A phenolic resin composition and its preparation method and application, and a method for preparing a cured relief pattern

Abstract

The present invention belongs to the technical field of semiconductor element coatings, and discloses a phenolic resin composition, a preparation method and application thereof, and a preparation method of a cured relief pattern. The phenolic resin composition comprises phenolic resin A, phenolic resin B, a photoacid generator, a crosslinking agent, and a solvent. The phenolic resin composition can be cured at a temperature below 250°C to obtain a cured film, and the cured film has good toughness, elasticity, and thermal stability, and can be applied to semiconductor elements made of raw materials with poor heat resistance, and used as a protective film, an interlayer insulating film, or an insulating layer of an organic electroluminescent element.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor element coatings, and in particular relates to a phenolic resin composition, a preparation method and application thereof, and a preparation method of a cured relief pattern. Background Art

[0002] In recent years, with the high integration and large-scale semiconductor elements and the thinning and miniaturization of packaging substrates, the surface protection layer or interlayer insulation film of semiconductor elements is required to have better electrical properties, heat resistance and mechanical properties. At present, polyimide is one of the materials that can meet the above requirements. The use of photosensitive polyimide as a raw material to prepare a cured film as a surface protection layer or interlayer insulation film of a semiconductor element has a simple pattern formation process, which can achieve the effect of shortening the complex manufacturing process.

[0003] The polyimide resin cured film is generally formed by spinning a solution containing a polyimide precursor obtained by the reaction of tetracarboxylic dianhydride and diamine into a thin film, and then heating at a temperature above 300°C to dehydrate and close the ring.

[0004] Since some semiconductor materials have poor heat resistance and can reach a low thermal curing temperature, the surface protection layer or interlayer insulation film is dehydrated and ring-closed at a relatively low temperature. However, due to incomplete imidization at low temperatures, the prepared cured film has problems such as high brittleness, low elasticity and poor thermal stability. Summary of the invention

[0005] The purpose of the present invention is to solve the defects of the existing cured film, such as high brittleness, low elasticity and poor thermal stability, and to provide a phenolic resin composition with good toughness, high elasticity and good thermal stability, a cured film and a preparation method and application thereof.

[0006] One of the purposes of the present invention is to provide a phenolic resin composition, which comprises a phenolic resin A having a structure as shown in formula (1), a phenolic resin B having a structure as shown in formula (2), a photoacid generator, a crosslinking agent and a solvent;

[0007]

[0008] In formula (1), R1 to R4 are each independently selected from a hydrogen atom, a C1 to C 10 A monovalent aliphatic group and a C1-C 10 One of the monovalent aliphatic groups, and n1≥2;

[0009] In formula (2), X is selected from hydrogen atom, C2 to C 10 Alkoxycarbonyl, C2~C 10Alkoxycarbonylalkyl, C2~C 10 one of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R5 is selected from C1~C 10 Hydrocarbon, C1~C 10 One of alkoxy, nitro and cyano, and n2≥2, m1=1, 2 or 3, m2=0, 1 or 2, 2≤(m1+m2)≤4;

[0010] Y in formula (1) and formula (2) is independently selected from a divalent organic group having a structure as shown in formula (3) or formula (4):

[0011]

[0012] In formula (3), R6 and R7 are each independently selected from a hydrogen atom, a C1-C 11 A monovalent organic group or a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;

[0013] In formula (4), R8~R 11 Each independently selected from a hydrogen atom, a C1-C 10 A monovalent aliphatic group, a C1-C 10 One of the monovalent aliphatic groups; R 12 One or more selected from halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups; m3=1, 2, 3 or 4.

[0014] In some specific embodiments, Y in the phenolic resin structure is a divalent organic group as shown in formula (5),

[0015]

[0016] In formula (5), R 13 It is a C1-C5 hydrocarbon group and / or a C1-C5 alkoxy group, m4=1, 2 or 3, m5=0, 1, 2 or 3, and 1≤(m4+m5)≤4.

[0017] In some specific embodiments, Y in the phenolic resin structure is a divalent organic group as shown in formula (6),

[0018]

[0019] In formula (6), R 13 It is a C1-C5 hydrocarbon group and / or a C1-C5 alkoxy group, and m5=0, 1, 2 or 3.

[0020] In some specific embodiments, the phenolic resin A is obtained by polymerizing a phenolic compound having a triptycene structure as shown in formula (7) and a polymer component having a structure as shown in formula (8) and / or formula (9) under the action of a catalyst:

[0021]

[0022] In formula (7), R 14 ~R 17 Each independently selected from a hydrogen atom, a C1-C 10 A monovalent aliphatic group and a C1-C 10 One of the monovalent aliphatic groups;

[0023] In formula (8), R 18 and R 19 Each independently selected from a hydrogen atom, a C1-C 11 A monovalent organic group and a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;

[0024] In formula (9), R 20 ~R 23 Each independently selected from a hydrogen atom, a C1-C 10 A monovalent aliphatic group, a C1-C 10 One of the monovalent aliphatic groups; R 24 One or more selected from halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups, m6 = 1, 2, 3 or 4; Z1 and Z2 are each independently selected from hydroxymethyl, alkoxymethyl and halogenated alkyl.

