High-hydrophobicity photosensitive polyimide photoresist composition and application thereof

Abstract

The invention discloses a photosensitive polyimide photoresist composition with high hydrophobicity. The photosensitive polyimide photoresist composition comprises polyamide acid resin, diazonaphthoquinone sulfonate, a thermal crosslinking agent, a hydrophobic agent, a surfactant, a dissolution accelerator and a solvent. The hydrophobic agent used in the photosensitive polyimide photoresist composition can reduce the adsorption of moisture in the production and storage process on one hand, so that the shelf life is prolonged; and on the other hand, the amount of water adsorbed on the photoresist film can be reduced, and the interaction between water and nitrogen molecules in the IUV process is reduced, so that the generated nitrogen is smoothly diffused out of the film surface, and the film surface does not generate bubbles.

Description

Technical Field

[0001] The invention relates to the technical field of photosensitive polyimide materials, and in particular to a highly hydrophobic photosensitive polyimide photoresist composition and application thereof. Background Art

[0002] Photosensitive polyimide (PSPI) is a type of organic material that has both imide rings and photosensitive genes on the polymer chain, and has excellent thermal stability, good mechanical properties, chemical and photosensitive properties. PSPI has two main functions in the electronics field: photoresist and electronic packaging. By adding sensitizers, stabilizers, etc. to photosensitive polyimide, "polyimide photoresist" can be obtained.

[0003] The water content in PSPI photoresist will affect the stability of polyamic acid, and after PSPI is coated into a photoresist film, the adsorption of water molecules will also affect the diffusion and overflow of nitrogen during the IUV process, forming bubbles on the film surface, which will affect the flatness (degree of planarization: DOP) after coating. Therefore, it is necessary to develop a highly hydrophobic photosensitive polyimide photoresist that can improve the storage stability, film surface flatness and device reliability of the photoresist. Summary of the invention

[0004] In order to solve the technical problems existing in the prior art, the present invention provides a photosensitive polyimide photoresist composition which can reduce the adsorption of moisture during the production and storage process, allow the generated nitrogen to diffuse smoothly out of the film surface, thereby preventing bubbles from being generated on the film surface and extending the shelf life, and its application in the field of electronic packaging.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0006] In one aspect, the present invention provides a highly hydrophobic photosensitive polyimide photoresist composition, comprising a polyamic acid resin, a diazonaphthoquinone sulfonate, a thermal crosslinking agent, a hydrophobizing agent, a surfactant, a dissolution accelerator and a solvent.

[0007] In a preferred embodiment, the photosensitive polyimide photoresist composition comprises 2% to 30% by mass of polyamic acid resin, 2% to 35% of naphthoquinone diazosulfonate (100% polyamic acid resin), 5% to 40% of thermal crosslinking agent (100% polyamic acid resin), 1% to 5% of hydrophobic agent (100% polyamic acid resin), 0.001% to 2% of surfactant (100% polyamic acid resin), 5% to 30% of dissolution promoter (100% polyamic acid resin) and solvent;

[0008] In a more preferred embodiment, the photosensitive polyimide photoresist includes 5% to 25% by mass of polyamic acid resin, 5% to 25% of diazonaphthoquinone sulfonate (100% polyamic acid resin), 10% to 25% of thermal crosslinking agent (100% polyamic acid resin), 1% to 3% of hydrophobic agent (100% polyamic acid resin), 0.05% to 0.8% of surfactant (100% polyamic acid resin), 5% to 25% of dissolution promoter (100% polyamic acid resin) and the remainder of solvent.

[0009] In a specific embodiment, the polyamic acid resin comprises a structure represented by formula (I):

[0010]

[0011] Wherein: R1 is selected from an acid dianhydride having an alicyclic structure, R2 is selected from a monocyclic or polycyclic aromatic diamine compound, and R3 or R4 is selected from hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms; preferably, the molar amount of R3 or R4 selected from hydrogen accounts for 20%-60% of the total molar fraction of R3 or R4 in the polyamic acid resin; the amount of n is 10-100, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, preferably 5-30.

