Silane coupling agent, method for preparing same, resin composition, cured film, and semiconductor device

Abstract

The invention relates to a silane coupling agent and a preparation method thereof, a resin composition, a cured film and a semiconductor device, the structural formula of the silane coupling agent is as shown in the formula (I): # imgabs0 # formula (I), in the formula (I), X1 and X2 are independently selected from any one of nitrogen atoms and carbon atoms; y is any one of an oxygen atom and a sulfur atom; r1 is any one of an alkyl group with a carbon atom number of 1-10 and an alkoxy group with a carbon atom number of 1-10; r1, R2, R3 and R4 are independently selected from any one of alkyl with the carbon atom number of 1-5 and alkoxy with the carbon atom number of 1-5, and R2, R3 and R4 are independently selected from any one of alkyl with the carbon atom number of 1-5 and alkoxy with the carbon atom number of 1-5. The silane coupling agent provided by the embodiment of the invention not only has good compatibility with an organic material, but also has good bonding ability with an inorganic interface, when the silane coupling agent is added into a resin composition, the adhesion of the cured resin composition with the surface of a base material can be improved, and the service life of the resin composition is prolonged. And the risk of layering of the cured resin composition and the base material is reduced.

Description

Technical Field

[0001] The present application relates to the technical field of resin compositions, and in particular to a silane coupling agent and a preparation method thereof, a resin composition, a cured film and a semiconductor device. Background Art

[0002] Polyimide (PI), polybenzoxazole (PBO) and other resins are widely used in surface passivation of integrated circuit chips and surface re-wiring (RDL) process of wafer-level packaging (WLP) due to their excellent heat resistance and mechanical properties after thermal curing. They play the role of stress buffering, expanding chip packaging area, protecting chips, etc. in chip packaging structure, and are key core materials for wafer-level packaging. However, traditional polyimide, polybenzoxazole and other resins often cause micro-holes or even cracks in the interface with substrates (such as metals, silicon, etc.) due to lack of adhesion. Summary of the invention

[0003] The embodiments of the present application provide a silane coupling agent and a preparation method thereof, a resin composition, a cured film and a semiconductor device to at least partially solve the above technical problems.

[0004] In order to achieve the above-mentioned object, according to the first aspect of the present application, a silane coupling agent is provided, and the structural formula of the silane coupling agent is shown in formula (I): Formula (I), In formula (I), X1 and X2 are each independently selected from a nitrogen atom and a carbon atom; Y is an oxygen atom and a sulfur atom; R1 is an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; R2, R3 and R4 are each independently selected from an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms.

[0005] Optionally, one of X1 and X2 is a nitrogen atom.

[0006] Alternatively, Y is a sulfur atom.

[0007] Optionally, R1 is a saturated alkyl group having 1 to 4 carbon atoms.

[0008] Optionally, R1 is a straight-chain saturated alkyl group having 2 to 3 carbon atoms.

[0009] Optionally, R2, R3 and R4 are each independently selected from any one of an alkyl group having 1 to 2 carbon atoms and an alkoxy group having 1 to 2 carbon atoms.

[0010] Optionally, the number of the alkoxy groups is less than or equal to 2 based on R2, R3 and R4.

[0011] Optionally, based on R2, R3 and R4, the number of the alkoxy groups is greater than the number of the alkyl groups.

[0012] Optionally, R2, R3 and R4 are each independently selected from any one of methyl, ethyl, methoxy and ethoxy, and based on R2, R3 and R4, the number of the methyl groups is 0 or 1, and the number of the ethyl groups is 0 or 1.

[0013] According to a second aspect of the present application, a method for preparing a silane coupling agent is provided, which is used to prepare the silane coupling agent as described above, comprising: The silane coupling agent is obtained by subjecting the first compound to a nucleophilic substitution reaction with the second compound, wherein the structural formula of the first compound is as shown in formula (II): Formula (II), In formula (II), Z is any one of a hydroxyl group and a thiol group, and R1, R2, R3 and R4 are the same as those in formula (I); The structural formula of the second compound is shown in formula (III): Formula (III), In formula (III), W is a halogen atom which replaces at least one hydrogen atom on the aromatic ring, and X1 and X2 are the same as those in formula (I).

[0014] Optionally, W is a fluorine atom or a chlorine atom, and the substitution number is 1.

[0015] Optionally, the molar ratio of the first compound to the second compound is 1:1.

[0016] Optionally, the first compound and the second compound undergo the nucleophilic substitution reaction in a polar solvent.

[0017] Optionally, the polar solvent is a polar aprotic solvent.

[0018] Optionally, the polar aprotic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N,N-diethylformamide.

[0019] Optionally, the first compound and the second compound undergo the nucleophilic substitution reaction under the catalysis of a basic catalyst.

[0020] Optionally, the alkaline catalyst includes at least one of an organic base and an inorganic base.

[0021] Optionally, the organic base includes triethylamine, pyridine, sodium methoxide, sodium ethoxide, and N,N - at least one of diisopropylethylamine.

[0022] Optionally, the inorganic base includes at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide.

[0023] Optionally, the molar ratio of the alkaline catalyst to the first compound is 1-10.

[0024] Optionally, the molar ratio of the alkaline catalyst to the first compound is 1 to 1.5.

[0025] Optionally, the reaction temperature of the nucleophilic substitution reaction is 10°C to 50°C.

[0026] Optionally, after the nucleophilic substitution reaction is completed, a reaction solution containing the silane coupling agent is obtained, and the method for preparing the silane coupling agent further comprises purifying the reaction solution to extract the silane coupling agent from the reaction solution.

[0027] According to a third aspect of the present application, a resin composition is provided, comprising a silane coupling agent and a resin, wherein the silane coupling agent is at least one of the silane coupling agent described above and a silane coupling agent prepared by the method for preparing the silane coupling agent described above.

[0028] Optionally, the mass ratio of the silane coupling agent to the resin is 0.001-0.1.

[0029] Optionally, the resin composition is a photosensitive resin composition, and the photosensitive resin composition further comprises a photoinitiator.

[0030] Optionally, the photosensitive resin composition further includes at least one of a cross-linking agent and a first solvent.

[0031] Optionally, the resin is an alkali-soluble resin.

[0032] Optionally, the alkali-soluble resin includes at least one of polyimide resin, polyamic acid resin, polyamic acid ester resin and polybenzoxazole resin.

[0033] According to a fourth aspect of the present application, a cured film is provided, wherein the cured film comprises a cured product of the above-mentioned resin composition.

[0034] Optionally, the cured film includes at least one of a surface protection film, an interlayer insulating film, an insulating film for redistribution, a metal bump stress buffer layer, and a passivation film for a semiconductor package element.

