Dendritic triazole compound for aluminum surface sealing agent, aluminum surface sealing agent, resin composition, and resin hardened product

Abstract

The application discloses a branched triazole compound for an aluminum surface sealing agent, an aluminum surface sealing agent, a resin composition and a resin hardened product, and relates to the technical field of sealing agents. A general formula of the branched triazole compound for the aluminum surface sealing agent is shown in formula (1). The cured film prepared from the resin composition added with the branched triazole compound has good adhesion to an aluminum or aluminum alloy base material, and can significantly improve the separation problem of the cured film from the aluminum or aluminum alloy base material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesives, in particular to a branched triazole-based compound for an aluminum surface adhesive, an aluminum surface adhesive, a resin composition, and a resin hardened product. BACKGROUND

[0002] At present, polyimide (PI) resin, polybenzoxazole (PBO) resin and the like with excellent heat resistance and adhesion have been widely used in surface protective films, interlayer insulating films, and cured films of semiconductor elements of electronic devices. To ensure the reliability of semiconductor packaging, the adhesion of the cured film, which is permanently retained in the device, to the surface material of the semiconductor chip is very important. If the adhesion of the cured film is poor, it is easy to cause cracking and separation of the cured film from the contact substrate, which may result in poor reliability of the device, or even short circuit and burning of the device. Among the substrates in contact with the cured film, copper and aluminum account for a large proportion.

[0003] However, the adhesion of the cured film to the surface of aluminum or aluminum alloy (hereinafter referred to as aluminum surface) is one of the most difficult problems to solve in wafer packaging. The main reason is that the aluminum surface is quickly oxidized and passivated, and it is difficult for general adhesives to form strong complexation with the aluminum oxide surface or Van der Waals force similar to that with the copper surface. In recent years, the redistribution of semiconductor packaging has developed towards miniaturization, and the adhesion of the cured film to the aluminum surface is a problem that must be solved. The actual solution is generally to increase the amount of azole and purine adhesives, but this will affect the lithography window and storage stability of the composition, and the adhesives in the composition may even precipitate during cold storage and transportation due to too high concentration. Another method is to chemically modify the existing adhesives, but the effect is very small. Therefore, it is urgent to develop a composition with good adhesion to aluminum or aluminum alloy surface. SUMMARY

[0004] Therefore, the present application provides a branched triazole-based compound for an aluminum surface adhesive, an aluminum surface adhesive, a resin composition, and a resin hardened product, aiming to solve the technical problem that the existing adhesives are not suitable for adhesion to aluminum surface.

[0005] In a first aspect, the embodiments of the present application provide a branched triazole-based compound for an aluminum surface adhesive, the general formula of the branched triazole-based compound is shown as formula (1):

[0006] Formula (1);

[0007] wherein A is an organic group having a carbon atom number of 0-50; R1 is selected from at least one of O, N, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon-oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, a heterocyclic group; R2 and R3 are independently selected from at least one of a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, a heterocyclic group; R4 is at least one of H, O, N, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon-oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, a heterocyclic group; n is an integer of 2-4; Z is a triazole residue having a structure of formula (2) as follows:

[0008] Formula (2).

[0009] It should be noted that the inventors have found that when n is 1 in formula (1), there is almost no close effect on the aluminum surface.

[0010] In some embodiments of the present application, A is an organic group having a carbon atom number of 0-20; and / or

[0011] R1 is selected from at least one of O, a divalent hydrocarbon group having a carbon atom number of 1-6, a substituted hydrocarbon group, a hydrocarbon-oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, a heterocyclic group; and / or

[0012] R2 and R3 are independently selected from at least one of a hydrogen atom, a monovalent hydrocarbon group having a carbon atom number of 1-10, a substituted hydrocarbon group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, a heterocyclic group; and / or

[0013] R4 is at least one of H, a monovalent hydrocarbon group having a carbon atom number of 1-10, a substituted hydrocarbon group, a hydrocarbon-oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, a heterocyclic group.

[0014] In some embodiments of the present application, A includes but is not limited to at least one of the following structures:

[0015]

[0016] wherein R5 is at least one of a divalent hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon-oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, a heterocyclic group; n1 is an integer of 1-4; n2 is an integer of 2-4; n3 is an integer of 2-4;

[0017] X1 includes at least one of the following structures

[0018] .

[0019] In some embodiments of the present application, R1 includes at least one of the following structures: .

[0020] In some embodiments of the present application, the branched triazole-based compound includes at least one of the compounds shown in the following formulas (3) to (12):

[0021]

[0022] .

[0023] The second aspect of the present application provides a resin composition including a resin matrix and the branched triazole-based compound.

[0024] In some embodiments of the present application, the mass percentage of the branched triazole-based compound to the resin matrix is greater than 0.1% and less than or equal to 5%; and / or

[0025] The resin composition is a negative photosensitive resin composition; and / or

[0026] The resin matrix includes at least one of a polyimide precursor resin, a polyimide-based resin, an acrylate-based resin, an epoxy-based resin, a polybenzoxazole precursor resin, a polybenzoxazole-based resin, a benzocyclobutene-based resin, and a silicone-based resin; and / or

[0027] The resin composition further includes at least one of a photoinitiator, a polymerization inhibitor, a silicon substrate adhesive, a thermal crosslinking agent, and a photocrosslinking agent.

