A compound, a photosensitive resin composition, and a preparation method and application thereof

Abstract

The present application discloses a compound, a photosensitive resin composition, a preparation method and an application thereof, belonging to the technical field of functional polymer materials. The compound has both nitrogen heterocycle and epoxy structure. By introducing the compound into the photosensitive resin composition, a condensation reaction is carried out with the resin and the same molecules to form a cross-linked structure, thereby improving the film-forming property, chemical resistance, mechanical properties and thermal stability of the cured film in application, and utilizing the presence of heterocyclic N atoms to reduce the dielectric constant of the cured film and suppress the discoloration problem of the copper or copper alloy substrate.

Description

Technical Field

[0001] The present application relates to a compound, a photosensitive resin composition, a preparation method and application thereof, and belongs to the technical field of functional polymer materials. Background Art

[0002] Photosensitive polyimide (PSPI) is a polymer composite material with excellent thermal, mechanical, electrical, and chemical properties, as well as photosensitivity. Upon UV exposure and development, it can produce three-dimensional patterns with fine structures, significantly simplifying the photolithography process. It is an ideal insulating material for microelectronics and semiconductor packaging. The trend toward lighter, higher-performance, and more multifunctional electronic products is placing higher demands on PSPI packaging materials.

[0003] Currently, the dielectric constants of some common PSPI packaging materials are relatively high (usually greater than 3), which cannot meet the performance requirements of low dielectric constant and low dielectric loss for the next generation of communication technology. On the other hand, with the integration of semiconductor devices and the miniaturization of chip size, the wiring and installation methods of semiconductor devices have changed. The previous gold or aluminum wiring has been replaced by copper or copper alloy wiring with lower resistance, and the previous lead-tin eutectic soldering has been replaced by ball grid array and chip size installation for higher density installation. The cured resin film is in direct contact with the copper or copper alloy and the solder bumps, which requires the cured resin film to have excellent heat resistance and chemical resistance, good adhesion to the copper or copper alloy substrate, and must not cause discoloration of the copper or copper alloy substrate.

[0004] In the prior art, multiple additives are usually added to improve the comprehensive properties of the cured film. In patent JP5446203B2, by adding heterocyclic compounds, the corrosion of the resin to copper or copper alloy is reduced and the adhesion is increased. In patent CN102375336B, by adding purine derivatives, cross-linking agents, and organic titanium compounds, the adhesion, heat resistance, and chemical resistance are increased, and the discoloration of the copper or copper alloy substrate is suppressed. In order to achieve comprehensive properties, multiple additives are added in the prior art, which often causes the additive content to be too much, which can reduce the performance of the resin material. In addition, there is a problem of whether the compatibility of multiple additives is matched, which easily causes another performance degradation while the performance is improved on the one hand. Summary of the Invention

[0005] To address the problem in the prior art of photosensitive polyimide (PSPI) packaging materials that excessive additives are often added to achieve comprehensiveness, which in turn affects the performance of the resin, the present application provides a compound, a photosensitive resin composition, and a preparation method thereof. The compound has both nitrogen heterocycle and epoxy structures. By introducing the compound into the photosensitive resin composition, a condensation reaction occurs with the resin and the same molecules to form a cross-linked structure, thereby improving the film-forming properties, chemical resistance, mechanical properties, and thermal stability of the cured film during application. The presence of heterocyclic N atoms is utilized to reduce the dielectric constant of the cured film and suppress discoloration of the copper or copper alloy substrate.

[0006] This application adopts the following technical solutions:

[0007] According to the first aspect of the present application, a compound is provided, wherein the compound has a structure shown in Formula I:

[0008]

[0009] In formula I, W is an organic group containing a nitrogen heterocyclic ring.

[0010] Optionally, W is selected from any one of the groups shown in formula II-a:

[0011]

[0012] The dotted lines represent access sites.

[0013] Optionally, the compound is at least one compound having a structure shown in Formula I-1 to Formula I-5:

[0014]

[0015] According to the second aspect of the present application, there is provided a method for preparing the above compound, comprising the following steps:

[0016] S1, heating a mixed solution containing a triamine compound and solvent I, and then dropwise adding a material containing epoxychloroalkane and solvent II to the mixed solution to undergo a ring-opening reaction;

[0017] S2. Add a strong base solution to the product of step S1, perform a cyclization reaction, and separate and purify to obtain the compound.

[0018] Optionally, the dropping rate of the epichlorohydrin and solvent II and the dropping rate of the strong base solution are independently 1 to 5 mL / min.

[0019] Optionally, the dropwise addition rate of the epoxychloroalkane and solvent II materials and the dropwise addition rate of the strong base solution are independently selected from any value among 1 mL / min, 1.5 mL / min, 2 mL / min, 2.5 mL / min, 3 mL / min, 3.5 mL / min, 4 mL / min, 4.5 mL / min, 5 mL / min, or any range value therebetween.

[0020] Optionally, in step S1, the molar ratio of the triamine compound to the epoxychloroalkane is 1:6-10.

[0021] Optionally, in step S1, the molar ratio of the triamine compound to the epoxychloroalkane is selected from any value of 1:6, 1:7, 1:8, 1:9, 1:10, or any range between the two.

[0022] Optionally, in step S1, the heating condition includes: heating to 35-60°C.

