A photosensitive resin composition, a method for producing the same, and a cured film and use thereof

Abstract

The application belongs to the technical field of semiconductor element coating, and discloses a photosensitive resin composition, a preparation method thereof, a cured film and application of the photosensitive resin composition. The photosensitive resin composition comprises a phenolic resin with a structure as shown in formula (1), a photoacid generator and a crosslinking agent. The photosensitive resin composition can be completely cured at a lower temperature, and the obtained cured film has good elasticity, tensile property and thermal stability, and can be applied in semiconductor elements with poor heat resistance. Meanwhile, the photosensitive resin composition has good alkali solubility, and can be used as raw material to prepare high-precision relief patterns, and has good application prospect.

Description

Technical Field

[0001] This invention belongs to the technical field of semiconductor element coatings, and particularly relates to a photosensitive resin composition, its preparation method, and its cured film and applications. Background Technology

[0002] In protective films for semiconductor devices, interlayer insulating films, insulating layers for organic electroluminescent devices, and planarization films for TFT substrates, polyimide resins, polyphenylene oxazole resins, and polyamide-imide resins, which have excellent heat resistance and mechanical properties, are mainly used as raw materials.

[0003] Polyimide resins are widely used in semiconductor device coatings because the cured films they produce exhibit better heat resistance and elasticity compared to other resins. Polyimide resin generally refers to a solution (so-called varnish) of a polyimide precursor (polyamic acid) obtained by reacting tetracarboxylic dianhydride and diamine. In application, this solution is thinned using methods such as spin coating, and then heated to dehydrate and close the polyimide precursor's ring, resulting in curing and the formation of a cured film. The thermosetting temperature of polyimide resins is typically above 300℃.

[0004] With the continuous development of technology in recent years, more and more materials with poor heat resistance are being used in the semiconductor field, thus requiring resins with lower curing temperatures. However, the thermosetting temperature of polyimide resins is usually above 300℃. When polyimide resins cure polyimide precursors at low temperatures, the imidization is incomplete, resulting in a brittle cured film with decreased physical properties and poor performance. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing cured films, such as high brittleness, low elasticity, and poor thermal stability, and to provide a photosensitive resin composition with good toughness, high elasticity, and good thermal stability, as well as its preparation method, cured film, and its application.

[0006] One object of the present invention is to provide a photosensitive resin composition comprising a phenolic resin with the structure shown in formula (1), a photoacid, and a crosslinking agent;

[0007]

[0008] In equation (1), R1 to R4 are each independently selected from hydrogen atoms, C1 to C4 atoms. 10 Monovalent aliphatic groups and C1-C1 groups in which some or all hydrogen atoms are replaced by fluorine atoms. 10 One of the monovalent aliphatic groups, where n1≥2; X is selected from hydrogen atoms, C2~C 10 alkoxycarbonyl, C2~C 10 alkoxycarbonyl alkyl, C2-C 10R5 is selected from one of alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl, wherein R5 is selected from C1 to C2. 10 hydrocarbon groups, C1-C 10 The alkoxy, nitro, and cyano groups are present, and n2 ≥ 2, m1 = 1, 2, or 3, m2 = 0, 1, or 2, and 2 ≤ (m1 + m2) ≤ 4; Y is a divalent organic group with the structure shown in formula (3) or formula (4):

[0009]

[0010] In equation (3), R6 and R7 are each independently selected from hydrogen atoms, C1 to C2 atoms. 11 One of the following: a monovalent organic group and a group containing a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group;

[0011] In equation (4), R8~R 11 Each is independently selected from hydrogen atoms, C1 to C2. 10 Monovalent aliphatic groups, C1-C1 groups with some or all hydrogen atoms replaced by fluorine atoms. 10 One of the monovalent aliphatic groups; R 12 It is selected from one or more of halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups, and m3 = 1, 2, 3 or 4.

[0012] In some specific embodiments, the Y in the phenolic resin structure is a divalent organic group with the structure of formula (5):

[0013]

[0014] In equation (5), R 13 It is a C1 to C5 hydrocarbon group and / or a C1 to C5 alkoxy group, m4 = 1, 2 or 3, m5 = 0, 1, 2 or 3, and 1 ≤ (m4 + m5) ≤ 4.

[0015] In some specific embodiments, Y in the phenolic resin structure is a divalent organic group with the structure shown in formula (6);

[0016]

[0017] In equation (6), R 13 It is a C1-C5 hydrocarbon group and / or a C1-C5 alkoxy group, where m5 = 0, 1, 2 or 3.

[0018] In some specific embodiments, in the phenolic resin, n1 / (n1+n2) = 0.15 to 0.50.

[0019] In some specific embodiments, the weight-average molecular weight of the phenolic resin is 2000 to 200000 Da.

[0020] In some specific embodiments, the photoacid-generating agent is a quinone diazo compound.

[0021] In some specific embodiments, the photoacid-producing agent is a compound having a diazono-1,2-benzoquinone structure and / or a compound having a diazono-1,2-naphthoquinone structure.

[0022] In some specific embodiments, the crosslinking agent is selected from one or more of epoxy compounds, oxacyclobutane compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, compounds containing unsaturated bonds, melamine and its derivatives, hydroxymethyl compounds, alkoxymethyl compounds, N-hydroxymethyl compounds, and N-alkoxymethyl compounds.

