A resin composition and its applications

Abstract

The present invention discloses a resin composition and its application, which comprises an alkali-soluble resin a and an alkali-soluble resin b. The alkali-soluble resin b includes at least one of a polyimide containing phenolic hydroxyl groups, a polybenzoxazole precursor containing phenolic hydroxyl groups, a polystyrene derivative containing phenolic hydroxyl groups, and a phenolic resin containing phenolic hydroxyl groups. Among them, at least a part of the phenolic hydroxyl groups in these polymers are substituted by tert-butoxycarbonyloxy groups. The alkali-soluble resin b is introduced into the resin composition of the present invention, and the phenolic hydroxyl groups therein are modified by tert-butoxycarbonyloxy groups, improving the light transmittance performance of the resin. Furthermore, it has higher sensitivity and better alkali resistance during the exposure and development process, improving the lithography performance of the photosensitive resin composition.

Description

Technical Field

[0001] The present invention relates to a resin composition, and particularly to a photosensitive resin composition having good lithography performance, and also relates to a cured film, a semiconductor electronic component and a semiconductor device formed by the resin composition. Background Art

[0002] Heat-resistant resins such as polyimide and polybenzoxazole have excellent heat resistance and electrical insulation properties, and therefore can be used for surface protective films, interlayer insulating films of semiconductor elements such as LSIs, insulating layers of organic electroluminescent elements, and the like.

[0003] As a photosensitive resin composition, it is required to have good light transmittance, high resolution after development, excellent film-forming properties after curing, excellent mechanical properties, excellent heat resistance, and good substrate adhesion.

[0004] In order to improve the lithography performance of the photosensitive resin composition, Patent Document 1 (CN103502889B) proposes a method using a polybenzoxazole precursor or a polybenzoxazole resin, which can improve the dissolution rate contrast between the exposed part and the unexposed part during development; Patent Document 2 (CN108027557B) proposes a method of a photosensitive resin composition containing a polyhydroxyamide with a low imidization rate, which can improve the mechanical properties and substrate adhesion of the photosensitive composition; Patent Document 3 (CN109863206B) proposes a method of a photosensitive resin composition containing a phenolic hydroxyl group-modified photosensitive resin composition, which improves the sensitivity and chemical stability resistance of the photosensitive resin composition. However, the above photosensitive resin compositions cannot simultaneously meet the requirements of high light transmittance, high development resolution, excellent mechanical properties, and excellent substrate adhesion. Summary of the Invention

[0005] Based on the deficiencies existing in the prior art, the present invention provides a resin composition. A phenolic hydroxyl group-modified alkali-soluble resin is introduced into the resin composition, and the phenolic hydroxyl group in the resin is modified with tert-butylcarbonyloxy, which improves the light transmittance performance of the resin composition, and further has higher resolution and better alkali resistance during the exposure and development process, so that the photosensitive resin composition has better lithography performance.

[0006] The resin composition of the present invention includes an alkali-soluble resin a and an alkali-soluble resin b.

[0007] In the present invention, the so-called alkali solubility means that: a solution in which the resin is dissolved in γ-butyrolactone is coated on a silicon wafer, pre-baked at 120 °C for 4 minutes to form a pre-baked film with a film thickness of 10 μm ± 0.5 μm, and the pre-baked film is immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23 ± 1 °C for 1 minute, and then rinsed with pure water. The dissolution rate calculated from the reduction of the film thickness at this time is 50 nm / minute or more.

[0008] Furthermore, the alkali-soluble resin a includes at least one of polyimide, polyimide precursor, and polybenzoxazole precursor, or at least one of copolymers of two or more of polyimide, polyimide precursor, and polybenzoxazole precursor; to meet the requirement of alkali solubility, groups that can be alkali-soluble, such as phenolic hydroxyl groups and carboxyl groups, are contained in the main chain of these resins.

[0009] Furthermore, the polyimide contains a structural unit represented by the following general formula (6).

[0010]

[0011] In general formula (6), X4 is from a dianhydride monomer and represents an organic group with a valence of 4 to 10, Y4 is from a diamine monomer and represents an organic group with a valence of 2 to 8, and there is no case where the phenolic hydroxyl group in Y4 is modified by tert-butoxycarbonyloxy. R 10 and R 11 each independently represents a carboxyl group, a sulfonic acid group, or a phenolic hydroxyl group. P and q each independently represent an integer from 0 to 6, such as 0, 1, 2, 3, 4, 5, 6.

[0012] Furthermore, the polybenzoxazole precursor contains a structural unit represented by the following general formula (7).

[0013]

[0014] In general formula (7), X5 and Y5 each independently represent an organic group with a valence of 2 to 8, X5 is from a dicarboxylic acid monomer or a diacyl chloride monomer, Y5 is from a diamine monomer, and there is no case where the phenolic hydroxyl group in Y5 is modified by tert-butoxycarbonyloxy. R 12 and R 13 each independently represents a phenolic hydroxyl group, a sulfonic acid group, or a carboxyl group, and R 12 can be a single group or different groups can coexist. Similarly, R 13 can be a single group or different groups can coexist. r and s each independently represent an integer from 0 to 6, such as 0, 1, 2, 3, 4, 5, 6, where r + s > 0.

[0015] Furthermore, the polyimide precursor contains a structural unit represented by the following general formula (8).

[0016]

[0017] In general formula (8), X6 and Y6 each independently represent an organic group with a valence of 2 to 8, X6 is from a dianhydride monomer, Y6 is from a diamine monomer, and there is no case where the phenolic hydroxyl group in Y6 is modified by tert-butoxycarbonyloxy. R 14 is a hydrogen atom or an alkyl group. When R14 When it is an alkyl group, it is introduced by an esterifying reagent.

[0018] Furthermore, the alkali-soluble resin a can be a resin obtained by copolymerizing the structural unit represented by the general formula (7) and the structural unit represented by the general formula (8).

[0019] Furthermore, the polyimide, polyimide precursor, polybenzoxazole precursor, and their copolymers containing the structural unit represented by the general formula (6) or / and (7) or / and (8) preferably have 5 to 100,000 structural units represented by the general formula (6) and / or (7) and / or (8), such as 5, 10, 50, 100, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000.

[0020] Furthermore, in the alkali-soluble resin a, in addition to the structural units represented by the general formulas (6), (7), and (8), other structural units may also be present. In this case, it is preferable to have 50% or more of the structural units represented by the general formula (6) and / or (7) and / or (8) in all the structural units, such as 50%, 60%, 70%, 80%, 90%, 100%.

[0021] Furthermore, when the alkali-soluble resin a is a polyimide precursor, the polyimide precursor is at least one of polyamic acid and polyamide ester. When the polyimide precursors are different, the reaction raw materials used are different. For example, when the polyimide precursor is polyamic acid, it can be obtained by reacting at least one dianhydride monomer and at least two diamine monomers. When the polyimide precursor is polyamide ester, it can be obtained by reacting at least one dianhydride monomer, at least two diamine monomers, and an esterifying reagent as raw materials. The specific reaction method is not limited. For example, the dianhydride monomer and diamine monomer can be reacted first to obtain polyamic acid, and then the esterifying reagent can be added for reaction to obtain polyamide ester; or the dianhydride monomer can be reacted with the esterifying reagent first, and then reacted with the diamine monomer to obtain polyamide ester.

[0022] Furthermore, when the alkali-soluble resin a is a polybenzoxazole precursor, regarding the manufacturing method of the polyhydroxyamide as the polybenzoxazole precursor, for example, a method of subjecting a diamine monomer and a dicarboxylic acid to a condensation reaction can be cited. Specifically, for example, a method of reacting a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a diamine monomer thereto; a method of dropping a solution of a dicarboxylic acid dichloride into a solution of a diamine monomer added with a tertiary amine such as pyridine; and so on.