[0023] Optionally, in step S1, the conditions for the ring-opening reaction include: reaction temperature of 35-60° C., and reaction time of 3-6 h.

[0024] Optionally, the molar ratio of the triamine compound to the strong base is 1:6-10.

[0025] Optionally, the molar ratio of the triamine compound to the strong base is selected from any value of 1:6, 1:7, 1:8, 1:9, 1:10, or any range therebetween.

[0026] Optionally, in step S2, the conditions for the cyclization reaction include: reaction temperature of 35-60° C., and reaction time of 1-5 h.

[0027] Optionally, solvent I and solvent II are independently selected from at least one of ethanol, ethylene glycol, glycerol, and ethylene glycol butyl ether.

[0028] Optionally, the concentration of the alkali in the strong alkali solution is 20 to 50 wt%.

[0029] Optionally, the strong alkaline solution is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution.

[0030] Optionally, the separation and purification includes at least one of extraction, washing, rotary evaporation, and drying.

[0031] Optionally, the triamine compound is selected from at least one of the compounds represented by the structure of Formula II-b:

[0032]

[0033] Optionally, the epichlorohydrin is selected from epichlorohydrin or epibromohydrin.

[0034] According to a third aspect of the present application, a photosensitive resin composition is provided, which is obtained by uniformly mixing raw materials including the following components:

[0035] A polyimide having a hydroxyl structure or a precursor resin thereof, a compound represented by the above formula I, a photosensitizer, and a solvent III.

[0036] Optionally, the photosensitive resin composition is obtained by mixing the above raw materials and then filtering.

[0037] Optionally, the weight ratio of the polyimide having a hydroxyl structure or its precursor resin to the compound is 1:0.001 to 0.2, preferably 1:0.01 to 0.1.

[0038] Optionally, the weight ratio of the polyimide having a hydroxyl structure or its precursor resin to the compound is selected from any value of 1:0.001, 1:0.01, 1:0.05, 1:0.1, 1:0.2 or any range therebetween.

[0039] Optionally, the solvent III is selected from at least one of methyl pyrrolidone, methyl ethyl ketone, acetone, γ-butyrolactone, ethyl acetate, ethyl lactate, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monoethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0040] Optionally, the weight ratio of the polyimide having a hydroxyl structure or its precursor resin to the solvent III is 1:1-20.

[0041] Optionally, the weight ratio of the polyimide having a hydroxyl structure or its precursor resin to the solvent III is selected from any value of 1:1, 1:1.5, 1:2, 1:5, 1:8, 1:15, 1:20, or any range therebetween.

[0042] Optionally, the preparation of the polyimide precursor having a hydroxyl structure refers to the technical solution in the patent publication number CN117304225A of the applicant.

[0043] Optionally, the polyimide precursor having a hydroxyl structure is polyamic acid or polyamic acid ester, as shown in Formula III:

[0044]

[0045] In formula III, A represents a tetravalent organic group having 4 to 40 carbon atoms; B represents a divalent organic group having 2 to 40 carbon atoms; R1 and R2 each independently represent a hydrogen atom or a saturated aliphatic group having 1 to 10 carbon atoms; m is an integer ≥1, and the groups in the brackets can be optionally the same or different.

[0046] Optionally, in Formula III, A is preferably an aromatic organic group having 6 or more carbon atoms, and further preferably at least one of the compounds represented by the structure of Formula III-a:

[0047]

[0048] Optionally, in Formula III, B is preferably an aromatic organic group having 6 or more carbon atoms and containing a hydroxyl structure, and is further preferably at least one of the compounds represented by Formula III-b:

[0049]

[0050] Optionally, the polyimide precursor having a hydroxyl structure further includes a capping agent; the capping agent is introduced during the resin synthesis process to improve the stability of the resin, and the capping agent is used in the following manner: the capping agent is added simultaneously with the diamine and dianhydride; or, the capping agent is added after the diamine and dianhydride react; or, the diamine or dianhydride is added after the capping agent reacts with the dianhydride or diamine.

[0051] Optionally, the end-capping agent is selected from at least one of monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride, and monoactive ester. The type and amount of the end-capping agent can be adjusted by those skilled in the art as needed.

[0052] Optionally, the method for preparing polyamic acid comprises the following steps: firstly subjecting dianhydride and diamine to a polymerization reaction, then adding a capping agent to continue the reaction, and obtaining a polyamic acid solution after the reaction is completed.

[0053] Alternatively, the polyamic acid ester is prepared by heating the polyamic acid in an esterification agent, during which the carboxylic acid functional groups in the polyamic acid are converted into carboxylate groups through an esterification reaction. The esterification reaction can be further reacted in the polyamic acid solution to obtain the polyamic acid ester.

[0054] The esterification rate of the polyamic acid is 40-90%; the temperature of the esterification reaction is 40-100° C., and the reaction time is 1-12 hours; the esterification reagent includes alcohol compounds such as methanol, ethanol, and n-butanol, and acetal compounds such as N,N-dimethylformamide dimethyl methylal (DMFDMA) and N,N-dimethylformamide dimethyl acetal (DMADEA); and the molar ratio of the polyamic acid to the esterification reagent is 1:1-10.

[0055] The polymer obtained by the above method is added to a large amount of water or methanol solution to precipitate, filter, and dry for isolation. This operation can remove unreacted monomers, dimers, trimers, and other oligomer components, thereby improving the film properties after thermal curing.

