Phenolic photosensitive resin and composition as well as preparation method and application of phenolic photosensitive resin and composition

Abstract

The invention belongs to the field of semiconductor packaging, and particularly relates to phenolic photosensitive resin, a composition, a preparation method and application. The preparation method of the phenolic photosensitive resin comprises the following steps: S1, carrying out prepolymerization reaction on an anthraquinone compound and a cresol compound in the presence of a catalyst under the protection of inert gas to obtain a prepolymer; and S2, carrying out polymerization reaction on the prepolymer and a benzoic acid compound under the protection of inert gas to obtain the phenolic photosensitive resin. The phenolic photosensitive resin composition obtained by adopting the method provided by the invention has good insulating property and mechanical property, solves the problem that the insulating property and the mechanical property cannot be met at the same time in the prior art, and can be well suitable for a semiconductor and display body device packaging process.

Description

Technical Field

[0001] The invention belongs to the field of semiconductor packaging, and in particular relates to a phenolic photosensitive resin and a composition as well as a preparation method and application thereof. Background Art

[0002] For a long time, polyimide resin or polybenzoxazole resin has been mostly used as surface protection film and interlayer insulation film in the field of semiconductor packaging applications. Such resins usually have excellent electrical and mechanical properties. Conventional photosensitive polyimide is difficult to melt and dissolve, and difficult to process and shape. It is usually used in the form of a precursor formed by opening the ring structure and dissolved in a solvent to form a composition. When used, it is coated into a thin film and heated to dehydrate and close the loop to form a cured film. This closed-loop process usually needs to be heated to above 300°C. With the continuous development of technology, the industry has further requirements for the curing temperature of surface protection films and interlayer insulation films. Materials with curing temperatures below 300°C or even below 250°C have become the mainstream of the market.

[0003] Phenolic photosensitive resin compositions refer to base resins with phenolic hydroxyl groups, which are combined with photosensitizers and curing agents to form reactive resin compositions. Such resin compositions can usually be cured by heating at 100-250°C, thus meeting market demand. However, existing phenolic photosensitive resin compositions usually have poor elasticity, insufficient mechanical strength, or cannot have both good insulation and mechanical properties. Summary of the invention

[0004] The first object of the present invention is to overcome the defects of the existing phenolic photosensitive resin composition in that the insulation performance and mechanical properties are poor, and to provide a phenolic photosensitive resin that can simultaneously meet the insulation performance and mechanical properties.

[0005] The second object of the present invention is to provide a method for preparing a phenolic photosensitive resin.

[0006] The third object of the present invention is to provide a phenolic photosensitive resin prepared by the above method.

[0007] A fourth object of the present invention is to provide a photosensitive resin composition.

[0008] A fifth object of the present invention is to provide an application of the photosensitive resin composition in a semiconductor device and a display device packaging process.

[0009] Specifically, the phenolic photosensitive resin provided by the present invention has a structure shown in formula (1):

[0010]

[0011] In formula (1), m1 R1 and m2 R2 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m1, m2, m3 and m4 are each independently an integer from 0 to 2, 0≤(m1+m3)≤3, 0≤(m2+m4)≤3; R3 and R5 are each independently absent or C1-C10 alkylene; m5 R4 are the same or different and are each independently H, C1-C10 alkyl or C1-C10 alkoxy; m5 is an integer from 0 to 3; m6 R6 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m6 is 0 or 1, and m7 is an integer from 0 to 5; n1 and n2 are each independently an integer from 1 to 100.

