A compound containing a nitrogen heterocycle and a siloxane structure, a photosensitive resin composition, and a preparation method and application thereof

Abstract

The present application discloses a nitrogen-containing heterocyclic and siloxane structure compound, a photosensitive resin composition, and a preparation method and application thereof. The nitrogen-containing heterocyclic and siloxane structure compound has the structure shown in Formula I. This compound has both a nitrogen heterocyclic and a siloxane structure. By introducing this compound into the photosensitive resin composition, it can effectively inhibit the discoloration of copper or copper alloy substrates after development, and at the same time significantly improve the adhesion between the cured film and the copper or copper alloy substrates. It can also reduce the dielectric constant of the cured film, improve the overall performance of the cured film, and have higher reliability; #imgabs0#

Description

Technical Field

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

[0002] Photosensitive polyimide (PSPI) is a kind of high molecular composite material with excellent thermal properties, mechanical properties, electrical properties and chemical properties, and at the same time has photosensitive characteristics. After ultraviolet exposure and development, a three-dimensional pattern with fine structure can be obtained, which significantly simplifies the photolithography process and is an ideal insulating material in the field of microelectronics and semiconductor packaging. With the light weight, high performance and multi-function of electronic products, higher requirements are put forward for PSPI packaging materials.

[0003] With the development of the integration of semiconductor devices and the miniaturization of chip size, the wiring method and installation method of semiconductor devices have changed. The wiring of gold or aluminum in the past has been changed to copper or copper alloy wiring with lower resistance, and the lead-tin eutectic soldering in the past has been changed to ball grid array and chip size installation with higher density. Since some active groups in the photosensitive resin composition are easy to react with copper or copper alloy, copper ions on the substrate surface will diffuse into the coating, causing the substrate to change color, thus affecting the dielectric properties; the copper ions diffused into the coating will cause oxidation and decomposition of components such as resin during thermal curing, resulting in gaps between the coating and the substrate and a decrease in adhesion, thus affecting the reliability of the device. Since the cured resin film is in direct contact with copper or copper alloy and solder bumps, it is required that the cured film has excellent adhesion to copper or copper alloy substrates. In addition, the dielectric constant of traditional PSPI materials is relatively high (usually greater than 3), and it is difficult to meet the performance requirements of low dielectric constant and low dielectric loss of next-generation semiconductor packaging materials, and low dielectric modification is required. Summary of the Invention

[0004] In order to solve the above problems, the present application provides a nitrogen-containing heterocyclic and siloxane structure compound, which has both a nitrogen heterocyclic and a siloxane structure. By introducing this compound into the photosensitive resin composition, the discoloration of copper or copper alloy substrates after development can be effectively inhibited, the adhesion of the cured film to copper or copper alloy substrates can be significantly improved, and the dielectric constant of the cured film can also be reduced.

[0005] According to the first aspect of the present application, there is provided a nitrogen-containing heterocyclic and siloxane structure compound, and the nitrogen-containing heterocyclic and siloxane structure compound has the structure shown in Formula I:

[0006]

[0007] In Formula I, W independently selects one of the groups shown in Formula II-a;

[0008]

[0009] Among them, the dotted line indicates the connection site.

[0010] Optionally, the nitrogen-containing heterocyclic and siloxane structure compound is selected from at least one of the structures shown in Formula I-1, Formula I-2, Formula I-3, Formula I-4, Formula I-5, Formula I-6, Formula I-7, and Formula I-8;

[0011]

[0012]

[0013] According to the second aspect of the present application, a preparation method of the above-mentioned nitrogen-containing heterocyclic and siloxane structure compound is provided, and the preparation method includes:

[0014] Under nitrogen protection, a mixture of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, an acyl chloride compound with a nitrogen-containing heterocyclic structure, a catalyst, and a solvent is reacted to obtain a nitrogen-containing heterocyclic and siloxane structure compound.

[0015] Optionally, the acyl chloride compound with a nitrogen-containing heterocyclic structure is selected from at least one of the structures shown in Formula II-b;

[0016]

[0017] Optionally, the molar ratio of 1,3-bis(3-aminopropyl)tetramethyldisiloxane to the acyl chloride compound with a nitrogen-containing heterocyclic structure is 1:2 to 2.5.

[0018] Optionally, the molar ratio of 1,3-bis(3-aminopropyl)tetramethyldisiloxane to the catalyst is 1:1 to 3.

[0019] Optionally, the catalyst is selected from triethylamine and / or pyridine.

[0020] Optionally, the solvent is selected from at least one of tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether, and toluene.

[0021] Optionally, the preparation method includes:

[0022] A mixed solution containing a solvent, a catalyst, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane is added dropwise to a solution of an acyl chloride compound with a nitrogen-containing heterocyclic structure, and reacted to obtain a nitrogen-containing heterocyclic and siloxane structure compound.