[0056] Optionally, the compound represented by Formula I in the photosensitive resin composition is at least one compound selected from the group consisting of compounds represented by Formulas I-1 to I-5.

[0057] Optionally, the amount of the photosensitizer used is 5 to 40% of the mass of the polyimide having a hydroxyl structure or its precursor resin.

[0058] Optionally, the amount of the photosensitive agent used is a ratio of the mass of the polyimide having a hydroxyl structure or its precursor resin selected from any value among 5%, 10%, 20%, 30%, 40% or any range between the two; preferably 10-30%.

[0059] Optionally, the photosensitive agent in the photosensitive resin composition is not strictly limited in this application, and those skilled in the art can select from the existing technology as needed, such as photoacid generators and photobase generators. From the perspective of dissolution contrast, the photosensitive agent is preferably a photoacid generator. The photoacid generator is a compound that generates acid by irradiation with ultraviolet light, visible light, etc., such as quinone diazide compounds, iodonium salt compounds, and sulfonium salt compounds. From the perspective of photosensitivity and stability, the photoacid generator is preferably a quinone diazide compound, a sulfonate compound formed by naphthoquinone diazide sulfonyl chloride and a low molecular weight polyphenol compound. Diazo naphthoquinone compounds have a dissolution inhibitory effect on the resin before exposure. After exposure, they can generate indanoic acid in the ultraviolet exposure area. The solubility of the exposed part in the alkaline aqueous solution increases, so that the exposed part can be removed, leaving the unexposed part, and finally the desired pattern is obtained. Among them, the difference in the dissolution rate of the exposed part and the unexposed part in the alkaline developer is the key to obtaining an excellent pattern.

[0060] The quinone diazide compound described in this application can be prepared from naphthoquinone diazide sulfonyl chloride and a low molecular weight polyphenol compound, or a commercial product can be directly purchased. Commercial quinone diazide compounds are preferred, such as NT-300 (esterification reaction product of 2,3,4-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid), 4NT-300 (esterification reaction product of 2,3,4,4-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid), and HP-190 (esterification reaction product of tris(4-hydroxyphenyl)ethane and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid) (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan). Using two or more of the above quinone diazide compounds can further increase the ratio of the dissolution rate of the exposed area to the unexposed area, thereby obtaining a highly sensitive photosensitive resin composition. The naphthoquinonediazidesulfonyl chloride is selected from any one of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride or a mixture of the two. The structural formulas of the 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride are as follows:

[0061]

[0062] The low molecular weight polyphenol compound described in the present application is selected from bisphenol A, trisphenol A, 4,4'-isopropylidene diphenol, 1,1'-bis-4-(hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenyl sulfone, 4,4-hexafluoroisopropylidene diphenol, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxy-p-cresol, 2,6-diacetoxymethyl-p-cresol, 4,4',4"-trihydroxytriphenylmethane, 1,1',1"-tris(4-hydroxyphenyl)ethane, 4,4'-[1-[4- At least one of [1-(4-hydroxyphenyl)1-methylethyl]phenyl]ethylene]bisphenol, methyl 3,4,5-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, isopentyl 3,4,5-trihydroxybenzoate, 2-ethylbutyl 3,4,5-trihydroxybenzoate, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, and 2,3,4,2',4'-pentahydroxybenzophenone.

[0063] Optionally, the photosensitive resin composition further includes a sensitizer.

[0064] Optionally, the amount of the sensitizer used is 1 to 20% of the mass of the polyimide having a hydroxyl structure or its precursor resin, preferably 5 to 15%.

[0065] Optionally, the amount of the sensitizer used is a ratio of the mass of the polyimide having a hydroxyl structure or its precursor resin selected from any value selected from 1%, 5%, 10%, 15%, 20% or any range between the two.

[0066] The addition of a sensitizer can improve photosensitivity. Typical sensitizers suitable for this application include organic compounds containing phenolic hydroxyl groups, hydroxyl groups, or carboxyl groups.

[0067] The compounds containing phenolic hydroxyl groups include BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (the above are trade names, available from Asahi Organic Materials Industries, Ltd.), Bis-Z, BisP-EZ, TrisP-HAP, TrisP-PA, TrisP-SA, BisP-MZ, BisP-PZ, BisP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisRS-26X (the above are trade names, available from Honshu Chemical Industry Co., Ltd.), at least one of 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 9,9-bis(4-hydroxyphenyl)fluorene, 4,4'-dihydroxydiphenylcyclohexane, bis(4-hydroxyphenyl)sulfide, 1,4-naphthalenediol, 2,3-naphthalenediol, 4,4',4"-trihydroxytriphenylmethane, 1,1',1"-tris(4-hydroxyphenyl)ethane, 2,3,4-trihydroxybenzophenone, and methyl 3,4,5-trihydroxybenzoate.

[0068] The organic compound containing hydroxyl groups refers to a saturated or unsaturated fatty alcohol containing 2 to 16 carbon atoms, including at least one of ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, pentanol, n-hexanol, cyclopropylmethanol, cyclohexylmethanol, 4-methyl-1-cyclohexylmethanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-tert-butylcyclohexanol, heptanol, octanol, cyclooctanol, 1-cyclohexyl-1-pentanol, 3,5,5-trimethylcyclohexanol, norbornene-2-methanol, cis-4-heptene-1-ol, cis-3-octen-1-ol, 2,7-octadienol, 2,4,4-methyl-2-pentanol, cyclohexylmethanol, cis-2-hexene-1-ol, n-hexanol, isopentanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, isobutanol, and neopentyl alcohol.