[0012] The preparation method of the phenolic photosensitive resin provided by the present invention comprises the following steps:

[0013] S1. The anthraquinone compound represented by formula (3) and the cresol compound represented by formula (4) are prepolymerized in the presence of a catalyst and under the protection of an inert gas to obtain a prepolymer;

[0014] S2. The prepolymer and the benzoic acid compound represented by formula (5) are polymerized under an inert gas to obtain a phenolic photosensitive resin;

[0015]

[0016] In formula (3), m1 R1 and m2 R2 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m1, m2, m3 and m4 are each independently an integer of 0-2, 0≤(m1+m3)≤3, 0≤(m2+m4)≤3;

[0017] In formula (4), R3 and R5 are each independently absent or a C1-C10 alkylene group; m5 R4 are the same or different and are each independently H, a C1-C10 alkyl group or a C1-C10 alkoxy group; X and X' are each independently hydroxyl or halogen; m5 is an integer of 0-3;

[0018] In formula (5), m6 R6 are the same or different and are independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m6 is 0 or 1, and m7 is an integer of 0-5.

[0019] The photosensitive resin composition provided by the present invention contains the above-mentioned phenolic photosensitive resin, a photosensitizer, a crosslinking agent and a solvent.

[0020] The phenolic photosensitive resin composition provided by the present invention has good insulation performance and mechanical properties, solves the problem that the prior art cannot simultaneously meet the insulation performance and mechanical properties, and can be well applied to the packaging process of semiconductor devices and display devices. DETAILED DESCRIPTION

[0021] The phenolic photosensitive resin provided by the present invention has a structure shown in formula (1):

[0022]

[0023] In formula (1), m1 R1 and m2 R2 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m1, m2, m3 and m4 are each independently an integer from 0 to 2, 0≤(m1+m3)≤3, 0≤(m2+m4)≤3; R3 and R5 are each independently absent or C1-C10 alkylene; m5 R4 are the same or different and are each independently H, C1-C10 alkyl or C1-C10 alkoxy; m5 is an integer from 0 to 3; m6 R6 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m6 is 0 or 1, and m7 is an integer from 0 to 5; n1 and n2 are each independently an integer from 1 to 100.

[0024] In the present invention, specific examples of the C1-C10 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, etc. Specific examples of the C1-C10 alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy ... Specific examples of the C1-C10 alkylene group include, but are not limited to, methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene, neopentylene, n-hexylene, isohexylene, n-heptylene, isoheptylene, n-octylene, isooctylene, n-nonylene, isononylene, n-decylene, isodecylene and the like.

[0025] In the present invention, m1 R1s may be completely identical, partially identical or completely different. m2 R2s may be completely identical, partially identical or completely different. m1 R1s and m2 R2s are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano, preferably each independently H, C1-C5 alkyl or C1-C5 alkoxy, more preferably each independently H, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy or isopropoxy.

[0026] In the present invention, m1, m2, m3 and m4 are each independently an integer of 0-2, specifically 0, 1 or 2. The sum of m1 and m3 can be specifically 0, 1, 2 or 3. The sum of m2 and m4 can be specifically 0, 1, 2 or 3. In a preferred embodiment, m1, m2, m3 and m4 are each independently 0 or 1, and the sum of m1 and m3 is 0, 1 or 2. The sum of m2 and m3 is 0, 1 or 2, and the elasticity of the obtained phenolic photosensitive resin is better.

[0027] In the present invention, R3 and R5 are each independently absent or C1-C10 alkylene, preferably absent or C1-C5 alkylene, specifically absent, methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene or neopentylene. m5 R4s can be completely the same, partially the same or completely different. m5 R4s are each independently C1-C10 alkyl or C1-C10 alkoxy, preferably each independently C1-C5 alkyl, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl. m5 is an integer of 0-3, specifically 0, 1, 2 or 3.

[0028] In the present invention, m6 R6 can be completely identical, partially identical or completely different. m6 R6 are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano, preferably H, C1-C5 alkyl or C1-C5 alkoxy, more preferably H or C1-C3 alkyl, specifically H, methyl, ethyl, n-propyl or isopropyl. m6 is 0 or 1. m7 is an integer of 0-5, specifically 0, 1, 2, 3, 4 or 5.