[0023] Optionally, during the dropping process, the temperature of the reaction system is controlled to be -10°C to 10°C, and after the dropping is completed, the reaction is continued at 25 ± 2°C for 5 to 8 hours.

[0024] Optionally, the temperature of the reaction system during the dropping process is independently selected from any value among -10°C, -8°C, -6°C, -4°C, -2°C, 0°C, 2°C, 4°C, 6°C, 8°C, 10°C or a range value between any two of the above.

[0025] Optionally, the reaction conditions are as follows: the temperature is controlled at -10°C to 10°C during the dropping process, and after the dropping is completed, the reaction continues at 25°C for 5 to 8 hours; after the reaction is completed, the triethylamine salt is filtered out, and the filtrate is evaporated under reduced pressure to remove residual triethylamine (pyridine), solvent, generated hydrochloric acid and other substances, and a purified nitrogen-containing heterocycle and siloxane structure compound is obtained.

[0026] According to the third aspect of the present application, a photosensitive resin composition is provided, which is obtained by uniformly mixing raw materials containing a polyimide precursor resin, a nitrogen-containing heterocycle and siloxane structure compound, a photoinitiator, a crosslinking agent, and a solvent I;

[0027] The nitrogen-containing heterocycle and siloxane structure compound is selected from the nitrogen-containing heterocycle and siloxane structure compound described above.

[0028] Optionally, the polyimide precursor resin is polyamic acid or polyamic acid ester and has the structure shown in Formula III:

[0029]

[0030] In Formula III, A is a tetravalent organic group with 2 to 16 carbon atoms; B is a divalent organic group with 2 to 20 carbon atoms;

[0031] n is an integer from 2 to 200;

[0032] R1 and R2 are independently selected from a hydrogen atom, a monovalent organic group having the structure shown in Formula IV, and a saturated aliphatic group with 1 to 4 carbon atoms;

[0033]

[0034] In Formula IV, R3, R4, and R5 are independently selected from a hydrogen atom or an organic group with 1 to 3 carbon atoms, m is an integer from 2 to 10, and * represents the attachment site.

[0035] Optionally, from the perspective of photosensitivity, R3 and R4 are preferably hydrogen atoms, and R5 is preferably a hydrogen atom or a methyl group.

[0036] Optionally, from the perspective of photosensitivity, m is preferably an integer from 2 to 4.

[0037] Optionally, in the polyimide precursor resin having the structure shown in Formula III, A is derived from an aromatic tetracarboxylic dianhydride.

[0038] Optionally, the aromatic tetracarboxylic dianhydride is selected from at least one of pyromellitic dianhydride, 4,4'-oxybisphthalic anhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane.

[0039] Optionally, in the polyimide precursor resin having the structure shown in Formula III, B is derived from an aromatic diamine.

[0040] Optionally, the aromatic diamine is selected from at least one of p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)benzene, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and 4,4'-diamino-2,2'-dimethylbicyclohexane.

[0041] Optionally, the compound having the structure shown in Formula IV is derived from an alcohol having an unsaturated double bond.

[0042] Optionally, the alcohols with unsaturated double bonds are selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0043] Optionally, the method for preparing the polyamide acid ester is as follows: First, an aromatic tetracarboxylic dianhydride reacts with an alcohol compound containing an unsaturated double bond to form a diacid diester, and then a polycondensation reaction is carried out with an aromatic diamine solution to form a polyamide acid ester solution.

[0044] After the amide polycondensation reaction is completed, if necessary, the by-products of the dehydrating condensing agent in the reaction solution are filtered out, and then the reaction solution is put into a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer. If necessary, operations such as redissolution and reprecipitation are repeated to purify the polymer, and vacuum drying is carried out to obtain the polyamide acid ester resin.

[0045] From the perspective of heat resistance and mechanical properties after heat treatment, the weight average molecular weight (Mw) of the above resin is 20,000 - 30,000. The weight average molecular weight (Mw) of the resin is measured by gel permeation chromatography (the instrument model is LC-20AD of Shimadzu Corporation, Japan) through standard polystyrene conversion, and the elution solvent is N-methylpyrrolidone.

[0046] Optionally, the mass ratio of the polyimide precursor resin to the nitrogen-containing heterocyclic and siloxane structure compound is 100:0.1 - 20.

[0047] Optionally, the mass ratio of the polyimide precursor resin to the nitrogen-containing heterocyclic and siloxane structure compound is 100:1 - 10.

[0048] Optionally, the mass ratio of the polyimide precursor resin to the photoinitiator is 100:0.1 - 30.

[0049] Optionally, the mass ratio of the polyimide precursor resin to the crosslinking agent is 100:0.1 - 30.

[0050] Optionally, the mass ratio of the polyimide precursor resin to the solvent I is 100:80 to 2000.