[0069] The organic compound containing a carboxyl group refers to a carboxylic acid compound containing 2 to 16 carbon atoms, including at least one of acetic acid, propionic acid, butyric acid, valeric acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-n-pentanoic acid, 4-methyl-n-pentanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, n-decanoic acid, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 10-undecenoic acid, p-methoxybenzoic acid, m-methylbenzoic acid, benzoic acid, mandelic acid, trans-2-hexenoic acid, 3,7-dimethyl-6-octanoic acid, sorbic acid, 3,5,5-trimethylhexanoic acid, lauric acid, and lauroleic acid.

[0070] Optionally, the photosensitive resin composition further includes a surfactant.

[0071] Optionally, the weight ratio of the surfactant to the polyimide having a hydroxyl structure or a precursor resin thereof is 0.0001 to 0.05:1.

[0072] Optionally, the weight ratio of the surfactant to the polyimide having a hydroxyl structure or a precursor resin thereof is selected from any value selected from 0.0001:1, 0.0005:1, 0.001:1, 0.005:1, 0.01:1, 0.03:1, 0.05:1 or any range therebetween.

[0073] Optionally, the surfactant is an acrylic ester copolymer; the acrylic ester copolymer is selected from the POLYFLOW series of surfactants or the SKB-FLOW series of surfactants; illustratively, the POLYFLOW series of surfactants can be selected from at least one of POLYFLOW No 7, POLYFLOW No36, POLYFLOW No56, POLYFLOW No77, POLYFLOW No90, POLYFLOW WS, and POLYFLOW WS-314 (trade names, Kyoeisha Chemical Co., Ltd.); the SKB-FLOW series of surfactants can be selected from at least one of SKB-FLOWSD, SKB-FLOW SL, SKB-FLOW P90, SKB-FLOW 1358, SKB-FLOW 1392, SKB-FLOW 1460D, and SKB-FLOW 90D (trade names, SKB, South Korea). The acrylic copolymer described in this application is preferably POLYFLOW No. 77, because POLYFLOW No. 77 has good compatibility with the system, can improve the leveling of the adhesive, and prevent bubbles or streaks during coating, thereby obtaining a resin film with uniform film thickness and avoiding affecting the performance of the film after curing.

[0074] Optionally, the photosensitive resin composition is obtained by uniformly mixing and then filtering raw materials including the following components: polyimide having a hydroxyl structure or a precursor resin thereof, the compound represented by the above formula I, a photosensitizer, and a solvent III.

[0075] Optionally, the photosensitive resin composition is obtained by uniformly mixing and filtering raw materials including the following components: a polyimide having a hydroxyl structure or a precursor resin thereof, a compound represented by the above formula I, a photosensitizer, a solvent III, a photosensitizer, and a surfactant;

[0076] The mixing process comprises: mixing a polyimide having a hydroxyl structure or a precursor resin thereof and a solvent III, and stirring; after the polyimide having a hydroxyl structure or a precursor resin thereof is fully dissolved, adding a photosensitive agent, and after dissolution, adding the compound represented by the above formula I and a surfactant, continuing to stir until completely dispersed, and then filtering using a 1.0 μm polytetrafluoroethylene filter membrane to obtain a photosensitive resin composition.

[0077] According to a fourth aspect of the present application, a polyimide film is provided, which is obtained by coating and curing the above-mentioned photosensitive resin composition.

[0078] The preparation process of the polyimide film in this application is not particularly limited to the base material to be coated. Those skilled in the art can make conventional selections. Examples of the base material include silicon wafers, aluminum wafers, silver wafers, copper wafers, copper alloy wafers, ceramic wafers, etc., preferably silicon wafers (e.g., 4-inch silicon wafers), aluminum wafers, silver wafers, and copper wafers. The specific coating method is also not particularly limited. Examples of the base material to be coated include spray coating, spin coating, and doctor blade coating. In the actual coating operation, the film thickness may vary due to differences in the coating method, rotation speed, viscosity, and composition. The coating method is preferably spin coating.

[0079] Optionally, the polyimide film has a cured relief pattern.

[0080] Optionally, the method for preparing the polyimide film having a cured relief pattern comprises: coating a photosensitive resin composition on a substrate, followed by drying, exposing, developing, and curing to obtain the polyimide film.

[0081] In the preparation process of the polyimide film with a solidified relief pattern in this application, the drying method can be baking. Specifically, baking can be performed in an oven, a heating table, an infrared lamp, etc., preferably using a heating table. More preferably, the drying temperature is 80-150°C and the drying time is 1 to 10 minutes. More preferably, the drying temperature is 100-130°C and the drying time is 2 to 5 minutes. After the drying operation is completed, the thickness of the photosensitive resin film layer is measured after natural cooling to 25°C.

[0082] In the preparation of the polyimide film with a cured relief pattern described herein, the exposure step involves exposing the dried photosensitive resin film layer to light through a patterned mask using an exposure device. Common active light sources include ultraviolet rays, X-rays, and electron beams. In this invention, mercury lamps are preferably used for exposure, including i-ray (365nm), h-ray (405nm), and g-ray (436nm) light sources.