[0035] According to a fifth aspect of the present application, a semiconductor device is provided, comprising the cured film as described above.

[0036] The silane coupling agent provided in the application example not only has good compatibility with organic materials, but also has good bonding ability with inorganic interfaces. In particular, the silane coupling agent contains both silane groups and benzotriazole groups, so that the silane coupling agent has better bonding ability to metal substrates (especially copper surfaces). In this way, when the silane coupling agent is added to the resin composition, the adhesion of the resin composition to the surface of the substrate after curing can be improved, and the risk of delamination between the cured film formed after the resin composition is cured and the substrate can be reduced.

[0037] Other features and advantages of the present application will be described in detail in the subsequent detailed description. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0039] According to a first aspect of an embodiment of the present application, an embodiment of the present application provides a silane coupling agent, and the structural formula of the silane coupling agent is shown in formula (I): Formula (I), In formula (I), X1 and X2 are each independently selected from a nitrogen atom and a carbon atom; Y is an oxygen atom and a sulfur atom; R1 is an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; R2, R3 and R4 are each independently selected from an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms.

[0040] As can be seen from formula (I), the silane coupling agent contains two types of groups, namely, silane groups and benzotriazole groups, and the silane groups are connected to the benzotriazole groups through Y. Y can be an oxygen atom or a sulfur atom. Oxygen and sulfur both belong to the oxygen family and have 6 outermost electrons. Therefore, the two have certain similarities in chemical properties.

[0041] Specifically, the aromatic ring of the benzotriazole group has X1 and X2, where X1 and X2 are independently selected from any one of a nitrogen atom and a carbon atom. As an example, X1 and X2 are both carbon atoms, so that the aromatic ring becomes a benzene ring. As an example, X1 and X2 are both nitrogen atoms, or one of X1 and X2 is a carbon atom and the other of X1 and X2 is a nitrogen atom, so that the aromatic ring becomes an azaaromatic ring.

[0042] The silane group includes R1, R2, R3 and R4. Among them, R1 can be an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms. Any one of R2, R3 and R4 can be an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms. That is to say, R2, R3 and R4 in the silane group can be the same or different. As an example, R2, R3 and R4 are all alkoxy groups, or R2, R3 and R4 are all alkyl groups, or one of R2, R3 and R4 is an alkoxy group and the other two are alkyl groups, or one of R2, R3 and R4 is an alkyl group and the other two are alkoxy groups.

[0043] Y is connected to the aromatic ring in the benzotriazole group, more specifically to the carbon atom on the aromatic ring. The carbon atom on the aromatic ring to which a single Y is specifically connected can be selected according to needs. As an example, a single Y can be connected to a carbon atom on the aromatic ring close to X1 or X2, or to a carbon atom on the aromatic ring far from X1 or X2, and can also be connected to the carbon atom when X1 or X2 is a carbon atom.

[0044] In addition, in formula (I), the number of silane groups can be one or more. When the number of silane groups is more than one, the number of Y is also more than one, so that different Ys can be connected to different carbon atoms on the aromatic ring. Optionally, the number of silane groups is one, which makes it easier to control the difficulty of preparing the silane coupling agent.

[0045] The silane coupling agent provided in the application example not only has good compatibility with organic materials, but also has good bonding ability with inorganic interfaces. In particular, the silane coupling agent contains both silane groups and benzotriazole groups, so that the silane coupling agent has better bonding ability to metal substrates (especially copper surfaces). In this way, when the silane coupling agent is added to the resin composition, the adhesion of the resin composition to the surface of the substrate after curing can be improved, and the risk of delamination between the cured film formed after the resin composition is cured and the substrate can be reduced.

[0046] At the same time, when the silane coupling agent is added to the resin composition, the silane coupling agent will not affect the storage stability of the resin composition. In addition, when the silane coupling agent is added to the resin composition, the resin composition can still maintain good adhesion to the substrate even at a low curing temperature (≤250°C).

[0047] In some embodiments, one of X1 and X2 is a nitrogen atom, that is, the aromatic ring is an azaaromatic ring having one nitrogen atom, which is conducive to improving the bonding ability of the benzotriazole group with the inorganic interface, thereby improving the adhesion of the resin composition to the substrate surface after curing.

[0048] In some embodiments, Y is a sulfur atom. This arrangement can reduce the difficulty of preparing the silane coupling agent.

[0049] In some embodiments, R1 is a saturated alkyl group having 1 to 4 carbon atoms. Within this range, the silane coupling agent and the resin can have good compatibility. As an example, R1 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CHCH(CH3)-, -CH2CH2CH2CH2-, -CHC(CH3)2-, -CH(CH3)CH(CH3)- or -CHCH(CH3)CH2-.

[0050] In some embodiments, R1 is a straight chain saturated alkyl group having 2 to 3 carbon atoms. The atomic arrangement of the straight chain saturated alkyl group is relatively regular, which can improve the solubility of the silane group and thus improve the bonding ability of the silane group with the inorganic interface. As an example, R1 is -CH2CH2- or -CH2CH2CH2-.

[0051] In some embodiments, R2, R3 and R4 are each independently selected from any one of an alkyl group having 1 to 2 carbon atoms and an alkoxy group having 1 to 2 carbon atoms. As an example, R2, R3 and R4 are each independently methyl (-CH3), ethyl (-CH2CH3), methoxy (-OCH3) or ethoxy (-OCH2CH3).

[0052] In some embodiments, the number of alkoxy groups based on R2, R3 and R4 is less than or equal to 2. That is, at least one of R2, R3 and R4 is an alkyl group, and at most two of the three are alkoxy groups. Generally, alkoxy groups are easily hydrolyzed with water and remove hydroxide ions (OH - ), increasing the number of alkoxy groups in the silane coupling agent is beneficial to improving the bonding ability of the silane coupling agent to the metal substrate (especially the copper surface), but too much alkoxy group will reduce the stability of the silane coupling agent because the probability of the silane coupling agent being attacked by water increases, thereby making the resin composition to which the silane coupling agent is added easily turbid. As an example, based on R2, R3 and R4, the number of alkoxy groups is 1 or 2.

[0053] In some embodiments, based on R2, R3 and R4, the number of alkoxy groups is greater than the number of alkyl groups. Increasing the number of alkoxy groups is beneficial to improving the bonding ability of the silane group to the inorganic interface. As an example, R2, R3 and R4 are all alkoxy groups, or two of R2, R3 and R4 are alkoxy groups and the other is an alkyl group. As an example, the metal material includes copper.