[0028] In some embodiments of the present application, the mass percentage of the branched triazole-based compound to the resin matrix is greater than or equal to 0.6% and less than or equal to 1%.

[0029] In some embodiments of the present application, the resin composition includes, by mass fraction,

[0030] a resin matrix 100 parts;

[0031] a branched triazole-based compound 0.5 to 2 parts;

[0032] a photoinitiator 0.5 to 5 parts;

[0033] a polymerization inhibitor 0.5 to 5 parts;

[0034] a photocrosslinking agent 0.5 to 8 parts;

[0035] a silicon substrate adhesive 0.5 to 8 parts;

[0036] a thermal crosslinking agent 0.5 to 8 parts.

[0037] The third aspect of the present application provides a resin hardened product obtained by hardening the resin composition.

[0038] Advantages:

[0039] The general formula of the branched triazole-based compound for an aluminum surface adhesive in the present application is shown as formula (1): Formula (1);

[0040] wherein A is an organic group having 0-50 carbon atoms; R1 is selected from at least one of O, N, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbonoxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group; R2 and R3 are independently selected from at least one of a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group; R4 is at least one of H, O, N, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbonoxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group; n is an integer of 2-4; and Z is a triazole residue having the structure of formula (2) as follows:

[0041] Formula (2). The cured film prepared from the resin composition to which the branched triazole-based compound in the present application is added has good adhesion to an aluminum or aluminum alloy substrate, and can significantly improve the separation problem of the cured film from the aluminum or aluminum alloy substrate. BRIEF DESCRIPTION OF DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the following embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort.

[0043] Figure 1 is a schematic diagram of a multi-layer redistribution layer (RDL) structure provided by the embodiments of the present application;

[0044] Figure 2 is a schematic diagram of a cutting surface of a multi-layer redistribution layer (RDL) structure provided by the embodiments of the present application;

[0045] Figure 3 is a schematic diagram of an evaluation reference for evaluating the separation degree between a cured film of a resin composition and an RDL in the present application. DETAILED DESCRIPTION

[0046] The experimental examples described in the present application are only some embodiments of the present application, but not all the embodiments. All other embodiments obtained by those skilled in the art without any creative effort fall within the scope of protection of the present application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application. As used in this description, the singular forms "a", "an" and "the" include plural references unless the context clearly dictates otherwise. The term "and / or" includes any and all combinations of one or more of the associated listed items.

[0048] In the description of the present application, the term "comprising" means "including, but not limited to". The use of the terms "first", "second", "third" and the like does not imply any order or sequence unless specifically stated.

[0049] In the present application, "at least one" means one or more, and "multiple" means two or more. "One or more", "at least one of the following (one)", or the like, means any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0050] Various embodiments of the present application can exist in the form of a range; it should be understood that the description in the form of a range is merely for the sake of convenience and brevity, and should not be construed as a hard limit on the scope of the present application; therefore, it should be considered that the described range has specifically disclosed all possible sub-ranges and single values within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the described range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated in this document, it refers to any cited number (fraction or integer) within the indicated range.

[0051] Polyimide (PI) resin, polybenzoxazole (PBO) resin, etc. having excellent heat resistance and adhesion have been widely used for surface protective films, interlayer insulating films, and curing films of semiconductor elements of electronic devices, etc. To ensure the reliability of semiconductor packaging, the adhesion of the curing film, which is permanently retained in the device, to the surface material of the semiconductor chip is very important. If the adhesion of the curing film is poor, it is easy to cause cracking and separation of the curing film from the contact substrate, which can result in poor reliability of the device, or even short circuit and burning of the device. Among the substrates in contact with the curing film, copper and aluminum account for a very large proportion.

[0052] There are many solutions to the problem of adhesion of the cured film to the copper surface. Some related technologies add urea, thiourea-based adhesion agents. Some related technologies add self-synthesized triazole copper adhesion agents. However, the representative patents above all add adhesion agents for the adhesion of the cured film to the copper surface. The main function of the adhesion agent is to increase the adhesion of the cured film to the copper surface and to inhibit discoloration of the copper surface during curing.

[0053] However, the adhesion of the cured film to the aluminum or aluminum alloy substrate surface (hereinafter referred to as the aluminum surface) is one of the most difficult problems to solve in wafer packaging. The main reason is that the aluminum surface is quickly oxidized and passivated, and it is difficult for general adhesion agents to form strong complexation or van der Waals forces with the aluminum oxide surface similar to the copper surface. In recent years, the redistribution of semiconductor packaging has developed towards miniaturization, and the adhesion of the cured film to the aluminum surface is a problem that must be solved. The actual solution is generally to increase the amount of azole and purine adhesion agents, but this will affect the lithography window and storage stability of the composition. The adhesion agent in the composition may even precipitate due to too high a concentration during cold storage and transportation. Another method is to chemically modify the existing adhesion agent, but the effect is very small. Therefore, there is an urgent need to develop a composition that can adhere well to the aluminum or aluminum alloy surface.

[0054] In view of this, the embodiments of the present application provide a branched triazole-based compound for an aluminum surface adhesion agent, the general formula of which is shown as (1):

[0055] Formula (1);

[0056] wherein A is an organic group with a carbon atom number of 0-50; R1 is selected from at least one of O (oxygen atom), N (nitrogen atom), hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, heterocyclic group; R2 and R3 are independently selected from at least one of H, hydrocarbon group, substituted hydrocarbon group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, heterocyclic group; R4 is at least one of H (hydrogen atom), O, N, hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, heterocyclic group; n is an integer of 2-4; Z is a triazole residue with the following structure (2):

[0057] (2).