[0023] Further, when the alkali-soluble resin a is a polyimide, as a method for producing the polyimide, for example, a method of imidizing the polyamic acid or polyamic acid ester obtained by the aforementioned method to obtain a polyimide can be cited. As the imidization method, chemical treatment based on acids, alkalis, etc., heat treatment, etc. can be cited.

[0024] Further, X4 in the above general formula (6) and X6 in the general formula (8) represent structural groups in the dianhydride monomer, and preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.

[0025] Further, the dianhydride monomer can also be selected from reports of prior art, such as one or more of pyromellitic dianhydride, 4,4'-oxybisphthalic anhydride, 3,3’,4,4’-biphenyltetracarboxylic dianhydride, 2,2’,3,3’-benzophenonetetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and the like.

[0026] Further, in the above general formula (7), X5 is introduced by the dicarboxylic acid compound monomer and is a divalent to octavalent organic group, and preferably an organic group having 5 to 40 carbon atoms containing an aromatic or cycloaliphatic group.

[0027] Examples of the dicarboxylic acid compound include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid; tricarboxylic acids such as trimellitic acid, pyromellitic acid, diphenyl ether trimellitic acid, biphenyl trimellitic acid; tetracarboxylic acids such as pyromellitic acid, 3,3’,4,4’-biphenyltetracarboxylic acid, 2,2’,3,3’-biphenyltetracarboxylic acid, 3,3’,4,4’-benzophenonetetracarboxylic acid, 2,2’,3,3’-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, butanetetracarboxylic acid and other aliphatic tetracarboxylic acids, and aliphatic tetracarboxylic acids containing cycloaliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these can be used.

[0028] Furthermore, Y4 in the general formula (6) above, Y5 in the general formula (7), and Y6 in the general formula (8) are introduced by diamine monomers, which are organic groups with a valence of 2 to 8, preferably organic groups with 5 to 40 carbon atoms containing aromatic or cycloaliphatic groups.

[0029] Furthermore, the diamine monomer can be selected from at least one of the following compounds: diamines containing hydroxyl groups such as 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)propane, and bis(3-amino-4-hydroxy)biphenyl; diamines containing sulfonic acid such as 3-sulfonic acid-4,4'-diaminodiphenyl ether; diamines containing mercapto groups such as dimercaptobenzene diamine; substituted or unsubstituted aromatic diamines; alicyclic diamines such as cyclohexanediamine and methylenebis(cyclohexylamine).

[0030] Furthermore, the substituted or unsubstituted aromatic diamines can be selected from the following compounds:

[0031]

[0032]

[0033] Furthermore, the diamine monomer can also be an aliphatic diamine having a siloxane structure to improve the adhesion between the resin composition and the substrate, and at the same time not reduce the heat resistance of the cured film formed by the resin composition. The aliphatic diamine having a siloxane structure can be bis(3-aminopropyl)tetramethyldisiloxane, which accounts for 1 to 15% of the total molar amount of the diamine monomer, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%.

[0034] Furthermore, in order to better adjust the molecular weight of the alkali-soluble resin a of the present invention, a certain amount of capping agent can be added during polymerization. The capping agent can be one or a combination of the following monofunctional aromatic amines and monofunctional aromatic anhydrides, but is not limited thereto:

[0035] Monofunctional aromatic amines: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-o-toluic acid, 3-amino-m-toluic acid, 1-amino-2-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-carboxy-2-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-8-aminonaphthalene, 3-amino-4,6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-3-hydroxyquinoline, 4-aminophenylacetylene, etc.

[0036] Monofunctional aromatic anhydrides: maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, cyclohexylpentanedicarboxylic anhydride, 4-alkynylphthalic anhydride, etc.

[0037] Furthermore, the introduction ratio of the above-mentioned capping agent accounts for 0.1% - 50% of the total molar amount of all diamine monomers or dianhydride monomers input, such as 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, and further preferably 1% - 30%; this dosage range can improve its storage stability and mechanical properties without reducing the molecular weight of the alkali-soluble resin a.

[0038] Furthermore, the esterification reagent can also be selected from the reports of the prior art, such as one or more of methanol, ethanol, n-butanol, 2-hydroxyethyl methacrylate, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide dimethyl ethyl acetal, 4-nitrobenzyl alcohol, etc.

[0039] Furthermore, for the detailed preparation methods of polyamic acid, polyamide ester, polyimide, and polybenzoxazole precursor, they can be selected through the reports of the prior art, which is not difficult for those skilled in the art.

[0040] Further, in the synthesis process of the alkali-soluble resin a, organic solvents are required. Examples of the organic solvents include: amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylallylurea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide; cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone; carbonates such as ethylene carbonate, propylene carbonate; diols such as triethylene glycol; phenols such as m-cresol, p-cresol; acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, ethyl lactate, etc., but are not limited to these.

[0041] Further, in the synthesis process of the above alkali-soluble resin a, the obtained product needs to be put into a large amount of water or a mixed solution of methanol and water, etc. to precipitate it, and then the pure alkali-soluble resin a is obtained by filtration and drying. The drying temperature is preferably 40 to 100 °C, more preferably 50 to 80 °C. Through this operation, oligomer components such as unreacted monomers, dimers, and trimers can be removed, and the film properties after thermal curing can be improved.

[0042] Further, the alkali-soluble resin b is a resin containing phenolic hydroxyl groups and the phenolic hydroxyl groups are modified. The alkali-soluble resin b includes at least one of a polyimide containing phenolic hydroxyl groups, a polybenzoxazole precursor containing phenolic hydroxyl groups, a polystyrene derivative containing phenolic hydroxyl groups, and a phenolic resin containing phenolic hydroxyl groups. Among them, at least a part of the phenolic hydroxyl groups in these polymers such as the polyimide containing phenolic hydroxyl groups, the polybenzoxazole precursor containing phenolic hydroxyl groups, the polystyrene derivative containing phenolic hydroxyl groups, and the phenolic resin containing phenolic hydroxyl groups are substituted by tert-butoxycarbonyloxy groups.

[0043] The substitution rate or modification rate of the phenolic hydroxyl groups can be measured by the following method. For example, from 1 1H-NMR, the "number of protons of phenolic hydroxyl groups" and the "number of protons of aromatic C-H" in the repeating structural unit of the resin containing phenolic hydroxyl groups before and after modification are obtained, and then the phenolic hydroxyl group content before and after modification is calculated, and further the phenolic hydroxyl group modification rate is obtained. The structural unit of the resin containing phenolic hydroxyl groups before modification can be analyzed by thermal decomposition GC / MS, for example.

[0044] Phenolic hydroxyl group content before modification = number of protons of phenolic hydroxyl groups before modification / number of protons of aromatic C-H before modification;

[0045] Phenolic hydroxyl group content after modification = number of protons of phenolic hydroxyl groups after modification / number of protons of aromatic C-H after modification;

[0046] Phenolic hydroxyl group modification rate = (Phenolic hydroxyl group content before modification - Phenolic hydroxyl group content after modification) / Phenolic hydroxyl group content before modification * 100%.

[0047] Furthermore, the modification rate of the phenolic hydroxyl groups in the alkali-soluble resin b is greater than or equal to 50%, such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc., and any range therebetween.