[0023] In some specific embodiments, the weight parts of each raw material in the photosensitive resin composition are as follows:

[0024] 95-120 parts of phenolic resin;

[0025] Photo-acid-producing agent: 1-30 parts;

[0026] Crosslinking agent 1 to 30 parts.

[0027] In some specific embodiments, the photosensitive resin composition further includes one or more of a thermogenic acid-producing agent, a surfactant, a silane coupling agent, a solubility promoter, and a crosslinking promoter.

[0028] A second objective of this invention is to provide a method for preparing a photosensitive resin composition, the method comprising the following steps:

[0029] S1. A phenolic compound with a structure of triterpenoid as shown in formula (7), a phenolic compound component with a structure of formula (8), and a polymer component with a structure of formula (9) and / or formula (10) are subjected to a polymerization reaction under the action of a catalyst to obtain a phenolic resin.

[0030] S2. The phenolic resin is mixed evenly with a photoacid-generating agent, a crosslinking agent, and optionally a heat-generating acid-generating agent, a surfactant, a silane coupling agent, a solubility promoter, and a crosslinking promoter to obtain the photosensitive resin composition.

[0031]

[0032] In equation (7), R 14 ~R 17 Each is independently selected from hydrogen atoms, C1 to C2. 10 Monovalent aliphatic groups and C1-C1 groups in which some or all hydrogen atoms are replaced by fluorine atoms. 10 One of the monovalent aliphatic groups;

[0033] In formula (8), X is selected from hydrogen atoms, C2~C 10 alkoxycarbonyl, C2~C 10 alkoxycarbonyl alkyl, C2-C 10 One of alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl, R 18 Selected from C1 to C 10 hydrocarbon groups, C1-C 10 One of alkoxy, nitro and cyano groups, m6 = 1, 2 or 3, m7 = 0, 1 or 2, 2≤(m6+m7)≤4;

[0034] In equation (9), R 19 and R 20 Each is independently selected from hydrogen atoms, C1 to C2. 11 One of the following: a monovalent organic group and a group containing a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group;

[0035] In equation (10), R 21 ~R 24 Each is independently selected from hydrogen atoms, C1 to C2. 10 Monovalent aliphatic groups, C1-C1 groups with some or all hydrogen atoms replaced by fluorine atoms. 10 One of the monovalent aliphatic groups; R 25 It is selected from one or more of halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups, m8 = 1, 2, 3 or 4, and Z1 and Z2 are each independently selected from hydroxymethyl, alkoxymethyl and haloalkyl.

[0036] A third objective of this invention is to provide a photosensitive resin composition prepared by the above method.

[0037] The fourth objective of this invention is to provide a cured film prepared by thermal curing the above-mentioned photosensitive resin composition at 150–300°C.

[0038] A fifth objective of this invention is to provide the application of photosensitive resin compositions and / or cured films in the preparation of protective films, interlayer insulating films, and insulating layers for organic electroluminescent elements.

[0039] In some specific embodiments, the photosensitive resin composition is used to prepare a cured embossed pattern, specifically:

[0040] A photosensitive resin layer is formed on the surface of a substrate using the aforementioned photosensitive resin composition;

[0041] The photosensitive resin layer is exposed;

[0042] An embossed pattern is obtained by removing the exposed or unexposed portions of the photosensitive resin layer using a developing solution.

[0043] The embossed pattern is heated and cured at 150–300°C.

[0044] Beneficial effects:

[0045] (1) A photosensitive resin composition is obtained by using phenolic resin containing both triterpenoid and benzene ring structures in the macromolecular chain as the matrix and adding photoacid generator, crosslinking agent and other components. The curing temperature is low and it can be completely cured at a low temperature. The cured film has good mechanical properties such as elasticity and tensile elongation. In addition, the cured film has good thermal stability, so that the photosensitive resin composition can still maintain a good state under complex temperature change conditions and has excellent applicability.

[0046] (2) The phenolic resin with a special structure contained in the photosensitive resin composition provided by the present invention has good alkali solubility. When it is applied to the preparation of relief patterns, a relief pattern with clear edges can be obtained, which improves the accuracy of relief pattern preparation. It can be applied to the production of high-precision semiconductor components and has great application prospects. Detailed Implementation

[0047] The photosensitive resin composition provided by this invention, compared with the polyamide-imide resin most commonly used in the prior art, can be completely cured at a lower temperature. The resulting cured film exhibits excellent mechanical properties such as elasticity and tensile elongation, as well as superior thermal stability, and has good application prospects. This photosensitive resin composition uses a phenolic resin with a special molecular structure as the matrix, specifically a block structure or a random structure, as shown in formula (1):

[0048]

[0049] In the structure of phenolic resin, the first basic unit is the triterpenoid structure and the second basic unit is the disubstituted benzene ring structure, forming a macromolecular chain of phenolic resin; and in the macromolecular chain of phenolic resin, R1 to R4 in each of the first basic units can be completely the same, partially the same or completely different, and X and R5 in each of the second basic units can be completely the same, partially the same or completely different.