[0029] In the present invention, n1 and n2 are each independently an integer of 1-100, specifically 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100. n1 / n2 is preferably 0.5-2.0, such as 0.5, 0.8, 1, 1.2, 1.5, 1.8 or 2. When n1 / n2 is preferably 0.5-2.0, the obtained phenolic photosensitive resin has better alkali solubility, better insulation performance and better mechanical properties.

[0030] In the present invention, the weight average molecular weight of the phenolic photosensitive resin is preferably 3000-20000 Daltons, more preferably 3000-10000 Daltons, such as 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000 Daltons or any value therebetween; the molecular weight distribution is preferably 2.0-4.0, more preferably 2.5-3.5, such as 2.5, 2.6, 2.8, 3, 3.2, 3.4, 3.5 or any value therebetween.

[0031] The preparation method of the phenolic photosensitive resin provided by the present invention comprises the following steps:

[0032] S1. Prepolymerizing an anthraquinone compound and a cresol compound in the presence of a catalyst and under inert gas protection to obtain a prepolymer;

[0033] S2. The prepolymer and the benzoic acid compound are subjected to polymerization reaction under the protection of an inert gas to obtain a phenolic photosensitive resin.

[0034] In the present invention, the anthraquinone compound has a structure shown in formula (3):

[0035]

[0036] In formula (3), m1 R1 and m2 R2 are the same or different, and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m1, m2, m3 and m4 are each independently an integer of 0-2, 0≤(m1+m3)≤3, 0≤(m2+m4)≤3. m1 R1 may be completely identical, partially identical or completely different. m2 R2 may be completely identical, partially identical or completely different. m1 R1 and m2 R2 are preferably each independently H, C1-C5 alkyl or C1-C5 alkoxy, more preferably each independently H, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy or isopropoxy. m1, m2, m3 and m4 are each independently an integer of 0-2, specifically 0, 1 or 2. The sum of m1 and m3 may specifically be 0, 1, 2 or 3. The sum of m2 and m4 can specifically be 0, 1, 2 or 3. m1, m2, m3 and m4 are preferably each independently 0 or 1, and the sum of m1 and m3 is preferably 0, 1 or 2. The sum of m2 and m3 is preferably 0, 1 or 2.

[0037] In the present invention, the cresol compound has a structure shown in formula (4):

[0038]

[0039] In formula (4), R3 and R5 are each independently absent or C1-C10 alkylene, preferably absent or C1-C5 alkylene, specifically absent, methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene or neopentylene. m5 R4s may be completely identical, partially identical or completely different. m5 R4s are each independently H, C1-C10 alkyl or C1-C10 alkoxy, preferably each independently C1-C5 alkyl, specifically H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl. X and X' are each independently hydroxyl or halogen. m5 is an integer of 0-3, specifically 0, 1, 2 or 3.

[0040] In the present invention, the benzoic acid compound has a structure shown in formula (5):

[0041]

[0042] In formula (5), m6 R6 can be completely identical, partially identical or completely different. m6 R6 are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano, preferably H, C1-C5 alkyl or C1-C5 alkoxy, more preferably H or C1-C3 alkyl, specifically H or methyl, ethyl, n-propyl or isopropyl. m6 is 0 or 1. m7 is an integer of 0-5, specifically 0, 1, 2, 3, 4 or 5.

[0043] In the present invention, the molar ratio of the anthraquinone compound to the cresol compound is preferably (1-4): 1, such as 1: 1, 1.5: 1, 2: 1, 2.5: 1, 3: 1, 3.5: 1 or 4: 1. The molar ratio of the anthraquinone compound to the benzoic acid compound is preferably 1: (1-2), such as 1: 1, 1: 1.1, 1: 1.2, 1: 1.3, 1: 1.4, 1: 1.5, 1: 1.6, 1: 1.7, 1: 1.8, 1: 1.9, 1: 2 or any value therebetween.