[0025] In some specific embodiments, the phenolic resin B is obtained by polymerizing a phenolic compound having a structure as shown in formula (10) and a polymer component having a structure as shown in formula (8) and / or formula (9) under the action of a catalyst:

[0026]

[0027] In formula (8), R 18 and R 19 Each independently selected from a hydrogen atom, a C1-C 11 A monovalent organic group and a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group;

[0028] In formula (9), R 20 ~R 23 Each independently selected from a hydrogen atom, a C1-C 10 A monovalent aliphatic group, a C1-C10 One of the monovalent aliphatic groups; R 24 One or more selected from halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups, m6 = 1, 2, 3 or 4; Z1 and Z2 are each independently selected from hydroxymethyl, alkoxymethyl and halogenated alkyl;

[0029] In formula (10), X is selected from hydrogen atom, C2~C 10 Alkoxycarbonyl, C2~C 10 Alkoxycarbonylalkyl, C2~C 10 One of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 25 Selected from C1~C 10 Hydrocarbon, C1~C 10 One of the alkoxy, nitro and cyano groups, m7=1, 2 or 3, m8=0, 1 or 2, 2≤(m7+m8)≤4.

[0030] In some specific embodiments, the photoacid generator is a quinone diazo compound.

[0031] In some specific embodiments, the photoacid generator is a compound having a diazo-1,2-benzoquinone structure and / or a compound having a diazo-1,2-naphthoquinone structure;

[0032] The crosslinking agent is selected from one or more of epoxy compounds, oxetane compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, compounds containing unsaturated bonds, melamine and its derivatives, methylol compounds, alkoxymethyl compounds, N-methylol compounds and N-alkoxymethyl compounds;

[0033] The solvent is selected from one or more of amide compounds, sulfoxide compounds, urea compounds, ketone compounds, ester compounds, lactone compounds, ether compounds, halogenated hydrocarbon compounds and hydrocarbon compounds.

[0034] In some specific embodiments, the weight parts of each raw material in the phenolic resin composition are as follows:

[0035]

[0036]

[0037] In some specific embodiments, the phenolic resin composition further comprises one or more of a thermal acid generator, a surfactant, a silane coupling agent, a dissolution accelerator and a cross-linking accelerator.

[0038] A second object of the present invention is to provide a method for preparing a phenolic resin composition, the method comprising the following steps:

[0039] A phenolic compound having a triptycene structure as shown in formula (7) and a polymer component as shown in formula (8) and / or formula (9) are polymerized under the action of a catalyst to obtain a phenolic resin A;

[0040] A phenolic compound having a structure such as that shown in formula (10) and a polymer component having a structure such as that shown in formula (8) and / or formula (9) are subjected to a polymerization reaction under the action of a catalyst to prepare a phenolic resin B;

[0041] Phenolic resin A, phenolic resin B, a photoacid generator, a crosslinking agent, a solvent, and optionally a thermal acid generator, a surfactant, a silane coupling agent, a dissolution accelerator, and a crosslinking accelerator are uniformly mixed to obtain a phenolic resin composition.

[0042] The third object of the present invention is to provide a phenolic resin composition prepared by the above method.

[0043] A fourth object of the present invention is to provide the use of the above-mentioned phenolic resin composition in preparing protective films, interlayer insulating films, and insulating layers of organic electroluminescent elements of semiconductor elements.

[0044] A fifth object of the present invention is to provide a method for preparing a solidified relief pattern, comprising the following steps:

[0045] Forming a photosensitive resin layer on the surface of a substrate using the phenolic resin composition;

[0046] exposing the photosensitive resin layer;

[0047] removing the exposed part or the unexposed part of the photosensitive resin layer by a developer to obtain a relief pattern;

[0048] The relief pattern is heated and cured.

[0049] Beneficial effects:

[0050] (1) The phenolic resin composition provided by the present invention has a relatively low thermal curing temperature and can be cured at a temperature below 250° C. to obtain a cured film. The cured film has good toughness and thermal stability, so that it can be used in semiconductor elements made of raw materials with poor heat resistance as a surface protection film, an interlayer insulation film, etc.

[0051] (2) The cured film obtained by thermally curing the phenolic resin composition provided by the present invention has good alkali solubility, and the cured relief pattern prepared using the phenolic resin composition as a raw material has a good shape, which can realize the high-precision preparation of semiconductor elements. DETAILED DESCRIPTION

[0052] The inventors have found through creative labor and a large number of experiments that when a phenolic resin A having a triptycene structure is compounded with a phenolic resin B having a benzene ring structure or a biphenyl structure, and a photoacid generator, a cross-linking agent, a solvent and other substances are added to prepare a phenolic resin composition, the phenolic resin composition can be cured at a temperature below 250°C to form a cured film, and the cured film has good electrical insulation, photosensitivity, flexibility and thermal stability, thereby effectively solving the problem in the prior art that polyimide resins are difficult to completely cure at low temperatures, resulting in decreased physical properties such as flexibility and thermal stability of the cured film.

[0053] In the present invention, the structure of phenolic resin A is shown in formula (1), and the structure of phenolic resin B is shown in formula (2).