[0048] In a specific embodiment of the present invention, the alkali-soluble resin b contains the structural formula shown in the following general formula (1):

[0049]

[0050] In the above formula (1), R1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, etc.; Z represents an organic group containing a polymer long-chain structure, such as a polyimide structure group, a polyimide precursor structure group, a polybenzoxazole precursor group, a polystyrene group, a phenolic resin group, etc.; R2 represents hydrogen or tert-butylcarbonyloxy, and in the alkali-soluble resin b, part or all of R2 is tert-butylcarbonyloxy.

[0051] In a specific embodiment of the present invention, the alkali-soluble resin b contains the polyimide structure shown in the following general formula (2):

[0052]

[0053] In the above general formula (2), X1 is derived from a dianhydride monomer, Y1 is derived from a diamine monomer, the diamine monomer contains phenolic hydroxyl groups, and R3 represents hydrogen or tert-butylcarbonyloxy.

[0054] In a specific embodiment of the present invention, the alkali-soluble resin b contains the polybenzoxazole precursor structure shown in the following general formula (3):

[0055]

[0056] In the above general formula (3), X2 is derived from a dicarboxylic acid monomer or a dicarboxylic acid derivative monomer, Y2 is derived from a diamine monomer, the diamine monomer contains phenolic hydroxyl groups, and R4 represents hydrogen or tert-butylcarbonyloxy.

[0057] In a specific embodiment of the present invention, the alkali-soluble resin b contains the polystyrene derivative structure shown in the following general formula (4):

[0058]

[0059] In the above general formula (4), R5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, or pentyl; R6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, or pentyl; R7 represents hydrogen or tert-butoxycarbonyloxy.

[0060] In a specific embodiment of the present invention, the alkali-soluble resin b contains a phenolic resin structure represented by the following general formula (5):

[0061]

[0062] In the above general formula (5), X3 represents -CH2-, -CHOCH2-, or a divalent aromatic group, R8 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, or pentyl; R9 represents hydrogen or tert-butoxycarbonyloxy.

[0063] As a method for manufacturing the above alkali-soluble resin b, for example, it can be obtained by modifying phenolic hydroxyl groups using a polyimide containing phenolic hydroxyl groups, a polybenzoxazole precursor containing phenolic hydroxyl groups, a polystyrene derivative containing phenolic hydroxyl groups, or a phenolic resin containing phenolic hydroxyl groups as raw materials. Examples of the modification method include reacting at least one of a polyimide containing phenolic hydroxyl groups, a polybenzoxazole precursor containing phenolic hydroxyl groups, a polystyrene derivative containing phenolic hydroxyl groups, a phenolic resin containing phenolic hydroxyl groups, etc. with di-tert-butyl dicarbonate under the catalysis of DMAP to convert the phenolic hydroxyl groups into tert-butoxycarbonyloxy groups.

[0064] Furthermore, the polyimide containing phenolic hydroxyl groups can be obtained by imidizing a polyamic acid or a polyamic acid ester containing phenolic hydroxyl groups. As the imidization method, chemical treatment based on acids, bases, etc., heat treatment, etc. can be cited. The polyamic acid or polyamic acid ester containing phenolic hydroxyl groups can be obtained according to the preparation methods of the above polyamic acid and polyamic acid ester, and phenolic hydroxyl groups can be introduced by selecting diamines containing phenolic hydroxyl groups.

[0065] Furthermore, the polybenzoxazole precursor containing phenolic hydroxyl groups can be obtained by a method of condensing a diamine containing phenolic hydroxyl groups with a dicarboxylic acid.

[0066] Furthermore, the polystyrene derivative containing phenolic hydroxyl groups can be obtained by polymerizing aromatic vinyl compounds. Examples of the aromatic vinyl compounds include aromatic vinyl compounds having phenolic hydroxyl groups such as p-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol; and aromatic vinyl compounds without hydroxyl groups such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene. Two or more of these aromatic vinyl compounds containing phenolic hydroxyl groups or any combination of aromatic vinyl compounds containing phenolic hydroxyl groups and aromatic vinyl compounds without hydroxyl groups can be used. The polymerization conditions can be carried out in the manner reported in the prior art.

[0067] Furthermore, the phenolic resin can be obtained, for example, by polymerizing phenols and aldehydes. Examples of the phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene bisphenol, methylene bis(p-cresol), resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. Two or more of these can be used. The polymerization conditions can be carried out in the manner reported in the prior art.

[0068] Furthermore, the reaction temperature of the polyimide containing phenolic hydroxyl groups, the polybenzoxazole precursor containing phenolic hydroxyl groups, the polystyrene derivative containing phenolic hydroxyl groups or the phenolic resin containing phenolic hydroxyl groups with di-tert-butyl dicarbonate is preferably carried out at room temperature conditions, and the modification of phenolic hydroxyl groups can be effectively carried out. The molar ratio of these resins containing phenolic hydroxyl groups to di-tert-butyl dicarbonate is preferably 1:1. The amount of DMAP is 3-6% of di-tert-butyl dicarbonate.

[0069] Furthermore, the molecular weight of the alkali-soluble resin b is 2000-50000.

[0070] Furthermore, the mass ratio of the alkali-soluble resin a to the alkali-soluble resin b is 1-9:1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, and any range values therebetween.

[0071] Further, the composition further comprises a photosensitizer, an auxiliary agent and a solvent.

[0072] Further, when the photosensitizer is a photoacid generator, when the alkali-soluble resin and the photoacid generator are used in combination, the resulting resin composition is a positive photosensitive resin composition.

[0073] Further, as the photoacid generator of the positive photosensitive resin composition, a quinone diazide compound can be preferably used. As the quinone diazide compound, compounds obtained by bonding a sulfonic acid of diazoquinone to a polyhydroxy compound through an ester bond, compounds obtained by bonding a sulfonic acid of diazoquinone to a polyamino compound through a sulfonamide bond, compounds obtained by bonding a sulfonic acid of diazoquinone to a polyhydroxy polyamino compound through an ester bond and / or a sulfonamide bond, etc. can be cited. All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds may not be substituted by quinone diazide groups, but preferably, on average, 40 mol% or more of the entire functional groups are substituted by quinone diazide groups. By using such a quinone diazide compound, a positive photosensitive resin composition that is sensitive to ordinary ultraviolet rays, namely the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, can be obtained.

[0074] Further, the quinone diazide compound preferably contains an ester of a phenolic compound and diazoquinone-4-sulfonyl. Thereby, higher sensitivity and higher resolution can be obtained under i-line exposure.

[0075] Preferably, the photosensitizer of the present invention is 4-hydroxyphenyl-2,3,4-trihydroxyphenylmethanone and 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid (Toagosei Co., Ltd., 4NT-300), 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid (Toagosei Co., Ltd., 4NT-350).

[0076] In the photosensitive resin composition of the present invention, based on 100 parts by mass of the total mass of the alkali-soluble resin a and the alkali-soluble resin b, the amount of the quinone diazide compound used as the photosensitizer is 1 to 50 parts by mass, such as 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, and preferably 10 to 40 parts by mass. By making the content of the quinone diazide compound within this range, the contrast between the exposed part and the unexposed part can be obtained, thereby enabling higher sensitization, and no residue is observed when the content is high. In addition, a sensitizer or the like can be added as needed.

[0077] Furthermore, the additive in the photosensitive resin composition is for improving the adhesion between the resin film and the substrate. The additive is a adhesion promoter, and preferably the adhesion promoter is a silane coupling agent, including one or a combination of more than one of p-styryltrimethoxysilane, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxymercaptopropylsilane, etc.