[0044] In the present invention, the conditions of the prepolymerization reaction preferably include a temperature of 100°C-140°C, such as 100°C, 110°C, 120°C, 130°C, 140°C or any value therebetween; and a time of 3-8h, such as 3h, 4h, 5h, 6h, 7h or 8h. The conditions of the polymerization reaction preferably include a temperature of 100°C-140°C, such as 100°C, 110°C, 120°C, 130°C, 140°C or any value therebetween; and a time of 3-8h, such as 3h, 4h, 5h, 6h, 7h or 8h.

[0045] The invention also provides a phenolic photosensitive resin prepared by the method.

[0046] The photosensitive resin composition provided by the present invention contains the above-mentioned phenolic photosensitive resin, photosensitizer, crosslinking agent and solvent. Wherein, based on the total weight of the photosensitive resin composition, the content of the phenolic photosensitive resin is preferably 5-40wt%, such as 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt% or any value therebetween; the content of the photosensitizer is preferably 0.5-3wt%, such as 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt% or other any value therebetween; the content of the cross-linking agent is 0.5-3wt%, such as 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt% or any value therebetween; the content of the solvent is preferably 54-95wt%, such as 54wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt% or any value therebetween.

[0047] In the present invention, the photosensitizer is preferably a quinone diazo compound, more preferably a diazo 1,2-benzoquinone compound and / or a diazo 1,2-naphthoquinone compound, and most preferably a diazo 1,2-naphthoquinone compound. The photosensitizer preferably has a structure shown in formula (6) to formula (9):

[0048]

[0049] In formula (6) to formula (9), Q is independently H or a structure represented by formula (10) to formula (11):

[0050]

[0051] In the present invention, the crosslinking agent is preferably a glycoluril compound and / or a melamine compound, preferably at least one compound selected from the group consisting of compounds having structures represented by formula (12) to formula (14):

[0052]

[0053] In the present invention, the solvent can be selected from at least one of ester solvents, lactone solvents, ether solvents, ketone solvents, hydrocarbon solvents, etc. Specific examples include but are not limited to: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, methyl lactate, ethyl lactate, butyl lactate, N-methyl-2-pyrrolidone, ethyl acetate, cyclopentanone and cyclohexanone.

[0054] In the present invention, the catalyst can be an acidic catalyst or a basic catalyst, preferably an acidic catalyst. Specific examples of the catalyst include, but are not limited to, one of hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, oxalic acid, anhydrous aluminum chloride and zinc chloride. In addition, the mass ratio of the catalyst to the anthraquinone compound is preferably (0.01-100):100, such as 0.01:100, 1:100, 5:100, 10:100, 15:100, 20:100, 30:100, 40:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value therebetween.

[0055] The present invention will be described in detail below through examples.

[0056] Synthesis Example 1 Synthesis of Phenolic Photosensitive Resin R1

[0057] S1. In a 0.5L three-necked flask equipped with a stirring device and a reflux condenser, 24.0g (0.1mol) of 1,5-dihydroxyanthraquinone, 180g of propylene glycol monomethyl ether (PGME), 42.0g (0.25mol) of 2,6-bis(hydroxymethyl)-p-cresol and 1.5g of p-toluenesulfonic acid were added, nitrogen was continuously introduced, and refluxed at 120°C for 3h. After cooling to room temperature, a prepolymer solution R1-1 was obtained.

[0058] S2. Add 15.4 (0.1 mol) of 3,5-dihydroxybenzoic acid into the prepolymer solution R1-1 obtained in step S1, continue to introduce nitrogen, and reflux at 120°C for 3 hours. After the reaction is completed, dilute the reaction product with 300g of PGME to obtain a reaction dilution. Under high-speed stirring, the above reaction dilution is added dropwise to 9L of water to disperse and precipitate the resin for recovery. The precipitated resin is washed with water, dehydrated, and then vacuum dried to obtain a phenolic photosensitive resin R1, which has a weight average molecular weight of 8400 Daltons and a molecular weight distribution of 2.83.

