3) Evaluation of chemical resistance

[0200] The color filter prepared according to the above method was immersed in an N-methyl-2-pyrrolidone (NMP) solution at 23°C for 30 minutes. Then, the color coordinates before and after immersion were measured using a microspectrophotometer (LambdaVision, LVmicroZ), and the color difference was calculated according to the following formula:

[0201]

[0202] Among them, L2 * L1 is the L value after impregnation. * a2 is the L value before impregnation. * a1 is the value of a after impregnation. * The value of a before impregnation, b2 * b1 is the b value after impregnation. * The value of b before impregnation;

[0203] The evaluation criteria for chemical resistance are as follows:

[0204] ○ indicates that △E*ab≤3, indicating good chemical resistance;

[0205] △ represents 3 < △E*ab < 6, indicating that the chemical resistance is qualified;

[0206] × indicates that △E*ab≥6, meaning the chemical resistance is unqualified;

[0207] (4) Adhesion evaluation

[0208] The conventional cross-cut test method was used for testing. Specifically, the photoresist surface was cut with a cross-cut knife, and then adhesive tape (3M 600 type) was applied and peeled off. Based on the standard test method, the following specifications were defined: 5B: 0% peeling; 4B: ≤5% peeling; 3B: >5% peeling, ≤15% peeling; 2B: >15% peeling, ≤35% peeling; 1B: >35% peeling, ≤65% peeling; 0B: >65% peeling.

[0209] (5) Evaluation of sun aging

[0210] One cycle: under conditions of 40±3℃ and 30% relative humidity, using an artificial sun (575W / m²). 2 Irradiate with 300-800nm ​​light for 20 hours, then turn off the light for 4 hours. This is one cycle. After 10 cycles, test the color difference before and after aging. The color difference calculation and evaluation method is the same as for chemical resistance.

[0211] (6) Small molecule outgas test: The mass loss of photoresist was measured at 230℃ for 2 hours using a TGA (Netzsch TG209F1 thermogravimetric analyzer). The mass percentage of small molecule outgas = mass loss of photoresist / initial mass of photoresist × 100%.

[0212] Table 3

[0213] Resolution / μm Curing rate / % Adhesion Chemical resistance Lightfastness Outgas / % Example 1 10 95 5B O O 0.58 Example 2 10 94 5B O O 0.65 Example 3 10 93 5B O O 0.76 Example 4 10 93 5B O O 0.86 Example 5 10 94 5B O O 0.62 Example 6 10 94 5B O O 0.84 Example 7 10 95 5B O O 0.78 Comparative Example 1 10 88 3B △ △ 2.87 Comparative Example 2 10 86 3B △ △ 2.95

[0214] The above results demonstrate that the photosensitive resin composition using the resin provided by this invention can achieve high curing rate, high adhesion, high chemical resistance, high light resistance, and low small molecule gas emission while ensuring resolution.

[0215] The applicant declares that the above embodiments illustrate the resin, its preparation method, and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin, characterized in that, The resin includes at least one heat-resistant structural unit, at least one heat-latent structural unit as shown in Formula I, and at least one structural unit containing an acidic group; in, The connection points representing structural units; R1 is selected from any one of C1-C5 straight-chain or branched alkylene groups; R3 is selected from any one of C3-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 cycloalkenyl, C2-C10 alkenyl, substituted or unsubstituted C6-C20 aryl. The substituents described in R3 are each independently selected from at least one of C1-C6 straight-chain or branched alkyl groups; R2 has the structure shown in equation a: Where -* represents the linking site of the group; R 11 any one selected from C1-C10 straight-chained or branched alkylene; R 12 is selected from a hydrogen atom or a methyl group.

2. The resin according to claim 1, characterized in that, The heat-resistant structural unit is derived from a heat-resistant monomer having a structure as shown in Formula II-1 and / or Formula II-2: wherein R 21 is selected from a hydrogen atom or a methyl group; R 22 any one selected from substituted or unsubstituted C1-C3 linear or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl; at least one -CH2- in said C1-C3 linear or branched alkyl is replaced by O or not; R 22 each of the substituents described in the substituents is independently selected from at least one of C1-C5 linear or branched alkyl, C3-C6 cycloalkyl unsubstituted or substituted with R', C3-C6 heterocycloalkyl, C3-C10 cycloalkenyl; R' is selected from at least one of hydroxyl-substituted C1-C3 straight-chain or branched alkyl groups; R 23 Selected from C6-C10 aryl, C6-C12 heteroaryl, Any one of them; -* represents the linking site of the group.

3. The resin according to claim 1, characterized in that, The heat-resistant structural units are derived from cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, ethylcyclohexyl methacrylate, 1,4-cyclohexanediol mono(meth)acrylate, rosin (meth)acrylate, norbornyl methacrylate, 5-methylnorbornyl methacrylate, 5-ethylnorbornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, and isobornyl methacrylate. The mixture comprises any one or a combination of at least two of the following: adamantane methacrylate, tetrahydrofurfuryl methacrylate, methyl methacrylate, α-styrene, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmaleimide, or N-benzylmaleimide. More preferably, it comprises any one or a combination of at least two of the following: dicyclopentyl methacrylate, methyl methacrylate, N-vinylmaleimide, or N-benzylmaleimide. More preferably, it comprises dicyclopentyl methacrylate and / or N-benzylmaleimide.