[0058] It should be noted that the organic group A can include C (carbon) atoms, as well as Si (silicon atoms), O, N, S (sulfur atoms), and other heteroatoms. Further, the organic group A is an organic group with a carbon atom number of 0-20.

[0059] Specifically, the organic group A includes but is not limited to at least one of the following structures:

[0060]

[0061] wherein: R5 is at least one of divalent hydrocarbon group, substituted hydrocarbon group, hydrocarbonoxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, heterocyclic group; integer 1≤n1≤4; integer 2≤n2≤4; integer 2≤n3≤4; X1 includes at least one of the following structures

[0062] .

[0063] In some embodiments of the present application, R1 is at least one of O, divalent hydrocarbon group, substituted hydrocarbon group, hydrocarbonoxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, heterocyclic group, with carbon atom number being 1 to 6.

[0064] Specifically, R1 can be, but is not limited to, at least one of the following structures: .

[0065] In some embodiments of the present application, R2 and R3 are independently selected from at least one of hydrogen atom, monovalent hydrocarbon group, substituted hydrocarbon group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, heterocyclic group, with carbon atom number being 1 to 10.

[0066] The branched triazolyl compound in the embodiments of the present application can be added into a resin composition as an aluminum surface adhesion agent. The branched triazolyl compound added in the resin composition does not aggregate and does not crystallize in the resin composition, and can be dispersed in the resin composition at a high concentration, so that the composition maintains good stability. The cured film prepared from the resin composition added with the branched triazolyl compound in the present application has good adhesion to an aluminum or aluminum alloy substrate, and can significantly improve the separation problem of the cured film from the aluminum or aluminum alloy substrate. The possible principle is that the multi-branch triazolyl residue can form coordination with aluminum atoms or aluminum oxide surface, and form hydrogen bond with aluminum oxide surface hydroxyl group, thereby achieving strong adhesion effect.

[0067] In some embodiments of the present application, the branched triazolyl compound includes at least one of the compounds shown in the following formulas (3) to (12):

[0068]

[0069] .

[0070] The embodiments of the present application also provide a preparation method of a branched triazolyl compound, including the following steps:

[0071] S10 provides a first solution, and the first solution includes a solvent and a reagent R2-NH2.

[0072] It is to be noted that the R2group in the reagent has been specifically described in the general formula (1) and will not be repeated here. Exemplarily, the solvent can be one or more of dichloromethane, tetrahydrofuran, chloroform, acetonitrile, carbon tetrachloride, toluene.

[0073] In some embodiments of the present application, the step of providing the first solution comprises:

[0074] S11 dissolving the reagent R2-NH2in a solvent to obtain a first solution.

[0075] Specifically, 1.0 eq of the reagent R2-NH2is dissolved in 5-30 times the volume of one or more of dry dichloromethane, tetrahydrofuran, chloroform, acetonitrile, carbon tetrachloride, toluene as a metering reference under a nitrogen atmosphere to obtain the first solution.

[0076] S20 azidation of the reagent R2-NH2in the first solution to generate R2-N3. 3。

[0077] In some embodiments of the present application, the step of azidation of the reagent R2-NH2in the first solution to generate R2-N3comprises:

[0078] S21 adding t-butyl nitrite (t-BuONO) and azidotrimethylsilane (TMSN3) in sequence in the first solution to generate R2-N3.

[0079] Specifically, 1.0 eq-2.0 eq of t-butyl nitrite (t-BuONO) is slowly added in the first solution under stirring, and then cooled to -5℃-0℃. Then 1.0 eq-2.0 eq of azidotrimethylsilane (TMSN3) is added dropwise in the solution cooled to -5℃-0℃. After the dropwise addition, -5℃-0℃ stirring is maintained for 1h-3h, followed by slowly rising to room temperature within 1h-3h, and then stirring at room temperature for 2h-4h to obtain a crude solution containing R2-N3. The reaction route is shown as follows:

[0080] .

[0081] S30 azido-alkynyl cycloaddition reaction of R2-N3with the reagent shown in the general formula (13) (i.e. the reagent shown as 04 in the following reaction path) to obtain a branched triazolyl compound as shown in the general formula (1);

[0082] (13).

[0083] It is to be noted that the groups A, R1, R3, R4and n in the general formula (13) have been specifically described in the foregoing and will not be repeated here.

[0084] Specifically, under a nitrogen atmosphere at room temperature, 0.01 eq-0.2 eq of CuSO4 (0.1 M -0.5 M) aqueous solution is added to the crude product solution, followed by 0.1 eq-0.5 eq of sodium ascorbate, followed by slow addition of a reagent represented by general formula (13), stirring at 20-50°C for 10-30h, after the reaction is completed, adding 5-10 times the volume of water as a solvent, then adding the same volume of ethyl acetate as the water, stirring and separating the organic phase. The organic phase is washed with saturated brine 3 times, dried with anhydrous magnesium sulfate, filtered to remove the solid, then evaporated to leave a little solvent, 1.0-5.0 times the volume of ethyl acetate corresponding to the R2-N3 reagent is added, 5-20 times the volume of n-hexane corresponding to the R2-N3 reagent is slowly added dropwise at 50-60°C, after the dropwise addition is complete, reflux stirring is performed for 1-3h, slowly reduced to room temperature within 3-5h, stirring at room temperature for 3-5h, filtered, and oven dried to obtain a branched triazolyl compound represented by general formula (1). The reaction scheme is shown below:

[0085] .

