Resin composition and application thereof

Abstract

The invention discloses a resin composition and application thereof, the resin composition comprises alkali-soluble resin a and alkali-soluble resin b, the alkali-soluble resin b comprises at least one of phenolic hydroxyl group-containing polyimide, phenolic hydroxyl group-containing polybenzoxazole precursor, phenolic hydroxyl group-containing polystyrene derivative and phenolic hydroxyl group-containing phenolic resin, at least a portion of the phenolic hydroxyl groups in the polymers are substituted with tert-butylcarbonyloxy groups. The alkali-soluble resin b is introduced into the resin composition, the phenolic hydroxyl group in the alkali-soluble resin b is modified by the tert-butyl carbonyloxy group, the light transmission performance of the resin is improved, the resin has higher light sensitivity and better alkali resistance in the exposure and development process, and the photoetching performance of the photosensitive resin composition is improved.

Description

Technical Field

[0001] The present invention relates to a resin composition, in particular to a photosensitive resin composition with good photolithography performance, and also 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 can therefore be used for surface protection films of semiconductor elements such as LSI, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like.

[0003] The photosensitive resin composition 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 photolithographic performance of the photosensitive resin composition, Patent Document 1 (CN103502889B) proposes a method of 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 resistance of the photosensitive resin composition. However, the above-mentioned 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 in the prior art, the present invention provides a resin composition, into which a phenolic hydroxyl-modified alkali-soluble resin is introduced, and the phenolic hydroxyl group in the resin is modified by a tert-butylcarbonyloxy group, thereby improving the light transmittance of the resin composition, thereby having higher resolution and better alkali resistance during exposure and development, and making the photosensitive resin composition have better lithography performance.

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

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

[0008] Furthermore, the alkali-soluble resin a includes at least one of polyimide, polyimide precursor, polybenzoxazole precursor, or at least one of copolymers of two or more of polyimide, polyimide precursor, polybenzoxazole precursor; in order to meet the requirements of alkali solubility, the main chains of these resins contain alkali-soluble groups, such as phenolic hydroxyl groups, carboxyl groups, etc.

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

[0010]

[0011] In the general formula (6), X4 is derived from a dianhydride monomer and represents a 4- to 10-valent organic group, and Y4 is derived from a diamine monomer and represents a 2- to 8-valent organic group. There is no case where the phenolic hydroxyl group in Y4 is modified by a tert-butylcarbonyloxy group. 10 and R 11 Each of p and q independently represents a carboxyl group, a sulfonic acid group or a phenolic hydroxyl group. P and q independently represent an integer of 0 to 6, for example, 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 the general formula (7), X5 and Y5 independently represent a divalent to octavalent organic group, X5 is derived from a dicarboxylic acid monomer or a diacyl chloride monomer, Y5 is derived from a diamine monomer, and Y5 does not contain a phenolic hydroxyl group modified by a tert-butylcarbonyloxy group. 12 and R 13 Each independently represents a phenolic hydroxyl group, a sulfonic acid group or a carboxyl group, and R 12 It can be a single group or a mixture of different groups. Similarly, R 13 It may be a single group or a mixture of different groups. r and s each independently represent an integer of 0 to 6, such as 0, 1, 2, 3, 4, 5, 6, wherein r+s>0.

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

[0016]

[0017] In the general formula (8), X6 and Y6 each independently represent an organic group having a valence of 2 to 8, X6 is derived from a dianhydride monomer, Y6 is derived from a diamine monomer, and Y6 does not contain a phenolic hydroxyl group modified by a tert-butylcarbonyloxy group. 14 is a hydrogen atom or an alkyl group, when R14 When it is an alkyl group, it is introduced by an esterification agent.

[0018] Furthermore, the alkali-soluble resin a may 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 copolymers thereof containing structural units 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), for example, 5, 10, 50, 100, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500 or 10000.

[0020] Furthermore, the alkali-soluble resin a may have other structural units in addition to the structural units represented by the general formulae (6), (7), and (8). In this case, it is preferred that the structural units represented by the general formulae (6) and / or (7) and / or (8) account for 50% or more of all the structural units, for example, 50%, 60%, 70%, 80%, 90%, or 100%.

[0021] Further, 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 precursor is different, the reaction raw materials used are different. For example, when the polyimide precursor is polyamic acid, at least one dianhydride monomer and at least two diamine monomers can be reacted to obtain. When the polyimide precursor is polyamic acid ester, it can be obtained by reacting at least one dianhydride monomer, at least two diamine monomers, and an esterification agent as raw materials. The specific reaction method is not limited. For example, the dianhydride monomer and the diamine monomer can be reacted to obtain polyamic acid, and then an esterification agent is added to react to obtain polyamic acid ester; or, the dianhydride monomer can be reacted with an esterification agent first, and then reacted with a diamine monomer to obtain polyamic acid ester.

[0022] Furthermore, when the alkali-soluble resin a is a polybenzoxazole precursor, the method for producing a polyhydroxyamide as a polybenzoxazole precursor includes, for example, a method of condensing a diamine monomer with a dicarboxylic acid. Specifically, for example, a method of reacting a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a diamine monomer thereto; a method of dripping a solution of a dicarboxylic acid dichloride into a solution of a diamine monomer to which a tertiary amine such as pyridine is added; and the like.