[0050] In equation (1), R1 to R4 are each independently selected from hydrogen atoms, C1 to C4 atoms. 10 Monovalent aliphatic groups and C1-C1 groups in which some or all hydrogen atoms are replaced by fluorine atoms. 10 One of the monovalent aliphatic groups, preferably each independently selected from hydrogen atoms or C1 to C5 aliphatic groups.

[0051] In formula (1), X is selected from hydrogen atoms, C2~C10 alkoxycarbonyl, C2~C 10 alkoxycarbonyl alkyl, C2-C 10 R5 is selected from one of alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl, wherein R5 is selected from C1 to C2. 10 hydrocarbon groups, C1-C 10 One of the alkoxy, nitro, and cyano groups.

[0052] In formula (1), n1≥2, n2≥2, m1=1, 2 or 3, m2=0, 1 or 2, 2≤(m1+m2)≤4.

[0053] In some preferred embodiments, X is a hydrogen atom, tert-butoxybutyl, and / or tetrahydropyranyl, and m1 = 1 or 2. When m1 = 2, the two X groups are in a meta position on the benzene ring, resulting in a good interaction between the phenolic resin and the photoacid generator in the photosensitive resin composition, which is beneficial for preparing higher precision embossed patterns. In other preferred embodiments, R5 is a C1-C3 hydrocarbon group and m2 = 1 or 2. In this case, the cured film obtained by curing the photosensitive resin composition has superior tensile properties.

[0054] In this invention, both the first basic unit and the second basic unit contain a Y group, which is a divalent organic group with the structure shown in formula (3) and / or formula (4).

[0055]

[0056] In this invention, the Y group in the first basic unit can be completely the same, partially the same, or completely different from the Y group in the second basic unit. The Y groups in each first basic unit can be completely the same, partially the same, or completely different. The Y groups in each second basic unit can be completely the same, partially the same, or completely different.

[0057] In some specific embodiments, R6 and R7 are each independently selected from hydrogen atoms, C1 to C2 atoms. 11 It is a monovalent organic group and a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group, preferably a C1 to C3 hydrocarbon group.

[0058] In some specific implementations, R8~R 11 Each is independently selected from hydrogen atoms, C1 to C2. 10 Monovalent aliphatic groups, C1-C1 groups with some or all hydrogen atoms replaced by fluorine atoms. 10 One of the monovalent aliphatic groups, R 12 It is selected from one or more of halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups, where m3 = 1, 2, 3 or 4.

[0059] In this invention, when the structure of the Y group is as shown in formula (5), the cured film obtained by curing the photosensitive resin composition has better thermal stability and is suitable for application scenarios with complex temperature changes.

[0060]

[0061] Specifically, in formula (5) R 13 The R group is a C1-C5 hydrocarbon group and / or a C1-C5 alkoxy group, preferably a C1-C3 hydrocarbon group or a C1-C3 alkoxy group, m4 = 1, 2 or 3, m5 = 0, 1, 2 or 3, and 1 ≤ (m4 + m5) ≤ 4; at the same time, in formula (5), multiple R groups 13 They can be exactly the same, partially the same, or completely different.

[0062] In this invention, when the structure of the Y group is specifically as shown in formula (6), the photosensitive resin composition has better photosensitivity, which results in a relief pattern with a better shape after exposure and development, and is beneficial to improving the accuracy of the preparation of the cured relief pattern.

[0063]

[0064] Specifically, R in equation (6) 13 The group is a C1-C5 hydrocarbon group and / or a C1-C5 alkoxy group, preferably a C1-C3 hydrocarbon group or a C1-C3 alkoxy group, where m5 = 0, 1, 2 or 3. Furthermore, in formula (6), multiple R groups... 13 They can be exactly the same, partially the same, or completely different.

[0065] In phenolic resin, n1 is any integer from 5 to 400, specifically 5, 6, 7, 8, 9, 10, 15, 20, 30, 45, 50, 75, 90, 100, 150, 180, 200, 250, 300, 350, 450, 500 and any value between them; n2 is any integer from 5 to 400, specifically 5, 10, 20, 25, 35, 40, 55, 80, 105, 120, 140, 190, 210, 280, 320, 350, 385, 400, 423, 453, 492, 500 and any value between them.

[0066] Based on the properties of the cured film obtained after curing the photosensitive resin composition, such as elasticity, tensile properties, and thermal stability, the ratio of n1 / (n1+n2) in the phenolic resin is creatively controlled between 0.15 and 0.50. This allows the various groups in the phenolic resin molecular structure to exert the best synergistic effect, and the prepared cured film has excellent elasticity, tensile properties, and thermal stability.

[0067] In this invention, the weight-average molecular weight of the phenolic resin is preferably 2,000 to 200,000, specifically 2,000, 5,000, 10,000, 15,000, 50,000, 100,000, 150,000, 200,000, and any value between them; preferably, the weight-average molecular weight of the phenolic resin is preferably 3,000 to 120,000, more preferably 3,000 to 40,000.