[0086] The present application also provides an aluminum surface adhesive, which comprises a branched triazolyl compound represented by general formula (1):

[0087] Formula (1).

[0088] Wherein, groups A, Z, R1, R2, R3 and R4 have been specifically described above and will not be repeated here.

[0089] The aluminum surface adhesive in the present application comprises a branched triazolyl compound, which is added to a resin composition. The branched triazolyl compound added in the present application does not aggregate and does not crystallize in the resin composition, and can be dispersed in the resin composition at a relatively high concentration, so that the composition maintains good stability. The cured film prepared from the resin composition added with the branched triazolyl compound in the present application has good adhesion to an aluminum or aluminum alloy substrate, and can significantly improve the separation problem of the cured film from the aluminum or aluminum alloy substrate.

[0090] The present application also provides a resin composition, which comprises a resin matrix and a branched triazolyl compound represented by general formula (1). Exemplarily, the resin composition can be a photosensitive resin composition.

[0091] In some embodiments of the present application, the mass percentage of the branched triazole-based compound to the resin matrix is greater than 0.1% and less than or equal to 5%. Exemplarily, the mass percentage of the branched triazole-based compound to the resin matrix is 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, and a value between any two of the above-mentioned values.

[0092] It should be noted that if the mass percentage of the branched triazole-based compound to the resin matrix is less than 0.1%, the effective functional groups are too few, thereby the adhesion of the cured film prepared from the resin composition to the aluminum or aluminum alloy substrate is improved to a small extent; if the mass percentage of the branched triazole-based compound to the resin matrix is greater than 5%, it is easy to cause the storage stability of the resin composition at room temperature to be unsatisfactory.

[0093] The mass percentage of the branched triazole-based compound to the resin matrix is greater than 0.5% and less than or equal to 2%. Exemplarily, the mass percentage of the branched triazole-based compound to the resin matrix is 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, and a value between any two of the above-mentioned values. Further, the mass percentage of the branched triazole-based compound to the resin matrix is greater than or equal to 0.6% and less than or equal to 1%. Still further, the mass percentage of the branched triazole-based compound to the resin matrix is greater than or equal to 0.7% and less than or equal to 0.9%. In this way, it is beneficial to improve the stability of the resin composition, and significantly provide the adhesion performance of the resin composition to the aluminum surface.

[0094] In some embodiments of the present application, the resin composition comprises, by mass fraction

[0095] resin matrix 100 parts;

[0096] branched triazole-based compound 0.1 to 5 parts;

[0097] photoinitiator 0.5-5 parts;

[0098] polymerization inhibitor 0.5-5 parts;

[0099] photocrosslinking agent 0.5-10 parts;

[0100] silicon substrate adhesive 0.5 to 10 parts;

[0101] a thermal crosslinking agent 3 to 5 parts.

[0102] The hardened product (e.g., cured film) formed from the resin composition described above has good adhesion to an aluminum surface, and can significantly improve the problem of separation of the resin cured film from an aluminum or aluminum alloy substrate.

[0103] In some embodiments of the present application, the resin composition is a negative photosensitive resin composition, and the effective components of the negative photosensitive resin composition include, in mass parts:

[0104] a negative photosensitive resin base 100 parts;

[0105] a branched triazene compound having a structure represented by general formula (1) 0.7 to 0.9 parts;

[0106] a photoinitiator 0.5 to 1.5 parts;

[0107] a polymerization inhibitor 0.5 to 1.5 parts;

[0108] a photo crosslinking agent 4 to 6 parts;

[0109] a silicon substrate adhesive 4 to 6 parts;

[0110] a thermal crosslinking agent 3 to 5 parts.

[0111] Further, the negative photosensitive resin composition further includes a solvent 10 g to 40 g. Illustratively, the negative photosensitive resin composition further includes a solvent 10 g, 20 g, 30 g, 40 g, and a value between any two of the above values.

[0112] In some embodiments of the present application, the resin base includes at least one of a polyimide precursor resin, a polyimide-based resin, an acrylate-based resin, an epoxy-based resin, a polybenzoxazole precursor resin, a polybenzoxazole-based resin, a benzocyclobutene-based resin, and a silicone-based resin.

[0113] In the present application, the photoinitiator is used to initiate a polymerization reaction, and the specific type of photoinitiator is not limited. Illustratively, the photoinitiator includes, but is not limited to, at least one of a free radical type photoinitiator, an ionic type photoinitiator.

[0114] In the present application, the polymerization inhibitor is used to prevent the polymerization of double bond groups at room temperature, and the specific type of polymerization inhibitor is not limited. Illustratively, the polymerization inhibitor includes, but is not limited to, at least one of a free radical trapping type polymerization inhibitor, an oxidation inhibition type polymerization inhibitor, and an anionic type polymerization inhibitor.

[0115] In the present application, the specific kind of the photo-crosslinking agent is not limited, which can provide additional crosslinking double bond groups at the time of development. Illustratively, the photo-crosslinking agent includes at least one of styrene-based photo-crosslinking agent, acrylate-based photo-crosslinking agent, phenol resin-based photo-crosslinking agent, siloxane-based photo-crosslinking agent, and epoxy-based photo-crosslinking agent.