[0051] Optionally, the mass ratio of the polyimide precursor resin to the solvent I independently selects any value from 80:100, 100:100, 100:150, 100:200, 100:250, 100:300, 100:350, 100:400, 100:500, 100:600, 100:700, 100:800, 100:900, 100:1000, 100:1500, 100:2000 or a range value between any two of the above.

[0052] Preferably, the mass ratio of the polyimide precursor resin to the solvent I is 100:100 to 1000.

[0053] More preferably, the mass ratio of the polyimide precursor resin to the solvent I is 100:150 to 500.

[0054] Optionally, the photoinitiator is selected from at least one of benzophenone compounds, benzylidene compounds, coumarin compounds, anthraquinone compounds, benzoin compounds, thioxanthone compounds, mercapto compounds, glycine compounds, oxime compounds, α-aminoalkylbenzophenone compounds, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylimidazole, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name: BAPO, manufactured by Wuhan Yuancheng Technology).

[0055] Among the above initiators, from the aspect of photosensitivity, oxime-based compounds are preferred.

[0056] Optionally, the oxime compounds are selected from at least one of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (trade name: OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(0-acetyl oxime) (trade name: OXE-02, manufactured by BASF).

[0057] Optionally, the crosslinking agent polymerizes with the resin and the same molecules to form a crosslinked network structure, which can improve the heat resistance and chemical resistance of the cured film formed by the photosensitive resin composition.

[0058] Optionally, the crosslinking agent is selected from tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, etc., but is not limited to these. The above crosslinking agent can be used alone or in combination of two or more.

[0059] Optionally, the solvent I is selected from at least one of N-methylpyrrolidone, methyl ethyl ketone, acetone, γ-butyrolactone, ethyl acetate, ethyl lactate, toluene, xylene, diethylene glycol monobutyl ether, propylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide.

[0060] Furthermore, in order to improve the stability of the photosensitive resin composition, the photosensitive resin composition may further include an inhibitor.

[0061] Optionally, the inhibitor includes at least one of hydroquinone, p-methoxyphenol, N-nitrosodiphenylamine, phenothiazine, p-tert-butylcatechol, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, ammonium salt of N-nitroso-N(1-naphthyl)hydroxylamine.

[0062] Optionally, the mass ratio of the polyimide precursor resin to the inhibitor is 100:0.1 to 10.

[0063] Optionally, the mass ratio of the polyimide precursor resin to the inhibitor independently selects any value from 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10 or the range value between any two of the above.

[0064] Preferably, the mass ratio of the polyimide precursor resin to the inhibitor is 100:0.5 to 5.

[0065] According to the fourth aspect of the present application, a preparation method of a photosensitive resin composition is provided, including: after dissolving and dispersing each component evenly, filtering to obtain it.

[0066] In one embodiment, the preparation method of the photosensitive resin composition includes: adding a polyimide precursor resin, an inhibitor, and a solvent into a three-necked flask, stirring until completely dissolved, adding a photoinitiator and a cross-linking agent in sequence, and continuing to stir until completely dispersed; and filtering using a 1 μm polytetrafluoroethylene filter membrane to obtain a photosensitive resin composition.

[0067] According to a fifth aspect of the present application, a polyimide film is provided, wherein the polyimide film is obtained by coating and curing a photosensitive resin composition;

[0068] The photosensitive resin composition is selected from the photosensitive resin composition described above.

[0069] In the preparation process of the polyimide film in this application, the substrate to be coated is not particularly limited, and those skilled in the art can make conventional selections, including silicon wafers, aluminum wafers, silver wafers, copper wafers, copper alloy wafers, ceramic wafers, etc. The specific coating method is also not particularly limited, and examples include spray coating, spin coating, and ink scraper method. In the actual coating operation process, the film thickness will also be different due to different coating methods, rotation speeds, viscosities, and composition components. The coating method is preferably spin coating.

[0070] Optionally, the polyimide film has a cured relief pattern.

[0071] 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 a polyimide film.

[0072] In the preparation process of the polyimide film with a solidified relief pattern in the present application, the drying method can be a baking operation, specifically, baking can be performed in an oven, a heating table, an infrared lamp, etc., preferably a heating table baking. More preferably, the drying temperature is 80 to 150°C, and the drying time is 1 to 10 minutes. More preferably, the drying temperature is 100 to 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 naturally cooling to 25°C.

[0073] In the preparation process of the polyimide film with a cured relief pattern in the present application, the specific exposure operation is to use an exposure device to expose the above-formed resin film through a mask with a pattern through the dried photosensitive resin film layer. Common active light rays include ultraviolet rays, X-rays, electron beams, etc. In the present invention, a mercury lamp is preferably used for exposure, which includes three light sources: i-line (365nm), h-line (405nm), and g-line (436nm).