[0078] In the photosensitive resin composition of the present invention, based on 100 parts by mass of the total mass of the alkali-soluble resin a and the alkali-soluble resin b, the amount of the silane coupling agent used as the additive is 0.01 to 5 parts by mass, such as 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts.

[0079] Furthermore, examples of the solvent in the photosensitive resin composition include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylallylurea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropanamide, etc.; ether solvents such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, etc.; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate, etc.; alcohol solvents such as diacetone alcohol, 3-methyl-3-methoxybutanol, etc.; aromatic hydrocarbon solvents such as toluene, xylene, etc. The solvent can be one kind or a combination of multiple kinds.

[0080] Regarding the content of the solvent, in order to dissolve the photosensitive resin composition, based on 100 parts by mass of the total mass of the alkali-soluble resin a and the alkali-soluble resin b, the solvent is 70 to 1800 parts by mass, such as 70 parts, 100 parts, 200 parts, 300 parts, 400 parts, 500 parts, 600 parts, 700 parts, 800 parts, 900 parts, 1000 parts, 1100 parts, 1200 parts, 1300 parts, 1400 parts, 1500 parts, 1600 parts, 1700 parts, 1800 parts. In order to form a coating film with a film thickness of 1 μm or more, the solvent is preferably 100 to 1500 parts by mass.

[0081] Furthermore, a method for manufacturing the resin composition of the present invention will be described. For example, the resin composition can be obtained by mixing and dissolving the above-mentioned alkali-soluble resins a and b, a photosensitizer, an auxiliary agent, a solvent, etc. As the dissolution method, heating and stirring can be cited. When heating is carried out, the heating temperature is preferably set within a range that does not damage the performance of the resin composition, usually from room temperature to 80°C. In addition, the dissolution order of each component is not particularly limited. When stirring is carried out, the rotation speed is preferably set within a range that does not impair the performance of the resin composition, usually from 200 rpm to 2000 rpm. When stirring is carried out, heating can also be carried out as needed, usually from room temperature to 80°C.

[0082] Furthermore, the viscosity of the resin composition of the present invention is preferably 2 to 5000 mPa·s, such as 2 mPa·s, 5 mPa·s, 10 mPa·s, 50 mPa·s, 100 mPa·s, 500 mPa·s, 1000 mPa·s, 1500 mPa·s, 2000 mPa·s, 2500 mPa·s, 3000 mPa·s, 3500 mPa·s, 4000 mPa·s, 4500 mPa·s, 5000 mPa·s. By adjusting the solid content concentration so that the viscosity is 2 mPa·s or more, it is easy to obtain a desired film thickness. On the other hand, when the viscosity is 5000 mPa·s or less, it is easy to obtain a coating film with high coating uniformity. A resin composition having such a viscosity can be easily obtained, for example, by making the solid content concentration 5 to 60% by mass.

[0083] In order to ensure the purity of the photosensitive resin composition, a filtration device such as filter paper, a filter membrane, or a filter can be used to filter the photosensitive resin composition. The filtration method is not particularly limited, and pressure filtration using a filter with a pore size of 0.2 to 5 μm is preferred.

[0084] As a method for coating the photosensitive resin composition on a substrate, spin coating, spray coating, roll coating, screen printing, or coating methods using a doctor blade coater, a calender coater, a slot coater, a roll coater, a comma roll coater, an intaglio coater, etc. can be cited. The coating film thickness varies depending on the coating method, the solid content of the resin composition, the viscosity of the resin composition, etc., and the film thickness after drying is preferably in the range of 0.5 to 100 μm.

[0085] The drying method can be selected from an oven, a hot plate, an infrared heater, etc. The drying temperature and drying time are controlled within a range that can volatilize the organic solvent, and it is preferably set within a range suitable for making the photosensitive resin composition film in an uncured or semi-cured state. Specifically, the drying temperature is preferably 40 to 120°C, and the drying time is preferably 1 to 60 minutes. Furthermore, stepwise heating can also be used, for example, heat treatment is carried out at 70°C, 80°C, and 90°C for 1 minute each.

[0086] The present invention provides a resin sheet, which is formed from the above resin composition.

[0087] Furthermore, the resin sheet of the present invention can be obtained, for example, by the following method: coating the above-mentioned resin composition on a peelable substrate such as polyethylene terephthalate (PET) to obtain a coated film of the resin composition, and drying it. A protective film can also be laminated on the coated film.

[0088] As the coating method, for example, spin coating method, slit coating method, dip coating method, spraying method, printing method, etc. can be cited. Among these, the slit coating method is preferred because it can coat with a small amount of coating liquid, which is advantageous in terms of cost reduction. The amount of coating liquid required for the slit coating method is about 1 / 5 to 1 / 10 of that of the spin coating method, for example. The coating speed is usually in the range of 10 mm / second to 400 mm / second. The film thickness of the coated film varies depending on the solid content concentration, viscosity, etc. of the resin composition. Usually, the coated film is dried to a film thickness of 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0089] Before coating, the substrate to be coated with the resin composition can be pretreated with a bonding improver, namely a silane coupling agent. Examples of the silane coupling agent include one or a combination of styryltrimethoxysilane, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxymercapto propylsilane, etc. Its function is to improve the bonding property and peelability. As the pretreatment method, for example, the following method can be cited: treating the surface of the substrate with a solution obtained by dissolving the silane coupling agent in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. at a concentration of 0.5 to 20% by mass. As the treatment method for the substrate surface, spin coating method, slot die coating method, bar coating method, dip coating method, spraying method, vapor treatment method, etc. can be cited.

[0090] After coating, a reduced-pressure drying treatment is carried out as needed. Usually, each substrate formed with a coated film is subjected to reduced-pressure drying. Regarding the reduced-pressure drying speed, the normal reduced-pressure drying time is mostly about 30 seconds to 100 seconds. In the state of having a coated substrate, the ultimate pressure in the vacuum chamber at the end of reduced-pressure drying is usually 100 Pa or less. By making the ultimate pressure 100 Pa or less, a drying state with reduced stickiness on the surface of the coated film can be achieved. Thus, surface contamination and generation of fine particles during subsequent substrate handling can be suppressed.

[0091] After coating or vacuum drying, the coated film is usually heated and dried. This process is also called pre-baking. Heating is carried out using a hot plate, an oven, infrared rays, etc. The heating temperature and heating time vary depending on the type and purpose of the coated film. The heating temperature is preferably 50°C to 180°C, and the heating time is preferably 1 minute to several hours.

[0092] When the resin sheet is photosensitive, a pattern can be formed. For example, by irradiating actinic rays through a mask having a desired pattern onto the photosensitive resin sheet for exposure and then developing it, a desired pattern can be formed.

[0093] The obtained photosensitive resin composition film is irradiated with actinic rays through a mask plate for exposure. As the actinic rays for exposure, there are ultraviolet rays, visible light, electron rays, X-rays, etc. In the present invention, i-ray (365 nm), h-ray (405 nm) or g-ray (436 nm) of a mercury lamp is preferably used.

[0094] When forming a pattern, after exposure, the unexposed portion is removed using a developer. As the developer, an aqueous solution of a basic compound such as tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, 1,6-hexanediamine, etc. is preferred. Optionally, one or more polar solvents selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc.; alcohols such as methanol, ethanol, isopropanol, etc.; esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc.; and compounds such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. can be added to these alkaline aqueous solutions.

[0095] For development, the above developer can be sprayed onto the film-attached surface of the substrate, or the film together with the substrate can be immersed in the developer. Ultrasonic waves can also be applied while the substrate is immersed in the developer. Additionally, the developer can be sprayed onto the film surface while rotating the substrate. The development time, development steps, and temperature of the developer are not limited as long as the unexposed portion can be removed. To process fine patterns or remove residues between patterns, it is preferred to perform further development after removing the unexposed portion.