[0023] Furthermore, when the alkali-soluble resin a is polyimide, examples of methods for producing polyimide include a method of obtaining polyimide by imidizing the polyamic acid or polyamic acid ester obtained by the above method. Examples of imidization methods include chemical treatment with acid, alkali, etc., and heat treatment.

[0024] Furthermore, X4 in the general formula (6) and X6 in the general formula (8) represent structural groups in the dianhydride monomer, preferably organic groups having 5 to 40 carbon atoms and containing aromatic rings or cyclic aliphatic groups.

[0025] Further, the dianhydride monomer can also be selected from reports in the prior art, such as one or more of pyromellitic dianhydride, 4,4'-oxydiphthalic 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'-(hexafluoroisopropylene)phthalic anhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and the like.

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

[0027] Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, diphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid and the like, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, triphenyl trimesic acid and the like, pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3 Aliphatic tetracarboxylic acids such as 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic acid, etc. can also be mentioned. Two or more of these can be used.

[0028] Furthermore, Y4 in the above general formula (6), Y5 in the general formula (7) and Y6 in the general formula (8) are introduced from diamine monomers, which are 2-8 valent organic groups, preferably organic groups with 5-40 carbon atoms containing aromatic or cyclic aliphatic groups.

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

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

[0031]

[0032]

[0033] Furthermore, the diamine monomer can also be an aliphatic diamine with a siloxane structure to improve the adhesion between the resin composition and the substrate, while not reducing the heat resistance of the cured film formed by the resin composition. The aliphatic diamine with 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] Further, in order to better adjust the molecular weight of the alkali-soluble resin a of the present invention, a certain end-capping agent may be added during polymerization, and the end-capping agent may be a combination of one or more 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-methyl benzoic acid, 3-amino-m-methyl benzoic 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, cyclohexanepentanedicarboxylic anhydride, 4-alkynylphthalic anhydride, etc.

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

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

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

[0040] Furthermore, in the synthesis process of the alkali-soluble resin a, an organic solvent is required. Examples of the organic solvent include: amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea, 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 and propylene carbonate; glycols such as triethylene glycol, phenols such as m-cresol and p-cresol; acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclopentane sulfone, dimethyl sulfoxide, tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, ethyl lactate, etc., but are not limited to these.

[0041] Furthermore, during the synthesis of the alkali-soluble resin a, the obtained product needs to be put into a large amount of water or a mixture of methanol and water to precipitate it, and then filtered and dried to obtain pure alkali-soluble resin a. The drying temperature is preferably 40 to 100° C., more preferably 50 to 80° C. Through this operation, unreacted monomers, dimers, trimers and other oligomer components can be removed, and the film properties after thermal curing can be improved.

[0042] Furthermore, the alkali-soluble resin b is a resin containing a phenolic hydroxyl group and the phenolic hydroxyl group is modified, and the alkali-soluble resin b includes at least one of a polyimide containing a phenolic hydroxyl group, a polybenzoxazole precursor containing a phenolic hydroxyl group, a polystyrene derivative containing a phenolic hydroxyl group, and a phenolic hydroxyl group-containing phenolic resin, wherein at least a part of the phenolic hydroxyl groups in the polymers such as the polyimide containing a phenolic hydroxyl group, the polybenzoxazole precursor containing a phenolic hydroxyl group, the polystyrene derivative containing a phenolic hydroxyl group, and the phenolic hydroxyl group are substituted by tert-butylcarbonyloxy.

[0043] The substitution rate or modification rate of the phenolic hydroxyl group can be measured by the following method. 1 H-NMR is used to determine the "number of protons of phenolic hydroxyl groups" and "number of protons of aromatic CH" in the repeating structural units of the phenolic hydroxyl group-containing resin before and after modification, and then the phenolic hydroxyl group content before and after modification is calculated to obtain the phenolic hydroxyl group modification rate. The structural units of the phenolic hydroxyl group-containing resin before modification can be analyzed, for example, by thermal decomposition GC / MS.

[0044] Phenolic hydroxyl content before modification = number of protons of phenolic hydroxyl before modification / number of protons of aromatic CH before modification;

[0045] Phenolic hydroxyl content after modification = number of protons of phenolic hydroxyl after modification / number of protons of aromatic CH after modification;

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

[0047] Furthermore, the modification rate of the phenolic hydroxyl group in the alkali-soluble resin b is greater than or equal to 50%, for example, 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 has a structural formula represented by 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 long-chain polymer structure, such as a polyimide structural group, a polyimide precursor structural group, a polybenzoxazole precursor group, a polystyrene group, a phenolic resin group, etc.; R2 represents hydrogen or a tert-butylcarbonyloxy group. In the alkali-soluble resin b, part or all of R2 is a tert-butylcarbonyloxy group.

[0051] In a specific embodiment of the present invention, the alkali-soluble resin b contains a polyimide structure represented by 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 a phenolic hydroxyl group, and R3 represents hydrogen or tert-butylcarbonyloxy.