[0074] In the above-mentioned method for preparing a polyimide film, a pattern is formed by removing the unexposed portion using a developer. Common developers include: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, isopropanol, ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, isobutyl ketone, aqueous tetramethylammonium hydroxide, etc. After development, it is preferably rinsed with deionized water, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, etc. For example, a developer and a rinsing solution are respectively poured into two glass petri dishes. The temperature of the developer is controlled at 25 ± 1 °C, and the exposed resin film is immersed in the developer, and then the timing starts. When the unexposed portion is completely exposed on the substrate, the development ends, the timing stops, and the time required for the whole process is recorded.

[0075] In the above-mentioned method for preparing a polyimide film, the temperature of the curing operation is 300 - 400 °C, preferably 350 °C. The pattern obtained after development and rinsing is subjected to thermal imidization to be converted into a cured film. This heat treatment usually selects a stepwise temperature increase and maintains a certain time at different temperatures or selects a continuous temperature increase within a certain temperature range. For example, a heat treatment method of performing heat treatment at 150 °C, 250 °C, and 350 °C for 30 minutes respectively, or a method of continuously heating from room temperature to 350 °C, etc. Inert gases such as nitrogen and argon are often used during curing. As a specific application example, first, the oxygen content in the oven cavity is controlled to be reduced to below 50 ppm, and then the temperature is raised to 150 °C and kept constant for 30 minutes, then raised to 250 °C and kept constant for 30 minutes, then raised to 350 °C and kept constant for 1 hour, and then cooled to room temperature, finally obtaining a cured relief pattern.

[0076] According to the sixth aspect of the present application, there is provided an application of the above-mentioned polyimide film in semiconductor elements.

[0077] The semiconductor element described in the present application preferably includes a polyimide film having a cured relief pattern.

[0078] The present application provides a compound having both a nitrogen heterocycle and a siloxane structure. By introducing this compound into the photosensitive resin composition, it can effectively inhibit the discoloration of copper or copper alloy substrates after development, simultaneously significantly improve the adhesion between the cured film and copper or copper alloy substrates, and can also reduce the dielectric constant of the cured film, thereby improving the overall performance of the cured film and making it more reliable.

[0079] The beneficial effects that can be produced by the present application include:

[0080] The compound provided by this application has both an azacycle and a siloxane structure. Among them, the azacycle group undergoes a complexation reaction with a copper or copper alloy substrate to form a stable complex, protecting the substrate from being corroded by the photosensitive resin composition, inhibiting the discoloration of the copper or copper alloy substrate, and at the same time enhancing the adhesion between the resin layer and the substrate; the presence of the siloxane structure further improves the adhesion of the cured film to the substrate. By introducing this compound into the photosensitive resin composition, the discoloration of the copper or copper alloy substrate after the development of the photosensitive resin composition can be effectively inhibited, and at the same time, the adhesion of the cured film to the copper or copper alloy substrate can be significantly improved. In addition, the dielectric constant of the cured film can be reduced, improving the overall performance of the cured film and making it more reliable. Description of the Drawings

[0081] Figure 1 It is a diagram showing the degree of discoloration of the copper or copper alloy substrate in the examples and comparative examples of this application. Detailed Description of the Invention

[0082] The following describes this application in detail with reference to the examples, but this application is not limited to these examples.

[0083] Unless otherwise specified, the raw materials in the examples of this application are all purchased through commercial channels.

[0084] The structural formulas and names of the following raw materials P-1, P-2, P-3, P-4, P-5, P-6, P-7, P-8 are shown in Table 1 below.

[0085] Table 1

[0086]

[0087]

[0088] Characterization of the Compound in this Application

[0089] (1) Infrared Test

[0090] The synthesized compound was tested using a Fourier transform infrared spectrometer (Bruker, Tensor-27, Germany) to detect whether the compound in this application was successfully prepared. If the spectrum shows that a vibration absorption peak of the C=O bond of -CONH appears at 1640 cm -1 ~1660 cm -1 and a vibration absorption peak of the C-N bond of -CONH appears at 1540 cm -1 ~1550 cm -1 , it can be proved that the compound of this application was successfully synthesized.

[0091] (2) NMR Test

[0092] The compound of this application was tested using a Bruker 400 nuclear magnetic resonance spectrometer at1 Characterization was carried out in the \(^1H\) spectrum mode (TMS as the internal standard and DMSO as the solvent).

[0093] Preparation of Compound I-1 in Preparation Example 1

[0094] Under a dry nitrogen stream, 32.32 g (0.2 mol) of P-1 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent were added to a 500 ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer, and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, cooled to below 0 °C in an ice bath, and a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent was slowly added dropwise. The temperature of the system was controlled at -10 °C to 10 °C. After the addition was completed, the temperature was raised to 25 °C and the reaction was continued for 8 h. After the reaction was completed, triethylamine hydrochloride was filtered, and the filtrate was distilled under reduced pressure to remove the residual triethylamine, hydrochloric acid, and solvent to obtain purified Compound I-1.