[0116] In the present application, the specific kind of the silicon substrate adhesive is not limited, which is used to improve the adhesion of the hardened product (e.g., cured film) of the negative photosensitive resin composition to the silicon material. Illustratively, the silicon substrate adhesive includes, but is not limited to, at least one of siloxane adhesive, epoxy resin adhesive, acrylate adhesive, and polyimide adhesive. Specifically, the silicon substrate adhesive can be 3-aminopropyl triethoxysilane.

[0117] In the present application, the specific kind of the thermal crosslinking agent is not limited, which can be tetramethoxymethyl glycoluril.

[0118] The resin composition can be selected from one or more of, but not limited to, the listed single solvent or solvent combination, such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylaceto urea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other ethers, acetone, methyl ethyl ketone, diisobutyl ketone and other ketones, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene and the like.

[0119] Compound Synthesis Example 1

[0120] (1) Preparation of branched triazole-based compound (compound shown in formula (3))

[0121]

[0122] Into a 1 L round-bottom flask, 02-1 (23.53 g, 0.25 mol, 1.0 eq) reagent was dissolved in 250 ml of dry acetonitrile under nitrogen atmosphere, and tert-butyl nitrite (30.94 g, 0.3 mol, 1.2 eq) was slowly added while stirring, and the mixture was cooled to 0°C, and azidotrimethylsilane (34.60 g, 0.3 mol, 1.2 eq) was slowly added dropwise. After the completion of the dropwise addition, the mixture was stirred at 0°C for 1 h, and then the temperature was slowly increased to room temperature over 1 h, and then the mixture was stirred at room temperature for 3 h to obtain a crude 03-1 solution, which was directly used in the next reaction without any treatment.

[0123] To the crude solution of 03, CuSO4(0.135 M, 93 ml, 0.0125 mol, 0.05 eq) aqueous solution was added under nitrogen atmosphere at room temperature, followed by sodium ascorbate (10.00 g, 0.05 mol, 0.2 eq), 04-1 (20.20 g, 0.07 mol, 0.28 eq) was added slowly at a temperature not exceeding 25 °C, stirred at 25 °C for 20 h, after the reaction was completed, the reaction solution was transferred out, 1.25 L of water was added, followed by 1.25 L of ethyl acetate, stirred and separated. The organic phase was washed with 500 ml of saturated brine for 3 times, dried with 50 g of anhydrous magnesium sulfate, after filtration to remove the solid, evaporated to slightly remain solvent (not evaporated to dryness), then 100 ml of ethyl acetate was added, 250 ml of n-hexane was added slowly at 60 °C, after the addition was completed, stirred at reflux for 1 h, slowly reduced to room temperature within 1 h, stirred at room temperature for 3 h, filtered, and dried at 50 °C under vacuum for 10 h to obtain the target product of formula (3).

[0124] The nuclear magnetic detection result of the target product is as follows:1H NMR (500 MHz, d-DMSO ) δ : 8.53 (dd, J = 15.0, 3.0 Hz, 4H), 8.02 (td, J = 14.9, 2.9 Hz, 4H), 7.88 (dd, J = 14.9, 3.2 Hz, 4H), 7.39 (td, J = 14.9, 3.2 Hz, 4H), 4.05 (s, 8H), 3.75 (s, 8H).

[0125] Compound synthesis example 2

[0126] (1) Preparation of branched triazole-based compound (compound shown in formula (4))

[0127] The difference from example 1 is that the reaction substrate 04-1 is replaced by 04-2 (23.00 g, 0.092 mol, 0.37 eq), and the amount of n-hexane added is changed to 300 ml.

[0128]

[0129] The results of nuclear magnetic detection are as follows:1H NMR (500 MHz, d-DMSO ) δ 8.52 (dd, J = 15.2, 3.0Hz, 3H), 8.02 (td, J = 14.9, 2.9 Hz, 3H), 7.90 (dd, J = 15.0, 3.2 Hz, 3H),7.40 (td, J = 15.3, 3.4 Hz, 3H), 4.11 (s, 6H), 3.77 (s, 6H), 3.35 (s, 2H).

[0130] Compound synthesis example 3

[0131] (1) Preparation of branched triazole compound (compound shown in formula (5))

[0132] The difference from example 1 is that only the reaction substrate 04-1 is changed to 04-3 (29.71 g, 0.14 mol, 0.56 eq), and the amount of n-hexane added is changed to 350 ml.

[0133]

[0134] The results of nuclear magnetic detection are as follows: 1 H NMR (500 MHz, d-DMSO ) δ 8.52 (dd, J = 15.0, 3.0Hz, 2H), 8.05 (s, 2H), 8.03 (td, J = 14.8, 2.9 Hz, 2H), 7.89 (dd, J = 15.0, 3.2Hz, 2H), 7.39 (td, J = 14.8, 3.2 Hz, 2H), 4.12 (s, 4H), 3.77 (s, 4H), 3.17 (s,4H).

[0135] Compound synthesis example 4

[0136] (1) Preparation of branched triazole compound (compound shown in formula (6))

[0137] The difference from example 1 is that only the reaction substrate 04-1 is changed to 04-4 (12.06 g, 0.092 mol, 0.37 eq).