[0054] In some embodiments, R2, R3 and R4 are each independently selected from any one of methyl, ethyl, methoxy and ethoxy, and based on R2, R3 and R4, the number of methyl groups is 0 or 1, and the number of ethyl groups is 0 or 1. As an example, R2, R3 and R4 are all methoxy groups, or R2, R3 and R4 are all ethoxy groups, or one of R2, R3 and R4 is ethoxy and the other two are methoxy groups, or one of R2, R3 and R4 is methoxy and the other two are ethoxy groups, or one of R2, R3 and R4 is methoxy and the other two are ethoxy groups, or one of R2, R3 and R4 is methoxy, one of ethoxy and one of methyl groups, or one of R2, R3 and R4 is methoxy, one of ethoxy and one of ethyl groups, or two of R2, R3 and R4 are methoxy and one of methyl groups, or two of R2, R3 and R4 are methoxy and one of ethyl groups, or two of R2, R3 and R4 are ethoxy and one of methyl groups, or two of R2, R3 and R4 are ethoxy and one of ethyl groups.

[0055] According to a second aspect of an embodiment of the present application, an embodiment of the present application provides a method for preparing a silane coupling agent, which is used to prepare the silane coupling agent as described above, comprising: The first compound and the second compound are subjected to a nucleophilic substitution reaction to obtain a silane coupling agent, wherein the structural formula of the first compound is as shown in formula (II): Formula (II), In formula (II), Z is any one of a hydroxyl group and a thiol group, and R1, R2, R3 and R4 are the same as those in formula (I); The structural formula of the second compound is shown in formula (III): Formula (III), In formula (III), W is a halogen atom which replaces at least one hydrogen atom on the aromatic ring, and X1 and X2 are the same as those in formula (I).

[0056] Since in formula (II), R1, R2, R3 and R4 are the same as those in formula (I); in formula (III), X1 and X2 are the same as those in formula (I), please refer to the above description and no further details will be given here.

[0057] In formula (II), Z may be a hydroxyl group or a thiol group.

[0058] In formula (III), W is a halogen atom. W is a substitution of at least one hydrogen atom on the aromatic ring, that is, at least one hydrogen atom on the aromatic ring is replaced by a halogen atom, that is, the number of halogen atoms on the aromatic ring is at least one. Specifically, the halogen atom is connected to a carbon atom on the aromatic ring. Usually, the specific carbon atom on the aromatic ring to which a single halogen atom is connected can be selected according to demand. As an example, a single halogen atom can be connected to a carbon atom on the aromatic ring close to X1 or X2, or to a carbon atom on the aromatic ring far away from X1 or X2, and can also be connected to the carbon atom when X1 or X2 is a carbon atom. Here, the halogen atom includes a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I).

[0059] The first compound and the second compound undergo a nucleophilic substitution reaction to generate a target silane coupling agent. Specifically, the first compound is a nucleophilic reagent, which removes protons under alkaline conditions and forms a bond with the carbon atom connected to the halogen atom on the second compound to form an intermediate, and then the halogen ion leaves as a leaving group to finally form a new oxygen ether or thioether compound, that is, the silane coupling agent shown in formula (II).

[0060] The silane coupling agent prepared by the preparation method of the silane coupling agent provided in the second aspect of the embodiment of the present application is the same as the silane coupling agent provided in the first aspect of the embodiment of the present application. Therefore, the silane coupling agent prepared by the preparation method of the silane coupling agent has all the beneficial effects of the above-mentioned silane coupling agent, which will not be repeated in this application.

[0061] In some embodiments, W is a fluorine atom or a chlorine atom, and the number of substitutions is 1. That is, only one hydrogen atom on the aromatic ring is replaced by a halogen atom, and the number of halogen atoms on the aromatic ring is one. As an example, there is a fluorine atom connected to the aromatic ring, or there is a chlorine atom connected to the aromatic ring. Since the halogen atom is connected to the aromatic ring, by designing the halogen atom as a fluorine atom or a chlorine atom, the difficulty of the halogen atom leaving can be reduced, and the rate of the nucleophilic substitution reaction can be increased.

[0062] In some embodiments, the molar ratio of the first compound to the second compound is 1: 1. When only one hydrogen atom on the aromatic ring of the second compound is replaced by a halogen atom, by controlling the molar ratio of the first compound as the reaction raw material to the second compound to be 1: 1, the first compound and the second compound can be completely reacted or substantially completely reacted, thereby improving the utilization rate of the raw materials and reducing waste.

[0063] In some embodiments, the first compound and the second compound undergo a nucleophilic substitution reaction in a polar solvent. A polar solvent refers to a solvent containing polar groups such as hydroxyl or carbonyl, that is, a solvent molecule is a polar molecule, and the molecule is polar because the center of gravity of the positive and negative charges in the molecule does not overlap. Polar solvents can stabilize intermediates through solvation, reduce the activation energy required for the formation of intermediates, and thus accelerate the rate of nucleophilic substitution reactions.

[0064] In some embodiments, the polar solvent is a polar aprotic solvent. Aprotic solvents refer to solvents whose proton self-transfer reaction is extremely weak or has no self-transfer tendency. Such solvents do not provide protons in chemical reactions and are therefore also called aprotic solvents. By controlling the polar solvent to be a polar aprotic solvent, the polar aprotic solvent is not easy to combine with a nucleophilic reagent, thereby reducing its nucleophilicity. In addition, the polar aprotic solvent can also improve the stability of the generated silane coupling agent and reduce the risk of the silane coupling agent reacting with the solvent and decomposing.

[0065] In some embodiments, the polar aprotic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N,N-diethylformamide.

[0066] In some embodiments, the first compound and the second compound undergo a nucleophilic substitution reaction under the catalysis of a basic catalyst. The basic catalyst can cause the first compound, which is a nucleophilic agent, to lose a proton through deprotonation, thereby enhancing its nucleophilicity.

[0067] In some embodiments, the basic catalyst includes at least one of an organic base and an inorganic base. Optionally, the organic base includes at least one of triethylamine, pyridine, sodium methoxide, sodium ethoxide, and N,N-diisopropylethylamine. Optionally, the inorganic base includes at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide.

[0068] In some embodiments, the molar ratio of the alkaline catalyst to the first compound is 1 to 10. In the case where only one hydrogen atom on the aromatic ring of the second compound is replaced by a halogen atom, the amount of the alkaline catalyst is controlled to be appropriately greater than the amount of the first compound as a nucleophile, that is, the alkaline catalyst is excessive, so that as many first compounds as possible can be promoted to lose protons and improve the efficiency of the reaction of the first compound. However, alkaline catalysts are generally corrosive, so the molar ratio of the alkaline catalyst to the first compound should not be too large, otherwise it will increase the damage to the generation setting, and it will also increase the difficulty of purifying the silane coupling agent. As an example, the molar ratio of the alkaline catalyst to the first compound is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0069] In some embodiments, the molar ratio of the alkaline catalyst to the first compound is 1 to 1.5. Within this range, the efficiency of the reaction of the first compound is better and the difficulty of purifying the silane coupling agent is less. As an example, the molar ratio of the alkaline catalyst to the first compound is 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5.