[0095]

[0096] The infrared spectrum information of Compound I-1 is as follows:

[0097] FT-IR: 1648 \(cm^{-1}\) -1 is the symmetric stretching vibration of \(C=O\) of -CONH, 1550 \(cm^{-1}\) -1 is the asymmetric stretching vibration of C-N of -CONH.

[0098] The \(^1H\) NMR spectrum information of Compound I-1 is as follows:

[0099] 1 \(^1H\) NMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 1.51 (m, 4H), 2.5 (s, 2H), 3.42 (t, 4H), 3.75 (s, 8H), 4.25 (s, 4H), 8.01 (s, 2H), 8.69 (s, 2H).

[0100] Preparation of Compound I-2 in Preparation Example 2

[0101] Under a dry nitrogen stream, 29.71 g (0.2 mol) of P-2 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent were added to a 500 ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer, and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, cooled to below 0 °C in an ice bath, and a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent was slowly added dropwise while controlling the system temperature at -10 °C to 10 °C. After the addition was completed, the temperature was raised to 25 °C and the reaction was continued for 8 h. After the reaction was completed, triethylamine hydrochloride was filtered off, and the filtrate was distilled under reduced pressure to remove the residual triethylamine, hydrochloric acid, and solvent, obtaining purified compound I-2.

[0102]

[0103] The infrared spectrum information of compound I-2 is as follows:

[0104] FT-IR: 1645 cm -1 is the symmetric stretching vibration of C=O for -CONH, 1548 cm -1 is the asymmetric stretching vibration of C-N for -CONH.

[0105] The 1H NMR spectrum information of compound I-2 is as follows:

[0106] 1 1H NMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 1.51 (m, 4H), 3.39 - 3.43 (m, 12H), 6.02 (s, 2H), 10.86 (s, 2H).

[0107] Preparation Example 3 Preparation of Compound I-3

[0108] Under a dry nitrogen stream, 28.51 g (0.2 mol) of P-3 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent were added to a 500 ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer, and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, cooled to below 0 °C in an ice bath, and a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent was slowly added dropwise while controlling the system temperature at -10 °C to 10 °C. After the addition was completed, the temperature was raised to 25 °C and the reaction was continued for 8 h. After the reaction was completed, triethylamine hydrochloride was filtered off, and the filtrate was distilled under reduced pressure to remove the residual triethylamine, hydrochloric acid, and solvent, obtaining purified compound I-3.

[0109]

[0110] The infrared spectrum information of Compound I-3 is as follows:

[0111] FT-IR: 1643 cm -1 is the symmetric stretching vibration of C=O for -CONH, 1545 cm -1 is the asymmetric stretching vibration of C-N for -CONH.

[0112] The proton nuclear magnetic resonance spectrum information of Compound I-3 is as follows:

[0113] 1 HNMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 1.51 (m, 4H), 3.18 (t, 4H), 8.06 (t, 2H), 8.93 (s, 2H), 9.23 (d, 4H).

[0114] Preparation of Compound I-4 in Preparation Example 4

[0115] Under a dry nitrogen stream, add 43.73 g (0.2 mol) of P-4 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent to a 500 ml four-necked flask equipped with a tetrafluoro stirrer, a thermometer, and a constant-pressure dropping funnel. Stir at room temperature until completely dissolved, cool to below 0 °C in an ice bath, and slowly add dropwise a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent. Control the system temperature at -10 °C to 10 °C. After the addition is completed, warm up to 25 °C and continue the reaction for 8 h. After the reaction is completed, filter the triethylamine hydrochloride, and distill the filtrate under reduced pressure to remove the residual triethylamine, hydrochloric acid, and solvent to obtain purified Compound I-4.

[0116]

[0117] The infrared spectrum information of Compound I-4 is as follows:

[0118] FT-IR: 1650 cm -1 is the symmetric stretching vibration of C=O for -CONH, 1547 cm -1 is the asymmetric stretching vibration of C-N for -CONH.

[0119] The proton nuclear magnetic resonance spectrum information of Compound I-4 is as follows:

[0120] 1 HNMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 1.55 (m, 4H), 3.43 (t, 4H), 7.22 (t, 2H), 7.95 - 8.00 (m, 8H), 8.44 (s, 2H), 8.73 (d, 4H).

[0121] Preparation Example 5 Preparation of Compound I-5

[0122] Under a dry nitrogen stream, 44.32 g (0.2 mol) of P-5 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent were added to a 500 ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer, and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, cooled to below 0 °C in an ice bath, and a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent was slowly added dropwise. The temperature of the system was controlled at -10 °C to 10 °C. After the addition was completed, the temperature was raised to 25 °C and the reaction was continued for 8 h. After the reaction was completed, triethylamine hydrochloride was filtered, and the filtrate was distilled under reduced pressure to remove the residual triethylamine, hydrochloric acid, and solvent to obtain purified Compound I-5.