[0054]

[0055] Formula (1), R1 to R4 are each independently selected from a hydrogen atom, a C1 to C 10 A monovalent aliphatic group and a C1-C 10 The monovalent aliphatic groups are preferably independently selected from a hydrogen atom and a C1-C5 monovalent aliphatic group. The C1-C5 monovalent aliphatic group may be, but is not limited to, a methyl group, an ethyl group, a propyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a propenyl group, a methoxy group, or an ethoxy group.

[0056] In formula (2), X is selected from hydrogen atom, C2 to C 10 Alkoxycarbonyl, C2~C 10 Alkoxycarbonylalkyl, C2~C 10 The alkyl group is one of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, and is preferably one of hydrogen atom, tert-butoxybutyl and tetrahydropyranyl.

[0057] In formula (2), R5 is selected from C1 to C 10 Hydrocarbon, C1~C 10 It is one of the alkoxy, nitro and cyano groups, preferably one of the methyl, ethyl, n-propyl and isopropyl groups.

[0058] In formula (2) B, m1=1, 2 or 3, m2=0, 1 or 2, and 2≤(m1+m2)≤4, wherein when m2=2, the two R5s may be the same or different.

[0059] In the present invention, the structures of phenolic resin A and phenolic resin B both contain Y, where Y is a divalent substituent group. The specific structures are shown in formula (3) or formula (4).

[0060]

[0061] In formula (3), R6 and R7 are each independently selected from a hydrogen atom, a C1-C 11 The monovalent organic group or one of a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group is preferably independently selected from one of a hydrogen atom, a methyl group, an ethyl group, a n-propyl group and an isopropyl group.

[0062] In formula (4), R8~R 11 Each independently selected from a hydrogen atom, a C1-C 10 A monovalent aliphatic group, a C1-C 10 The monovalent aliphatic group is preferably selected from a hydrogen atom or a C1-C3 monovalent aliphatic group. The C1-C3 monovalent aliphatic group may be, but is not limited to, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a propenyl group or a methoxy group.

[0063] In formula (4), m3 = 1, 2, 3 or 4, R 12 is selected from one or more of a halogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, and a monovalent organic group. Specifically, when m3=1, R 12 It can be but not limited to one of hydroxyl, carboxyl and sulfonic acid groups; when m3=2, 3 or 4, at least one R 12 is hydroxyl group, other R 12 The group may be, but is not limited to, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a carboxyl group, a methyl group, an ethyl group, an n-butyl group, and a sulfonic acid group.

[0064] When Y in phenolic resin A and / or phenolic resin B is a divalent organic group with a structure such as formula (5), m4=1, 2 or 3, m5=0, 1, 2 or 3, and 1≤(m4+m5)≤4, the cured film prepared from the phenolic resin composition has better thermal stability, can maintain a good morphology at high temperatures or in an operating environment with complex temperature changes, and has stronger applicability.

[0065]

[0066] When Y in the phenolic resin A and / or the phenolic resin B is a divalent organic group having a structure as shown in formula (6), and m5=0, 1, 2 or 3, the phenolic resin composition has a higher sensitivity to the light source during the process of preparing the cured relief pattern, which is conducive to the formation of a high-precision relief pattern and can also greatly improve the production quality of semiconductor components.

[0067]

[0068] The polymerization degree of the phenolic resin A added to the phenolic resin composition of the present invention is greater than 2, that is, n1≥2; preferably 5 to 500, that is, n1 is any integer between 5 and 500, specifically 5, 6, 7, 8, 9, 10, 20, 25, 50, 100, 150, 240, 250, 320, 350, 400, 460, 480, 500 and any value therebetween. In addition, the weight average molecular weight of the phenolic resin A is preferably 2000 to 200000 Da, more preferably 3000 to 120000 Da, and most preferably 3000 to 40000 Da.

[0069] The polymerization degree of the phenolic resin B added to the phenolic resin composition of the present invention is greater than 2, that is, n2≥2; preferably 5 to 500, that is, n2 is any integer between 5 and 500, specifically 5, 6, 9, 10, 15, 17, 23, 25, 45, 100, 150, 250, 250, 300, 350, 400, 440, 485, 500 and any value therebetween. In addition, the weight average molecular weight of the phenolic resin B is preferably 2000 to 200000 Da, more preferably 3000 to 120000 Da, and most preferably 3000 to 40000 Da.

[0070] In the present invention, the phenolic resin A and the phenolic resin B are synthesized by polymerization reaction of phenolic compounds and polymeric components under the action of a catalyst.

[0071] The structure of the phenolic compound having a triptycene structure used in the synthesis of phenolic resin A is shown in formula (7), and the structure of the polymer component is shown in formula (8) and / or formula (9).

[0072]

[0073] R in formula (7) 14 ~R 17 The groups are the same as the R1 to R4 groups in the synthesized phenolic resin A, that is, R in formula (7) 14 ~R 17 Each independently selected from a hydrogen atom, a C1-C 10 A monovalent aliphatic group and a C1-C 10 The phenolic compound having a triptycene structure used in the synthesis of phenolic resin A may specifically be, but is not limited to, one or more of 1,4-dihydroxytriptycene, 2,6-di-tert-butyl-1,4-dihydroxytriptycene, 2-tert-butyl-5-methyl-1,4-dihydroxytriptycene, 2-fluoromethyl-1,4-dihydroxytriptycene and 3(2-fluoroethyl)-6-ethyl-1,4-dihydroxytriptycene.