[0054] In a specific embodiment of the present invention, the alkali-soluble resin b contains a polybenzoxazole precursor structure represented by 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 a phenolic hydroxyl group, and R4 represents hydrogen or tert-butylcarbonyloxy.

[0057] In a specific embodiment of the present invention, the alkali-soluble resin b contains a polystyrene derivative structure represented by 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, and pentyl; R6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, and pentyl; R7 represents hydrogen or tert-butylcarbonyloxy.

[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, and pentyl; R9 represents hydrogen or tert-butylcarbonyloxy.

[0063] As a method for producing the alkali-soluble resin b, for example, a method of using a polyimide containing a phenolic hydroxyl group, a polybenzoxazole precursor containing a phenolic hydroxyl group, a polystyrene derivative containing a phenolic hydroxyl group, or a phenolic resin containing a phenolic hydroxyl group as a raw material and modifying the phenolic hydroxyl group. The modification method includes reacting at least one of the polyimide containing a phenolic hydroxyl group, the polybenzoxazole precursor containing a phenolic hydroxyl group, the polystyrene derivative containing a phenolic hydroxyl group, and the phenolic resin containing a phenolic hydroxyl group with di-tert-butyl dicarbonate under DMAP catalysis to convert the phenolic hydroxyl group into a tert-butylcarbonyloxy group.

[0064] Furthermore, the polyimide containing phenolic hydroxyl groups can be obtained by imidizing polyamic acid or polyamic acid ester containing phenolic hydroxyl groups. As the imidization method, chemical treatment based on acid, alkali, 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 method of the above-mentioned polyamic acid and polyamic acid ester, and the phenolic hydroxyl group can be introduced by selecting a diamine containing a phenolic hydroxyl group.

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

[0066] Furthermore, the polystyrene derivative containing a phenolic hydroxyl group can be obtained by polymerizing an aromatic vinyl compound. As the aromatic vinyl compound, for example, there can be mentioned: aromatic vinyl compounds having phenolic hydroxyl groups such as p-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol; aromatic vinyl compounds not having hydroxyl groups such as styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. Two or more of these aromatic vinyl compounds containing a phenolic hydroxyl group or any combination of an aromatic vinyl compound containing a phenolic hydroxyl group and an aromatic vinyl compound not containing a hydroxyl group can be used. The polymerization conditions can be carried out according to the methods 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-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylcresol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebis(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, and the like. As aldehydes, for example, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. can be mentioned. Two or more of these can be used. The polymerization conditions can be carried out according to the methods reported in the prior art.

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

[0069] Furthermore, the molecular weight of the alkali-soluble resin b is 2,000 to 50,000.

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

[0071] Furthermore, the composition also includes a photosensitizer, an auxiliary agent and a solvent.

[0072] Furthermore, when the photosensitizer is a photoacid generator, when the alkali-soluble resin and the photoacid generator are used together, the obtained resin composition is a positive photosensitive resin composition.

[0073] Furthermore, as a photoacid generator for a positive photosensitive resin composition, a quinonediazide compound can be preferably used. As a quinonediazide compound, there can be cited a compound obtained by ester-bonding a sulfonic acid of a quinonediazide to a polyhydroxy compound, a compound obtained by ester-bonding a sulfonic acid of a quinonediazide to a polyamino compound, and a compound obtained by ester-bonding a sulfonic acid of a quinonediazide to a polyhydroxypolyamino compound. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted by quinonediazide groups, but preferably, on average, more than 40 mol% of the functional groups as a whole are substituted by quinonediazide groups. By using such a quinonediazide compound, a positive photosensitive resin composition that is sensitive to the usual ultraviolet rays, i.e., the i-line (wavelength 365nm), h-line (wavelength 405nm), and g-line (wavelength 436nm) of a mercury lamp can be obtained.

[0074] Furthermore, the quinonediazide compound preferably comprises an ester of a phenol compound and naphthoquinonediazide-4-sulfonyl group. Thus, 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-trihydroxyphenyl ketone and 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid (Toyo Gosei Kogyo Co., Ltd., 4NT-300), 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxo-1-naphthalenesulfonic acid (Toyo Gosei Kogyo Co., Ltd., 4NT-350).

[0076] In the photosensitive resin composition of the present invention, the amount of the photosensitive agent quinone diazide compound used is 1 to 50 parts by mass, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, preferably 10 to 40 parts by mass, based on 100 parts by mass of the total mass of the alkali-soluble resin a and the alkali-soluble resin b. 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 achieving higher sensitivity, 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 auxiliary agent in the photosensitive resin composition is to improve the adhesion between the resin film and the substrate, and the auxiliary agent is an adhesion promoter, wherein the adhesion promoter is preferably a silane coupling agent, including a combination of one or more of p-phenylenediamine trimethoxysilane, trimethoxyaminopropyl silane, trimethoxyepoxysilane, trimethoxyvinyl silane, triethoxyvinyl silane, trimethoxymercaptopropyl silane, etc.

[0078] In the photosensitive resin composition of the present invention, based on 100 parts by weight of the total weight of the alkali-soluble resin a and the alkali-soluble resin b, the amount of the auxiliary silane coupling agent used is 0.01 to 5 parts by weight, for example, 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, and 5.0 parts.