[0070] In some embodiments, the reaction temperature of the nucleophilic substitution reaction is 10° C. to 50° C. As an example, the reaction temperature is 10° C., 20° C., 30° C., 40° C. or 50° C.

[0071] In some embodiments, after the nucleophilic substitution reaction is completed, a reaction solution containing a silane coupling agent is obtained, and the method for preparing the silane coupling agent further includes purifying the reaction solution to extract the silane coupling agent from the reaction solution.

[0072] In some embodiments, the purification process includes filtering to remove by-products in the reaction solution, collecting the obtained filtrate, and then distilling and purifying to obtain the silane coupling agent. In the case where an alkaline catalyst is also added during the reaction, the alkaline catalyst is also removed by filtering. As an example, a poor solvent for the alkaline catalyst (i.e., a solvent in which the alkaline catalyst is insoluble) is added to the reaction solution to precipitate the alkaline catalyst, and then the precipitated alkaline catalyst is removed by filtering.

[0073] According to the third aspect of the embodiment of the present application, the embodiment of the present application provides a resin composition, which includes a silane coupling agent and a resin, and the silane coupling agent is at least one of the silane coupling agent as described above and the silane coupling agent prepared by the preparation method of the silane coupling agent as described above.

[0074] According to the third aspect of the present application, a resin composition is provided, which includes the above-mentioned silane coupling agent. The resin composition has all the beneficial effects of the above-mentioned silane coupling agent, which will not be described in detail in the present application.

[0075] In some embodiments, the mass ratio of the silane coupling agent to the resin is 0.001 to 0.1. In general, in the resin composition, the mass ratio of the silane coupling agent to the resin should not be too small, otherwise when the resin composition is applied on the surface of the substrate, the coverage of the silane coupling agent on the surface of the substrate is low, and a better adhesion promotion effect cannot be exerted; however, the mass ratio of the silane coupling agent to the resin should not be too large, otherwise the stability and mechanical properties of the resin composition may be impaired. As an example, the mass ratio of the silane coupling agent to the resin is 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1.

[0076] In some embodiments, the mass ratio of the silane coupling agent to the resin is 0.01 to 0.05. Within this range, the resin composition has better bonding effect, mechanical properties and stability. Optionally, the mass ratio of the silane coupling agent to the resin is 0.01 to 0.03.

[0077] In some embodiments, the resin composition is a photosensitive resin composition, and the photosensitive resin composition further includes a photoinitiator. When the resin composition further includes a photoinitiator, the resin composition is a photosensitive resin composition. Optionally, the photoinitiator includes an oxime ester photoinitiator, such as OXE-1. During the use of the photosensitive resin composition, the resin can be further polymerized under the action of the photoinitiator under light conditions.

[0078] In some embodiments, the photosensitive resin composition further comprises at least one of a crosslinking agent and a first solvent. Optionally, the crosslinking agent comprises trimethylolpropane triacrylate. Optionally, the first solvent comprises N-methylpyrrolidone.

[0079] In some embodiments, the resin is an alkali-soluble resin. An alkali-soluble resin is a polymer material having a specific alkali-soluble group, and such resin can be applied to a photosensitive resin composition and has good developability and pattern forming properties.

[0080] In some embodiments, the alkali-soluble resin includes at least one of a polyimide-based resin, a polyamic acid-based resin, a polyamic acid ester-based resin, and a polybenzoxazole-based resin.

[0081] According to a fourth aspect of an embodiment of the present application, an embodiment of the present application provides a cured film, which includes a cured product of the resin composition as described above.

[0082] The cured film includes a cured product of the resin composition. The cured film has all the beneficial effects of the resin composition, which will not be described in detail in this application.

[0083] In some embodiments, the cured film includes at least one of a surface protection film for a semiconductor package element, an interlayer insulating film, a redistribution insulating film, a metal bump stress buffer layer, and a passivation film. As an example, the cured film is a surface protection film for a semiconductor package element; or the cured film is an interlayer insulating film for a semiconductor package element; or the cured film is a redistribution insulating film for a semiconductor package element; or the cured film is a metal bump stress buffer layer for a semiconductor package element; or the cured film is a passivation film for a semiconductor package element.

[0084] According to a fifth aspect of an embodiment of the present application, an embodiment of the present application provides a semiconductor device, and the semiconductor device includes the cured film as described above.

[0085] In some embodiments, a semiconductor device includes a semiconductor package element including a cured film.

[0086] The following is a description with reference to specific embodiments.

[0087] Example 1 This embodiment provides a silane coupling agent, and the structural formula of the silane coupling agent is as follows: .

[0088] The preparation method of the silane coupling agent comprises: Add 6.18 g (0.04 mol, CAS No. 36258-82-9) of 4-chloro-3H-[1,2,3]triazolo[4,5-c]pyridine and 6.63 g (0.048 mol) of potassium carbonate to a 250 mL three-necked flask equipped with a stirrer and a thermometer, and 50 mL of anhydrous N-methylpyrrolidone as solvent, and start stirring. At the same time, weigh 3-mercaptopropylmethyldimethoxysilane (0.04 mol, CAS No. 31001-77-1) and dissolve it in 50 mL of anhydrous N-methylpyrrolidone. Slowly add the 3-mercaptopropylmethyldimethoxysilane solution to the above three-necked flask at room temperature while stirring. After the addition is completed, continue the reaction for 18 h.

[0089] After the reaction is completed, 60 g of ethyl acetate is slowly added to the reaction system and stirred for 1 h to fully precipitate the potassium salt in the system, and then the reaction solution is filtered with 5 μm and 0.5 μm filter papers in turn. After filtration, the ethyl acetate in the system is removed by rotary evaporation in a 35°C water bath, and N-methylpyrrolidone containing silane coupling agent A1 of benzotriazole group is obtained after reduced pressure distillation, and the concentration is 10.4% (the concentration is converted from the integral ratio of the solvent and silane coupling agent A1 in the nuclear magnetic hydrogen spectrum).

[0090] The nuclear magnetic information of silane coupling agent A1 is as follows: 1H NMR (CDCl3): δ=0.15(s, 3H), 0.61(m, 2H), 1.65(m, 2H), 3.10(m, 2H), 3.55(s, 6H), 7.50(d, 1H), 8.31(d, 1H).

[0091] Example 2 This embodiment provides a silane coupling agent, and the structural formula of the silane coupling agent is as follows: .