[0083] In the preparation process of the polyimide film with a solidified relief pattern in the present application, a developer is used to remove the exposed part to form a pattern and complete the development. The choice of developer can be made by a person skilled in the art in conventional ways, such as aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. The specific operation of development is as follows: pour the developer and the rinse solution into two glass culture dishes respectively, control the temperature of the developer to be 25±1°C, immerse the exposed resin film in the developer, and then start timing. After the exposed part is completely exposed to the substrate, the development is completed, the timing is stopped, and the time required for the whole process is recorded. If necessary, the resin film can be baked before development, and the baking temperature is 60-150°C, preferably 60-120°C, and the baking time is 5s-60min. After rinsing, the resin film is heated and dried in the range of 60-200°C, and the drying time is controlled to be 1-60min.

[0084] In the preparation process of the polyimide film or the polyimide film with a cured relief pattern in the present application, the temperature of the curing operation is 300-400°C, preferably 350°C. The pattern obtained after development and rinsing is thermally imidized to convert it into a cured film. The heating treatment usually selects a staged temperature increase, and maintains a certain time at different temperatures or selects a certain temperature range for continuous temperature increase. For example, a heat treatment method is performed at 150°C, 250°C, and 350°C for 30 minutes respectively, or a method of continuously heating from room temperature to 350°C. Inert gases such as nitrogen and argon are often used during curing. As a specific application example, the oxygen content in the oven cavity is first controlled to be lowered to below 50ppm, and then the temperature is started to be raised to 150°C and kept at a constant temperature for 30 minutes, then the temperature is raised to 250°C and kept at a constant temperature for 30 minutes, then the temperature is raised to 350°C and kept at a constant temperature for 1 hour, and then the temperature is lowered to room temperature to finally obtain a cured relief pattern.

[0085] According to a fifth aspect of the present application, there is provided a use of at least one of the above-mentioned compound, the above-mentioned photosensitive resin composition, and the above-mentioned polyimide film in the manufacture of a semiconductor element.

[0086] Optionally, the semiconductor element comprises the polyimide film or the polyimide film having a cured relief pattern.

[0087] Because the polyimide film obtained by curing the photosensitive resin composition described herein has high heat resistance and high mechanical strength, applications include using the polyimide film obtained by curing the photosensitive resin composition described herein as a surface protective film for semiconductor components, an interlayer dielectric or insulating layer, and an insulating layer for protecting circuit board circuits. Electronic devices using the surface protective layer, interlayer insulating layer, etc. obtained from the photosensitive resin composition provided herein, such as magnetoresistive memory, polymer memory, and phase change memory, can also be used.

[0088] The beneficial effects of this application include:

[0089] The compounds provided herein possess both nitrogen heterocyclic and epoxy structures. By introducing these compounds into a photosensitive resin composition, they undergo condensation reactions with the resin and similar molecules to form a cross-linked structure, thereby improving the film-forming properties, chemical resistance, mechanical properties, and thermal stability of the cured film. Furthermore, the presence of heterocyclic nitrogen atoms can reduce the dielectric constant of the cured film, suppress discoloration of the copper or copper alloy substrate, and enhance the overall performance and reliability of the cured film. BRIEF DESCRIPTION OF THE DRAWINGS

[0090] Figure 1 The following is a comparison of the chemical resistance microscope photos of the cured films of Example 1 of the present application and Comparative Examples 1 and 2. DETAILED DESCRIPTION

[0091] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0092] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0093] Unless otherwise specified, conventional methods were used for testing, and instrument settings were those recommended by the manufacturer.

[0094] The structural formulas and names of the raw materials P-1, P-2, P-3, P-4, P-5, P-6, ODPA, and HFHA involved in the specific embodiments of the present application are shown in Table 1 below, where P-1 to P-5 were synthesized through Synthesis Examples 1-5.

[0095] Table 1

[0096]

[0097]

[0098] Synthesis example 1

[0099] Compound C-1 has the following structure:

[0100]

[0101] The synthesis method of compound C-1 is as follows:

[0102] 57.06 g (0.5 mol) of P-1 and an appropriate amount of anhydrous ethanol were added to a three-necked flask equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, and the temperature was raised to 60°C. A mixture of 323.89 g (3.5 mol) of epichlorohydrin and anhydrous ethanol was added to the constant pressure dropping funnel and slowly added dropwise. After the addition of epichlorohydrin was completed, the reaction was allowed to proceed for 6 hours. After confirming that the reaction of P-1 was complete by HPLC, 450 g of a 30% sodium hydroxide aqueous solution was slowly added dropwise using a constant pressure dropping funnel, and the addition rate was controlled at 3 mL / min. After the addition was completed, the temperature was maintained at 50°C for a closed-loop reaction for 3 hours. Finally, the mixture was extracted with toluene, stirred, and allowed to stand for stratification. The oil phase was washed with an appropriate amount of deionized water until the pH was neutral. The oil phase was distilled under reduced pressure to remove excess epichlorohydrin and solvent to obtain a colorless transparent liquid.