[0079] Furthermore, the solvent in the photosensitive resin composition can 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-dimethylpropylene urea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, etc.; tetrahydrofuran, dioxane, propylene glycol, etc. Ether solvents such as monomethyl ether and propylene glycol monoethyl ether; ketone solvents such as acetone, methyl ethyl ketone, and diisobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, and methyl lactate; alcohol solvents such as diacetone alcohol and 3-methyl-3-methoxybutanol; aromatic hydrocarbon solvents such as toluene and xylene, etc. The solvent can be one kind or a combination of multiple kinds.

[0080] As for the content of the solvent, in order to dissolve the photosensitive resin composition, the solvent is 70 to 1800 parts by mass, for example, 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, and 1800 parts, based on 100 parts by mass of the total mass of the alkali-soluble resin a and the alkali-soluble resin b. 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] Further, the method for producing the resin composition of the present invention is 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 and a solvent. As the method of dissolving, heating and stirring can be cited. In the case of heating, the heating temperature is preferably set within a range that does not damage the performance of the resin composition, usually room temperature to 80°C. In addition, there is no particular restriction on the dissolution order of the components. In the case of stirring, the rotation speed is preferably set within a range that does not damage the performance of the resin composition, usually 200rpm to 2000rpm. In the case of stirring, heating can also be performed as needed, usually room temperature to 80°C.

[0082] Further, 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 above 2 mPa·s, it is easy to obtain the desired film thickness. On the other hand, when the viscosity is below 5000 mPa·s, it is easy to obtain a coating film with high coating uniformity. A resin composition with 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, the photosensitive resin composition may be filtered using a filtering device such as filter paper, filter membrane, filter, etc. The filtering method is not particularly limited, but preferably, pressure filtration is performed using a filter with a pore size of 0.2 to 5 μm.

[0084] As a method for coating the photosensitive resin composition on the substrate, spin coating, spray coating, roll coating, screen printing, or coating methods using a blade coater, a calender coater, a slit coater, a roll coater, a comma roll coater, a gravure 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 an oven, a heating plate, an infrared heater, etc. The drying temperature and the drying time can be controlled within the range that allows the organic solvent to volatilize. It is preferred to appropriately set the photosensitive resin composition film to an uncured or semi-cured state. The specific drying temperature is preferably 40 to 120°C, and the drying time is preferably 1 to 60 minutes. Furthermore, staged heating can also be used, for example, heat treatment 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 coating the aforementioned resin composition on a releasable substrate such as polyethylene terephthalate (PET) to obtain a coating film of the resin composition, and drying the coating film. A protective film may be further laminated on the coating film.

[0088] As the coating method, for example, spin coating, slit coating, dip coating, spray coating, printing and the like can be cited. Among these, the slit coating method is preferred because it can be coated 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 compared to, for example, the spin coating method. The coating speed is usually in the range of 10 mm / sec to 400 mm / sec. The film thickness of the coating film varies depending on the solid content concentration, viscosity, etc. of the resin composition. Usually, the coating is performed in a manner such that the film thickness after drying becomes 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0089] The substrate to be coated with the resin composition can be pre-treated with a close-fitting improver, i.e., a silane coupling agent, before coating. The close-fitting improver can be listed as a combination of one or more of p-phenylenediamine trimethoxysilane, trimethoxyaminopropyl silane, trimethoxyepoxysilane, trimethoxyvinyl silane, triethoxyvinyl silane, trimethoxymercaptopropyl silane, etc., which acts to improve the close-fitting property and the peeling property. As a pre-treatment method, for example, the following method can be cited: using a solution obtained by dissolving a silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate at 0.5 to 20 mass %, the surface of the substrate is treated. As a method for treating the surface of the substrate, methods such as spin coating, slit die coating, rod coating, dip coating, spray coating, and steam treatment can be cited.

[0090] After coating, a reduced pressure drying treatment is performed as needed. Usually, each substrate with a coating film formed thereon is dried under reduced pressure. As for the reduced pressure drying speed, the general reduced pressure drying time is mostly about 30 seconds to 100 seconds. In the state where there is a coated substrate, the ultimate pressure in the vacuum chamber at the end of the reduced pressure drying is usually below 100 Pa. By making the ultimate pressure below 100 Pa, a dry state in which the stickiness of the coating film surface is reduced can be achieved, thereby suppressing surface contamination and the generation of particles during subsequent substrate transportation.

[0091] After coating or drying under reduced pressure, the coating film is usually heated and dried. This process is also called pre-baking. Drying uses a hot plate, an oven, infrared rays, etc. The heating temperature and heating time vary depending on the type and purpose of the coating 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 has photosensitivity, a pattern can be formed. For example, a desired pattern can be formed by irradiating a photosensitive resin sheet with actinic rays through a mask having a desired pattern, exposing the sheet, and developing the sheet.

[0093] The obtained photosensitive resin composition film is exposed to chemical rays through a mask. Chemical rays used for exposure include ultraviolet rays, visible rays, electron rays, X-rays, etc. In the present invention, it is preferred to use i-rays (365nm), h-rays (405nm) or g-rays (436nm) of a mercury lamp.