[0092] The preparation method of the silane coupling agent comprises: Add 6.18 g (0.04 mol, CAS No. 120641-09-0) of 6-chloro-3H-[1,2,3]triazolo[4,5-c]pyridine and 6.63 g (0.048 mol) of potassium carbonate to a 250 mL three-necked flask equipped with a stirrer and a thermometer, and 50 mL of anhydrous N-methylpyrrolidone as solvent, and start stirring. At the same time, weigh 3-mercaptopropylmethyldimethoxysilane (0.04 mol, CAS No. 31001-77-1) and dissolve it in 50 mL of anhydrous N-methylpyrrolidone. Slowly add the 3-mercaptopropylmethyldimethoxysilane solution to the three-necked flask at room temperature while stirring. After the addition is completed, continue the reaction for 18 h.

[0093] After the reaction is completed, 60 g of ethyl acetate is slowly added to the reaction system and stirred for 1 h to fully precipitate the potassium salt in the system, and then the reaction solution is filtered with 5 μm and 0.5 μm filter papers in turn. After filtration, the ethyl acetate in the system is removed by rotary evaporation in a 35°C water bath, and N-methylpyrrolidone containing silane coupling agent A2 of benzotriazole group is obtained after reduced pressure distillation, and the concentration is 10.5% (the concentration is converted from the integral ratio of the solvent and silane coupling agent A2 in the nuclear magnetic hydrogen spectrum).

[0094] The nuclear magnetic information of silane coupling agent A2 is as follows: 1H NMR (CDCl3): δ=0.15(s, 3H), 0.61(m, 2H), 1.65(m, 2H), 3.08(m, 2H), 3.55(s, 6H), 7.29(s, 1H), 8.48(s, 1H).

[0095] Example 3 This embodiment provides a silane coupling agent, and the structural formula of the silane coupling agent is as follows: .

[0096] The preparation method of the silane coupling agent comprises: Add 6.18 g (0.04 mol, CAS No. 120641-09-0) of 6-chloro-3H-[1,2,3]triazolo[4,5-c]pyridine and 6.63 g (0.048 mol) of potassium carbonate to a 250 mL three-necked flask equipped with a stirrer and a thermometer, and 50 mL of anhydrous N-methylpyrrolidone as solvent, and start stirring. At the same time, weigh 3-mercaptopropyltrimethoxysilane (0.04 mol, CAS No. 4420-74-0) and dissolve it in 50 mL of anhydrous N-methylpyrrolidone. Slowly add the 3-mercaptopropyltrimethoxysilane solution to the three-necked flask at room temperature while stirring. After the addition is completed, continue the reaction for 18 h.

[0097] After the reaction is completed, 60 g of ethyl acetate is slowly added to the reaction system and stirred for 1 h to fully precipitate the potassium salt in the system, and then the reaction solution is filtered with 5 μm and 0.5 μm filter papers in turn. After filtration, the ethyl acetate in the system is removed by rotary evaporation in a 35°C water bath, and N-methylpyrrolidone containing silane coupling agent A3 of benzotriazole group is obtained after reduced pressure distillation, and the concentration is 10.2% (the concentration is converted from the integral ratio of the solvent and silane coupling agent A3 in the nuclear magnetic hydrogen spectrum).

[0098] The nuclear magnetic information of silane coupling agent A3 is as follows: 1H NMR (CDCl3): δ=0.58(m, 2H), 1.65(m, 2H), 3.08(m, 2H), 3.57(s, 9H), 7.29(s, 1H), 8.48(s, 1H).

[0099] Example 4 This embodiment provides a silane coupling agent, and the structural formula of the silane coupling agent is as follows: .

[0100] The preparation method of the silane coupling agent comprises: Add 5.48 g (0.04 mol, CAS No. 18225-90-6) of 5-fluoro-1H-benzotriazole and 6.63 g (0.048 mol) of potassium carbonate to a 250 mL three-necked flask equipped with a stirrer and a thermometer, and stir. At the same time, weigh 3-mercaptopropylmethyldimethoxysilane (0.04 mol, CAS No. 31001-77-1) and dissolve it in 50 mL of anhydrous N-methylpyrrolidone. Slowly add the 3-mercaptopropylmethyldimethoxysilane solution to the three-necked flask at room temperature (20-30°C) while stirring. After the addition is completed, continue the reaction for 18 h.

[0101] After the reaction is completed, 60 g of ethyl acetate is slowly added to the reaction system and stirred for 1 h to fully precipitate the potassium salt in the system, and then the reaction solution is filtered with 5 μm and 0.5 μm filter papers in turn. After filtration, the ethyl acetate in the system is removed by rotary evaporation in a 35°C water bath, and N-methylpyrrolidone of silane coupling agent A4 containing benzotriazole groups is obtained after reduced pressure distillation, and the concentration is 10.7% (the concentration is converted from the integral ratio of the solvent and silane coupling agent A4 in the nuclear magnetic hydrogen spectrum).

[0102] The nuclear magnetic information of silane coupling agent A4 is as follows: 1H NMR (CDCl3): δ=0.15(m, 3H), 0.61(m, 2H), 1.65(m, 2H), 2.93(m, 2H), 3.55(s, 6H), 7.37(d, 1H), 7.86(d, 1H), 7.91(s, 1H).

[0103] Example 5 This embodiment provides a silane coupling agent, and the structural formula of the silane coupling agent is as follows: .

[0104] The preparation method of the silane coupling agent comprises: Add 5.48 g (0.04 mol, CAS No. 243464-29-1) of 7-fluoro-1H-benzotriazole and 6.63 g (0.048 mol) of potassium carbonate to a 250 mL three-necked flask equipped with a stirrer and a thermometer, and stir. At the same time, weigh 3-mercaptopropylmethyldimethoxysilane (0.04 mol, CAS No. 31001-77-1) and dissolve it in 50 mL of anhydrous N-methylpyrrolidone. Slowly add the 3-mercaptopropylmethyldimethoxysilane solution to the three-necked flask while stirring at room temperature (20-30°C). After the addition is completed, continue the reaction for 18 h.

[0105] After the reaction is completed, 60 g of ethyl acetate is slowly added to the reaction system and stirred for 1 h to fully precipitate the potassium salt in the system, and then the reaction solution is filtered with 5 μm and 0.5 μm filter papers in turn. After filtration, the ethyl acetate in the system is removed by rotary evaporation in a 35°C water bath, and N-methylpyrrolidone of silane coupling agent A5 containing benzotriazole groups is obtained after reduced pressure distillation, and the concentration is 10.9% (the concentration is converted from the integral ratio of the solvent and silane coupling agent A5 in the nuclear magnetic hydrogen spectrum).