[0059] Synthesis Example 2 Synthesis of Phenolic Photosensitive Resin R2

[0060] S1. In a 0.5L three-necked flask equipped with a stirring device and a reflux condenser, 24.0g (0.1mol) of 1,5-dihydroxyanthraquinone, 180g of propylene glycol monomethyl ether (PGME), 42.0g (0.25mol) of 2,6-bis(hydroxymethyl)-p-cresol and 1.5g of p-toluenesulfonic acid were added, nitrogen was continuously introduced, and refluxed at 120°C for 3h. After cooling to room temperature, a prepolymer solution R2-1 was obtained.

[0061] S2. Add 23.1 (0.15 mol) of 3,5-dihydroxybenzoic acid into the prepolymer solution R2-1 obtained in step S1, continue to introduce nitrogen, and reflux at 120°C for 3 hours. After the reaction is completed, dilute the reaction product with 300g of PGME to obtain a reaction dilution. Under high-speed stirring, the above reaction dilution is added dropwise to 9L of water to disperse and precipitate the resin for recovery. The precipitated resin is washed with water, dehydrated, and then vacuum dried to obtain a phenolic photosensitive resin R2, which has a weight average molecular weight of 9700 and a molecular weight distribution of 2.94.

[0062] Synthesis Example 3 Synthesis of Phenolic Photosensitive Resin R3

[0063] S1. In a 0.5L three-necked flask equipped with a stirring device and a reflux condenser, 24.0g (0.1mol) of 1,5-dihydroxyanthraquinone, 180g of propylene glycol monomethyl ether (PGME), 45.4g (0.27mol) of 2,6-bis(hydroxymethyl)-p-cresol and 1.5g of p-toluenesulfonic acid were added, nitrogen was continuously introduced, and refluxed at 120°C for 3h. After cooling to room temperature, a prepolymer solution R3-1 was obtained.

[0064] S2. Add 15.4 (0.1 mol) of 3,5-dihydroxybenzoic acid into the prepolymer solution R3-1 obtained in step S1, continue to introduce nitrogen, and reflux at 120°C for 3 hours. After the reaction is completed, dilute the reaction product with 300g of PGME to obtain a reaction dilution. Under high-speed stirring, the above reaction dilution is added dropwise to 9L of water to disperse and precipitate the resin for recovery. The precipitated resin is washed with water, dehydrated, and then vacuum dried to obtain a phenolic photosensitive resin R3 with a weight average molecular weight of 7000 and a molecular weight distribution of 2.86.

[0065] Synthesis Example 4 Synthesis of Phenolic Photosensitive Resin R4

[0066] S1. In a 0.5L three-necked flask equipped with a stirring device and a reflux condenser, 24.0g (0.1mol) of 1,5-dihydroxyanthraquinone, 180g of propylene glycol monomethyl ether (PGME), 51.2g (0.25mol) of 2,6-bis(chloromethyl)-4-methylphenol and 1.5g of p-toluenesulfonic acid were added, nitrogen was continuously introduced, and refluxed at 120°C for 3h. After cooling to room temperature, a prepolymer solution R4-1 was obtained.

[0067] S2. Add 23.1 (0.15 mol) of 3,5-dihydroxybenzoic acid into the prepolymer solution R4-1 obtained in step S1, continue to introduce nitrogen, and reflux at 120°C for 3 hours. After the reaction is completed, dilute the reaction product with 300g of PGME to obtain a reaction dilution. Add the above reaction dilution dropwise into 9L of water under high-speed stirring to disperse and precipitate the resin for recovery. Wash the precipitated resin with water, dehydrate it, and then vacuum dry it to obtain a phenolic photosensitive resin R4 with a weight average molecular weight of 10700 and a molecular weight distribution of 3.04.