[0094] When forming a pattern, the unexposed part is removed with a developer after exposure. As a developer, 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 and other alkaline compound aqueous solutions are preferred. Depending on the circumstances, one or more polar solvents selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide and the like; alcohols such as methanol, ethanol, isopropanol; esters such as ethyl lactate and propylene glycol azomethyl ether acetate; compounds such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may also be added to these alkaline aqueous solutions.

[0095] The development can be carried out by spraying the above-mentioned developer on the film-attached surface of the substrate or immersing the film together with the substrate in the developer. Ultrasonic waves can also be applied while immersing the substrate in the developer. In addition, the developer can be sprayed on 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 part can be removed. In order to process fine patterns or remove residues between patterns, it is preferred to further develop after removing the unexposed part.

[0096] After development, the film may be rinsed with water. Alcohol such as ethanol or isopropyl alcohol and ethyl lactate, propylene glycol monomethyl ether acetate, etc. may be added to water for rinsing.

[0097] In order to further improve the resolution and expand the development process range, a baking treatment may be performed before development. The baking treatment temperature is preferably 50 to 180° C., more preferably 60 to 120° C. The baking treatment time is preferably 5 s to 60 min.

[0098] From the viewpoint of reducing the solvent, solid content, water content, etc. of the photosensitive resin composition film remaining after pattern formation, it is preferably heated and dried at 60 to 200° C. The heating and drying time is preferably 1 to 60 minutes.

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

[0100] Furthermore, the heating temperature during curing is 150° C. to 450° C., more preferably 180° C. to 350° C. The heating treatment during curing can be performed by stepwise heating or continuous heating within a 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, but is preferably 0.5 μm to 100 μm.

[0102] The photosensitive resin composition of the present invention is suitable for surface protection films of semiconductor elements, ultra-thin flexible circuit boards, interlayer insulating films, and insulating layers of organic electroluminescent elements. In the present invention, a semiconductor electronic component or semiconductor device is specifically provided, wherein the semiconductor electronic component or semiconductor device is provided with an interlayer insulating layer and / or a surface protection film, and the interlayer insulating layer and / or the surface protection layer comprises the above-mentioned cured film.

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

[0104] When preparing a semiconductor electronic component or a semiconductor device, the steps may be: coating a photosensitive resin composition on a semiconductor wafer having an image sensor element formed thereon to form a photosensitive resin composition cured film. Exposing and developing the photosensitive resin composition cured film, removing the resin film on the sensor portion, and retaining the resin film around the sensor 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, to which an alkali-soluble resin A whose phenolic hydroxyl group is modified by a tert-butylcarbonyloxy group is added, thereby improving the light transmittance of the resin, thereby having higher sensitivity and better alkali resistance during exposure and development, improving the photolithography performance of the photosensitive resin composition, and reducing 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 photolithographic performance of the photosensitive resin composition, but also improves the mechanical properties and substrate adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0108] Figure 1 The modified polyimide resin prepared in Synthesis Example 5 1 H-NMR spectrum. DETAILED DESCRIPTION

[0109] In order to make the purpose, technical scheme 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 part of the embodiments of the present invention, rather than all the embodiments. Based on the technical scheme of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention. If the specific conditions are not specified in the embodiments, they shall be carried out according to the conventional conditions or the conditions recommended by the manufacturer.

[0110] Furthermore, the weight average molecular weight Mw and number average molecular weight Mn of the resin in the examples of the present invention can be easily measured as polystyrene-equivalent values ​​by gel permeation chromatography (GPC).

[0111] Synthesis of resin polymer

[0112] Synthesis Example 1: Synthesis of polyimide

[0113] Under nitrogen flow, 31.02g (0.1mol) of 4,4'-oxydiphthalic anhydride (ODPA) and 100g of N-methylpyrrolidone (NMP) were added to a 500mL 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. Take another three-necked flask equipped with a stirrer, and add 31.13g (0.085mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), 1.24g (0.005mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 100g of N-methylpyrrolidone in turn, and stir and dissolve 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 2h after the addition was completed. After the reaction was completed, 2.18g (0.02mol) of 3-aminophenol as a capping agent was added, and the reaction was carried out at 50°C for 2h. Then the temperature was raised to 180°C and the reaction was continued for 3 hours. After the reaction was completed, the reaction solution was poured into 3L of deionized water, and the polymer was precipitated to obtain a white precipitate. After filtering, it was washed three times with deionized water, placed in a vacuum oven, and dried at 50°C for 72 hours to obtain polyimide A-1. The number average molecular weight was determined to be 14537 and the weight average molecular weight was 19602. Synthesis Example 2: Synthesis of polybenzoxazole precursor

[0114] Under a dry nitrogen gas 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 hours. After filtering the reaction mixture, the reaction mixture was put into a 3L solution of water / methanol = 3 / 1 (volume ratio) to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried in a vacuum dryer at 80°C for 24 hours to obtain a polybenzoxazole (PBO) precursor (A-2). It was determined that the number average molecular weight of the polybenzoxazole precursor A-2 was 11624 and the weight average molecular weight was 15489.