[0074] The structure of the phenolic compound used in the synthesis of phenolic resin B is shown in formula (10), and the structure of the polymer component is shown in formula (8) and / or formula (9).

[0075]

[0076] R in formula (10) 25 The R5 and X groups are the same as the R5 and X groups in the synthesized phenolic resin B, that is, X in formula (10) is selected from hydrogen atoms, C2 to C 10 Alkoxycarbonyl, C2~C 10 Alkoxycarbonylalkyl, C2~C 10 One of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 25 Selected from C1~C 10 Hydrocarbon, C1~C 10 The phenolic compound used in the synthesis of phenolic resin B may be one of phenol, resorcinol, 2-methylresorcinol and 4-methoxyresorcinol.

[0077] The polymer components used in the synthesis of phenolic resin A and phenolic resin B may be completely identical, non-completely identical or completely different. R in formula (8) 18 and R 19 Each independently selected from a hydrogen atom, a C1-C 11 A monovalent organic group and a group containing a carboxyl group, a sulfonic acid group and a phenolic hydroxyl group; R in formula (9) 20 ~R 23 Each independently selected from a hydrogen atom, a C1-C 10 A monovalent aliphatic group, a C1-C 10 One of the monovalent aliphatic groups; R 24 One or more selected from halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups and monovalent organic groups, m6 = 1, 2, 3 or 4; Z1 and Z2 are each independently selected from hydroxymethyl, alkoxymethyl and halogenated alkyl.

[0078] In some specific embodiments, the catalyst used in the polymerization reaction may be an acidic catalyst or a basic catalyst, preferably an acidic catalyst. When the catalyst is an acidic catalyst, it may be, but not limited to, one or more of an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and an organic acid such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid.

[0079] In some specific embodiments, the organic solvent used in the synthesis process of phenolic resin A and phenolic resin B can be but is not limited to one or more of (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.

[0080] The photoacid generator added to the phenolic resin composition of the present invention is selected to be a quinone diazo compound, which undergoes thermal decomposition during curing, so the content of the photoacid generator remaining in the cured film is extremely low, which can reduce the impact of the residual photoacid generator on the performance of the cured film. Specifically, the photoacid generator is a compound having a diazo 1,2-benzoquinone structure or a compound having a diazo 1,2-naphthoquinone structure, wherein the compound having a diazo 1,2-naphthoquinone structure is preferably a compound having a structure as shown in formulas (11) to (14).

[0081]

[0082] Q in formulae (11) to (14) may be a hydrogen atom and / or a group described in formulae (15) and (16).

[0083]

[0084] The crosslinking agent added to the phenolic resin composition of the present invention may be, but is not limited to, one or more of epoxy compounds, oxetane compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, compounds containing unsaturated bonds, melamine compounds, methylol compounds or alkoxymethyl compounds, N-methylol compounds and N-alkoxymethyl compounds.

[0085] In some preferred embodiments, when the crosslinking agent is selected as one or more of epoxy compounds, oxetane compounds, isocyanate compounds, methylol compounds or alkoxymethyl compounds, N-methylol compounds and N-alkoxymethyl compounds, the thermal properties and mechanical properties of the cured film after the phenolic resin composition is cured to form a film can be improved.

[0086] In some specific embodiments, the solvent added to the phenolic resin composition may be, but is not limited to, one or more of amide compounds, sulfoxide compounds, urea compounds, ketone compounds, ester compounds, lactone compounds, ether compounds, halogenated hydrocarbon compounds and hydrocarbon compounds; specifically, the solvent added to the phenolic resin composition may be 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, styrene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane or xylene. From the viewpoint of the solubility of the resin, the stability of the resin composition and the adhesion to the substrate, the solvent is more preferably one or more of dimethyl sulfoxide, tetramethyl urea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol and tetrahydrofurfuryl alcohol.

[0087] In some specific embodiments, the weight parts of each raw material in the phenolic resin composition are as follows:

[0088]

[0089] It is worth noting that when the input weight ratio of phenolic resin A to phenolic resin B is controlled at 5:95 to 95:5, the thermal and mechanical properties of the cured film after curing are good. When the input weight ratio of phenolic resin A to phenolic resin B is controlled at 10:90 to 60:40, the film properties and alkali solubility of the cured film are better. When the input weight ratio of phenolic resin A to phenolic resin B is controlled at 15:85 to 50:50, the film properties and alkali solubility of the cured film are the best.

[0090] One or more of a surfactant, a silane coupling agent, a dissolution accelerator and a thermal acid generator may be added to the phenolic resin composition provided by the present invention as required.

[0091] In some specific embodiments, the surfactant may be, but is not limited to, one or more nonionic surfactants such as propylene glycol, polyethylene glycols such as polyoxyethylene lauryl ether, or their derivatives. The amount of surfactant added is preferably 0.01 to 10% of the total mass of phenolic resin A and phenolic resin B.

[0092] The addition of silane coupling agent can improve the storage stability of the phenolic resin composition. 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. The addition amount of the silane coupling agent is preferably 0.01 to 15% of the total mass of the phenolic resin A and the phenolic resin B.