[0068] In this invention, the photoacid generator can decompose and volatilize during the thermosetting process, so that only a very small amount of photoacid generator remains in the final cured film, or there is no residual photoacid generator, thus reducing the impact of residual photoacid generator on the properties of the cured film. The photoacid generator is specifically a quinone diazonium compound, which may be, but is not limited to, compounds having a diazonium 1,2-benzoquinone structure or a diazonium 1,2-naphthoquinone structure. Among them, compounds with a diazonium 1,2-naphthoquinone structure are preferably compounds with structures as shown in formulas (11) to (14).

[0069]

[0070] Q in formulas (11) to (14) can be a hydrogen atom, a group represented by formula (15) or formula (16).

[0071]

[0072] In this invention, the crosslinking agent may be, but is not limited to, one or more of epoxy compounds, oxetine compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, compounds containing unsaturated bonds, melamine and its derivatives, hydroxymethyl compounds, alkoxymethyl compounds, N-hydroxymethyl compounds, and N-alkoxymethyl compounds. When the crosslinking agent is selected as one or more of epoxy compounds, oxetine compounds, isocyanate compounds, hydroxymethyl compounds, or alkoxymethyl compounds, N-hydroxymethyl compounds, and N-alkoxymethyl compounds, the cured film obtained after curing the photosensitive resin composition exhibits excellent thermophysical and mechanical properties.

[0073] In some specific embodiments, the mass fractions of phenolic resin, photoacid generator, and crosslinking agent in the photosensitive resin composition are as follows:

[0074] 95-120 parts of phenolic resin;

[0075] Photo-acid-producing agent: 1-30 parts;

[0076] Crosslinking agent 1 to 30 parts.

[0077] In some specific embodiments, when the mass ratio of photoacid generator to phenolic resin is (5-30):100 and the mass ratio of crosslinking agent to phenolic resin is (0.5-50):100, the three components can exert a good synergistic effect, resulting in better performance of the photosensitive resin composition.

[0078] In some specific embodiments, the photosensitive resin composition further includes a solvent for dissolving other substances in the photosensitive resin composition to form a solution system, which is beneficial for the storage and transportation of the photosensitive resin composition. The solvent may be, but is not limited to, one or more of amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbon solvents. Specifically, it may be, but is not limited to, one or more of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, methyl isobutyl ketone, cyclopentanone, cyclohexanone, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, and xylene. In addition, the preferred mass ratio of solvent to phenolic resin is (100-1000):100. At this ratio, the phenolic resin, photoacid generator, and crosslinking agent can be well dispersed in the solvent to form a stable solution system. Meanwhile, the appropriate solvent content will not affect the film formation of the photosensitive resin composition.

[0079] The photosensitive resin composition provided by the present invention also includes surfactants, silane coupling agents, solubilizers, and thermal acid-generating agents.

[0080] In some specific embodiments, the surfactant may be, but is not limited to, polyethylene glycol nonionic surfactants such as polypropylene glycol and polyoxyethylene lauryl ether, and the mass ratio of surfactant to phenolic resin is (0.01-10):100.

[0081] In this invention, the addition of a silane coupling agent can improve the stability of the photosensitive resin composition solution system, which is beneficial for transportation and storage. In some specific embodiments, the silane coupling agent can be, but is not limited to, one or more of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, and triphenylsilanol. Furthermore, the mass ratio of the silane coupling agent to the phenolic resin is (0.1–15):100.

[0082] In some specific embodiments, the solubility accelerator is a compound having hydroxyl and / or carboxyl groups, specifically, but not limited to, one or more of p-isopropylphenylphenol, bisphenol, and resorcinol compounds, preferably one or more of 3-phenyllactic acid, 2,4-dimethylbenzoic acid, and 2,4,6-trimethylbenzoic acid. Furthermore, the mass ratio of the solubility accelerator to the phenolic resin is (0.1–20):100.

[0083] In some specific embodiments, the thermally generated acid agent may be, but is not limited to, one or more of ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, p-toluenesulfonic acid, and 2-methoxyethyl ester. Furthermore, the preferred mass ratio of the thermally generated acid agent to the phenolic resin is (0.5–5):100.

[0084] The method for preparing the photosensitive resin composition provided by the present invention includes the following steps:

[0085] S1. The polymer components with the structure of triterpenoid shown in formula (7), the polymer components with the structure of benzene ring shown in formula (8), and the phenolic compounds with the structures of formula (9) and / or formula (10) are polymerized under the action of a catalyst to obtain phenolic resin.

[0086] S2. The phenolic resin is mixed evenly with a photoacid-generating agent, a crosslinking agent, and optionally a heat-generating acid-generating agent, a surfactant, a silane coupling agent, a solubility promoter, and a crosslinking promoter to obtain the photosensitive resin composition.

[0087]

[0088] In equation (7), R 14 ~R 17 Each is independently selected from hydrogen atoms, C1 to C2. 10 Monovalent aliphatic groups and C1-C1 groups in which some or all hydrogen atoms are replaced by fluorine atoms. 10 One of the monovalent aliphatic groups;

[0089] In formula (8), X is selected from hydrogen atoms, C2~C 10 alkoxycarbonyl, C2~C 10 alkoxycarbonyl alkyl, C2-C 10 One of alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl, R 18 Selected from C1 to C 10 hydrocarbon groups, C1-C 10 One of alkoxy, nitro and cyano groups, m6 = 1, 2 or 3, m7 = 0, 1 or 2, 2≤(m6+m7)≤4;

[0090] In equation (9), R19 and R 20 Each is independently selected from hydrogen atoms, C1 to C2. 11 One of the following: a monovalent organic group and a group containing a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group;

[0091] In equation (10), R 21 ~R 24 Each is independently selected from hydrogen atoms, C1 to C2. 10 Monovalent aliphatic groups, C1-C1 groups with some or all hydrogen atoms replaced by fluorine atoms. 10 One of the monovalent aliphatic groups; R 25 It is selected from one or more of halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups, m8 = 1, 2, 3 or 4, and Z1 and Z2 are each independently selected from hydroxymethyl, alkoxymethyl and haloalkyl.