[0103] 1 HNMR(DMSO): δ: 2.36(m,6H), 2.49(m,6H), 2.54(m,6H), 2.60(m,6H), 2.79(m,6H), 3.04(m,6H), 3.29(m,6H).

[0104] Synthesis example 2

[0105] Compound C-2 has the following structure:

[0106]

[0107] The synthesis method of compound C-2 is as follows:

[0108] 62.57 g (0.5 mol) of P-2 and an appropriate amount of anhydrous ethanol were added to a three-necked flask equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, and the temperature was raised to 60°C. A mixture of 323.89 g (3.5 mol) of epichlorohydrin and anhydrous ethanol was added to the constant pressure dropping funnel and slowly added dropwise. After the addition of epichlorohydrin was completed, the reaction was allowed to proceed for 6 hours. After confirming that the reaction of P-1 was complete by HPLC, 450 g of a 30% sodium hydroxide aqueous solution was slowly added dropwise using a constant pressure dropping funnel, and the addition rate was controlled at 3 mL / min. After the addition was completed, the temperature was maintained at 50°C for a closed-loop reaction for 3 hours. Finally, the mixture was extracted with toluene, stirred, and allowed to stand for stratification. The oil phase was washed with an appropriate amount of deionized water until the pH was neutral. The oil phase was distilled under reduced pressure to remove excess epichlorohydrin and solvent to obtain a colorless transparent liquid.

[0109] 1HNMR (DMSO): δ: 2.36 (m, 6H), 2.49 (m, 6H), 2.60 (m, 6H), 3.04 (m, 6H), 3.29 (m, 6H), 4.74 (s, 1H).

[0110] Synthesis example 3

[0111] Compound C-3 has the following structure:

[0112]

[0113] The synthesis method of compound C-3 is as follows:

[0114] 63.06 g (0.5 mol) of P-3 and an appropriate amount of anhydrous ethanol were added to a three-necked flask equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, and the temperature was raised to 60°C. A mixture of 323.89 g (3.5 mol) of epichlorohydrin and anhydrous ethanol was added to the constant pressure dropping funnel and slowly added dropwise. After the addition of epichlorohydrin was completed, the reaction was allowed to proceed for 6 hours. After confirming that the reaction of P-1 was complete by HPLC, 450 g of a 30% sodium hydroxide aqueous solution was slowly added dropwise using a constant pressure dropping funnel, and the addition rate was controlled at 3 mL / min. After the addition was completed, the temperature was maintained at 50°C for a closed-loop reaction for 3 hours. Finally, the mixture was extracted with toluene, stirred, and allowed to stand for stratification. The oil phase was washed with an appropriate amount of deionized water until the pH was neutral. The oil phase was distilled under reduced pressure to remove excess epichlorohydrin and solvent to obtain a colorless transparent liquid.

[0115] 1 HNMR (DMSO): δ: 2.36 (m, 6H), 2.49 (m, 6H), 2.60 (m, 6H), 3.04 (m, 6H), 3.29 (m, 6H), 4.74 (s, 1H).

[0116] Synthesis example 4

[0117] Compound C-4 has the following structure:

[0118]

[0119] The synthesis method of compound C-4 is as follows:

[0120] 177.21 g (0.5 mol) of P-4 and an appropriate amount of anhydrous ethanol were added to a three-necked flask equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, and the temperature was raised to 60°C. A mixture of 323.89 g (3.5 mol) of epichlorohydrin and anhydrous ethanol was added to the constant pressure dropping funnel and slowly added dropwise. After the addition of epichlorohydrin was completed, the reaction was allowed to proceed for 6 hours. After confirming that the reaction of P-1 was complete by HPLC, 450 g of a 30% sodium hydroxide aqueous solution was slowly added dropwise using a constant pressure dropping funnel, and the addition rate was controlled at 3 mL / min. After the addition was completed, the temperature was maintained at 50°C for a closed-loop reaction for 3 hours. Finally, the mixture was extracted with toluene, stirred, and allowed to stand for stratification. The oil phase was washed with an appropriate amount of deionized water until the pH was neutral. The oil phase was distilled under reduced pressure to remove excess epichlorohydrin and solvent to obtain a colorless transparent liquid.

[0121] 1 HNMR (DMSO): δ: 2.36 (m, 6H), 2.49 (m, 6H), 2.60 (m, 6H), 3.33 (m, 6H), 3.58 (m, 6H), 6.92 (d, 6H), 7.87 (d, 6H).

[0122] Synthesis example 5

[0123] Compound C-5 has the following structure:

[0124]

[0125] The synthesis method of compound C-5 is as follows:

[0126] P-5 144.18g (0.5mol) and an appropriate amount of anhydrous ethanol were added to a three-necked flask equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, and the temperature was raised to 60°C. A mixture of 323.89g (3.5mol) of epichlorohydrin and anhydrous ethanol was added to the constant pressure dropping funnel and slowly added dropwise. After the addition of epichlorohydrin was completed, the reaction was allowed to proceed for 6h. After confirming that the reaction of P-1 was complete by HPLC, 450g of a 30% sodium hydroxide aqueous solution was slowly added dropwise using a constant pressure dropping funnel, and the addition rate was controlled at 3mL / min. After the addition was completed, the temperature was maintained at 50°C for a closed-loop reaction for 3h. Finally, the mixture was extracted with toluene, stirred, and allowed to stand for stratification. The oil phase was washed with an appropriate amount of deionized water until the pH was neutral. The oil phase was distilled under reduced pressure to remove excess epichlorohydrin and solvent to obtain a colorless transparent liquid.