[0093] In some specific embodiments, the dissolution promoter may be, but is not limited to, one or more of p-isopropylphenylphenol, bisphenols, resorcinols, 3-phenyllactic acid, 2,4-dimethylbenzoic acid, and 2,4,6-trimethylbenzoic acid. The amount of the dissolution promoter added is preferably 0.01 to 20% of the total mass of the phenolic resin A and the phenolic resin B.

[0094] The addition of the thermal acid generator improves the bonding strength between the cured film and the substrate after the phenolic resin composition is cured. In some specific embodiments, the thermal acid generator can be, but is not limited to, one or more of ethyl sulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, p-toluenesulfonic acid, and 2-methoxyethyl ester. The addition amount of the thermal acid generator is preferably 0.5 to 5% of the total mass of the phenolic resin A and the phenolic resin B.

[0095] The present application also provides a method for preparing a phenolic resin composition, which specifically comprises the following steps:

[0096] A phenolic compound having a triptycene structure as shown in formula (7) and a polymer component as shown in formula (8) and / or formula (9) are polymerized under the action of a catalyst to obtain a phenolic resin A;

[0097] A phenolic compound having a structure such as that shown in formula (10) and a polymer component having a structure such as that shown in formula (8) and / or formula (9) are subjected to a polymerization reaction under the action of a catalyst to prepare a phenolic resin B;

[0098] Phenolic resin A, phenolic resin B, a photoacid generator, a crosslinking agent, a solvent, and optionally a thermal acid generator, a surfactant, a silane coupling agent, a dissolution accelerator, and a crosslinking accelerator are uniformly mixed to obtain a phenolic resin composition.

[0099] In some specific embodiments, the synthesis order of phenolic resin A and phenolic resin B is not particularly limited. Phenolic resin A can be prepared first and then phenolic resin B, or phenolic resin B can be prepared first and then phenolic resin A, or the preparation of phenolic resin A and phenolic resin B can be carried out simultaneously.

[0100] The reagents used in the preparation method have been introduced in the previous section and will not be discussed in detail here.

[0101] The present application provides the use of the phenolic resin composition in preparing a protective film of a semiconductor element, an interlayer insulating film, and an insulating layer of an organic electroluminescent element.

[0102] The present application also provides a method for preparing a cured relief pattern (a method for using a phenolic resin composition in preparing a cured relief pattern), which specifically comprises the following steps:

[0103] A photosensitive resin layer is formed on the surface of a substrate using a phenolic resin composition;

[0104] exposing the photosensitive resin layer;

[0105] removing the exposed part or the unexposed part of the photosensitive resin layer by a developer to obtain a relief pattern;

[0106] The relief pattern is heated and cured.

[0107] In some specific embodiments, the phenolic resin composition is coated on a suitable support or substrate surface by spray coating, dipping, printing, roller coating, etc., and pre-baked at 80-140° C. to form a photosensitive resin layer on the support or substrate surface.

[0108] In some specific embodiments, the photosensitive resin layer is irradiated with X-rays, electron beams, ultraviolet rays, etc. to form a relief pattern. In some preferred embodiments, one or more of g-rays, h-rays and i-rays of a mercury lamp are selected for irradiation, which can improve the resolution of the relief pattern and facilitate operation.

[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. To further improve the imaging effect, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of quaternary ammonium salts.

[0110] Specifically, after development, the photosensitive resin layer is washed with a rinse solution and then heated for curing. The rinse solution may be, but is not limited to, one or more of distilled water, methanol, ethanol and isopropanol.

[0111] In some specific embodiments, the heating and curing temperature is 150-300° C. More preferably, the heating and curing temperature of the photosensitive resin layer is below 250° C., and the material of the support or substrate can be a semiconductor material with poor heat resistance.

[0112] Embodiments of the present invention are described in detail below, and the examples of the embodiments are intended to be used to explain the present invention, but should not be construed as limiting the present invention. In the embodiments, if specific techniques or conditions are not specified, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not specified for reagents or instruments used, they are all conventional products that can be obtained commercially.

[0113] Preparation Example 1. Synthesis of 1,4-dihydroxytriptycene

[0114] S1. In a three-necked flask equipped with magnetic stirring, 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, continue to heat to reflux and maintain for 6 hours.

[0115] S2. The reaction solution in S1 was cooled to room temperature. A large amount of solid precipitated. 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%.

[0116] S3. Add the orange product into a three-necked flask equipped with a magnetic stirrer, nitrogen protection and reflux device, and add 300 mL of acetic acid, and heat to reflux; after the product is completely dissolved, slowly drop 4 mL of hydrobromic acid, continue the reaction for 2 h, cool, filter and vacuum dry to obtain a white 1,4-dihydroxytriptycene powder with a structure as shown in formula (17) and a yield of 88%.

[0117]

[0118] Preparation Example 2. Synthesis of 2,6-di-tert-butyl-1,4-dihydroxytriptycene

[0119] S1. In a three-necked flask equipped with magnetic stirring, 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, continue to heat to reflux and maintain for 6 hours.

[0120] S2. The reaction solution in S1 was cooled to room temperature. A large amount of solid precipitated. The solid was filtered and the filter cake was washed with a small amount of toluene. After vacuum drying, 17.9 g of an orange product was obtained with a yield of 80%.