[0012] Preferably, R1 is selected from one or more of 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and 3,4-dicarboxylic acid-1,2,3,4-tetrahydro-1-naphthalene dibutyric dianhydride; more preferably, R1 is 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride.

[0013] Preferably, R2 is selected from one or more of 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminodiphenyl sulfide, and 4,4'-diaminobenzanilide; more preferably, R2 is 2,2'-bis(trifluoromethyl)benzidine.

[0014] More preferably, the mass average molecular weight (M w ) is 5000-50000, for example, including but not limited to 5000, 7000, 9000, 10000, 12000, 15000, 17000, 20000, 22000, 25000, 27000, 30000, 32000, 35000, 37000, 40000, 42000, 45000, 47000, and 50000.

[0015] In a specific embodiment, the diazonaphthoquinone sulfonate is diazonaphthoquinone-4-sulfonate or diazonaphthoquinone-5-sulfonate; preferably, the diazonaphthoquinone sulfonate is diazonaphthoquinone-5-sulfonate.

[0016] In a specific embodiment, the thermal crosslinking agent is one or more of HMOM-TRHAP, TMOM-BPAP, NIKALAC MX-270, EPICLON-HP-4032, and EPICLON HP-7200, preferably EPICLON-HP-4032.

[0017] In a specific embodiment, the hydrophobic agent is at least one of polypentafluoropropyl methacrylate, polyoctafluoropentyl methacrylate, polydimethylsiloxane, polymethyl methacrylate, hexafluorobisphenol A, and pentafluorophenol; preferably, the hydrophobic agent is hexafluorobisphenol A.

[0018] The key point of the present invention is that the added hydrophobic agent can block the adsorption of water during the production and storage process of the photosensitive polyimide photoresist composition, reduce the possibility of hydrolysis and cross-linking of the polyamic acid resin, and thus extend the shelf life; on the other hand, since the bond energy (29 kj / mol) of the OH...N hydrogen bond formed between water molecules and nitrogen molecules is greater than the OH...O hydrogen bond (21 kj / mol) between water molecules, the nitrogen generated during the IUV process combines with the water molecules for adsorption, which is a spontaneous process, and the added hydrophobic agent can reduce the amount of water adsorbed on the photoresist film, reduce the interaction between water and nitrogen molecules during the IUV process, and allow the generated nitrogen to diffuse out of the film surface smoothly, thereby preventing bubbles from being generated on the film surface.

[0019] In a specific embodiment, the surfactant is one or more of BYK-378, BYK-306, BYK-333, BYK-3760, KP-341, KP-358, KP-545, and KP-549; preferably, the surfactant is BYK-333; more preferably, the amount of the surfactant is 0.1 to 0.5 wt% (100% polyamic acid resin).

[0020] In a specific embodiment, the dissolution promoter is added to compensate for the insufficient solubility of the polyamic acid resin, and is specifically one or more of 4,4'-dihydroxybiphenyl, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, bisphenol A, and 4,4'-methylenebis(2,6-di-tert-butylphenol); preferably, the dissolution promoter is 1,1,1-tris(4-hydroxyphenyl)ethane.

[0021] In a specific embodiment, the solvent is one or more of N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate, and ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone.

[0022] On the other hand, the present invention provides the use of the photosensitive polyimide photoresist composition in wafer-level / panel-level packaging rewiring layers, electronic component interlayer insulating layers, and semiconductor surface protective films.

[0023] By adopting the above technical solution, the present invention can achieve the following beneficial effects:

[0024] (1) The hydrophobic agent contained in the photosensitive polyimide photoresist composition of the present invention can reduce the adsorption of water during production and storage, thereby extending the shelf life.