[0068] Synthesis Example 5 Synthesis of Phenolic Photosensitive Resin R5

[0069] S1. In a 0.5L three-necked flask equipped with a stirring device and a reflux condenser, 25.4g (0.1mol) of 1,5-dihydroxy-3-methyl-9,10-anthraquinone, 180g of propylene glycol monomethyl ether (PGME), 51.2g (0.25mol) of 2,6-bis(chloromethyl)-4-methylphenol and 1.5g of p-toluenesulfonic acid were added, nitrogen was continuously introduced, and refluxed at 120°C for 3h. After cooling to room temperature, a prepolymer solution R5-1 was obtained.

[0070] S2. Add 23.1 (0.15 mol) of 3,5-dihydroxybenzoic acid into the prepolymer solution R5-1 obtained in step S1, continue to introduce nitrogen, and reflux at 120°C for 3 hours. After the reaction is completed, dilute the reaction product with 300g of PGME to obtain a reaction dilution. Under high-speed stirring, the above reaction dilution is added dropwise to 9L of water to disperse and precipitate the resin for recovery. The precipitated resin is washed with water, dehydrated, and then vacuum dried to obtain a phenolic photosensitive resin R5 with a weight average molecular weight of 9900 and a molecular weight distribution of 3.00.

[0071] Comparative Synthesis Example 1 Synthesis of Phenolic Photosensitive Resin R6

[0072] In a 0.5L three-necked flask with a stirring device and a reflux condenser, 13.2g (0.12mol) of resorcinol, 180g of propylene glycol monomethyl ether (PGME), 9.8g (0.1mol) of 37wt% formaldehyde solution and 1.0g of p-toluenesulfonic acid were added, and nitrogen was continuously introduced. The reaction was refluxed at 120°C for 6h. After the reaction was completed, the product was diluted with 300g of PGME to obtain a reaction dilution. Under high-speed stirring, the above reaction dilution was added dropwise to 9L of water to disperse and precipitate the resin for recovery. The precipitated resin was washed with water, dehydrated, and then vacuum dried to obtain a phenolic photosensitive resin R6 with a weight average molecular weight of 9000 and a molecular weight distribution of 2.47.

[0073] Comparative Synthesis Example 2 Synthesis of Phenolic Photosensitive Resin R7

[0074] In a 0.5L three-necked flask with a stirring device and a reflux condenser, add 13.2 (0.12 mol) of resorcinol, 180 g of propylene glycol monomethyl ether (PGME), 16.8 g (0.1 mol) of 2,6-bis (hydroxymethyl)-p-cresol and 1.0 g of p-toluenesulfonic acid, continue to introduce nitrogen, reflux at 120°C for 6 hours, and after the reaction is completed, dilute the product with 300 g of PGME to obtain a reaction dilution. Under high-speed stirring, the above reaction dilution is added dropwise to 9L of water to disperse and precipitate the resin for recovery. The precipitated resin is washed with water, dehydrated and then vacuum dried to obtain a phenolic photosensitive resin R7 with a weight average molecular weight of 9700 and a molecular weight distribution of 2.68.

[0075] Comparative Synthesis Example 3 Synthesis of Phenolic Photosensitive Resin R8

[0076] The resin was prepared according to the method of Synthesis Example 1, except that step S2 was not included, and the reaction time of step S1 was extended to 6 hours before post-treatment. The remaining conditions were the same as those of Synthesis Example 1. The specific steps were as follows:

[0077] 24.0 g (0.1 mol) of 1,5-dihydroxyanthraquinone, 180 g of propylene glycol monomethyl ether (PGME), 42.0 g (0.25 mol) of 2,6-bis(hydroxymethyl)-p-cresol and 1.5 g of p-toluenesulfonic acid were added to a 0.5 L three-necked flask equipped with a stirring device and a reflux condenser, and nitrogen was continuously introduced. The mixture was refluxed at 120°C for 6 h. After the reaction was completed, the reaction product was diluted with 300 g of PGME to obtain a reaction dilution. Under high-speed stirring, the reaction dilution was added dropwise to 9 L of water to disperse and precipitate the resin for recovery. The precipitated resin was washed with water, dehydrated and then vacuum dried to obtain a phenolic photosensitive resin R8 with a weight average molecular weight of 4200 Daltons and a molecular weight distribution of 2.16.