[0127] 1HNMR(DMSO): δ: 2.36(m,6H),2.49(m,6H),2.60(m,6H),3.33(m,6H),3.58(m,6H) ),6.03(d,1H),6.87~6.90(m,4H),7.40(d,1H),7.55~7.56(d,3H),7.76(d,1H).

[0128] Example 1

[0129] (1) Synthesis of polyimide precursor resin

[0130] Under a nitrogen flow, 31.02 g (0.1 mol) of ODPA and 100.00 g of NMP were added sequentially to a 500 mL three-necked flask equipped with a stirrer, a dropping funnel, and a thermometer. Stir and dissolve at room temperature to obtain a dianhydride solution. To another three-necked flask equipped with a stirrer, 54.41 g (0.09 mol) of HFHA and 100.00 g of NMP were added sequentially and stirred to dissolve to obtain a diamine solution. The diamine solution was added dropwise to the dianhydride solution. After the addition was complete, the mixture was reacted at room temperature for 1 hour, then at 50°C for 2 hours. After the reaction was complete, 2.18 g (0.02 mol) of 3-aminophenol was added as a capping agent. After the reaction was completed at 50°C for 2 hours, a solution of 23.83 g (0.2 mol) of N,N-dimethylformamide dimethyl acetal diluted with 45.00 g of NMP was added dropwise. After the addition was complete, the mixture was reacted at 50°C for 3 hours. After the reaction is complete, the reaction solution is poured into 3 L of deionized water to precipitate a polymer to obtain a white precipitate. The precipitate is filtered, washed three times with deionized water, and dried in a vacuum oven at 80° C. for 72 h to obtain a polyimide precursor resin.

[0131] The molecular weight of the polyimide precursor resin powder was measured by standard polystyrene conversion. The eluent was N-methylpyrrolidone and the column oven temperature was 40° C. The measured weight average molecular weight (Mw) was 21,000 to 25,000.

[0132] (2) Preparation of photosensitive resin composition

[0133] 10.0 g of the polyimide precursor resin synthesized in the above steps and 20 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask. After the resin was fully dissolved, 0.5 g of compound C-1, 2.0 g of the photosensitive agent quinone diazide compound NT-300 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan), and 0.1 g of POLYFLOW NO.77 (Kyoeisha Chemical Co., Ltd.) were added. Stirring was continued until fully dissolved, and then filter pressure was used with a 1.0 μm polytetrafluoroethylene filter to obtain a photosensitive resin composition, which was labeled D-1.

[0134] Examples 2 to 10, Comparative Examples 1 to 2

[0135] The synthesis of the polyimide precursor resin and the preparation of the photosensitive resin composition are the same as those in Example 1, except that the addition ratios of the compounds in the preparation of the photosensitive resin composition are different, as shown in Table 2.

[0136] Table 2 Addition ratio of different compounds

[0137]

[0138] Test Example 1 Film Formation Test

[0139] The film-forming properties were tested using a coating machine to coat the photosensitive resin composition onto a 4-inch silicon substrate. The film was then soft-baked on a heating plate at 120°C for 3 minutes to obtain a 10-20 μm thick soft-baked film. The film was then heat-treated in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1). The heat treatment process was as follows: first, the temperature was raised to 150°C and held constant for 30 minutes, then raised to 250°C and held constant for 30 minutes, then raised to 350°C and held constant for 1 hour, and then cooled to room temperature to obtain a cured film.

[0140] Place the silicon wafer with the cured film in a hydrofluoric acid solution to corrode and remove the film.

[0141] The specific evaluation criteria are as follows:

[0142] "Excellent": film-forming, no breakage when folded in half;

[0143] "Good": film formed, with the folded part broken;

[0144] "Poor": Unable to form film, fragmented.

[0145] The photosensitive resin compositions synthesized in Examples 1 to 10 and Comparative Examples 1 to 2 were tested using the above-mentioned film-forming property test method. The results are shown in Table 3.

[0146] Test Example 2 Heat Resistance Test

[0147] The heat resistance test method is: usually the 5% thermal weight loss temperature is used to measure the heat resistance of the material.

[0148] 10 mg of each cured film obtained in the film-forming properties test of Test Example 1 was placed in a standard aluminum container and measured using a thermogravimetric analyzer (TGA55, TA Instruments). The test conditions were: a temperature increase from room temperature to 600°C at a rate of 10°C / min. The results are shown in Table 3.

[0149] Test Example 3 Tensile Strength Test

[0150] The tensile strength test method was as follows: The different cured films obtained in the film-forming properties test of Test Example 1 were cut into sample strips (length <3 cm, width <8 mm) meeting the test requirements using a mold. The sample strips were then subjected to tensile strength testing using a dynamic mechanical analyzer (DMA850, manufactured by TA Instruments) with a tensile force range of 0-18 N at a rate of 3 N / min, a temperature range of 30-400°C, and a rate of 3°C / min. The results are shown in Table 3.

[0151] Test Example 4 Dielectric Performance Test

[0152] The dielectric properties were tested by cutting the different cured films obtained in the film-forming properties test in Test Example 1 into 2 cm × 2 cm pieces. The dielectric constant of the polyimide films was measured using an Agilent E5071C vector network analyzer using the resonant cavity method at a test frequency of 1 MHz. The results are shown in Table 3.