[0121] S3. Add the orange product into a three-necked flask equipped with a magnetic stirrer, nitrogen protection and reflux device, and add 400 mL of acetic acid, and heat to reflux; after the product is completely dissolved, slowly drop 4 mL of hydrobromic acid, continue the reaction for 2 h, cool, filter and vacuum dry to obtain a white 2,6-di-tert-butyl-1,4-dihydroxytriptycene powder, the structure of which is shown in formula (18), and the yield is 88%.

[0122]

[0123] Preparation Example 3. Synthesis of Phenolic Resin A

[0124] S1. Nitrogen is replaced in a 1L three-necked flask with a Dean-Stark water separator. In the flask, 171.7 g of 1,4-dihydroxytriptycene (0.60 mol) prepared in Preparation Example 1, 3.81 g of p-toluenesulfonic acid (0.02 mol), 84.0 g of 2,6-bis(hydroxymethyl)-p-cresol (0.5 mol) and 200 g of propylene glycol monomethyl ether are added. The mixture is stirred at 60°C until the protective agent is completely dissolved. The mixture is heated to 80°C in an oil bath and reacted for 12 hours.

[0125] S2, after the reaction is completed, the mixture is cooled, and then 200g of propylene glycol monomethyl ether is added and stirred. The diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, washed, dehydrated and then vacuum dried to obtain phenolic resin A with a yield of 77%.

[0126] The weight average molecular weight of the phenolic resin A synthesized in this preparation example is 7900.

[0127] Preparation Example 4. Synthesis of Phenolic Resin A

[0128] S1. Nitrogen is replaced in a 1L three-necked flask with a Dean-Stark water separator. 239g of 2,6-di-tert-butyl-1,4-dihydroxytriptycene (0.60mol) prepared in Preparation Example 2, 3.81g of p-toluenesulfonic acid (0.02mol), 84.0g of 2,6-bis(hydroxymethyl)-p-cresol (0.5mol) and 200g of propylene glycol monomethyl ether are added to the flask. The mixture is stirred at 60°C until the protective agent is completely dissolved. The mixture is heated to 80°C in an oil bath and reacted for 12h.

[0129] S2, after the reaction is completed, the mixture is cooled, and then 200g of propylene glycol monomethyl ether is added and stirred. The diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, washed, dehydrated and then vacuum dried to obtain phenolic resin A with a yield of 79%.

[0130] The weight average molecular weight of the phenolic resin A synthesized in this preparation example is 7400.

[0131] Preparation Example 5. Synthesis of Phenolic Resin A

[0132] S1. Nitrogen is replaced in a 1L three-necked flask with a Dean-Stark water separator. In the flask, 171.7g of 1,4-dihydroxytriptycene (0.60mol) prepared in Preparation Example 1, 3.81g of p-toluenesulfonic acid (0.02mol), 41.0g of 37wt% formaldehyde solution (0.5mol) and 200g of propylene glycol monomethyl ether are added. The mixture is stirred at 60°C until the protective body is completely dissolved. The mixture is heated to 80°C in an oil bath and reacted for 12h.

[0133] S2, after the reaction is completed, the mixture is cooled, and then 200g of propylene glycol monomethyl ether is added and stirred. The diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, washed, dehydrated and then vacuum dried to obtain phenolic resin A with a yield of 72%.

[0134] The main reactions in this preparation example are:

[0135]

[0136] The weight average molecular weight of the phenolic resin A synthesized in this preparation example is 8500.

[0137] Preparation Example 6. Synthesis of Phenolic Resin A

[0138] S1. Nitrogen is replaced in a 1L three-necked flask with a Dean-Stark water separator. In the flask, 239g of 2,6-di-tert-butyl-1,4-dihydroxytriptycene (0.60mol) prepared in Preparation Example 2, 3.81g of p-toluenesulfonic acid (0.02mol), 41.0g of 37wt% formaldehyde solution (0.5mol) and 200g of propylene glycol monomethyl ether are added. The mixture is stirred at 60°C until the protective body is completely dissolved. The mixture is heated to 80°C in an oil bath and reacted for 12h.

[0139] S2, after the reaction is completed, the mixture is cooled, and then 200g of propylene glycol monomethyl ether is added and stirred. The diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, washed, dehydrated and then vacuum dried to obtain phenolic resin A with a yield of 80%.

[0140] The weight average molecular weight of the phenolic resin A synthesized in this preparation example is 8400.

[0141] Preparation Example 7. Synthesis of Phenolic Resin B

[0142] S1. Nitrogen is replaced in a 1L three-necked flask with a Dean-Stark water separator. In the flask, 66.1g of resorcinol (0.60mol), 3.81g of p-toluenesulfonic acid (0.02mol), 84.0g of 2,6-bis(hydroxymethyl)-p-cresol (0.5mol) and 150g of propylene glycol monomethyl ether are added. The mixture is stirred at 60°C until the protective agent is completely dissolved. The mixture is heated to 80°C in an oil bath and reacted for 12h.

[0143] S2, after the reaction is completed, the mixture is cooled, and then 100g of propylene glycol monomethyl ether is added and stirred. The diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, washed, dehydrated and then vacuum dried to obtain phenolic resin B with a yield of 75%.

[0144] The weight average molecular weight of the phenolic resin B synthesized in this preparation example is 12,300.