4. The resin according to claim 2 or 3, characterized in that, The structural unit containing the acidic group is derived from any one or a combination of at least two of the following: a monomer containing an acidic group having the structure shown in Formula III; propynic acid; or unsaturated acid anhydride. R 31 Selected from any one of the following: hydrogen atom, carboxyl-substituted or unsubstituted C1-C10 straight-chain or branched alkyl group, halogen, cyano group; R 32 R 33 Each is independently selected from any one of hydrogen atom, C1-C10 straight-chain or branched alkyl, C6-C15 aryl, C4-C15 heteroaryl, carboxyl, and L-OOC-; L is selected from any one of C1-C10 straight-chain or branched alkyl groups; Preferably, the unsaturated anhydride includes any one or a combination of at least two of maleic anhydride, itaconic anhydride, or citraconic anhydride; Preferably, the structural unit containing the acidic group is derived from a monomer and / or propynic acid having an acidic group having a structure as shown in Formula III.

5. The resin according to any one of claims 1-4, characterized in that, The structural unit containing the acidic group is derived from any one or a combination of at least two of (meth)acrylic acid, α-bromoacrylic acid, β-furanyl(meth)acrylic acid, crotonic acid, propynic acid, cinnamic acid, α-cyanocinonic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, or citraconic acid, with (meth)acrylic acid being more preferred.

6. The resin according to any one of claims 1-5, characterized in that, The R 11 Selected from any one of C1-C6 straight-chain or branched alkylene groups; Preferably, R3 is selected from any one of isopropyl, tert-butyl, 2-ethylhexyl, cyclohexyl, norbornenyl, isobornel, 4-tert-butylcyclohexyl or biphenyl, and more preferably tert-butyl; Preferably, the thermal latency structural unit is selected from any one of the following structural units: in, The connection point represents the structural unit.

7. The resin according to claim 1, characterized in that, The resin comprises at least one heat-resistant structural unit as shown in Formula IV-1, at least one heat-latent structural unit as shown in Formula IV-2, and at least one structural unit containing an acidic group as shown in Formula IV-3. in, The connection points representing structural units; R1, R2, and R3 have the same range as in Equation I.

8. The resin according to claim 7, characterized in that, R3 is selected from any one of isopropyl, tert-butyl, 2-ethylhexyl, cyclohexyl, norbornenyl, isobornel, 4-tert-butylcyclohexyl or biphenyl, and is more preferably tert-butyl.

9. The resin according to any one of claims 1-8, characterized in that, The resin contains 55-65% of the heat-resistant structural unit, 10-30% of the heat-latent structural unit, and 5-15% of the structural unit containing acidic groups. Preferably, the acid value of the resin is 34-61 mg KOH / g; Preferably, the weight-average molecular weight of the resin is 9600-13200.

10. A method for preparing the resin according to any one of claims 1-9, characterized in that, The preparation method includes the following steps: (1) A heat-resistant monomer, a monomer containing an acidic group, and monomer A react to obtain a first copolymer; (2) The first copolymer reacts with monomer B to obtain the resin; The monomer A has the structure shown in Formula I-1, and the monomer B has the structure shown in Formula I-2; Among them, R1, R2, and R3 have the same range as in Equation I.

11. The preparation method according to claim 10, characterized in that, The monomer A includes ethyl isocyanate methacrylate; Preferably, the monomer B comprises at least one of tert-butylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, 1,4-tert-butylcyclohexylaminoethyl methacrylate, 2-ethylhexylaminoethyl methacrylate, or isobornylaminoethyl methacrylate, and more preferably tert-butylaminoethyl methacrylate. Preferably, the reaction time in step (1) is 2-4 hours; Preferably, the reaction temperature in step (1) is 60-85°C; Preferably, the reaction in step (1) is carried out in the presence of an initiator; Preferably, the reaction described in step (1) is carried out in the presence of the first solvent; Preferably, the first solvent comprises propylene glycol monomethyl ether acetate and / or propylene glycol monomethyl ether; Preferably, the reaction time in step (2) is 3-5 hours; Preferably, the reaction temperature in step (2) is 50-70°C; Preferably, both the reaction in step (1) and the reaction in step (2) are carried out under a nitrogen atmosphere.

12. A photosensitive resin composition, characterized in that, The components of the photosensitive resin composition include the resin as described in any one of claims 1-9.

13. The photosensitive resin composition according to claim 12, characterized in that, The photosensitive resin composition also includes multifunctional monomers; Preferably, the multifunctional monomer includes any one or a combination of at least two of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(hydroxyethyl) isocyanurate di(meth)acrylate, or tri(hydroxyethyl) isocyanurate tri(meth)acrylate. Preferably, the mass ratio of the resin to the multifunctional monomer is 1:(0.3-1); Preferably, the photosensitive resin composition further includes any one or a combination of at least two of the following: a photoinitiator, a co-initiator, an additive, an organic solvent, or a colorant; Preferably, the mass ratio of the photoinitiator to the co-initiator is 1:(0.001-1.1); Preferably, the mass ratio of the resin to the photoinitiator is 1:(0.001-0.1); Preferably, the mass ratio of the resin to the additive is 1:(0.001-0.1); Preferably, the mass ratio of the resin to the organic solvent is 1:(1-8); Preferably, the mass ratio of the resin to the colorant is 1:(2-5); Preferably, the additive includes any one or a combination of at least two of the following: leveling agent, polymerization inhibitor, or adhesion promoter.

14. The use of a photosensitive resin composition as described in claim 12 or 13 in a display device or semiconductor device.

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