[0153] Test Example 5 Copper discoloration test

[0154] The copper discoloration test method involves evenly coating the composition on a copper substrate, then soft-baking it on a heating plate at 120°C for 3 minutes to obtain a soft-baked film with a thickness of 10-20 μm. After standing at room temperature for 12 hours, the soft-baked film is dissolved in a developer. The discoloration of the copper substrate after the soft-baked film is dissolved is evaluated according to the following criteria:

[0155] “Best”: No discoloration of the copper substrate was observed even under visual observation with a 200x optical microscope;

[0156] "Good": No discoloration of the copper substrate was observed visually, but slight discoloration of the copper substrate was observed under a 200x optical microscope.

[0157] “Slightly better”: Slight discoloration of the copper substrate was visually confirmed;

[0158] "Poor": Severe discoloration of the copper substrate was confirmed visually.

[0159] The photosensitive resin compositions synthesized in Examples 1 to 10 and Comparative Examples 1 to 2 were tested using the copper discoloration test method. The results are shown in Table 3.

[0160] Test Example 6 Chemical Resistance

[0161] The chemical resistance test method is as follows: the silicon wafers with different cured films obtained in the film-forming test of Test Example 1 were immersed in a 10wt% sodium hydroxide (NaOH) aqueous solution, a 10vol% sulfuric acid aqueous solution, N-methylpyrrolidone (NMP), and a stripping solution at 25°C for 15 minutes, respectively. They were then rinsed with deionized water for 10 minutes. After air-drying, the cured film surface was observed under an optical microscope for abnormalities such as cracks. The results are shown in Table 3.

[0162] Table 3 Film forming properties, thermal stability, tensile strength, dielectric properties, copper discoloration test, and chemical resistance evaluation

[0163]

[0164]

[0165] As can be seen from the data in Table 3, the present application provides a compound containing a nitrogen heterocycle and an epoxy structure and applies it to a photosensitive resin composition. This not only improves the film-forming properties, chemical resistance, mechanical properties, and thermal stability of the cured film, but also reduces the dielectric constant of the cured film, suppresses discoloration of the copper or copper alloy substrate, and thus improves the overall performance of the cured film and increases reliability.

[0166] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A compound, characterized in that The compound has the structure shown in Formula I: Formula I; In Formula I, W is selected from any one of the groups represented by formula II-a: Formula II-a; The dotted lines represent access sites.

2. The method for preparing the compound according to claim 1, characterized in that: The steps include: S1, heating a mixed solution containing a triamine compound and solvent I, and then dropwise adding a material containing epoxychloroalkane and solvent II to the mixed solution to undergo a ring-opening reaction; S2. Add a strong base solution to the product of step S1, perform a cyclization reaction, and separate and purify to obtain the compound.

3. The preparation method according to claim 2, characterized in that The dropping rate of the epichlorohydrin and solvent II and the dropping rate of the strong base solution are independently 1-5 mL / min.

4. The preparation method according to claim 2, characterized in that In step S1, the molar ratio of the triamine compound to the epichlorohydrin is 1:6-10.

5. The preparation method according to claim 2, characterized in that In step S1, the heating condition is: heating to 35-60°C.

6. The preparation method according to claim 2, characterized in that In step S1, the conditions for the ring-opening reaction are: reaction temperature 35-60° C., and reaction time 3-6 h.

7. The preparation method according to claim 2, characterized in that The molar ratio of the triamine compound to the strong base is 1:6-10.

8. The preparation method according to claim 2, characterized in that In step S2, the conditions for the cyclization reaction are: reaction temperature 35-60° C., and reaction time 1-5 h.

9. The preparation method according to claim 2, characterized in that Solvent I and solvent II are independently selected from at least one of ethanol, ethylene glycol, glycerol, and ethylene glycol butyl ether.

10. The preparation method according to claim 2, characterized in that The concentration of the alkali in the strong alkali solution is 20-50 wt %.

11. The preparation method according to claim 2, characterized in that The epichlorohydrin is selected from epichlorohydrin or epibromohydrin.

12. A photosensitive resin composition, characterized in that The raw materials comprising the following components are mixed uniformly to obtain: A polyimide having a hydroxyl structure or a precursor resin thereof, the compound according to claim 1, a photosensitizer, and a solvent III.

13. The photosensitive resin composition according to claim 12, wherein The weight ratio of the polyimide having a hydroxyl structure or its precursor resin to the compound is 1:0.001-0.

2.

14. The preparation method according to claim 12, characterized in that The solvent III is selected from at least one of methyl pyrrolidone, methyl ethyl ketone, acetone, γ-butyrolactone, ethyl acetate, ethyl lactate, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monoethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

15. The preparation method according to claim 12, characterized in that The weight ratio of the polyimide having a hydroxyl structure or its precursor resin to the solvent III is 1:1-20.

16. A polyimide film, characterized in that: The photosensitive resin composition according to any one of claims 12 to 15 is obtained by coating and curing.

17. Use of at least one of the compound according to claim 1, the photosensitive resin composition according to any one of claims 12 to 15, and the polyimide film according to claim 16 in the manufacture of a semiconductor device.

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