[0145] Preparation Example 8. Synthesis of Phenolic Resin B

[0146] S1. Nitrogen is replaced in a 1L three-necked flask with a Dean-Stark water separator. In the flask, 66.1g of resorcinol (0.60mol), 3.81g of p-toluenesulfonic acid (0.02mol), 41.0g of 37wt% formaldehyde solution (0.5mol) and 150g of propylene glycol monomethyl ether are added. The mixture is stirred at 60°C until the protective body is completely dissolved. The mixture is heated to 80°C in an oil bath and the reaction is carried out for 12h.

[0147] S2, after the reaction is completed, the mixture is cooled, and then 100g of propylene glycol monomethyl ether is added and stirred. The diluted reaction solution is added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, washed, dehydrated and then vacuum dried to obtain phenolic resin B with a yield of 68%.

[0148] The weight average molecular weight of the phenolic resin B synthesized in this preparation example is 12100.

[0149] Example 1.

[0150] The present embodiment provides a phenolic resin composition, comprising 11.4 wt% of phenolic resin A provided in Preparation Example 3, 26.6 wt% of phenolic resin B provided in Preparation Example 7, 4.9 wt% of a photosensitizer, 3.7 wt% of a cross-linking agent, and 53.4 wt% of γ-butyrolactone. The photosensitizer has a structure as shown in Formula (19), 83% of Q in the photosensitizer has a structure as shown in Formula (21), and 17% of Q is a hydrogen atom. The cross-linking agent has a structure as shown in Formula (20).

[0151]

[0152] Example 2.

[0153] The phenolic resin composition provided in this embodiment is substantially the same as that provided in Example 1, except that the structure of the photosensitizer is as shown in formula (22).

[0154]

[0155] Example 3.

[0156] The phenolic resin composition provided in this embodiment is substantially the same as that provided in Example 1, except that the structure of the cross-linking agent is as shown in formula (23).

[0157]

[0158] Examples 4 to 8.

[0159] The phenolic resin compositions provided in Examples 4 to 8 are substantially the same as those in Example 1, and the differences are detailed in Table 1.

[0160] Table 1. Phenolic resin composition

[0161]

[0162] Comparative Example 1.

[0163] The phenolic resin composition provided in this comparative example is substantially the same as that in Example 1, except that the phenolic resin A in the phenolic resin composition is replaced by the phenolic resin B prepared in Preparation Example 7 of equal mass.

[0164] Comparative Example 2.

[0165] The phenolic resin composition provided in this comparative example is substantially the same as that in Example 5, except that the phenolic resin A in the phenolic resin composition is replaced by the phenolic resin B prepared in Preparation Example 8 of equal mass.

[0166] Experimental example.

[0167] (1) Determination of elongation and Young's modulus:

[0168] The phenolic resin compositions provided in Examples 1 to 8 and Comparative Examples 1 and 2 were respectively spin-coated on a silicon wafer, heated on a hot plate at 120°C for 3 minutes, and cured at 230°C for 1 hour under nitrogen protection to obtain a cured film with a thickness of 10 μm. The cured film was cut using a dicing saw, and the cut cured film was peeled off from the wafer using a hydrofluoric acid aqueous solution to obtain a sample with a width of 3 mm and a length of 40 mm. The above sample was left to stand for 24 hours in an atmosphere with a temperature of 23°C and a humidity of 50%, and was measured using a universal testing machine at an experimental speed of 40 mm / min and a load sensor rated value of 2 kgf. The average value of the five largest values ​​in the test results was taken, and the test results are shown in Table 2.

[0169] (2) Thermal cycle stability test:

[0170] The phenolic resin compositions provided in Examples 1 to 8 and Comparative Examples 1 and 2 were spin-coated on silicon wafers, heated on a hot plate at 120° C. for 3 min, and then cured at 230° C. for 1 h under nitrogen protection to obtain a cured film with a thickness of 10 μm. A thermal cycle oven was used to perform 500 cycle tests at -65° C. to 135° C., each for 30 min. Finally, an optical microscope was used to observe the surface of the film to see if there were any cracks. The test results are shown in Table 2.

[0171] Table 2. Performance test of cured film

[0172]

[0173] As shown in Table 2, the phenolic resin compositions provided in Examples 1 to 8 of the present invention are thermally cured at a relatively low temperature of 230°C, and the Young's modulus of the prepared cured film is 1.7 to 2.4 GPa, the elongation is 15 to 24%, the toughness is good and the elasticity is suitable. In addition, the cured film prepared using the phenolic resin compositions provided in Examples 1 to 8 as raw materials is in good condition after 500 cycles at -65°C to 135°C, and no cracks are generated, which has better thermal stability than that of only adding phenolic resin B in Comparative Examples 1 and 2.

[0174] The phenolic resin compositions provided in Examples 1 to 8 of the present invention can be thermally cured at a relatively low temperature to form a cured film, and the cured film has good toughness, elasticity and thermal stability, and can be used as surface protective films for semiconductor devices and light-emitting devices, interlayer insulating films, insulating films for rewiring, protective films for flip-chip devices, protective films for devices with bump structures, and interlayer insulating films for multilayer circuits, etc.

[0175] 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 purpose of the present invention.