[0123]

[0124] The infrared spectrum information of Compound I-5 is as follows:

[0125] FT-IR: 1646 cm -1 is the symmetric stretching vibration of C=O for -CONH, 1548 cm -1 is the asymmetric stretching vibration of C-N for -CONH.

[0126] The proton nuclear magnetic resonance spectrum information of Compound I-5 is as follows:

[0127] 1 HNMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 0.99 (d, 6H), 1.51 (m, 4H), 3.18 (t, 4H), 3.39 (m, 2H), 3.9 (s, 2H), 7.33 (m, 2H), 7.50 (d, 4H), 7.63 (t, 4H), 8.21 (s, 2H).

[0128] Preparation Example 6 Preparation of Compound I-6

[0129] Under a dry nitrogen stream, 29.31 g (0.2 mol) of P-6 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent were added to a 500 ml four-necked flask equipped with a tetrafluoro stirrer, a thermometer, and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, cooled to below 0 °C in an ice bath, and a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent was slowly added dropwise while controlling the system temperature at -10 °C to 10 °C. After the addition was completed, the temperature was raised to 25 °C and the reaction was continued for 8 h. After the reaction was completed, triethylamine hydrochloride was filtered off, and the filtrate was distilled under reduced pressure to remove the remaining triethylamine, hydrochloric acid, and solvent, obtaining purified compound I-6.

[0130]

[0131] The infrared information of compound I-6 is as follows:

[0132] FT-IR: 1650 cm -1 is the symmetric stretching vibration of C=O for -CONH, 1545 cm -1 is the asymmetric stretching vibration of C-N for CO-NH.

[0133] The proton nuclear magnetic resonance information of compound I-6 is as follows:

[0134] 1 HNMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 1.51 (m, 4H), 3.43 (t, 4H), 5.60 (s, 4H), 8.01 (s, 2H), 9.45 (s, 2H).

[0135] Preparation Example 7 Preparation of Compound I-7

[0136] Under a dry nitrogen stream, 48.93 g (0.2 mol) of P-7 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent were added to a 500 ml four-necked flask equipped with a tetrafluoro stirrer, a thermometer, and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, cooled to below 0 °C in an ice bath, and a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent was slowly added dropwise while controlling the system temperature at -10 °C to 10 °C. After the addition was completed, the temperature was raised to 25 °C and the reaction was continued for 8 h. After the reaction was completed, triethylamine hydrochloride was filtered off, and the filtrate was distilled under reduced pressure to remove the remaining triethylamine, hydrochloric acid, and solvent, obtaining purified compound I-7.

[0137]

[0138] The infrared spectrum information of Compound I-7 is as follows:

[0139] FT-IR: 1647 cm -1 is the symmetric stretching vibration of C=O of -CONH, 1548 cm -1 is the asymmetric stretching vibration of C-N of -CONH.

[0140] The proton nuclear magnetic resonance spectrum information of Compound I-7 is as follows:

[0141] 1 HNMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 1.55 (m, 4H), 3.43 (t, 4H), 7.95 - 8.00 (m, 8H), 8.44 (s, 2H), 15.0 (s, 2H).

[0142] Preparation Example 8 Preparation of Compound I-8

[0143] Under a dry nitrogen stream, add 48.34 g (0.2 mol) of P-8 and 100 g of tetrahydrofuran (hereinafter referred to as THF) solvent to a 500 ml four-necked flask equipped with a tetrafluoro stirrer, a thermometer, and a constant pressure dropping funnel. Stir at room temperature until completely dissolved, cool to below 0 °C in an ice bath, and slowly add dropwise a mixed solution containing 24.85 g (0.1 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 20.22 (0.2 mol) of triethylamine, and 80 g of THF solvent. Control the system temperature at -10 °C to 10 °C. After the addition, warm up to 25 °C and continue the reaction for 8 h. After the reaction, filter the triethylamine hydrochloride, and distill the filtrate under reduced pressure to remove the residual triethylamine, hydrochloric acid, and solvent to obtain purified Compound I-8.

[0144]

[0145] The infrared spectrum information of Compound I-8 is as follows:

[0146] FT-IR: 1649 cm -1 is the symmetric stretching vibration of C=O of -CONH, 1550 cm -1 is the asymmetric stretching vibration of C-N of -CONH.

[0147] The proton nuclear magnetic resonance spectrum information of Compound I-8 is as follows:

[0148] 1HNMR (DMSO): δ: 0.22 (s, 12H), 0.61 (t, 4H), 1.51 (m, 4H), 3.43 (t, 4H), 4.26 (s, 4H), 4.63 (s, 4H), 7.51~7.53 (m, 4H), 8.01~8.02 (m, 4H), 8.18 (m, 2H).

[0149] Synthesis Example 1 Synthesis of Polyimide Precursor Resin

[0150] Put 31.02 g (0.1 mol) of 4,4'-oxybisphthalic anhydride (ODPA) into a 500 mL three-necked flask, add 26.03 g (0.2 mol) of 2-hydroxyethyl methacrylate (HEMA) and 100.00 g of γ-butyrolactone (GBL), and dropwise add 15.82 g of pyridine (0.2 mol) with stirring below 10 °C to obtain a reaction mixture. After naturally rising to 25 °C, stir for 12 h.