[0138]

[0139] The results of nuclear magnetic detection are as follows: 1H NMR (500 MHz, d-DMSO ) δ 8.52 (dd, J = 15.0, 2.9Hz, 3H), 8.45 (s, 3H), 8.01 (td, J = 14.9, 2.9 Hz, 3H), 7.89 (dd, J = 14.9, 3.2Hz, 3H), 7.41 (td, J = 14.9, 3.3 Hz, 3H), 3.63 (s, 6H)。

[0140] Compound Synthesis Example 5

[0141] (1) Preparation of branched triazolyl compound (compound shown in formula (7))

[0142] The difference between it and Example 1 is that the reaction substrate 04-1 is changed to 04-5 (22.10 g, 0.092 mol, 0.37 eq), and the amount of n-hexane added is changed to 300 ml.

[0143]

[0144] The nuclear magnetic detection results are as follows: 1 H NMR (500 MHz, d-DMSO ) δ 8.53 (dd, J = 15.1, 3.0Hz, 3H), 8.26 (s, 3H), 8.03 (td, J = 14.9, 2.9 Hz, 3H), 7.93 (dd, J = 14.9, 3.2Hz, 3H), 7.40 (td, J = 14.9, 3.3 Hz, 3H), 6.08 (s, 3H), 5.22 (s, 6H)。

[0145] Compound Synthesis Example 6

[0146] (1) Preparation of branched triazolyl compound (compound shown in formula (8))

[0147] The difference between it and Example 1 is that the reaction substrate 02-1 is changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the amount of n-hexane added is changed to 220 ml.

[0148]

[0149] The nuclear magnetic detection results are as follows: 1H NMR (500 MHz, d-DMSO ) δ 8.33 (s, 4H), 7.69 ~7.61 (m, 8H), 7.60 ~ 7.44 (m, 12H), 4.10 (s, 8H), 3.78 (s, 8H).

[0150] Compound Synthesis Example 7

[0151] (1) Preparation of branched triazolyl compound (compound shown in formula (9))

[0152] The difference between it and Example 2 is that the reaction substrate 02-1 is changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the amount of n-hexane added is changed to 250 ml.

[0153]

[0154] The nuclear magnetic detection result is as follows: 1 H NMR (500 MHz, d-DMSO ) δ 8.23 (s, 3H), 7.71 –7.63 (m, 6H), 7.61 – 7.45 (m, 9H), 4.12 (s, 6H), 3.79 (s, 6H), 3.57 (s, 2H).

[0155] Compound Synthesis Example 8

[0156] (1) Preparation of branched triazolyl compound (compound shown in formula (10))

[0157] The difference between it and Example 3 is that the reaction substrate 02-1 is changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the amount of n-hexane added is changed to 300 ml.

[0158]

[0159] The nuclear magnetic detection result is as follows: 1 H NMR (500 MHz, d-DMSO ) δ 8.28 (s, 2H), 7.72 –7.64 (m, 4H), 7.62 – 7.46 (m, 6H), 4.11 (s, 4H), 3.79 (s, 4H), 3.39 (s, 4H).

[0160] Compound Synthesis Example 9

[0161] (1) Preparation of branched triazolyl compound (compound shown in formula (11))

[0162] The difference from Example 4 is that the reaction substrate 02-1 is changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the amount of n-hexane to be added is changed to 220 ml.

[0163]

[0164] The results of nuclear magnetic detection are as follows: 1 H NMR (500 MHz, d-DMSO ) δ 8.29 (s, 3H), 7.70 –7.60 (m, 6H), 7.59 – 7.45 (m, 9H), 3.58 (s, 6H).

[0165] Compound synthesis example 10

[0166] (1) Preparation of branched triazole-based compound (compound shown in formula (12))

[0167] The difference from Example 5 is that the reaction substrate 02-1 is changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the amount of n-hexane to be added is changed to 250 ml.

[0168]

[0169] The results of nuclear magnetic detection are as follows: 1 H NMR (500 MHz, d-DMSO ) δ 8.41 (s, 3H), 7.71 ~7.62 (m, 6H), 7.62 ~ 7.45 (m, 9H), 6.07 (s, 3H), 5.24 (s, 6H).

[0170] Composition example 1

[0171] Preparation of negative photosensitive resin composition

[0172] (1) Preparation of polyimide precursor B-1

[0173] Take ODPA 93.21g (300mmol) into a 1L split-body glass reactor, rinse the weighing container with 100ml γ-butyrolactone (GBL) to ensure all ODPA is transferred into the reactor, add HEMA 78.08g (600mmol) in one go at room temperature, mix with 50ml GBL, set the anchor stirrer to 150r / min, use a circulating thermostatic cooler to control the temperature at 25℃, add 52.2g (660mmol) pyridine dropwise over 1h, add 90ml GBL after the dropwise addition is complete, maintain the stirring speed and reaction temperature, and stir for 16h. Reduce the reaction system to -15℃, set the stirrer to 200r / min, and add 86.66g (660mmol) DCC in 120ml GBL dropwise at a uniform speed over 1h, and stir for another 1h after the addition is complete. Dissolve 56.13g (279mmol) ODA in 240ml NMP, heat to 50℃ under N2, and add to the reaction system dropwise at a uniform speed over 1h while the stirrer is set to 300r / min. If ODA precipitates, heat to keep it from precipitating. Stir for 1h at low temperature, then raise the temperature to 25℃ at a uniform speed over 1h, set the stirrer to 400r / min, and react at room temperature for another 4h. Add 20ml ethanol, stir for 1h, and quench.