[0115] Synthesis Example 3: Synthesis of polyhydroxystyrene resin

[0116] To a mixed solution of 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 the mixture was polymerized while stirring for 3 hours. Then, 0.1 mol of methanol was added to the reaction solution to stop the polymerization reaction. The obtained reaction mixture was injected 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 hours, it was injected into 3 L of water to precipitate the polymer, and p-tert-butoxystyrene was deprotected and 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 37 wt% formaldehyde aqueous 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, and then the flask was immersed in an oil bath to reflux the reaction solution while performing a polycondensation reaction for 7 hours. After that, the temperature of the oil bath was cooled to room temperature over 3 hours, and 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 a solid content concentration adjusted to 50 wt%. The weight average molecular weight thereof was measured to be 7582.

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

[0120] Take 6.36g (0.01mol) of polyimide resin (A-1), add 20g of N-methylpyrrolidone (NMP), stir and dissolve, then add 0.0611g (0.5mmol) of p-dimethylaminopyridine (DMAP) and 2.18g (0.01mol) of di-tert-butyl dicarbonate in turn, and stir and react at room temperature for 2h. After the reaction is completed, pour the reaction solution into 500ml of pure water to precipitate a white solid, wash it with 2L of pure water 3 times, filter to obtain a resin solid, dry it under a vacuum environment at 60°C for 24h, and obtain a modified polyimide resin A-5 in which the phenolic hydroxyl group is replaced by tert-butyl carbonyloxy. After measurement, the number average molecular weight is 14662, the weight average molecular weight is 19851, and the modification rate is characterized and calculated by nuclear magnetic hydrogen spectrum, and the phenolic hydroxyl modification rate is 65%.

[0121] Synthesis Example 6: Synthesis of modified polybenzoxazole precursor resin

[0122] A modified polybenzoxazole precursor resin A-6 in which the phenolic hydroxyl group is replaced by a tert-butylcarbonyloxy group is prepared in the same manner as in Synthesis Example 5, except that 6.36 g (0.01 mol) of the polyimide resin (A-1) is replaced by 5.90 g (0.01 mol) of the polybenzoxazole precursor (A-2). The number average molecular weight and weight average molecular weight of the modified polybenzoxazole precursor resin A-6 are determined to be 15008 and 19997, respectively. The modification rate is calculated by nuclear magnetic hydrogen spectrum, and the modification rate of the phenolic hydroxyl group is 62%.

[0123] Synthesis Example 7: Synthesis of modified polyhydroxystyrene resin

[0124] The modified polyhydroxystyrene resin A-7 in which the phenolic hydroxyl group is replaced by tert-butylcarbonyloxy group was prepared in the same manner as in Synthesis Example 5, except that 6.32 g (0.01 mol) of the polyimide resin (A-1) was replaced by 1.58 g (0.01 mol) of the polyhydroxystyrene resin (A-3). The weight average molecular weight of the modified polyhydroxystyrene resin A-7 was measured to be 3875, and the modification rate was calculated by nuclear magnetic hydrogen spectrum, and the modification rate of the phenolic hydroxyl group was 82%.

[0125] Synthesis Example 8: Synthesis of modified phenolic resin

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

[0127] Synthesis Example 9: Synthesis of Alkali-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, and NMP (20 g) and 1,1'-(4,4'-oxybenzoyl)diimidazole PBOM (28.67 g, 0.08 mol) were added simultaneously, and the mixture was reacted 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 mixture was reacted 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 terminal blocking agent were added simultaneously, and the mixture was reacted at 85°C for 30 minutes. Furthermore, NMP (30g) and 4,4'-oxydiphthalic anhydride (ODPA) (2.17g, 0.007mol) were added at the same time, and the mixture was reacted at 85°C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, and NMP (67g) and acetic acid (48.02g, 0.50mol) were added at the same time, and stirred at room temperature for 1 hour. After the stirring was completed, the solution was put into 3L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a ventilated dryer at 50°C for 72h to obtain a powder of an alkali-soluble polyamide resin (A-9). The weight average molecular weight of the alkali-soluble polyamide resin (A-9) was tested to be 20650.

[0129] Example 1

[0130] 5.0 g of the polyimide (A-1) obtained above, 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-oxy-1-naphthalenesulfonic acid quinone diazide compound 4NT-350 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 0.04 g of KBM-1403 (p-phenylenediamine trimethoxysilane, Shin-Etsu Chemical, Japan) were added. After sufficient dissolution, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition Q-1.

[0131] Example 2

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

[0133] Example 3

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

[0135] Example 4

[0136] A 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] A photosensitive resin composition Q-5 was prepared in the same manner as in Example 1, except that 5.0 g of polyimide resin (A-1) was replaced by 7 g of polyimide resin (A-1), and 5.0 g of modified polyimide resin (A-5) was replaced by 3.0 g of modified polybenzoxazole precursor resin (A-6).