[0096] After development, rinsing treatment with water can also be carried out. Rinsing treatment can also be carried out by adding alcohols such as ethanol, isopropanol, etc. and esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc. to water.

[0097] In order to further improve the resolution and expand the developing process range, baking treatment can be carried out before development. As the temperature of the baking treatment, 50-180°C is preferred, and 60-120°C is more preferred. The baking treatment time is preferably 5 s to 60 min.

[0098] From the perspective of reducing solvents, solid contents, moisture, etc. of the photosensitive resin composition film remaining after pattern formation, heating and drying is preferably carried out under the condition of 60-200°C. The heating and drying time is preferably 1-60 min.

[0099] The present invention provides a cured film which is obtained by curing the above resin sheet or by curing the above resin composition.

[0100] Furthermore, the heating temperature during curing is 150°C to 450°C, and more preferably 180°C to 350°C. The heating treatment during curing can be selected to increase the temperature step by step or continuously within the specified temperature range. The heating treatment time is preferably 30 min to 5 h.

[0101] Furthermore, the film thickness of the cured film can be set arbitrarily, and preferably 0.5 μm to 100 μm.

[0102] The photosensitive resin composition of the present invention is applicable to surface protective films of semiconductor elements, ultra-thin flexible printed circuit boards, interlayer insulating films, insulating layers of organic light-emitting devices, etc. In the present invention, a semiconductor electronic component or a semiconductor device is specifically provided, and the semiconductor electronic component or the semiconductor device is provided with an interlayer insulating layer and / or a surface protective film, and the interlayer insulating layer and / or the surface protective layer contains the above cured film.

[0103] Furthermore, in the above semiconductor electronic component or semiconductor device, a plurality of substrates are bonded by the cured film of the photosensitive resin composition of the present invention, or a substrate is bonded to other components. The cured film of the photosensitive resin composition can be directly prepared by coating the photosensitive resin composition on a substrate as a raw material.

[0104] When preparing a semiconductor electronic component or a semiconductor device, the steps can be: coating a photosensitive resin composition on a semiconductor wafer on which an image sensor element is formed to form a photosensitive resin composition cured film. The photosensitive resin composition cured film is exposed and developed, the resin film on the sensor part is removed, and the resin film around the sensor is retained to obtain a sensor wafer with a wiring pattern.

[0105] The present invention has the following beneficial effects:

[0106] 1. The present invention provides a photosensitive resin composition. An alkali-soluble resin a with phenolic hydroxyl groups modified by tert-butoxycarbonyloxy is added to the resin composition, which improves the light transmittance of the resin, and thus has higher photosensitivity and better alkali resistance during the exposure and development process, improves the lithography performance of the photosensitive resin composition, and reduces the chromaticity of the cured film.

[0107] 2. The present invention uses the alkali-soluble resin a and the alkali-soluble resin b in combination, which not only improves the lithography performance of the photosensitive resin composition, but also enhances the mechanical properties and the adhesion to the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0108] Figure 1 1H-NMR spectrum of the modified polyimide resin prepared in Synthesis Example 5 1 graph. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0109] In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the embodiments of the present invention will be described clearly and completely below. The described embodiments are some, but not all, of the embodiments of the present invention. Based on the technical solutions of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present invention. For those conditions not specified in the embodiments, they shall be carried out according to conventional conditions or conditions recommended by the manufacturer.

[0110] Furthermore, for the weight average molecular weight Mw and the number average molecular weight Mn of the resin in the embodiments of the present invention, they can be easily measured in the form of values converted with polystyrene by gel permeation chromatography (GPC).

[0111] Synthesis of Resin Polymer

[0112] Synthesis Example 1: Synthesis of Polyimide

[0113] Under a nitrogen stream, 31.02 g (0.1 mol) of 4,4'-oxydiphthalic anhydride (ODPA) and 100 g of N-methylpyrrolidone (NMP) were successively added to a 500 mL three-necked flask equipped with a stirrer, a dropping funnel, and a thermometer, and stirred and dissolved at room temperature to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was successively added with 31.13 g (0.085 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 100 g of N-methylpyrrolidone, and stirred and dissolved to obtain a diamine solution. The diamine solution was added dropwise to the above dianhydride solution, and the reaction was carried out at 50 °C for 2 h after the addition was completed. After the reaction was completed, 2.18 g (0.02 mol) of 3-aminophenol as a capping agent was added, and the reaction was carried out at 50 °C for 2 h. Then the temperature was raised to 180 °C, and the reaction was carried out for 3 h. After the reaction was completed, the reaction solution was poured into 3 L of deionized water, and the polymer was precipitated to obtain a white precipitate. After filtration, it was washed three times with deionized water, placed in a vacuum oven, and dried at 50 °C for 72 h to obtain polyimide A-1. It was measured that its number-average molecular weight was 14,537 and its weight-average molecular weight was 19,602. Synthesis Example 2: Synthesis of polybenzoxazole precursor

[0114] Under a dry nitrogen stream, 59.02 g (0.2 mol) of diphenyl ether-4,4'-dicarbonyl chloride, 65.93 g (0.18 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), and 4.36 g (0.04 mol) of 3-aminophenol were dissolved in 570 g of NMP, and then reacted at 75 °C for 12 h. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water / methanol = 3 / 1 (volume ratio) of 3 L to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and dried in a vacuum dryer at 80 °C for 24 h to obtain a polybenzoxazole (PBO) precursor (A-2). It was measured that the number-average molecular weight of the polybenzoxazole precursor A-2 was 11,624 and the weight-average molecular weight was 15,489.

[0115] Synthesis Example 3: Synthesis of polyhydroxystyrene resin

[0116] To a mixed solution containing 500 mL of tetrahydrofuran and 0.64 g (0.01 mol) of sec-butyl lithium as an initiator, 132.2 g (0.75 mol) of p-tert-butoxystyrene and 26.0 g (0.25 mol) of styrene were added, and polymerization was carried out while stirring for 3 h. Then, 0.1 mol of methanol was added to the reaction solution to stop the polymerization reaction. The obtained reaction mixture was poured into methanol, and the precipitated polymer was dried to obtain a white polymer. The obtained white polymer was dissolved in 400 mL of acetone, a small amount of concentrated hydrochloric acid was added at 60 °C, and after stirring for 7 h, it was poured into 3 L of water to precipitate the polymer, and p-tert-butoxystyrene was deprotected to be converted into hydroxystyrene. The obtained reaction product was washed and dried to obtain a purified hydroxystyrene resin (A-3). The weight-average molecular weight of the obtained hydroxystyrene resin (A-3) was 3789.

[0117] Synthesis Example 4: Synthesis of phenolic resin

[0118] Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g (0.93 mol of formaldehyde) of 37 wt% aqueous formaldehyde solution, 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were added to a 500 ml flask. Then, the flask was immersed in an oil bath to reflux the reaction solution, and a polycondensation reaction was carried out for 7 h. Then, after cooling the temperature of the oil bath to room temperature over 3 h, the pressure in the flask was reduced to 40 - 67 hPa to remove the volatile components, the resin was cooled to room temperature, and γ-butyrolactone (GBL) was added to obtain a solution (A-4) of a phenolic resin as an alkali-soluble resin with the solid component concentration adjusted to 50 wt%. Its weight-average molecular weight was measured to be 7582.