[0106] The nuclear magnetic information of silane coupling agent A5 is as follows: 1H NMR (CDCl3): δ=0.15(m, 3H), 0.61(m, 2H), 1.65(m, 2H), 2.93(m, 2H), 3.55(s, 6H), 7.30-7.37(m, 2H), 7.74(d, 1H).

[0107] Example 6 This embodiment provides a silane coupling agent, and the structural formula of the silane coupling agent is as follows: .

[0108] The preparation method of the silane coupling agent comprises: Add 5.48 g of 7-fluoro-1H-benzotriazole (0.04 mol, Merck, CAS No. 243464-29-1) and 6.63 g of potassium carbonate (0.048 mol, J&K) to a 250 mL three-necked flask equipped with a stirrer and a thermometer, and 50 mL of anhydrous N-methylpyrrolidone as solvent, and start stirring. At the same time, weigh 3-mercaptopropyltrimethoxysilane (0.04 mol, CAS No. 4420-74-0) and dissolve it in 50 mL of anhydrous N-methylpyrrolidone. Slowly add the 3-mercaptopropyltrimethoxysilane solution to the above three-necked flask at room temperature (20-30°C) while stirring. After the addition is completed, continue the reaction for 18 h.

[0109] After the reaction is completed, 60 g of ethyl acetate is slowly added to the reaction system and stirred for 1 h to fully precipitate the potassium salt in the system, and then the reaction solution is filtered with 5 μm and 0.5 μm filter papers in turn. After filtration, the ethyl acetate in the system is removed by rotary evaporation in a 35°C water bath, and N-methylpyrrolidone containing silane coupling agent A6 of benzotriazole group is obtained after reduced pressure distillation, and the concentration is 10.8% (the concentration is converted from the integral ratio of the solvent and silane coupling agent A6 in the nuclear magnetic hydrogen spectrum).

[0110] The nuclear magnetic information of silane coupling agent A6 is as follows: 1H NMR (CDCl3): δ=0.56(m, 2H), 1.65(m, 2H), 2.94(m, 2H), 3.57(s, 9H), 7.30-7.37(m, 2H), 7.74(d, 1H).

[0111] Synthesis example 1 Preparation of polyamic acid ester polymer R1: 31.0 g of 4,4'-biphenyl ether dianhydride (abbreviated as ODPA, 0.1 mol) and 120 mL of anhydrous N-methylpyrrolidone were added to a double-layer jacketed 500 mL reactor equipped with a stirrer and a thermometer, and the reaction system was placed under nitrogen conditions and the temperature was raised to 40°C. Subsequently, a solution of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (33.0 g, 0.09 mol) in anhydrous N-methylpyrrolidone (120 mL) was slowly added dropwise, and the above solution was pre-dissolved 8 h in advance. After the addition was completed, the above reaction solution was further reacted at 40°C for 4 h, and then 3-aminophenol (2.18 g, 0.02 mol) dissolved in 10 mL of anhydrous N-methylpyrrolidone was added as a capping agent, and the reaction was continued at 40°C for 2 h. After that, N,N-dimethylformamide dimethyl acetal (21.4 g, 0.18 mol) diluted with 50 mL of anhydrous N-methylpyrrolidone was slowly added dropwise, and the mixture was reacted at 40°C for 3 h. After the reaction, the solution was poured into 3 L of deionized water, and the precipitate of the polymer solid was collected by filtration. After washing the solvent and by-product residues with a large amount of deionized water, the polymer solid was dried in a vacuum dryer at 80°C for 48 hours to obtain a polyamic acid ester polymer R1.

[0112] The molecular weight of the polyamic acid ester polymer R1 was determined by gel permeation chromatography. The column model was waters Styragel HR 4, and the mobile phase was 0.05 mol / L LiCl in N-methylpyrrolidone. The number average molecular weight of the polyamic acid ester polymer R1 was 1.6×10 4 .

[0113] Synthesis example 2 Preparation of polyamic acid ester polymer R2: 31.0 g of 4,4'-biphenyl ether dianhydride (abbreviated as ODPA, 0.1 mol) and 120 mL of anhydrous N-methylpyrrolidone were added to a double-layer jacketed 500 mL reactor equipped with a stirrer and a thermometer, and the reaction system was placed under nitrogen conditions and the temperature was raised to 40°C. Subsequently, a solution of bis(3-amino-4-hydroxyphenyl) sulfone (25.2 g, 0.09 mol) in anhydrous N-methylpyrrolidone (120 mL) was slowly added dropwise, and the above solution was pre-dissolved 8 h in advance. After the addition was completed, the above reaction solution was further reacted at 40°C for 4 h, and then 3-aminophenol (2.18 g, 0.02 mol) dissolved in 10 mL of anhydrous N-methylpyrrolidone was added as a capping agent, and the reaction was continued at 40°C for 2 h. After that, N,N-dimethylformamide dimethyl acetal (21.4 g, 0.18 mol) diluted with 50 mL of anhydrous N-methylpyrrolidone was slowly added dropwise, and the mixture was reacted at 40°C for 3 h. After the reaction, the solution was put into 3 L of deionized water, and the precipitate of the polymer solid was collected by filtration. After washing the solvent and by-product residues with a large amount of deionized water, the polymer solid was dried in a vacuum dryer at 80°C for 48 hours to obtain a polyamic acid ester polymer R2.

[0114] The molecular weight of the polyamic acid ester polymer R2 was determined by gel permeation chromatography. The column model was waters Styragel HR 4, and the mobile phase was 0.05 mol / L LiCl in N-methylpyrrolidone. The number average molecular weight of the polyamic acid ester polymer R2 was 1.8×10 4 .