[0174] Filter the quenched reaction solution, immediately pour the filtrate into 10L methanol to precipitate, separate the blocky material, dissolve it in 1.5L GBL, stir for 5h, pass through ion exchange resin, collect the resin solution, and drop it into 10L deionized water. Filter to obtain small flaky solids, wash the filter cake with 1L methanol three times, filter and dry, vacuum dry at 50℃ for 24h, and obtain polyimide precursor B-1. (Mn=11542 Mw=20200 PDI=1.75)

[0175] (2) Preparation of a negative photosensitive resin composition

[0176] Take 100ml wide-mouth glass bottles, and add 0.1g photoinitiator TR-PBG-305 (Qingli Xinxie), 0.1g thermal inhibitor p-hydroxyanisole (MEHQ), 0.5g photocrosslinker triethylene glycol dimethacrylate (TEGDMA), 0.5g 3-aminopropyl triethoxysilane, 0.4g tetramethoxymethyl glycoluril (MX270), 80mg branched triazole compound (formula (3)) prepared in Example 1, and 20g N-methyl pyrrolidone (NMP) in sequence, and shake on a shaker until the components are dissolved. Then add 10.0g of the prepared polyimide precursor B-1 to the above solution, continue to shake until completely dissolved, and filter using a 1.0um filter membrane to obtain a negative photosensitive resin composition. The viscosity is 3200±500cp at 25℃.

[0177] Composition Example 2

[0178] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (4) is added in the preparation of the negative photosensitive resin composition.

[0179] Composition example 3

[0180] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (5) is added in the preparation of the negative photosensitive resin composition.

[0181] Composition example 4

[0182] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (6) is added in the preparation of the negative photosensitive resin composition.

[0183] Composition example 5

[0184] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (7) is added in the preparation of the negative photosensitive resin composition.

[0185] Composition example 6

[0186] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (8) is added in the preparation of the negative photosensitive resin composition.

[0187] Composition example 7

[0188] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (9) is added in the preparation of the negative photosensitive resin composition.

[0189] Composition example 8

[0190] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (10) is added in the preparation of the negative photosensitive resin composition.

[0191] Composition example 9

[0192] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (11) is added in the preparation of the negative photosensitive resin composition.

[0193] Composition example 10

[0194] The difference from the composition example 1 is that a branched triazolyl compound of the structure of formula (12) is added in the preparation of the negative photosensitive resin composition.

[0195] Composition example 11

[0196] The difference from the composition example 1 is that the amount of the branched triazolyl compound of the structure of formula (3) added in the preparation of the negative photosensitive resin composition is changed to 10 mg.

[0197] Composition example 12

[0198] The difference from the composition example 1 is that the amount of the branched triazolyl compound of the structure of formula (3) added in the preparation of the negative photosensitive resin composition is changed to 50 mg.

[0199] Composition comparative example 1

[0200] The difference from the composition example 1 is that the amount of the branched triazolyl compound of the structure of formula (3) added in the preparation of the negative photosensitive resin composition is changed to 0 mg.

[0201] Composition comparative example 2

[0202] The difference from the example 1 is that the branched triazolyl compound of the structure of formula (3) is replaced by benzimidazole in the preparation of the negative photosensitive resin composition.

[0203] Composition comparative example 3

[0204] The difference from the example 1 is that the branched triazolyl compound of the structure of formula (3) is replaced by guanine in the preparation of the negative photosensitive resin composition.

[0205] Composition comparative example 4

[0206] The difference from the example 1 is that the branched triazolyl compound of the structure of formula (3) is replaced by 8-azaguanine in the preparation of the negative photosensitive resin composition.

[0207] Experimental test

[0208] (1) Molecular weight test

[0209] The weight average molecular weight (Mw) of the resin is determined by gel permeation chromatography (converted into standard polystyrene). The chromatograph used in the determination is UltiMate 3000 of Thermo Fisher, the chromatographic column is Styragel HR3 / 4 DMF of Waters, and the detector is RI Detector RefractoMax520 of Thermo Fisher.

[0210] (2) Viscosity test

[0211] 0.5 mL of the resin composition sample is taken by a disposable dropper and added into the sample cell of the cone and plate viscometer (BROOKFIELD DV2T RV), the appropriate range is selected, and the viscosity test is carried out by controlling the sample temperature at 25±0.1℃.

[0212] (3) Adhesion peel test between the cured film of the composition and the aluminum substrate

[0213] The resin composition sample was uniformly coated onto a PVD aluminum substrate using a spin coater. The substrate was then placed on a 120°C heating stage (NDK-2K) and baked for 3 minutes to obtain a soft-baked film with a thickness of 15±1.5 μm. The film was then heat-treated in a vacuum oxygen-free oven (AMSEMI-HCM-500D): baked at 140°C for 30 minutes, then heated to 350°C over 1 hour at a rate of 3.5°C / min, and held at 350°C for 1 hour to obtain the cured film. The cured film was then subjected to a 100-hour PCT aging test in a PCT test chamber (121°C, 2 atmospheres of saturated vapor; ESPEC EHS-222MD). Using a cross-cut tester (Biuged BGD 502 / 2A), a grid of 10 rows and 10 columns was drawn on the cured film after the PCT test. Finally, a peel test was performed using tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998 Cross-cut test for paint and varnish films. The number of squares peeled off was recorded as the peel status after the PCT test.