[0119] Synthesis Example 5: Synthesis of modified polyimide resin

[0120] 6.36 g (0.01 mol) of polyimide resin (A-1) was taken and added to 20 g of N-methylpyrrolidone (NMP), stirred and dissolved, then 0.0611 g (0.5 mmol) of p-dimethylaminopyridine (DMAP) and 2.18 g (0.01 mol) of di-tert-butyl dicarbonate were added in sequence, and the reaction was stirred at room temperature for 2 h. After the reaction was completed, the reaction solution was poured into 500 ml of pure water to precipitate a white solid, washed 3 times with 2 L of pure water, filtered to obtain a resin solid, and dried in a vacuum environment at 60 °C for 24 h to obtain a modified polyimide resin A-5 in which the phenolic hydroxyl group was replaced by tert-butoxycarbonyloxy. It was measured that the number-average molecular weight was 14662, the weight-average molecular weight was 19851, and the modification rate of the phenolic hydroxyl group was 65% by nuclear magnetic resonance hydrogen spectrum characterization and calculation.

[0121] Synthesis Example 6: Synthesis of Modified Polybenzoxazole Precursor Resin

[0122] The modified polybenzoxazole precursor resin A-6 with phenolic hydroxyl groups substituted by tert-butoxycarbonyloxy groups was prepared in the same manner as in Synthesis Example 5, except that 6.36 g (0.01 mol) of polyimide resin (A-1) was replaced with 5.90 g (0.01 mol) of polybenzoxazole precursor (A-2). It was determined that the number-average molecular weight of the modified polybenzoxazole precursor resin A-6 was 15008, and the weight-average molecular weight was 19997. The modification rate was characterized and calculated by 1H NMR, and the modification rate of phenolic hydroxyl groups was 62%.

[0123] Synthesis Example 7: Synthesis of Modified Polyhydroxystyrene Resin

[0124] The modified polyhydroxystyrene resin A-7 with phenolic hydroxyl groups substituted by tert-butoxycarbonyloxy groups was prepared in the same manner as in Synthesis Example 5, except that 6.32 g (0.01 mol) of polyimide resin (A-1) was replaced with 1.58 g (0.01 mol) of polyhydroxystyrene resin (A-3). It was determined that the weight-average molecular weight of the modified polyhydroxystyrene resin A-7 was 3875. The modification rate was characterized and calculated by 1H NMR, and the modification rate of phenolic hydroxyl groups was 82%.

[0125] Synthesis Example 8: Synthesis of Modified Phenolic Resin

[0126] Take 1.0 g of the phenolic resin (A-4) solution in Synthesis Example 4, add 20 g of N-methylpyrrolidone (NMP), stir to dissolve, and then add 0.0611 g (0.5 mmol) of DMAP and 2.18 g (0.01 mol) of di-tert-butyl dicarbonate in sequence, and stir and react at room temperature for 2 h. After the reaction, a modified phenolic resin solution (A-8) with a solid content of 50% wt in which phenolic hydroxyl groups were substituted by tert-butoxycarbonyloxy groups was obtained. It was determined that the weight-average molecular weight of the modified phenolic resin A-8 was 7700. The modification rate was characterized and calculated by 1H NMR, and the modification rate of phenolic hydroxyl groups was 76%.

[0127] Synthesis Example 9: Synthesis of Alkaline-Soluble Polyamide Resin (Copolymer Resin of Polybenzoxazole Precursor and Polyimide Precursor)

[0128] Under a dry nitrogen stream, BAHF (36.63 g, 0.1 mol) was dissolved in 205 g of NMP. To this, NMP (20 g) and 1,1'-(4,4'-oxydibenzoyl) diimidazole PBOM (28.67 g, 0.08 mol) were added simultaneously, and the reaction was carried out at 85 °C for 3 hours. Next, NMP (20 g), BAHF (0.37 g, 0.001 mol), and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (1.49 g, 0.006 mol) were added simultaneously, and the reaction was carried out at 85 °C for 30 minutes. Next, NMP (10 g) and 5-norbornene-2,3-dicarboxylic anhydride (6.57 g, 0.04 mol) as a capping agent were added simultaneously, and the reaction was carried out at 85 °C for 30 minutes. Further, NMP (30 g) and 4,4'-oxybisphthalic anhydride (ODPA) (2.17 g, 0.007 mol) were added simultaneously, and the reaction was carried out at 85 °C for 1 hour. After the reaction was completed, it was cooled to room temperature, and NMP (67 g) and acetic acid (48.02 g, 0.50 mol) were added simultaneously, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using a ventilated dryer at 50 °C for 72 h to obtain a powder of an alkali-soluble polyamide resin (A-9). After testing, the weight-average molecular weight of the alkali-soluble polyamide resin (A-9) was 20,650.

[0129] Example 1

[0130] 5.0 g of the above-obtained polyimide (A-1), 5.0 g of the modified polyimide resin (A-5), and 20.0 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask and stirred. After the resin was completely dissolved, 2.0 g of 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid quinone diazide 4NT-350 (manufactured by Toyo Gosei Co., Ltd., Japan), 0.04 g of KBM-1403 (p-styryltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., Japan) were added. After complete dissolution, it was pressure-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition Q-1.

[0131] Example 2

[0132] The photosensitive resin composition Q-2 was prepared in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) was replaced with 7 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified polyimide resin (A-5).

[0133] Example 3

[0134] The photosensitive resin composition Q-3 was prepared in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) was replaced with 9 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide resin (A-5) was replaced with 1.0 g of the modified polyimide resin (A-5).

[0135] Example 4

[0136] The photosensitive resin composition Q-4 was prepared in the same manner as in Example 1, except that 5.0 g of the modified polyimide resin (A-5) was replaced with 5.0 g of the modified polybenzoxazole precursor resin (A-6).

[0137] Example 5

[0138] The photosensitive resin composition Q-5 was prepared in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) was replaced with 7 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified polybenzoxazole precursor resin (A-6).

[0139] Example 6

[0140] The photosensitive resin composition Q-6 was prepared in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) was replaced with 9 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide (A-5) was replaced with 1.0 g of the modified polybenzoxazole precursor (A-6).

[0141] Example 7

[0142] The photosensitive resin composition Q-7 was prepared in the same manner as in Example 1, except that 5.0 g of the modified polyimide resin (A-5) was replaced with 5.0 g of the modified hydroxystyrene resin (A-7).

[0143] Example 8

[0144] The photosensitive resin composition Q-8 was prepared in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) was replaced with 7 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified phenolic resin solution (A-7).

[0145] Example 9

[0146] The photosensitive resin composition Q-9 was prepared in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) was replaced with 9 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide resin (A-5) was replaced with 1.0 g of the modified phenolic resin solution (A-7).

[0147] Example 10

[0148] Prepare the photosensitive resin composition Q-10 in the same manner as in Example 1, except that 5.0 g of the modified polyimide resin (A-5) is replaced with 5.0 g of the modified phenolic resin solution (A-8).

[0149] Example 11

[0150] Prepare the photosensitive resin composition Q-11 in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) is replaced with 7 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide resin (A-5) is replaced with 3.0 g of the modified phenolic resin solution (A-8).

[0151] Example 12

[0152] Prepare the photosensitive resin composition Q-12 in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) is replaced with 9 g of the polyimide resin (A-1), and 5.0 g of the modified polyimide resin (A-5) is replaced with 1.0 g of the modified phenolic resin solution (A-8).

[0153] Example 13

[0154] Prepare the photosensitive resin composition Q-13 in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) is replaced with 7.0 g of the polybenzoxazole precursor resin (A-2), and 5.0 g of the modified polyimide resin (A-5) is replaced with 3.0 g of the modified polyimide resin (A-5).