[0115] Application Example 1 10.0 g of the polyamic acid ester polymer R1 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Then, 0.2 g of the silane coupling agent A1 obtained in Example 1 (i.e., 1.92 g of the solution of the silane coupling agent A1) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0116] Application Example 2 10.0 g of the polyamic acid ester polymer R1 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Then, 0.2 g of the silane coupling agent A2 obtained in Example 2 (i.e., 1.90 g of the solution of the silane coupling agent A2) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0117] Application Example 3 10.0 g of the polyamic acid ester polymer R1 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Subsequently, 0.2 g of the silane coupling agent A3 obtained in Example 3 (i.e., 1.96 g of the solution of the silane coupling agent A3) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0118] Application Example 4 10.0 g of the polyamic acid ester polymer R1 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Subsequently, 0.2 g of the silane coupling agent A4 obtained in Example 4 (i.e., 1.87 g of the solution of the silane coupling agent A4) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0119] Application Example 5 10.0 g of the polyamic acid ester polymer R1 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Subsequently, 0.2 g of the silane coupling agent A5 obtained in Example 5 (i.e., 1.83 g of the solution of the silane coupling agent A5) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0120] Application Example 6 10.0 g of the polyamic acid ester polymer R1 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Subsequently, 0.2 g of the silane coupling agent A6 obtained in Example 6 (i.e., 1.85 g of the solution of the silane coupling agent A6) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0121] Application Example 7 10.0 g of the above-mentioned polyamic acid ester polymer R1 and 31.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until uniformly dissolved. Subsequently, 0.1 g of the silane coupling agent A1 obtained in Example 1 and 0.1 g of the silane coupling agent A2 obtained in Example 2 (i.e., 0.96 g and 0.95 g of the solutions of silane coupling agent A1 and silane coupling agent A2, respectively) and 0.3 g of the photoinitiator OXE-1 (molecular formula C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0122] Application Example 8 10.0 g of the polyamic acid ester polymer R2 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Then, 0.2 g of the silane coupling agent A1 obtained in Example 1 (i.e., 1.92 g of the solution of the silane coupling agent A1) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0123] Application Example 9 10.0 g of the polyamic acid ester polymer R2 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Subsequently, 0.2 g of the silane coupling agent A2 obtained in Example 2 (i.e., 1.90 g of the solution of the silane coupling agent A2) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0124] Application Example 10 10.0 g of the polyamic acid ester polymer R1 and 30.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Then, 0.1 g of the silane coupling agent A2 obtained in Example 2 (i.e., 0.95 g of the solution of the silane coupling agent A2) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0125] Application Example 11 10.0 g of the polyamic acid ester polymer R1 and 27.0 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Then, 0.5 g of the silane coupling agent A2 obtained in Example 2 (i.e., 4.76 g of the solution of the silane coupling agent A2) and 0.3 g of the photoinitiator OXE-1 (molecular formula: C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0126] Comparative Example 1 10.0 g of the above-mentioned polyamic acid ester polymer R1 and 31.7 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Subsequently, 0.2 g of silane coupling agent 3-mercaptopropylmethyldimethoxysilane and 0.3 g of photoinitiator OXE-1 (molecular formula C 27 H 27NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0127] Comparative Example 2 10.0 g of the above-mentioned polyamic acid ester polymer R1 and 31.70 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Then, 0.1 g of silane coupling agent 3-mercaptopropylmethyldimethoxysilane and 0.1 g of copper surface auxiliary agent 3H-1,2,3-triazolo[4,5-C]pyridine, 0.3 g of photoinitiator OXE-1 (molecular formula C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0128] Comparative Example 3 10.0 g of the above-mentioned polyamic acid ester polymer R1 and 31.7 g of electronic grade N-methylpyrrolidone were added to a 250 mL three-necked flask and stirred until dissolved uniformly. Then, 0.2 g of copper surface additive 3H-1,2,3-triazolo[4,5-C]pyridine and 0.3 g of photoinitiator OXE-1 (molecular formula C 27 H 27 NO3S, purity ≥98%) and 6.0g of cross-linking agent trimethylolpropane triacrylate (abbreviated as TMPTA, purity ≥95%) are fully dissolved, filtered using a 0.5μm filter membrane to obtain the corresponding photosensitive resin composition.

[0129] The type and amount of the polyamic acid ester polymer and the type and amount of the additives in each application example and comparative example are recorded in Table 1.

[0130] Table 1

[0131] The photosensitive resin compositions prepared according to the examples and comparative examples were tested as follows, and the test results are recorded in Table 3: 1. Copper surface adhesion test: The photosensitive resin composition was spin-coated onto an 8-inch silicon wafer that had been sputtered with 0.1μm titanium and 0.4μm copper in sequence by a coating machine, and pre-baked on a hot plate at 105°C for 180 seconds to form a coating film about 8μm thick. A temperature-programmed curing furnace was used to heat the wafer at 250°C for 2 hours in a nitrogen atmosphere to obtain a cured resin coating film about 7μm thick. The coated silicon wafer was placed in a high-temperature and high-humidity accelerated aging test chamber. The test conditions were 130°C and 85%RH for 264 hours. After the accelerated aging test, the adhesion characteristics of the cured resin coating film and the copper surface were evaluated according to the crosscut method of JIS K 5600-5-6. Please refer to Table 2 for the evaluation criteria: Table 2

[0132] 2. Glue stability test: Visual observation is adopted. If the photosensitive resin composition becomes turbid or has precipitates within 14 days, it is recorded as "white turbidity". If it is still clear and has good fluidity, it is recorded as "normal".

[0133] 3. Copper surface adhesion stability test: The photosensitive resin composition was placed at room temperature and in an air environment for 14 days, and the adhesion characteristics of the cured resin coating and the copper surface 14 days after opening the bottle were tested and evaluated again according to the above copper surface adhesion test method. Please refer to Table 2 for the evaluation criteria.

[0134] Table 3

[0135] From the test results in Table 3, it can be seen that compared with Comparative Examples 1 to 3, the silane coupling agent provided in Examples 1 to 6 of the present application is applied to the photosensitive resin composition (i.e., Application Examples 1 to 11), and the photosensitive resin composition is cured at a relatively low temperature (250°C), and the formed cured resin coating can still maintain good copper surface adhesion with the copper surface, indicating that the silane coupling agent provided in the embodiment of the present application can effectively improve the adhesion between the photosensitive resin composition and the copper surface, and its performance is close to or even better than that of the copper surface auxiliary agent (Comparative Example 3) provided in the related art. In addition, except for Application Examples 3 and Application Examples 6, the photosensitive resin compositions of other application examples can still be cured at a relatively low temperature (250°C) and maintain good copper surface adhesion with the copper surface even after being placed for 14 days, which indicates that the silane coupling agent provided in the embodiment of the present application is added to the photosensitive resin composition, and the silane coupling agent is not easy to affect the storage stability of the photosensitive resin composition. Abnormal glue stability occurred in Application Examples 3 and 6 because the number of alkoxy groups in the silane coupling agents used in Application Examples 3 and 6 was too large. Compared with the silane coupling agents used in Application Examples 1, 2, 4 and 5, the number of methoxy groups in the silane coupling agents used in Application Examples 3 and 6 was three, so when the silane coupling agents in the photosensitive resin composition were stored under room temperature and air environment, the silane coupling agents were attacked by water in the air and hydrolyzed, thereby affecting the storage stability of the photosensitive resin composition.