[0092] In some specific embodiments, the tripterene structure polymer component may be, but is not limited to, one or more of 1,4-dihydroxytripterene, 2,6-di-tert-butyl-1,4-dihydroxytripterene, 2-tert-butyl-5-methyl-1,4-dihydroxytripterene, 2-fluoromethyl-1,4-dihydroxytripterene, and 3(2-fluoroethyl)-6-ethyl-1,4-dihydroxytripterene; the benzene ring structure polymer component may be, but is not limited to, one or more of phenol, resorcinol, 2-methylresorcinol, 4-methoxyresorcinol, catechol, hydroquinone, and / or pyrogallol.

[0093] In some specific embodiments, from the perspective of reaction control and the stability of the obtained photosensitive resin, the molar ratio of the total amount of the trimerene structure polymerization component and the benzene ring structure polymerization component to the amount of the phenolic compound is preferably 1:(1-4), more preferably 1:(1-2.3).

[0094] In some specific embodiments, the catalyst can be an acidic catalyst or a basic catalyst, preferably an acidic catalyst, specifically one or more of inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, but not limited to them.

[0095] In some specific embodiments, phenolic compounds and polymer components are dissolved in an organic solvent at 55–60°C, and then reacted at 80–85°C for 10–14 hours to obtain a reaction solution containing phenolic resin. After diluting the reaction solution with an organic solvent, a large amount of water is added and a solid precipitates out, which is the phenolic resin.

[0096] In some specific embodiments, the organic solvent used in the polymerization reaction may be, but is not limited to, one or more of bis(2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.

[0097] The present invention also provides a photosensitive resin composition prepared by the above method.

[0098] The present invention also provides a cured film, which is prepared by thermosetting the above-mentioned photosensitive resin composition at 150-300°C. This cured film exhibits excellent physical properties such as elasticity and tensile strength, and maintains good condition even under complex temperature variations, without cracking or deformation, demonstrating good thermal stability.

[0099] The present invention also provides the application of the photosensitive resin composition and / or cured film in the preparation of protective films, interlayer insulating films, and insulating layers for organic electroluminescent elements.

[0100] When using a photosensitive resin composition to prepare a cured embossed pattern, the specific steps include:

[0101] A photosensitive resin layer is formed on the surface of a substrate using the aforementioned photosensitive resin composition;

[0102] The photosensitive resin layer is exposed;

[0103] An embossed pattern is obtained by removing the exposed or unexposed portions of the photosensitive resin layer using a developing solution.

[0104] The embossed pattern is heated and cured at 150–300°C.

[0105] In some specific implementations, in order to improve the adhesion between the embossed pattern and the substrate, a silane coupling agent can be pre-coated on the surface of the substrate as an adhesive aid.

[0106] In some specific embodiments, there are various methods for forming a photosensitive resin layer on the substrate surface using the photosensitive resin composition, which may be, but are not limited to, one or more of spin coating, spraying, dipping, printing, and roll coating.

[0107] Furthermore, the process of forming a photosensitive resin layer on the substrate surface using the photosensitive resin composition also includes a baking step: placing the substrate with the photosensitive resin composition on its surface at 80-120°C for a period of time to allow the solvent in the photosensitive resin composition to evaporate, thereby forming a photosensitive resin layer on the surface of the substrate.

[0108] When exposing the photosensitive resin layer, the light source used can be X-rays, electron beams, ultraviolet rays, etc., preferably chemical rays with a wavelength of 200-500 nm; in order to further improve the resolution of the cured relief pattern, the light source used is more preferably gamma rays, h rays or i rays from a mercury lamp.

[0109] In some specific embodiments, the developer may be, but is not limited to, one or more aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide, and the best developing effect can be achieved when the concentration of the aqueous solution is 0.5 to 10 wt%.

[0110] In this invention, after development, the substrate needs to be rinsed with a rinsing solution to remove the developer from the surface. The rinsing solution can be, but is not limited to, common substances such as distilled water, methanol, ethanol, and isopropyl ketone.

[0111] The examples provided are intended to explain the invention and should not be construed as limiting it. Where specific techniques or conditions are not specified in the examples, they should be performed according to the techniques or conditions described in the literature or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0112] Preparation Example 1.1: Synthesis of 4-dihydroxytriptene

[0113] S1. In a three-necked flask equipped with a magnetic stirrer, nitrogen protection and reflux device, add 12.1 g of p-benzoquinone (112 mmol) and 10 g of anthracene (56 mmol), then add 100 mL of toluene, heat until the solid is completely dissolved, and continue to heat to reflux and maintain for 6 h.