[0139] Example 6

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

[0141] Example 7

[0142] A 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] A photosensitive resin composition Q-8 was prepared in the same manner as in Example 1, except that 5.0 g of polyimide resin (A-1) was replaced by 7 g of polyimide resin (A-1), and 5.0 g of modified polyimide resin (A-5) was replaced by 3.0 g of modified phenolic resin solution (A-7).

[0145] Example 9

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

[0147] Example 10

[0148] A photosensitive resin composition Q-10 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 phenolic resin solution (A-8).

[0149] Embodiment 11

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

[0151] Example 12

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

[0153] Embodiment 13

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

[0155] Embodiment 14

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

[0157] Embodiment 15

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

[0159] Example 16

[0160] A 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 by 7.0 g of the polybenzoxazole precursor resin (A-2), and 5.0 g of the modified polyimide resin (A-5) was replaced by 3.0 g of the modified phenolic resin solution (A-8).

[0161] Embodiment 17

[0162] A 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 by 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced by 3.0 g of the modified polyimide resin (A-5).

[0163] Embodiment 18

[0164] A 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 by 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced by 3.0 g of the modified polybenzoxazole resin (A-6).

[0165] Embodiment 19

[0166] A 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 by 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced by 3.0 g of the modified polystyrene resin (A-7).

[0167] Embodiment 20

[0168] A 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 by 7.0 g of the alkali-soluble polyamide resin (A-9), and 5.0 g of the modified polyimide resin (A-5) was replaced by 3.0 g of the modified phenolic resin solution (A-8).

[0169] Comparative Example 1

[0170] 10.0 g of the polyimide (A-1) obtained above 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-oxy-1-naphthalenesulfonic acid quinonediazide compound 4NT-350 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 0.04 g of KBM-1403 (p-phenylenediamine trimethoxysilane, Shin-Etsu Chemical, Japan) were added. After fully dissolved, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition R-1.

[0171] Comparative Example 2

[0172] 10.0 g of the polybenzoxazole precursor (A-2) obtained above 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-oxy-1-naphthalenesulfonic acid quinone diazide compound 4NT-350 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 0.04 g of KBM-1403 (p-phenylenediamine trimethoxysilane, Shin-Etsu Chemical, Japan) were added. After fully dissolved, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition R-2.

[0173] Comparative Example 3

[0174] 10 g of the alkali-soluble polyamide resin (A-9) obtained above 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-oxy-1-naphthalenesulfonic acid quinone diazide compound 4NT-350 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 0.04 g of KBM-1403 (p-phenylenediamine trimethoxysilane, Shin-Etsu Chemical, Japan) were added. After fully dissolved, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition R-3.

[0175] Comparative Example 4

[0176] 10.0 g of the modified polyimide (A-5) obtained above 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-oxy-1-naphthalenesulfonic acid quinone diazide compound 4NT-350 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 0.04 g of KBM-1403 (p-phenylenediamine trimethoxysilane, Shin-Etsu Chemical, Japan) were added. After fully dissolved, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition R-4.

[0177] Comparative Example 5

[0178] A 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] A 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 components of the photosensitive resin compositions of the above examples and comparative examples are specifically shown in Table 1.

[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. Light transmittance test of resin composition

[0187] The photosensitive resin composition samples of the above-mentioned examples and comparative examples were coated on a glass sheet, and then soft-baked at 120°C for 3 minutes using a heating table to obtain a resin film with a film thickness of 2 μm. The transmittance spectrum of the above-obtained resin film at a wavelength of 300nm-800nm ​​was measured using an ultraviolet-visible spectrophotometer. As a result, the case where the transmittance of each wavelength of 365nm-436nm was less than 50% was considered insufficient (C), the case where the transmittance of each wavelength of 365nm-436nm was higher than 50% and lower than 70% was considered good (B), and the case where the transmittance of each wavelength of 365nm-436nm was higher than 70% was considered excellent (A).

[0188] 2. Resolution test

[0189] The photosensitive resin composition samples of the above examples and comparative examples were coated on a 4-inch silicon wafer, and then soft-baked at 120°C for 3 minutes using a heating table to obtain a resin film with a thickness of 7 μm. The UV lamp (i and g lines) was used with an exposure amount of 120 mJ / cm 2, and expose through a mask. After exposure, spray develop with 2.38% tetramethylammonium hydroxide developer for 60 seconds to remove the unexposed part. Use an optical microscope (MX63-F, Olympus) to observe the pattern at a magnification of 100 times, and take the minimum size of the through-hole pattern as the resolution.

[0190] 3. Film forming test

[0191] The photosensitive resin composition samples of the above-mentioned embodiments and comparative examples were coated on a 4-inch silicon wafer, and then soft-baked at 120°C for 3 minutes using a heating table to obtain a resin film with a film thickness of 15 μm. The film was then placed in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1) for heat treatment. Specifically as follows: first, the temperature was raised to 150°C for 1 hour of heat treatment, then the temperature was raised to 200°C for 1 hour of heat treatment after 20 minutes, and finally the temperature was raised to 300°C for 20 minutes and continued to be heat treated for 1.5 hours, and finally a cured film was obtained. The silicon wafer with the cured film was placed in a hydrofluoric acid solution, and the silicon wafer was corroded and stripped. The resin film evaluation criteria are as follows: "Excellent": The photosensitive resin composition can form a film, has good toughness, and does not break when folded in half; "Good": The photosensitive resin composition can form a film, has good toughness, and breaks when folded in half; "Poor": The photosensitive resin composition cannot form a film and is in the form of fragments.