[0025] (2) The hydrophobic agent contained in the photosensitive polyimide photoresist composition of the present invention can reduce the amount of water adsorbed on the photoresist film, reduce the interaction between water and nitrogen molecules during the IUV process, and allow the generated nitrogen to diffuse smoothly out of the film surface, thereby preventing bubbles from being generated on the film surface and improving the flatness of the film surface. DETAILED DESCRIPTION

[0026] In order to better understand the technical solution of the present invention, the following examples will further illustrate the method provided by the present invention, but the present invention is not limited to the listed examples, and should also include any other known changes within the scope of the claims of the present invention.

[0027] Unless otherwise specified, other raw materials and reagents used in the examples and comparative examples of the present invention can be purchased through commercial channels.

[0028] The polyamic acid resin used is prepared according to the synthesis method in patent CN109348718A.

[0029] The specific steps of preparing polyamic acid resin include:

[0030] Under a dry nitrogen flow, add 2.24g (10mmol) 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, 3.2g (10mmol) 2,2'-bis (trifluoromethyl) benzidine, 0.1g cyclohexanol (1mmol) and 50g N-methylpyrrolidone to a 100mL four-necked flask, and heat and stir at 60°C. After 8 hours, cool to room temperature. Pour the obtained mixture into a large amount of deionized water for precipitation and washing, and then filter out the white precipitate. The precipitation and filtration process is repeated three times. Finally, the obtained white polyamic acid polymer is placed in a vacuum oven and dried for 72h to obtain polyamic acid resin powder PAA-1. The molecular weight is 12000 according to gel permeation chromatography, and the amount of R3 or R4 selected from hydrogen in the polyamic acid determined by acid-base neutralization reaction accounts for 35% of the total molar fraction of R3 or R4 in the polyamic acid resin.

[0031] Under a dry nitrogen flow, 2.688 g (12 mmol) was added to a 100 mL four-necked flask.

[0032] 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, 3.2g (10mmol) 2,2'-bis (trifluoromethyl) benzidine, 0.1g cyclohexanol (1mmol) and 50g N-methylpyrrolidone, heated and stirred at 60°C. After 8 hours, it was cooled to room temperature. The obtained mixture was poured into a large amount of deionized water for precipitation and washing, and then the white precipitate was filtered out by suction. The precipitation and filtration process was repeated three times. The white polyamic acid polymer obtained was placed in a vacuum oven and dried for 72h to obtain polyamic acid resin powder PAA-2. The molecular weight was characterized by gel permeation chromatography and was 14000. The amount of R3 or R4 of the polyamic acid selected from hydrogen accounted for 36% of the total molar fraction of R3 or R4 of the polyamic acid resin.

[0033] Preparation steps of photosensitive polyimide photoresist composition:

[0034] Table 1 shows the ingredients and contents of the photosensitive polyimide photoresist compositions in comparative examples 1 to 3 and embodiments 1 to 11 of the present invention. According to Table 1, firstly, polyamic acid resin, diazonaphthoquinone sulfonate, thermal crosslinking agent, hydrophobic agent, surfactant, dissolution promoter and solvent are accurately weighed in sequence, mixed, shaken for 4 hours with an oscillator, filtered with a 0.22 μm filter membrane, and continued to shake for 1 hour after filtration, to obtain the embodiments and comparative examples of the photosensitive polyimide photoresist compositions of the present invention.

[0035] Table 1 Compositions of photosensitive polyimide photoresist compositions of comparative examples 1 to 3 and embodiments 1 to 11

[0036]

[0037]

[0038]

[0039] In order to verify the effect of the photoresist of the present invention, the photosensitive polyimide photoresist compositions of Comparative Examples 1 to 3 and Examples 1 to 11 were used to perform viscosity and bubble tests.

[0040] The viscosity test conditions are as follows: a photosensitive polyimide photoresist composition that has been stored for 12 months is tested using a rotational viscometer.

[0041] 5 The bubble test conditions are as follows: Spin-coat the photosensitive polyimide photoresist composition using a 50r / 5s+200r / 30s process, then heat and bake at 120°C for 120s to obtain a glass sheet coated with photoresist.

[0042] ABM / 6 / 350 / NUV / DCCD / BSV / M lithography machine for exposure, energy is 500mJ / cm 2 , observe under a microscope whether bubbles are generated and the conditions of bubble generation.