[0155] Example 14

[0156] Prepare the photosensitive resin composition Q-14 in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) is replaced with 7.0 g of the polybenzoxazole precursor resin (A-2), and 5.0 g of the modified polyimide resin (A-5) is replaced with 3.0 g of the modified polybenzoxazole resin (A-6).

[0157] Example 15

[0158] Prepare the photosensitive resin composition Q-15 in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) is replaced with 7.0 g of the polybenzoxazole precursor resin (A-2), and 5.0 g of the modified polyimide resin (A-5) is replaced with 3.0 g of the modified polystyrene resin (A-7).

[0159] Example 16

[0160] The photosensitive resin composition Q-16 was prepared in the same manner as in Example 1, except that: 5.0 g of the polyimide resin (A-1) was replaced with 7.0 g of the polybenzoxazole precursor resin (A-2), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified phenolic resin solution (A-8).

[0161] Example 17

[0162] The photosensitive resin composition Q-17 was prepared in the same manner as in Example 1, except that: 5.0 g of the polyimide resin (A-1) was replaced with 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified polyimide resin (A-5).

[0163] Example 18

[0164] The photosensitive resin composition Q-18 was prepared in the same manner as in Example 1, except that: 5.0 g of the polyimide resin (A-1) was replaced with 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified polybenzoxazole resin (A-6).

[0165] Example 19

[0166] The photosensitive resin composition Q-19 was prepared in the same manner as in Example 1, except that: 5.0 g of the polyimide resin (A-1) was replaced with 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified polystyrene resin (A-7).

[0167] Example 20

[0168] The photosensitive resin composition Q-20 was prepared in the same manner as in Example 1, except that: 5.0 g of the polyimide resin (A-1) was replaced with 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced with 3.0 g of the modified phenolic resin solution (A-8).

[0169] Comparative Example 1

[0170] 10.0 g of the above-obtained polyimide (A-1) and 20.0 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask and stirred. After the resin was completely dissolved, 2.0 g of 2,3,4,4'-tetrahydroxybenzophenone, 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid quinone diazide 4NT-350 (manufactured by Toyo Gosei Co., Ltd., Japan), and 0.04 g of KBM-1403 (p-styryltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., Japan) were added. After complete dissolution, it was pressure-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition R-1.

[0171] Comparative Example 2

[0172] 10.0 g of the above-obtained polybenzoxazole precursor (A-2) and 20.0 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask and stirred. After the resin was completely dissolved, 2.0 g of 2,3,4,4'-tetrahydroxybenzophenone, 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid quinone diazide 4NT-350 (manufactured by Toyo Gosei Co., Ltd., Japan), and 0.04 g of KBM-1403 (p-styryltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., Japan) were added. After complete dissolution, it was pressure-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition R-2.

[0173] Comparative Example 3

[0174] 10 g of the above-obtained alkali-soluble polyamide resin (A-9) and 20.0 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask and stirred. After the resin was completely dissolved, 2.0 g of 2,3,4,4'-tetrahydroxybenzophenone, 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid quinone diazide 4NT-350 (manufactured by Toyo Gosei Co., Ltd., Japan), and 0.04 g of KBM-1403 (p-styryltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., Japan) were added. After complete dissolution, it was pressure-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition R-3.

[0175] Comparative Example 4

[0176] 10.0 g of the above-obtained modified polyimide (A-5) and 20.0 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask and stirred. After the resin was completely dissolved, 2.0 g of 2,3,4,4'-tetrahydroxybenzophenone, 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid quinone diazide 4NT-350 (manufactured by Toyo Gosei Co., Ltd., Japan), and 0.04 g of KBM-1403 (p-styryltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., Japan) were added. After complete dissolution, it was pressure-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition R-4.

[0177] Comparative Example 5

[0178] The photosensitive resin composition R-5 was prepared in the same manner as in Example 1, except that 5.0 g of the modified polyimide resin (A-5) was replaced with 5.0 g of the polybenzoxazole precursor (A-2).

[0179] Comparative Example 6

[0180] The photosensitive resin composition R-6 was prepared in the same manner as in Example 1, except that 5.0 g of the polyimide resin (A-1) was replaced with 5.0 g of the modified polybenzoxazole resin (A-6).

[0181] The component details of the photosensitive resin compositions in the above examples and comparative examples are shown in Table 1 specifically.

[0182] Table 1

[0183]

[0184]

[0185] The light transmittance, resolution, film-forming properties, mechanical properties, thermal stability, and adhesion of the photosensitive resin compositions prepared in the above examples and comparative examples were tested as follows:

[0186] 1. Test of the light transmittance of the resin composition

[0187] The samples of the photosensitive resin compositions in the above examples and comparative examples were coated on glass slides, and then soft-baked on a heating stage at 120 °C for 3 minutes to obtain resin films with a film thickness of 2 μm. The obtained resin films were used to measure the transmittance spectra at wavelengths of 300 nm - 800 nm using a UV-visible spectrophotometer. As a result, the case where the transmittance at each wavelength of 365 nm - 436 nm was less than 50% was regarded as insufficient (C), the case where the transmittance at each wavelength of 365 nm - 436 nm was higher than 50% and lower than 70% was regarded as good (B), and the case where the light transmittance at each wavelength of 365 nm - 436 nm was higher than 70% was regarded as excellent (A).

[0188] 2. Resolution test

[0189] The samples of the photosensitive resin compositions in the above examples and comparative examples were coated on 4-inch silicon wafers, and then soft-baked on a heating stage at 120 °C for 3 minutes to obtain resin films with a film thickness of 7 μm. Using a UV lamp (i and g lines), an exposure dose of 120 mJ / cm 2, Exposure is carried out through a mask. After exposure, spray development is performed using a 2.38% tetramethylammonium hydroxide developer for 60 s to remove the unexposed part. An optical microscope (MX63-F, Olympus) is used to observe the pattern at a magnification of 100 times, and the minimum size for resolving the through-hole pattern is taken as the resolution.

[0190] 3. Film-forming property test

[0191] The photosensitive resin composition samples of the above examples and comparative examples are coated on 4-inch silicon wafers, and then soft-baked on a heating stage at 120 °C for 3 minutes to obtain a resin film with a film thickness of 15 μm. Then the film is placed in a vacuum anaerobic oven (Zhenping Technology Co., Ltd., MOLZK-32D1) for heat treatment. Specifically as follows: First, the temperature is raised to 150 °C for 1 hour of heat treatment, then the temperature is raised to 200 °C in 20 minutes for 1 hour of heat treatment, and finally the temperature is raised to 300 °C in 20 minutes and continued for 1.5 hours of heat treatment to finally obtain a cured film. The silicon wafer with the cured film is placed in a hydrofluoric acid solution to etch and remove the film from the silicon wafer. The resin film-forming evaluation criteria are as follows: "Excellent": The photosensitive resin composition can form a film with good toughness and does not break when folded; "Good": The photosensitive resin composition can form a film with good toughness and breaks when folded; "Poor": The photosensitive resin composition cannot form a film and is in a fragmented state.

[0192] 4. Tensile strength and elongation at break test

[0193] The resin film with a film thickness of 15 μm obtained by the method described in the above resin film-forming property test is cut into sample strips with a size of 40 mm in length and 5 mm in width, and the tensile strength and elongation at break of the sample strips are tested using TA's TMA 450 at a temperature of 150 °C, a tensile force range of 0-18 N, and a rate of 3 N / min.