[0114] S2. The reaction solution in S1 was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered and the filter cake was washed with a small amount of toluene. After vacuum drying, 13.6 g of orange product was obtained, with a yield of 85%.

[0115] S3. Add the orange product to a three-necked flask equipped with a magnetic stirrer, nitrogen protection and reflux device, and add 300 mL of acetic acid. Heat to reflux. After the product is completely dissolved, slowly add 4 mL of hydrobromic acid and continue the reaction for 2 h. Cool, filter and vacuum dry to obtain white 1,4-dihydroxytriptene powder with the structure shown in formula (17) and a yield of 88%.

[0116]

[0117] Preparation Example 2.2: Synthesis of 6-di-tert-butyl-1,4-dihydroxytriptene

[0118] S1. In a three-necked flask equipped with a magnetic stirrer, nitrogen protection and reflux device, add 12.1 g of p-benzoquinone (112 mmol) and 16.3 g of 2,6-di-tert-butylanthracene (56 mmol), then add 100 mL of toluene, heat until the solid is completely dissolved, and then continue to heat to reflux and maintain for 6 h.

[0119] S2. The reaction solution in S1 was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered and the filter cake was washed with a small amount of toluene. After vacuum drying, 17.9 g of orange product was obtained, with a yield of 80%.

[0120] S3. Add the orange product to a three-necked flask equipped with a magnetic stirrer, nitrogen protection and reflux device, and add 400 mL of acetic acid. Heat to reflux. After the product is completely dissolved, slowly add 4 mL of hydrobromic acid and continue the reaction for 2 h. Cool, filter and vacuum dry to obtain white 2,6-di-tert-butyl-1,4-dihydroxytriptene powder with the structure shown in formula (18) and a yield of 88%.

[0121]

[0122] Example 1.

[0123] The photosensitive resin composition provided in this embodiment includes 38 wt% phenolic resin, 4.9 wt% photosensitizer, 3.7 wt% crosslinking agent, and 53.4 wt% γ-butyrolactone. After uniform mixing of the above components, the mixture is filtered through a membrane filter with a pore size of 1 μm. The phenolic resin is prepared by polymerizing 1,4-dihydroxytriptene, resorcinol, and 2,6-bis(hydroxymethyl)-p-cresol provided in Preparation Example 1 under the catalysis of p-toluenesulfonic acid. The specific preparation includes the following steps:

[0124] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 91.8g of resorcinol (0.833mol), 128.8g of 1,4-dihydroxytriptene (0.45mol), 3.81g of p-toluenesulfonic acid (0.02mol), 83g of 2,6-bis(hydroxymethyl)-p-cresol (0.50mol), and 166g of propylene glycol monomethyl ether were added. The mixture was stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and maintained at this temperature for 12 hours.

[0125] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 50g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 6L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 74%. The weight-average molecular weight of this phenolic resin is 6500.

[0126] In the positive photosensitive resin composition provided in this embodiment, the structure of the photosensitizer is shown in formula (19), 83% of the Q in the photosensitizer has the structure shown in formula (20), and 17% of the Q is a hydrogen atom. The structure of the crosslinking agent is shown in formula (21).

[0127]

[0128] Example 2.

[0129] The photosensitive resin composition provided in this embodiment is basically the same as that in Example 1, except that the phenolic resin contained in the photosensitive resin composition is different. In this embodiment, the phenolic resin is prepared through the following steps:

[0130] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 113.8g of resorcinol (1.033mol), 71.6g of 1,4-dihydroxytriptene (0.25mol), 3.81g of p-toluenesulfonic acid (0.02mol), 83g of 2,6-bis(hydroxymethyl)-p-cresol (0.50mol), and 166g of propylene glycol monomethyl ether were added. The mixture was stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and maintained at this temperature for 12 hours.

[0131] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 50g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 6L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 77%. The weight-average molecular weight of this phenolic resin is 6900.

[0132] Example 3.

[0133] The photosensitive resin composition provided in this embodiment is basically the same as that in Example 1, except that the phenolic resin contained in the photosensitive resin composition is different. In this embodiment, the phenolic resin is prepared through the following steps:

[0134] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 113.8g of resorcinol (1.033mol), 71.6g of 1,4-dihydroxytriptene (0.25mol), 3.81g of p-toluenesulfonic acid (0.02mol), 149g of 2,6-bis(hydroxymethyl)-p-cresol (0.90mol), and 200g of propylene glycol monomethyl ether were added. The mixture was stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and maintained at this temperature for 12 hours.

[0135] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 100g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 82%. The weight-average molecular weight of this phenolic resin is 10500.

[0136] Example 4.

[0137] The photosensitive resin composition provided in this embodiment is basically the same as that in Example 3, except that the crosslinking agent in the photosensitive resin composition has the structure of formula (22).

[0138]

[0139] Example 5.

[0140] The photosensitive resin composition provided in this embodiment is basically the same as that in Example 4, except that the structure of the photosensitizer in the photosensitive resin composition is as shown in formula (23).

[0141]

[0142] Example 6.