[0043] Table 2 Viscosity and bubbles of Comparative Examples 1 to 3 and Examples 1 to 11

[0044]

[0045]

[0046] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be understood that the present invention is not limited to these embodiments and various modifications, changes and changes can be made without departing from the spirit and scope of the present invention. Therefore, the scope of the present invention should only be limited by the claims and their equivalents.

Claims

1. A highly hydrophobic photosensitive polyimide photoresist composition, characterized in that: The photosensitive polyimide photoresist composition comprises 2% to 30% by weight of a polyamic acid resin, 2% to 35% by weight of a naphthoquinone sulfonate, 5% to 40% by weight of a thermal crosslinking agent, 1% to 5% by weight of a hydrophobic agent, 0.001% to 2% by weight of a surfactant, 5% to 30% by weight of a dissolution accelerator, and a solvent, based on the weight of the polyamic acid resin.

2. The photosensitive polyimide photoresist composition according to claim 1, characterized in that: The photosensitive polyimide photoresist composition comprises 5% to 25% by mass of a polyamic acid resin, 5% to 25% by mass of a naphthoquinone sulfonate, 10% to 25% by mass of a thermal crosslinker, 1% to 3% by mass of a hydrophobic agent, 0.05% to 0.8% by mass of a surfactant, 5% to 25% by mass of a dissolution accelerator, and a solvent, based on the mass of the polyamic acid resin, based on the mass of the polyamic acid resin.

3. The photosensitive polyimide photoresist composition according to claim 1 or 2, characterized in that: The polyamic acid resin comprises a structure represented by chemical formula (I), Wherein: R1 is selected from an acid dianhydride having an alicyclic structure, R2 is selected from a monocyclic or polycyclic aromatic diamine compound, and R3 or R4 is selected from hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms; preferably, the molar amount of R3 or R4 selected from hydrogen accounts for 20%-60% of the total molar fraction of R3 or R4 in the polyamic acid resin; preferably, the amount of n is 10-100, more preferably 5-30; more preferably, the mass average molecular weight of the polyamic acid resin is 5000-50000.

4. The photosensitive polyimide photoresist composition according to claim 1 or 2, characterized in that: The diazonaphthoquinone sulfonate is diazonaphthoquinone-4-sulfonate or diazonaphthoquinone-5-sulfonate; preferably, the diazonaphthoquinone sulfonate is diazonaphthoquinone-5-sulfonate.

5. The photosensitive polyimide photoresist composition according to claim 1 or 2, characterized in that: The thermal crosslinking agent is one or more of HMOM-TRHAP, TMOM-BPAP, NIKALAC MX-270, EPICLON-HP-4032, and EPICLON HP-7200.

6. The photosensitive polyimide photoresist composition according to claim 1 or 2, characterized in that: The hydrophobic agent is at least one of polypentafluoropropyl methacrylate, polyoctafluoropentyl methacrylate, polydimethylsiloxane, polymethyl methacrylate, hexafluorobisphenol A, and pentafluorophenol.

7. The photosensitive polyimide photoresist composition according to claim 1 or 2, characterized in that: The surfactant is one or more of BYK-378, BYK-306, BYK-333, BYK-3760, KP-341, KP-358, KP-545, and KP-549.

8. The photosensitive polyimide photoresist composition according to claim 1 or 2, characterized in that: The dissolution promoter is one or more of 4,4'-dihydroxybiphenyl, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, bisphenol A, and 4,4'-methylenebis(2,6-di-tert-butylphenol); preferably, the dissolution promoter is 1,1,1-tris(4-hydroxyphenyl)ethane.

9. The photosensitive polyimide photoresist composition according to claim 1 or 2, characterized in that: The solvent is one or more of N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, and methyl lactate.

10. Use of the highly hydrophobic photosensitive polyimide photoresist composition according to any one of claims 1 to 9 in wafer-level / panel-level packaging rewiring layers, electronic component interlayer insulating layers, and semiconductor surface protection films.

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