[0194] 5. 5% thermal weight loss temperature test

[0195] The thermal stability of the material is measured by the temperature of 5% thermal weight loss, because the temperature of 5% weight loss can be accurately determined, and at the time of 5% weight loss, the material basically still maintains its basic structure and available properties. The higher the 5% thermal weight loss temperature, the better the thermal stability.

[0196] Approximately 15 mg of the resin film with a film thickness of 15 μm obtained by the method described in the above resin film-forming property test is loaded into an aluminum standard container, and measured using a thermogravimetric analyzer TGA-50 (manufactured by Shimadzu Corporation). Test conditions: Hold at 60 °C for 30 minutes, and then raise the temperature at a rate of 5 °C / min to 600 °C. The 5% thermal weight loss temperature is read from the obtained thermogravimetric curve.

[0197] 6. Adhesion test

[0198] Using a spin coater, the photosensitive resin composition samples of the above examples and comparative examples were uniformly coated onto a copper substrate, and then placed on a heating table at 120 °C for 3 minutes of soft baking to obtain a resin film with a film thickness of 15 μm. Using a cross cutter (BYK-Gardner A-5125), the resin film was scribed into a grid of 10 rows × 10 columns, and then the film was placed in a vacuum and oxygen-free oven (MOLZK-32D1) for heat treatment: heat treatment was carried out at 170 °C for 30 minutes, then it was heated to 350 °C over 1 hour and treated at 350 °C for 1 hour, and finally a cured film was obtained. The cured film was placed in a PCT test chamber for a 200-hour PCT aging test (121 °C, 2 atm saturated steam; Dongguan Hongjin Technology PCT-30). After the PCT test was completed, a peeling test was carried out using a tape (special transparent 3M tape) with reference to the cross-cut test of paint and varnish films in the national standard GB / T 9286-1998, and the number of peeled grids was recorded as the peeling situation after the PCT test.

[0199] When the number of peeled pieces in the adhesion peeling experiment is less than 5, it is regarded as "optimal", when it is less than 10, it is regarded as "good", when it is less than 30, it is regarded as "slightly good", and when it is greater than or equal to 30, it is regarded as "poor".

[0200] The photosensitive resin composition prepared above was evaluated according to the test method described above, and the results are shown in Table 2.

[0201] Table 2

[0202]

[0203]

[0204] From the results of Examples 1 to 12 and Comparative Example 1, it can be seen that when the alkali-soluble resin a and the alkali-soluble resin b are combined in different ratios, when the ratio reaches 7:3, the photosensitive resin composition obtained has the best lithography performance and mechanical properties after film formation, the highest 5% thermal weight loss temperature indicating the best thermal stability, and the strongest adhesion to the substrate. If the amount of the alkali-soluble resin a is relatively high, the transmittance of the photosensitive resin composition is relatively low, and thus the resolution is poor; if the amount of the alkali-soluble resin b is relatively high, although the transmittance of the photosensitive resin composition is high and the development resolution is high, the 5% thermal weight loss temperature after film formation is relatively low.

[0205] It can be seen from the results of Examples 2, 5, 8, 11, 13 to 20 and Comparative Examples 1 to 6 that the photosensitive resin composition obtained by combining and compounding different alkali-soluble resins a and alkali-soluble resin b modified with tert-butoxycarbonyloxy phenolic hydroxyl groups significantly improves the light transmittance, can well improve the lithography performance, and at the same time, the film-forming performance, mechanical properties and adhesion are also significantly improved. Among them, the addition of polystyrene resin modified with tert-butoxycarbonyloxy not only improves the resolution of the photosensitive resin composition, but also has better mechanical properties and thermal stability after film formation, and has stronger adhesion to the substrate.

[0206] It can be seen from the results of Examples 2, 5, 8, 11, 13 to 20 that under the condition of the optimal ratio (7:3) of alkali-soluble resin a and alkali-soluble resin b, the photosensitive resin composition formed by polyamide A-9 in alkali-soluble resin a and modified polyethylene resin in alkali-soluble resin b has the most excellent light transmittance, lithography performance, film-forming performance, thermal stability and adhesion to the substrate after PCT experiment, and the mechanical properties are the best.

Claims

1. A resin composition, characterized in that include: Alkali-soluble resin a: includes at least one of polyimide, polyimide precursor, polybenzoxazole precursor, or at least one of their copolymers; Alkali-soluble resin b: at least one of polystyrene derivatives containing phenolic hydroxyl groups, wherein at least a portion of the phenolic hydroxyl groups in the polystyrene derivatives are substituted with tert-butylcarbonyloxy groups, and the substitution rate of the phenolic hydroxyl groups is greater than or equal to 50%; The mass ratio of the alkali-soluble resin a to the alkali-soluble resin b is 1-3:

1.

2. The resin composition according to claim 1, characterized in that: In the alkali-soluble resin b, the polystyrene derivative containing a phenolic hydroxyl group contains a structural unit represented by the following formula (4): In formula (4), R5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R7 represents hydrogen or a tert-butylcarbonyloxy group.

3. The resin composition according to claim 1, characterized in that: In the alkali-soluble resin a, the polyimide contains a structural unit represented by the following formula (6), the polybenzoxazole precursor contains a structural unit represented by the following formula (7), and the polyimide precursor contains a structural unit represented by the following formula (8): In formula (6), X4 is derived from a dianhydride monomer and represents a 4- to 10-valent organic group, Y4 is derived from a diamine monomer and represents a 2- to 8-valent organic group, and there is no case where the phenolic hydroxyl group in Y4 is modified by a tert-butylcarbonyloxy group; R 10 and R 11 Each independently represents a carboxyl group, a sulfonic acid group or a phenolic hydroxyl group; P and q each independently represent an integer of 0 to 6; In formula (7), X5 and Y5 independently represent an organic group with a valence of 2 to 8, X5 is derived from a dicarboxylic acid monomer or a diacyl chloride monomer, Y5 is derived from a diamine monomer, and there is no phenolic hydroxyl group in Y5 modified by a tert-butylcarbonyloxy group; R 12 and R 13 Each independently represents a phenolic hydroxyl group, a sulfonic acid group or a carboxyl group; r and s each independently represent an integer from 0 to 6, and r+s>0; In formula (8), X6 and Y6 independently represent an organic group with a valence of 2 to 8, X6 is derived from a dianhydride monomer, Y6 is derived from a diamine monomer, and there is no case where the phenolic hydroxyl group in Y6 is modified by a tert-butylcarbonyloxy group; R 14 is a hydrogen atom or an alkyl group.

4. The resin composition according to any one of claims 1 to 3, characterized in that: It also includes sensitizers, additives and solvents.

5. The resin composition according to claim 4, characterized in that: The total amount of the alkali-soluble resin a and the alkali-soluble resin b is 100 parts by weight, the photosensitizer is 1 to 50 parts by weight, the auxiliary agent is 0.01 to 5 parts by weight, and the solvent is 70 to 1800 parts by weight.

6. A resin sheet, characterized in that: The resin composition is formed from the resin composition according to any one of claims 1 to 5.

7. A cured film, characterized in that: The resin sheet is obtained by curing the resin sheet according to claim 6, or is obtained by curing the resin composition according to any one of claims 1 to 5.

8. A semiconductor electronic component, characterized in that: The semiconductor electronic component is provided with an interlayer insulating layer and / or a surface protective film, and the interlayer insulating layer and / or the surface protective layer comprises the cured film according to claim 7.

9. A semiconductor device, characterized in that: The semiconductor device is provided with an interlayer insulating layer and / or a surface protective film, and the interlayer insulating layer and / or the surface protective layer comprises the cured film according to claim 7.

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