[0151] Next, under ice bath conditions, add the reaction mixture to a 50.00 g GBL solution containing 41.25 g (0.2 mol) of dicyclohexylcarbodiimide (DCC) with stirring over 40 min. Under nitrogen protection, add a 70.00 g GBL solution containing 19.03 g (0.095 mol) of 4,4'-diaminodiphenyl ether (ODA) over 60 min. Naturally rise to 25 °C, add 80.00 g of GBL, continue stirring for 12 h, then add 6.00 g of ethanol and stir for 1 h. Filter to remove the precipitate formed in the reaction mixture to obtain a reaction solution.

[0152] Add the obtained reaction solution to 1 L of ethanol to precipitate the polymer. Then dissolve the precipitated polymer in 300 mL of tetrahydrofuran. Drop the obtained polymer solution into 5 L of ultrapure water to precipitate a polymer precipitate. Filter out the obtained precipitate and perform vacuum drying at 50 °C for 72 h to obtain a polymer powder, namely the polyimide precursor resin.

[0153] The weight-average molecular weight (Mw) of the resin was measured by gel permeation chromatography (standard polystyrene conversion), and a GPC system of Shimadzu Corporation, Japan was used in the measurement. The weight-average molecular weight (Mw) of the obtained polyimide precursor resin was 25,000 - 30,000.

[0154] Example 1

[0155] In a three-necked flask equipped with stirring, 10.0 g of a polyimide precursor resin and 0.1 g of the polymerization inhibitor p-methoxyphenol (MEHQ) were dissolved in 20.0 g of N-methylpyrrolidone (NMP), and stirred until completely dissolved. Then, 0.5 g of Compound I-1, 0.5 g of the photoinitiator 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (OXE-01), and 2.0 g of the crosslinker tetraethylene glycol dimethacrylate (TEGDMA) were added in sequence, and stirring was continued until completely and evenly dispersed. It was pressure-filtered through a 1.0 μm filter membrane to obtain the photosensitive resin composition Q-1, and the viscosity measured at 25 °C was 2000-3000 cp. The viscosity of the photosensitive resin composition was measured using a rotational viscometer (Brookfield DV2T RV) at 25 ± 0.1 °C.

[0156] Examples 2-14, Comparative Example 1

[0157] The preparation method of the photosensitive resin composition was the same as that of Example 1, except that the addition ratios of the compounds in the preparation of the photosensitive resin composition were different, as shown in Table 2.

[0158] Table 2

[0159]

[0160]

[0161] It should be noted that the effect evaluation of the photosensitive resin composition in the examples and comparative examples was carried out according to the following method.

[0162] (1) Copper discoloration test

[0163] The photosensitive resin composition was spin-coated onto a copper or copper alloy substrate, and then soft-baked on a heating stage at 120 °C for 3 minutes to obtain a photosensitive resin film with a film thickness of 10-20 μm. After exposure, it was developed in a developer to completely dissolve the unexposed part. The discoloration of the copper or copper alloy substrate after development was observed using a 100-fold optical microscope. As shown in the appendix Figure 1 The discoloration degree of the copper or copper alloy substrate was divided into three grades: no discoloration, slight discoloration, and severe discoloration ( Figure 1 The small squares are the photolithography patterns remaining on the copper substrate after development).

[0164] (2) Adhesion peel test

[0165] Use a spin coater to evenly coat a sample of the photosensitive resin composition onto a copper or copper alloy substrate. Place it on a heating table at 120 °C for 3 minutes of soft baking to obtain a resin film with a film thickness of 10 - 20 μm. Use a cross cutter (BYK-Gardner A-5125) to scratch the resin film into a grid of 10 rows × 10 columns, and then place the film in a vacuum and oxygen-free oven (MOLZK-32D1) for heat treatment: start heating to 150 °C and hold for 30 minutes, then heat to 250 °C and hold for 30 minutes, then heat to 350 °C and hold for 1 hour, and cool to room temperature to finally obtain a cured film. Place the cured film in a PCT test chamber for a 200-hour PCT aging test (121 °C, 2 atm saturated steam; Dongguan Hongjin Technology PCT-30). After the PCT test is completed, use a tape (special transparent 3M tape) to conduct a peel test with reference to the cross-cut test of paint and varnish films in the national standard GB / T 9286-1998, and record the number of peeled grids as the peeling situation after the PCT test.

[0166] When the number of peeled grids in the adhesion peel test is less than 5, it is regarded as "excellent"; when it is less than 10, it is regarded as "good"; when it is greater than or equal to 10, it is regarded as "poor".