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

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

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

[0195] The temperature of 5% thermal weight loss is used to measure the thermal stability of the material, because the temperature of 5% thermal weight loss can be determined very accurately. At the same time, when the weight loss is 5%, the material basically maintains its basic structure and usable performance. The higher the 5% thermal weight loss temperature, the better the thermal stability.

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

[0197] 6. Adhesion test

[0198] The photosensitive resin composition samples of the above-mentioned embodiments and comparative examples were uniformly coated on a copper substrate using a coating machine, and then placed on a heating table at 120°C for 3 minutes for soft baking to obtain a resin film with a film thickness of 15 μm. The resin film was engraved with a grid of 10 rows × 10 columns using a gridding machine (BYK-Gardner A-5125), and then the film was placed in a vacuum oxygen-free oven (MOLZK-32D1) for heat treatment: heat treatment at 170°C for 30 minutes, then the temperature was raised to 350°C after 1 hour, and treated at 350°C for 1 hour to finally obtain a cured film. The cured film was placed in a PCT test chamber for a 200-hour PCT aging test (121°C, 2 atmospheres of saturated steam; PCT-30, Dongguan Hongjin Technology). After the PCT test was completed, a peeling test was performed using tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998 for the cross-cutting test of paint and varnish films. The number of cross-cuttings peeled off was recorded as the peeling condition after the PCT test.

[0199] In the adhesive peeling test, the number of peeled pieces was considered "best" when it was less than 5, "good" when it was less than 10, "slightly good" when it was less than 30, and "poor" when it was 30 or more.

[0200] The photosensitive resin composition prepared above was evaluated according to the test method described above. 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 proportions, when the ratio reaches 7:3, the photosensitive resin composition has the best photolithographic performance and mechanical properties after film formation, and the highest 5% thermal weight loss temperature indicates that it has the best thermal stability and the strongest adhesion to the substrate. If the amount of alkali-soluble resin a is high, the transmittance of the photosensitive resin composition is low, and thus the resolution is poor; if the amount of alkali-soluble resin b is 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 low.

[0205] From the results of Examples 2, 5, 8, 11, 13 to 20 and Comparative Examples 1 to 6, it can be seen that the photosensitive resin composition obtained by compounding different alkali-soluble resins a with alkali-soluble resins b having phenolic hydroxyl groups modified by tert-butylcarbonyloxy groups significantly improves light transmittance, can greatly improve photolithography performance, and also significantly improves film-forming performance, mechanical properties and adhesion. Among them, the addition of polystyrene resin modified with tert-butylcarbonyloxy groups 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] From the results of Examples 2, 5, 8, 11, and 13 to 20, it can be seen that under the optimal ratio of alkali-soluble resin a to alkali-soluble resin b (7:3), 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 best light transmittance, photolithography performance, film-forming performance, thermal stability, and adhesion to the substrate after PCT experiment, and also has the best mechanical properties.

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: includes at least one of polyimide containing phenolic hydroxyl group, polybenzoxazole precursor containing phenolic hydroxyl group, polystyrene derivative containing phenolic hydroxyl group, and phenolic hydroxyl group-containing phenolic resin, wherein at least a part of the phenolic hydroxyl groups in these polymers are substituted by tert-butylcarbonyloxy group.

2. The resin composition according to claim 1, characterized in that: In the alkali-soluble resin b, the polyimide containing a phenolic hydroxyl group contains a structural unit represented by the following formula (2), the polybenzoxazole precursor containing a phenolic hydroxyl group contains a structural unit represented by the following formula (3), the polystyrene derivative containing a phenolic hydroxyl group contains a structural unit represented by the following formula (4), and the phenolic resin containing a phenolic hydroxyl group contains a structural unit represented by the following formula (5): In formula (2), X1 is derived from a dianhydride monomer, Y1 is derived from a diamine monomer, the diamine monomer contains a phenolic hydroxyl group, and R3 represents hydrogen or tert-butylcarbonyloxy; In 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 a phenolic hydroxyl group, and R4 represents hydrogen or tert-butylcarbonyloxy; 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 tert-butylcarbonyloxy; In 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, and R9 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: In the alkali-soluble resin b, the substitution rate of the phenolic hydroxyl group is 50% or more.

5. The resin composition according to any one of claims 1 to 3, characterized in that: The mass ratio of the alkali-soluble resin a to the alkali-soluble resin b is 1-9:

1.

6. The resin composition according to any one of claims 1 to 3, characterized in that: It also includes a photosensitizer, an auxiliary agent and a solvent; preferably, the total amount of the alkali-soluble resin a and the alkali-soluble resin b is 100 parts by mass, the photosensitizer is 1 to 50 parts by mass, the auxiliary agent is 0.01 to 5 parts by mass, and the solvent is 70 to 1800 parts by mass.

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

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

9. 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 8 .

10. 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 8 .

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