[0078] Comparative Synthesis Example 4 Synthesis of Phenolic Photosensitive Resin R9

[0079] A phenolic photosensitive resin was prepared according to the method of Synthesis Example 1, except that all the raw materials were added at the same time and then reacted in one step. The specific steps are as follows:

[0080] 24.0g (0.1mol) of 1,5-dihydroxyanthraquinone, 180g of propylene glycol monomethyl ether (PGME), 42.0g (0.25mol) of 2,6-bis(hydroxymethyl)-p-cresol, 1.5g of p-toluenesulfonic acid, and 15.4 (0.1mol) of 3,5-dihydroxybenzoic acid were added to a 0.5L three-necked flask with a stirring device and a reflux condenser, and nitrogen was continuously introduced. The mixture was refluxed at 120°C for 6h. After the reaction was completed, the reaction product was diluted with 300g of PGME to obtain a reaction dilution. Under high-speed stirring, the reaction dilution was added dropwise to 9L of water to disperse and precipitate the resin for recovery. The precipitated resin was washed with water, dehydrated, and then vacuum dried to obtain a phenolic photosensitive resin R9 with a weight average molecular weight of 9200 Daltons and a molecular weight distribution of 3.22.

[0081] Example 1

[0082] The above-mentioned phenolic photosensitive resin R1, photoacid generator and crosslinker are dissolved in PGME, and the mass ratio of phenolic photosensitive resin R1, photosensitizer, crosslinker and PGME is 30:2.5:3:64.5, and the obtained solution is filtered with a 0.1 μm filter to obtain a photosensitive resin composition. The structure of the photosensitizer is shown in formula (14). The structure of the crosslinker is shown in formula (15).

[0083]

[0084] Example 2

[0085] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R2 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0086] Example 3

[0087] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R3 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0088] Example 4

[0089] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R4 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0090] Example 5

[0091] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R5 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0092] Comparative Example 1

[0093] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R6 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0094] Comparative Example 2

[0095] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R7 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0096] Comparative Example 3

[0097] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R8 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0098] Comparative Example 4

[0099] A photosensitive resin composition was prepared according to the method of Example 1, except that the phenolic photosensitive resin R1 was replaced by the phenolic photosensitive resin R9 in the same weight portion, and the other conditions were the same as those of Example 1 to obtain a photosensitive resin composition.

[0100] Test Case

[0101] The photosensitive resin compositions obtained in the above embodiments and comparative examples were coated on wafers respectively, and then pre-dried at 120°C. After drying, the temperature was raised to 200°C for curing. The cured photosensitive film was peeled off from the surface of the silicon wafer using a dilute hydrochloric acid solution and cut into appropriate sizes to test its tensile strength, elongation at break and resistivity.

[0102] The tensile strength was tested according to the method disclosed in ASTM D882.

[0103] The elongation at break is measured according to the method disclosed in ASTM D882.

[0104] The resistivity is tested according to the method disclosed in GB / T 1551-2021.

[0105] The results are shown in Table 1.

[0106] Table 1

[0107] project Tensile strength / MPa Elongation at break / % Resistivity / Ω·cm Example 1 124 27 1.14E+15 Example 2 119 31 1.02E+15 Example 3 125 25 1.10E+15 Example 4 129 34 1.13E+15 Example 5 121 31 1.13E+15 Comparative Example 1 74 11 9.21E+14 Comparative Example 2 108 20 1.01E+11 Comparative Example 3 57 12 1.23E+10 Comparative Example 4 115 25 1.10E+14

[0108] It can be seen from Table 1 that the cured films formed by curing the photosensitive resin compositions of Examples 1-5 not only have higher tensile strength and elongation at break than the cured films formed by curing the comparative examples 1-4, but also have better insulation properties, and are more suitable for surface protection films and interlayer insulation films of semiconductor devices.