[0167] (3) Dielectric constant

[0168] Refer to the national standard GB / T 31838.6-2021 Solid insulating materials - Dielectric and resistive properties - Part 6: Dielectric properties (AC method) - Relative permittivity and dissipation factor (frequency 0.1 Hz - 10 MHz). Use a DMS2000 high and low temperature dielectric impedance spectrometer to measure the dielectric constant of the cured film at 25 °C, and record the value at a frequency of 1 MHz.

[0169] Evaluate the above-prepared photosensitive resin composition according to the copper discoloration experiment, adhesion peel experiment, and dielectric property test methods described above, and the results are shown in Table 3.

[0170] Table 3

[0171]

[0172]

[0173] It can be seen from the data in Table 3 that the present application provides a compound containing a nitrogen heterocycle and a siloxane structure. By introducing this compound into the photosensitive resin composition, the discoloration of the copper or copper alloy substrate after development can be effectively inhibited, the adhesion between the cured film and the copper or copper alloy substrate can be significantly improved, and the dielectric constant of the cured film can be reduced, so that the overall performance of the cured film is improved and the reliability is higher.

[0174] As described above, these are only several embodiments of the present application and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the relevant art can make some changes or modifications within the scope of the technical solution of the present application by using the disclosed technical content, which are equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. A compound containing a nitrogen heterocycle and a siloxane structure, characterized in that, The nitrogen-containing heterocyclic and siloxane structure compound has the structure shown in Formula I: In Formula I, W is independently selected from one of the groups shown in Formula II-a; Among them, the dashed line represents the connection site.

2. The compound containing a nitrogen heterocycle and a siloxane structure according to claim 1, characterized in that, The nitrogen-containing heterocyclic and siloxane structure compound is selected from at least one of the structures shown in Formula I-1, Formula I-2, Formula I-3, Formula I-4, Formula I-5, Formula I-6, Formula I-7, and Formula I-8; 3. The preparation method of the nitrogen-containing heterocyclic and siloxane structure compound according to any one of claims 1 to 2, characterized in that, The preparation method includes: Under nitrogen protection, a mixture of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, an acyl chloride compound with a nitrogen-containing heterocyclic structure, a catalyst, and a solvent is reacted to obtain a nitrogen-containing heterocyclic and siloxane structure compound.

4. The preparation method according to claim 3, wherein The acyl chloride compound with a nitrogen-containing heterocyclic structure is selected from at least one of the structures shown in Formula II-b; 5. The preparation method according to claim 3, characterized in that, The molar ratio of 1,3-bis(3-aminopropyl)tetramethyldisiloxane to the acyl chloride compound with a nitrogen-containing heterocyclic structure is 1:2 to 2.

5.

6. The preparation method according to claim 3, wherein The molar ratio of 1,3-bis(3-aminopropyl)tetramethyldisiloxane to the catalyst is 1:1 to 3.

7. The preparation method according to claim 3, characterized in that, The catalyst is selected from triethylamine and / or pyridine.

8. The preparation method according to claim 3, characterized in that The solvent is selected from at least one of tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether, and toluene.

9. The preparation method according to claim 3, wherein The preparation method includes: A mixed solution containing a solvent, a catalyst, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane is dropped into a solution of an acyl chloride compound with a nitrogen-containing heterocyclic structure and reacted to obtain a nitrogen-containing heterocyclic and siloxane structure compound.

10. The preparation method according to claim 9, characterized in that, During the dropping process, the temperature of the reaction system is controlled at -10°C to 10°C, and after the dropping is completed, the reaction is continued at 25 ± 2°C for 5 to 8 hours.

11. A photosensitive resin composition, characterized in that, The photosensitive resin composition is obtained by uniformly mixing raw materials including a polyimide precursor resin, a nitrogen-containing heterocyclic and siloxane structure compound, a photoinitiator, a crosslinking agent, and Solvent I; The nitrogen-containing heterocyclic and siloxane structure compound is selected from the nitrogen-containing heterocyclic and siloxane structure compounds described in any one of Claims 1 to 2.

12. The photosensitive resin composition according to claim 11, wherein The mass ratio of the polyimide precursor resin to the nitrogen-containing heterocyclic and siloxane structure compound is 100:0.1 to 20.

13. The photosensitive resin composition according to claim 11, wherein, The mass ratio of the polyimide precursor resin to the photoinitiator is 100:0.1 to 30.

14. The photosensitive resin composition according to claim 11, wherein The mass ratio of the polyimide precursor resin to the crosslinking agent is 100:0.1 to 30.

15. The photosensitive resin composition according to claim 11, wherein The mass ratio of the polyimide precursor resin to Solvent I is 100:80 to 2000.

16. A polyimide film, characterized in that, The polyimide film is obtained by coating and curing the photosensitive resin composition; The photosensitive resin composition is selected from the photosensitive resin compositions described in any one of Claims 11 to 15.

17. Application of the polyimide film according to Claim 16 in semiconductor elements.

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