Claims

1. A phenolic resin composition, characterized in that: The phenolic resin composition comprises a phenolic resin A having a structure as shown in formula (1), a phenolic resin B having a structure as shown in formula (2), a photoacid generator, a crosslinking agent and a solvent; Formula (1), Formula (2), In formula (1), R1 to R4 are each independently selected from a hydrogen atom, a C1 to C 10 A monovalent aliphatic group and a C1~C 10 One of the monovalent aliphatic groups, and n1≥2; In formula (2), X is selected from hydrogen atom, C2~C 10 Alkoxycarbonyl, C2~C 10 Alkoxycarbonylalkyl, C2~C 10 one of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R5 is selected from C1~C 10 Hydrocarbon, C1~C 10 One of alkoxy, nitro and cyano, and n2≥2, m1=1, 2 or 3, m2=0, 1 or 2, 2≤(m1+m2)≤4; Y in formula (1) and formula (2) is independently selected from a divalent organic group having a structure as shown in formula (3): Formula (3) In formula (3), R6 and R7 are each independently selected from a hydrogen atom or a C1~C 11 A monovalent organic group.

2. The phenolic resin composition according to claim 1, characterized in that: The phenolic resin A is obtained by polymerizing a phenolic compound having a triptycene structure as shown in formula (7) and a polymer component having a structure as shown in formula (8) under the action of a catalyst: Formula (7), Formula (8), In formula (7), R 14 ~R 17 Each independently selected from a hydrogen atom, a C1~C 10 A monovalent aliphatic group and a C1~C 10 One of the monovalent aliphatic groups; In formula (8), R 18 and R 19 Each independently selected from a hydrogen atom or a C1~C 11 A monovalent organic group.

3. The phenolic resin composition according to claim 1, characterized in that: The phenolic resin B is obtained by polymerizing a phenolic compound having a structure as shown in formula (10) and a polymer component having a structure as shown in formula (8) under the action of a catalyst: Formula (8), Formula (10), In formula (8), R 18 and R 19 Each independently selected from a hydrogen atom or a C1~C 11 A monovalent organic group; In formula (10), X is selected from hydrogen atom, C2~C 10 Alkoxycarbonyl, C2~C 10 Alkoxycarbonylalkyl, C2~C 10 One of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 25 Selected from C1~C 10 Hydrocarbon, C1~C 10 One of the alkoxy, nitro and cyano groups, m7=1, 2 or 3, m8=0, 1 or 2, 2≤(m7+m8)≤4.

4. The phenolic resin composition according to claim 1, characterized in that: The photoacid generator is a quinone diazo compound; the photoacid generator is a compound having a diazo-1,2-benzoquinone structure and / or a compound having a diazo-1,2-naphthoquinone structure; The cross-linking agent is selected from one or more of epoxy compounds, oxetane compounds, oxazoline compounds, carbodiimide compounds, aldehydes, isocyanate compounds, melamine and its derivatives, methylol compounds and alkoxymethyl compounds; The solvent is selected from one or more of amide compounds, sulfoxide compounds, urea compounds, ketone compounds, ester compounds, lactone compounds, ether compounds, halogenated hydrocarbon compounds and hydrocarbon compounds.

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

6. The phenolic resin composition according to claim 1, characterized in that: The phenolic resin composition further comprises one or more of a thermal acid generator, a surfactant, a silane coupling agent, a dissolution accelerator and a cross-linking accelerator.

7. A method for preparing a phenolic resin composition, characterized in that: The method comprises the following steps: A phenolic compound having a triptycene structure as shown in formula (7) and a polymer component as shown in formula (8) are polymerized under the action of a catalyst to obtain a phenolic resin A; Formula (7), Formula (8), In formula (7), R 14 ~R 17 Each independently selected from a hydrogen atom, a C1~C 10 A monovalent aliphatic group and a C1~C 10 One of the monovalent aliphatic groups; In formula (8), R 18 and R 19 Each independently selected from a hydrogen atom or a C1~C 11 A monovalent organic group; A phenolic compound having a structure such as that shown in formula (10) and a polymer component having a structure such as that shown in formula (8) are polymerized under the action of a catalyst to prepare a phenolic resin B; Formula (10), In formula (10), X is selected from hydrogen atom, C2~C 10 Alkoxycarbonyl, C2~C 10 Alkoxycarbonylalkyl, C2~C 10 One of alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl, R 25 Selected from C1~C 10 Hydrocarbon, C1~C 10 One of alkoxy, nitro and cyano, m7=1, 2 or 3, m8=0, 1 or 2, 2≤(m7+m8)≤4; Phenolic resin A, phenolic resin B, a photoacid generator, a crosslinking agent, a solvent, and optionally a thermal acid generator, a surfactant, a silane coupling agent, a dissolution accelerator, and a crosslinking accelerator are uniformly mixed to obtain a phenolic resin composition.

8. The phenolic resin composition prepared by the method according to claim 7.

9. Use of the phenolic resin composition according to any one of claims 1 to 6 and 8 in preparing protective films, interlayer insulating films and insulating layers of organic electroluminescent elements of semiconductor elements.

10. A method for preparing a solidified relief pattern, characterized in that: The specific steps include: Forming a photosensitive resin layer on the surface of a substrate using the phenolic resin composition according to any one of claims 1 to 6 and 8; exposing the photosensitive resin layer; removing the exposed part or the unexposed part of the photosensitive resin layer by a developer to obtain a relief pattern; The relief pattern is heated and cured.

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