[0109] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A phenolic photosensitive resin, characterized in that: The phenolic photosensitive resin has a structure shown in formula (1): In formula (1), m1 R1 and m2 R2 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m1, m2, m3 and m4 are each independently an integer from 0 to 2, 0≤(m1+m3)≤3, 0≤(m2+m4)≤3; R3 and R5 are each independently absent or C1-C10 alkylene; m5 R4 are the same or different and are each independently H, C1-C10 alkyl or C1-C10 alkoxy; m5 is an integer from 0 to 3; m6 R6 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m6 is 0 or 1, and m7 is an integer from 0 to 5; n1 and n2 are each independently an integer from 1 to 100.

2. The phenolic photosensitive resin according to claim 1, characterized in that: The weight average molecular weight of the phenolic photosensitive resin is 3000-20000 Daltons, and the molecular weight distribution is 2.0-4.

0.

3. The phenolic photosensitive resin according to claim 1, characterized in that: n1 / n2 is 0.5-2.

0.

4. A method for preparing a phenolic photosensitive resin, characterized in that: The method comprises the following steps: S1. The anthraquinone compound represented by formula (3) and the cresol compound represented by formula (4) are prepolymerized in the presence of a catalyst and under the protection of an inert gas to obtain a prepolymer; S2. The prepolymer and the benzoic acid compound represented by formula (5) are polymerized under an inert gas to obtain a phenolic photosensitive resin; In formula (3), m1 R1 and m2 R2 are the same or different and are each independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m1, m2, m3 and m4 are each independently an integer of 0-2, 0≤(m1+m3)≤3, 0≤(m2+m4)≤3; In formula (4), R3 and R5 are each independently absent or a C1-C10 alkylene group; m5 R4 are the same or different and are each independently H, a C1-C10 alkyl group or a C1-C10 alkoxy group; X and X' are each independently hydroxyl or halogen; m5 is an integer of 0-3; In formula (5), m6 R6 are the same or different and are independently H, C1-C10 alkyl, C1-C10 alkoxy, nitro or cyano; m6 is 0 or 1, and m7 is an integer of 0-5.

5. The method for preparing a phenolic photosensitive resin according to claim 4, characterized in that: The molar ratio of the anthraquinone compound to the cresol compound is (1-4):1; the molar ratio of the anthraquinone compound to the benzoic acid compound is 1:(1-2).

6. The method for preparing a phenolic photosensitive resin according to claim 4, characterized in that: The conditions of the prepolymerization reaction include a temperature of 100° C.-140° C. and a time of 3-8 hours; the conditions of the polymerization reaction include a temperature of 100° C.-140° C. and a time of 3-8 hours.

7. A phenolic photosensitive resin prepared by the method according to any one of claims 4 to 7.

8. A photosensitive resin composition, characterized in that The photosensitive resin composition contains the phenolic photosensitive resin according to any one of claims 1 to 3, a photosensitizer, a crosslinking agent and a solvent.

9. The photosensitive resin composition according to claim 8, characterized in that: Based on the total weight of the photosensitive resin composition, the content of the phenolic photosensitive resin is 5-40wt%, the content of the photosensitizer is 0.5-3wt%, the content of the crosslinking agent is 0.5-3wt%, and the content of the solvent is 54-95wt%; Preferably, the photosensitizer is a quinone diazo compound; Preferably, the cross-linking agent is a glycoluril compound and / or a melamine compound; Preferably, the solvent is selected from at least one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone and ethyl lactate.

10. Use of the photosensitive resin composition according to claim 8 or 9 in semiconductor device and display device packaging processes.

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