[0143] The photosensitive resin composition provided in this embodiment is basically the same as that in Example 1, except that the phenolic resin contained in the photosensitive resin composition is different. In this embodiment, it is prepared through the following steps:

[0144] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 113.8g of resorcinol (1.033mol), 71.6g of 1,4-dihydroxytriptene (0.25mol), 3.81g of p-toluenesulfonic acid (0.02mol), 73.8g of 37wt% formaldehyde solution (0.90mol), and 150g of propylene glycol monomethyl ether were added. The mixture was stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and maintained at this temperature for 12 hours.

[0145] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 50g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 80%. The weight-average molecular weight of this phenolic resin is 10800.

[0146] Example 7.

[0147] The photosensitive resin composition provided in this embodiment is basically the same as that in Example 1, except that the phenolic resin contained in the photosensitive resin composition is different. In this embodiment, it is prepared through the following steps:

[0148] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 113.8g of resorcinol (1.033mol), 99.6g of 2,6-di-tert-butyl-1,4-dihydroxytriphenylene (0.25mol), 3.81g of p-toluenesulfonic acid (0.02mol), 149g of 2,6-bis(hydroxymethyl)-p-cresol (0.90mol), and 200g of propylene glycol monomethyl ether were added. The mixture was stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and maintained at this temperature for 12 hours.

[0149] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 100g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 75%. The weight-average molecular weight of this phenolic resin is 9100.

[0150] Example 8.

[0151] The photosensitive resin composition provided in this embodiment is basically the same as that in Example 1, except that the phenolic resin contained in the photosensitive resin composition is different. In this embodiment, it is prepared through the following steps:

[0152] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 113.8g of resorcinol (1.033mol), 99.6g of 2,6-di-tert-butyl-1,4-dihydroxytriptene (0.25mol), 3.81g of p-toluenesulfonic acid (0.02mol), 73.8g of 37wt% formaldehyde solution (0.90mol), and 150g of propylene glycol monomethyl ether were added. The mixture was stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and maintained at this temperature for 12 hours.

[0153] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 100g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 83%. The weight-average molecular weight of this phenolic resin is 9600.

[0154] Comparative Example 1.

[0155] The photosensitive resin composition provided in this comparative example is basically the same as that in Example 1, except that the phenolic resin contained in the photosensitive resin composition is different. In this comparative example, the phenolic resin is prepared by the following steps:

[0156] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 141.0g of resorcinol (1.28mol), 3.81g of p-toluenesulfonic acid (0.02mol), 149g of 2,6-bis(hydroxymethyl)-p-cresol (0.90mol), and 200g of propylene glycol monomethyl ether were added and stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and maintained at this temperature for 12 hours.

[0157] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 100g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 70%. The weight-average molecular weight of this phenolic resin is 11500.

[0158] Comparative Example 2.

[0159] The photosensitive resin composition provided in this comparative example is basically the same as that in Example 1, except that the phenolic resin contained in the photosensitive resin composition is different. In this comparative example, the phenolic resin is prepared by the following steps:

[0160] S1. Nitrogen gas was used to purge a 1L three-necked flask equipped with a Dean-Stark water separator. Then, 141.0g of resorcinol (1.28mol), 3.81g of p-toluenesulfonic acid (0.02mol), 73.8g of 37wt% formaldehyde solution (0.9mol), and 150g of propylene glycol monomethyl ether were added and stirred at 60°C until the solids were completely dissolved. The mixture was then heated to 80°C in an oil bath and kept at this temperature for 12 hours.

[0161] S2. After the reaction is complete, the reaction vessel is cooled in the atmosphere, and 100g of propylene glycol monomethyl ether is added and stirred until homogeneous. Then, the diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin. After filtration, washing with water, dehydration, and vacuum drying, phenolic resin is obtained with a yield of 68%. The weight-average molecular weight of this phenolic resin is 11900.

[0162] Test example.

[0163] (1) Test of elongation and Young's modulus: The photosensitive resins provided in Examples 1 to 8 and Comparative Examples 1 and 2 were spin-coated onto a silicon wafer. After heating with a hot plate at 120°C for 3 min, the wafer was cured at 230°C for 1 h under chlorine protection to obtain a cured film with a thickness of 10 μm. The cured film was cut into several samples with a width of 3 mm and a length of 40 mm using a cutting saw. Then, the samples were peeled off from the wafer using a hydrofluoric acid aqueous solution. The samples were placed in an atmosphere with a temperature of 23°C and a humidity of 50% for more than 24 h. The test was performed using a test chamber with an experimental speed of 40 mm / min and a load sensor rated value of 2 kgf. The final experimental result was the average of the five largest values. The results are shown in Table 1.

[0164] (2) Thermal cycling performance test: Examples 1 to 8 and Comparative Examples 1 and 2 were spin-coated onto ghost wafers and heated with a hot plate at 120°C for 3 min. Then, the films were cured at 230°C for 1 h under chlorine protection to obtain a cured film with a thickness of 10 μm. The films were then subjected to 500 cycles of thermal cycling test at -65°C to 135°C for 30 min each time. The films were then observed for cracks on the surface using an optical microscope. The results are shown in Table 1.