[0136] However, compared with Application Example 1, Application Example 2, Application Example 4, and Application Example 5, when the number of methoxy groups in the silane coupling agent is the same, the stability of the photosensitive resin composition provided by Comparative Example 1 is worse, and it is more likely to become turbid during storage in the air. This is because the silane coupling agent used in Comparative Example 1 is 3-mercaptopropylmethyldimethoxysilane, and compared with silane coupling agent A1, silane coupling agent A2, silane coupling agent A4, and silane coupling agent A5 used in Application Example 1, Application Example 2, Application Example 4, and Application Example 5, 3-mercaptopropylmethyldimethoxysilane has less steric hindrance, so the methoxy group in 3-mercaptopropylmethyldimethoxysilane is more likely to react with water, thereby reducing the storage stability of the photosensitive resin composition.

[0137] Compared with Application Example 1, Application Example 2, and Application Example 4, the stability of the photosensitive resin composition provided in Comparative Example 3 is worse. It is speculated that this may be because the aromatic rings on the copper surface auxiliary agent 3H-1,2,3-triazolo[4,5-C]pyridine used in Comparative Example 3 interact with each other (stacking), which is difficult to dissolve and precipitates after static storage. Although the silane coupling agents A1, A2, A4, and A5 used in Application Examples 1, 2, 4, and 5 also have aromatic rings, due to the increase in steric hindrance, the aromatic rings on the silane coupling agents A1, A2, A4, and A5 are not easy to interact with each other, thereby improving the stability of the photosensitive resin composition.

[0138] It can be understood that the photosensitive resin composition in Comparative Example 2 contains both 3-mercaptopropylmethyldimethoxysilane and 3H-1,2,3-triazolo[4,5-C]pyridine, and the storage stability of the photosensitive resin composition is also poor.

[0139] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more features. In the description of this application, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0140] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0141] The embodiments, implementation methods and related technical features of the present application can be combined and replaced with each other without conflict.

[0142] The above are only preferred embodiments of the present application and do not constitute any form of limitation to the present application. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present application without departing from the content of the technical solution of the present application are still within the scope of the technical solution of the present application.

Claims

1. A silane coupling agent, characterized in that: The structural formula of the silane coupling agent is shown in formula (I): Formula (I), In formula (I), X1 and X2 are each independently selected from a nitrogen atom and a carbon atom; Y is an oxygen atom and a sulfur atom; R1 is an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; R2, R3 and R4 are each independently selected from an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms.

2. The silane coupling agent according to claim 1, characterized in that wherein one of X1 and X2 is a nitrogen atom; and / or, Y is a sulfur atom; and / or, R1 is a saturated alkyl group having 1 to 4 carbon atoms.

3. The silane coupling agent according to claim 2, characterized in that: R1 is a straight-chain saturated alkyl group having 2 to 3 carbon atoms.

4. The silane coupling agent according to any one of claims 1 to 3, characterized in that: R2, R3 and R4 are each independently selected from any one of an alkyl group having 1 to 2 carbon atoms and an alkoxy group having 1 to 2 carbon atoms.

5. The silane coupling agent according to claim 4, characterized in that: The number of the alkoxy groups is less than or equal to 2 based on R2, R3 and R4.

6. The silane coupling agent according to claim 4, characterized in that: The number of the alkoxy groups is greater than the number of the alkyl groups based on R2, R3 and R4.

7. The silane coupling agent according to claim 6, characterized in that: R2, R3 and R4 are each independently selected from any one of methyl, ethyl, methoxy and ethoxy groups, and the number of the methyl groups is 0 or 1, and the number of the ethyl groups is 0 or 1 based on R2, R3 and R4.

8. A method for preparing a silane coupling agent, for preparing the silane coupling agent according to any one of claims 1 to 7, characterized in that: include: The silane coupling agent is obtained by subjecting the first compound to a nucleophilic substitution reaction with the second compound, wherein the structural formula of the first compound is as shown in formula (II): Formula (II), In formula (II), Z is any one of a hydroxyl group and a thiol group, and R1, R2, R3 and R4 are the same as those in formula (I); The structural formula of the second compound is shown in formula (III): Formula (III), In formula (III), W is a halogen atom which replaces at least one hydrogen atom on the aromatic ring, and X1 and X2 are the same as those in formula (I).

9. The method for preparing a silane coupling agent according to claim 8, characterized in that: The first compound and the second compound undergo the nucleophilic substitution reaction in a polar solvent.

10. The method for preparing a silane coupling agent according to claim 9, characterized in that: The polar solvent is a polar aprotic solvent; the polar aprotic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N,N-diethylformamide.

11. The method for preparing a silane coupling agent according to claim 8, characterized in that: The first compound and the second compound undergo the nucleophilic substitution reaction under the catalysis of a basic catalyst.

12. The method for preparing a silane coupling agent according to claim 11, characterized in that: The alkaline catalyst includes at least one of an organic base and an inorganic base; the organic base includes triethylamine, pyridine, sodium methoxide, sodium ethoxide, and N,N -diisopropylethylamine; and / or, the inorganic base comprises at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide; and / or, the molar ratio of the alkaline catalyst to the first compound is 1 to 10.

13. The method for preparing a silane coupling agent according to claim 12, characterized in that: The molar ratio of the basic catalyst to the first compound is 1 to 1.

5.

14. The method for preparing a silane coupling agent according to any one of claims 8 to 13, characterized in that: The reaction temperature of the nucleophilic substitution reaction is 10°C to 50°C; and / or, W is a fluorine atom or a chlorine atom, and the substitution number is 1; and / or, The molar ratio of the first compound to the second compound is 1:1; and / or, After the nucleophilic substitution reaction is completed, a reaction liquid containing the silane coupling agent is obtained. The preparation method of the silane coupling agent also includes purifying the reaction liquid to extract the silane coupling agent from the reaction liquid.

15. A resin composition, characterized in that The invention comprises a silane coupling agent and a resin, wherein the silane coupling agent is at least one of the silane coupling agent according to any one of claims 1 to 7 and the silane coupling agent prepared by the preparation method of the silane coupling agent according to any one of claims 8 to 14.

16. The resin composition according to claim 15, characterized in that The mass ratio of the silane coupling agent to the resin is 0.001-0.1; and / or, the resin composition is a photosensitive resin composition, and the photosensitive resin composition further comprises at least one of a photoinitiator, a cross-linking agent and a first solvent.

17. The resin composition according to claim 15 or 16, characterized in that The resin is an alkali-soluble resin; the alkali-soluble resin includes at least one of polyimide resin, polyamic acid resin, polyamic acid ester resin and polybenzoxazole resin.

18. A cured film, characterized in that: The cured film comprises a cured product of the resin composition according to any one of claims 15 to 17.

19. The cured film according to claim 18, characterized in that The cured film includes at least one of a surface protection film, an interlayer insulating film, an insulating film for redistribution, a metal bump stress buffer layer, and a passivation film for a semiconductor package element.

20. A semiconductor device, characterized in that: The semiconductor device comprises the cured film according to claim 18 or 19.

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