[0165] Table 1. Mechanical properties and thermal cycling properties of the cured film

[0166]

[0167] The experimental results show that, compared with Comparative Examples 1 and 2, the cured films obtained by curing the photosensitive resin compositions provided by the present invention at a lower temperature of 230°C exhibit higher Young's modulus and elongation, indicating better elasticity and elongation properties. Notably, the cured films obtained by thermosetting the phenolic resin prepared using the method provided in Example 4 as a matrix show better elasticity and elongation properties compared to Examples 1 and 6-8. Furthermore, the results of the thermal cycling test indicate that the cured films provided in Examples 1-8 of the present invention maintain a good condition after 500 cycles from -65°C to 135°C, with no surface cracks. Compared with Comparative Examples 1 and 2, they exhibit superior thermal stability and are suitable for applications with complex temperature variations, demonstrating good applicability.

[0168] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: This includes phenolic resins, photoacid generators, and crosslinking agents; The preparation of the phenolic resin includes: polymerizing a phenolic compound with a structure of triterpenoid as shown in formula (7), a phenolic compound component with a structure of formula (8), and a polymeric component with a structure of formula (9) and / or formula (10) under the action of a catalyst to obtain the phenolic resin. Equation (7), Equation (8), Equation (9), In equation (7), R 14 ~R 17 Each is independently selected from hydrogen atoms, C1~C 10 Monovalent aliphatic groups and C1~C groups in which some or all hydrogen atoms are replaced by fluorine atoms 10 One of the monovalent aliphatic groups; In formula (8), X is selected from hydrogen atom, C2~C 10 alkoxycarbonyl, C2~C 10 alkoxycarbonyl alkyl, C2~C 10 One of alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl, R 18 Selected from one of the following: C1~C10 hydrocarbon group, C1~C10 alkoxy group, nitro group and cyano group, m6=1, 2 or 3, m7=0, 1 or 2, 2≤(m6+m7)≤4; In equation (9), R 19 For hydrogen atoms, R 20 C1~C 11 One of the monovalent organic groups; The compound shown in formula (10) is 2,6-bis(hydroxymethyl)-p-cresol.

2. The photosensitive resin composition according to claim 1, characterized in that: The weight-average molecular weight of the phenolic resin is 2000~200000 Da.

3. The photosensitive resin composition according to claim 1, characterized in that: The photoacid-producing agent is a quinone diazonium compound.

4. The photosensitive resin composition according to claim 1, characterized in that: The photoacid-producing agent is a compound having a diazo-1,2-benzoquinone structure and / or a compound having a diazo-1,2-naphthoquinone structure; the crosslinking agent is selected from one or more of epoxy compounds, oxacyclobutane compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, melamine and its derivatives, N-hydroxymethyl compounds and N-alkoxymethyl compounds.

5. The photosensitive resin composition according to claim 1, characterized in that: The weight parts of each raw material in the photosensitive resin composition are as follows:

6. The photosensitive resin composition according to claim 1, characterized in that: The photosensitive resin composition further includes one or more of the following: a heat-generating acid agent, a surfactant, a silane coupling agent, a solubility promoter, and a crosslinking promoter.

7. A method for preparing a photosensitive resin composition, characterized in that: Includes the following steps: S1. A phenolic compound with a structure of triterpenoid as shown in formula (7), a phenolic compound component with a structure of formula (8), and a polymer component with a structure of formula (9) and / or formula (10) are subjected to a polymerization reaction under the action of a catalyst to obtain a phenolic resin. S2. The phenolic resin is mixed evenly with a photoacid-generating agent, a crosslinking agent, and optionally a heat-generating acid-generating agent, a surfactant, a silane coupling agent, a solubility promoter, and a crosslinking promoter to obtain the photosensitive resin composition. Equation (7), Equation (8), Equation (9), In equation (7), R 14 ~R 17 Each is independently selected from hydrogen atoms, C1~C 10 Monovalent aliphatic groups and C1~C groups in which some or all hydrogen atoms are replaced by fluorine atoms 10 One of the monovalent aliphatic groups; In formula (8), X is selected from hydrogen atom, C2~C 10 alkoxycarbonyl, C2~C 10 alkoxycarbonyl alkyl, C2~C 10 One of alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl, R 18 Selected from C1~C 10 hydrocarbon group, C1~C 10 One of alkoxy, nitro and cyano groups, m6=1, 2 or 3, m7=0, 1 or 2, 2≤(m6+m7)≤4; In equation (9), R 19 For hydrogen atoms, R 20 C1~C 11 One of the monovalent organic groups; The compound shown in formula (10) is 2,6-bis(hydroxymethyl)-p-cresol.

8. A cured film, characterized in that, The cured film is obtained by heat curing the photosensitive resin composition according to any one of claims 1 to 6 at 150 to 300°C.

9. The use of the photosensitive resin composition according to any one of claims 1 to 6 or the cured film according to claim 8 in the preparation of protective films, interlayer insulating films, and insulating layers for organic electroluminescent elements.

10. The application according to claim 9, characterized in that, The photosensitive resin composition is used to prepare cured embossed patterns, specifically: A photosensitive resin layer is formed on the surface of a substrate using the aforementioned photosensitive resin composition; The photosensitive resin layer is exposed; An embossed pattern is obtained by removing the exposed or unexposed portions of the photosensitive resin layer using a developing solution. The embossed pattern is heated and cured at 150~300℃.

Images