[0214] In the adhesive peel test, 0 peeled pieces are considered "excellent", more than 0 but less than 10 are considered "good", more than or equal to 10 but less than 20 are considered "medium", more than or equal to 20 but less than 30 are considered "poor", and more than or equal to 30 or completely peeled off are considered "very poor".

[0215] (4) Separation test of the resin composition cured film and aluminum substrate in redistribution (RDL)

[0216] A resin composition containing a branched triazole aluminum adhesive is applied to an aluminum multilayer redistribution (RDL) structure, combining... Figure 1 Describe the RDL structure. For example... Figure 1 As shown, 1 is a silicon chip, 2 is an aluminum substrate, 3 is a SiN passivation film, 4 is an interlayer insulating film PI (1) formed by curing the resin composition in this application, 5 is a retained Ti seed layer, 6 is a redistribution (RDL) metal Al (RDL1), 7 is an interlayer insulating film PI (2) formed by the resin composition in this application, 8 is a retained Ti seed layer, 9 is a solder bump under metal Al (UBM), and 10 is a solder bump.

[0217] Next, the manufacturing method of the multi-layer RDL structure is described. The aluminum substrate 2 and SiN passivation film 3 for input and output are prepared on the silicon chip 1; the patterned interlayer insulating film 4 formed from the resin composition of the present application is prepared on 3 by spin coating, exposure, and development; the Ti seed layer 5 is prepared by sputtering process and then the RDL metal Al (RDL1) 6 is formed by evaporation process; the structure 7-9 is prepared by repeating the process steps 3-5; finally, the solder bump 10 is prepared by ball mounting process. Thus, the multi-layer RDL structure separated by the interlayer insulating film formed from the resin composition of the present application is prepared.

[0218] In order to test the adhesion of the cured resin composition film 7 to the aluminum substrate of the RDL, the center line of the solder bump 10 is cut (as shown in FIG. 2) and the separation of the interface is observed by focused ion beam microscope FIB. The separation degree between the cured resin composition film and the RDL is evaluated according to the evaluation criteria shown in FIG. 3. As shown in FIG. 4, the separation degree between the cured resin film and the RDL is divided into four levels: severe separation, moderate separation, slight separation, and no separation. The more serious the separation, the worse the adhesion. Figure 2 Figure 3 Figure 3

[0219] The relevant performance tests are conducted on the prepared experimental examples, and the test results are shown in Table 2.

[0220] Table 1

[0221]

[0222] Table 2

[0223]

[0224] The composition examples 1 to 12 and the composition comparative example 1 differ in whether the branched triazole-based compound of the present application is added to the resin composition, as shown in Table 1. As can be seen from Table 1 and Table 2, the addition of the branched triazole-based compound of the present application to the resin composition is beneficial to improve the adhesion performance, aging resistance, and adhesion performance between the cured film and the aluminum substrate.

[0225] ​​​The composition examples 1, 11 and 12 are different in the content of the branched triazole compound in the resin composition, the mass percentage of the branched triazole compound to the resin matrix is 0.8% in example 1, 0.1% in example 11 and 0.5% in example 12. It can be seen that the mass percentage of the branched triazole compound to the resin matrix in the resin composition is greater than or equal to 0.5%, which is beneficial to improve the bonding performance, aging resistance and adhesion between the cured film prepared and the aluminum substrate.

[0226] The above describes the technical solutions provided by the embodiments of the present application in detail, and the principles and implementation manners of the present application are described by applying specific examples; the above example descriptions are only used to help understand the method of the present application and its core idea; meanwhile, according to the idea of the present application, the specific implementation manners and application ranges will be changed by those skilled in the art, and the above description of the present application should not be understood as a limitation.

Claims

1. Use of a dendrimeric triazolyl compound as an aluminum surface sealing agent, characterized in that, A general formula of the branched triazolyl compound is shown as formula (1): Formula (1); wherein A is ； R1 is selected from one of divalent hydrocarbon groups having 1 to 6 carbon atoms, and hydrocarbon oxy groups; R2 is selected from one of H, monovalent hydrocarbon groups having 1 to 10 carbon atoms, aryl groups, and heterocyclic groups; R3 is one of aryl groups and heterocyclic groups having 1 to 10 carbon atoms; and R4 is one of monovalent hydrocarbon groups and hydrocarbon oxy groups having 1 to 10 carbon atoms; n is an integer of 2 to 4; and Z is a triazolyl residue having a structure shown as formula (2): Formula (2).

2. Use of a branched triazolyl compound as an aluminum surface sealing agent, characterized in that, The branched triazolyl compound includes at least one of compounds shown as formulae (3) to (12): 。 3. The use of the dendritic triazolyl compound according to claim 2 as an aluminum surface adhesion agent, characterized by, The branched triazolyl compound includes at least one of the formula (3) to the formula (5), the formula (7) to the formula (10), and the formula (12).

4. A resin composition characterized by comprising: The resin composition includes a resin matrix and the branched triazolyl compound according to any one of claims 1 to 3. The resin composition includes, in terms of mass fraction: The resin matrix 100 parts; The branched triazolyl compound 0.1 to 5 parts; The photoinitiator 0.5 to 5 parts; The polymerization inhibitor 0.5 to 5 parts; The photocrosslinking agent 0.5 to 10 parts; The silicone-based adhesive 0.5 to 10 parts; The thermal crosslinking agent 0.5 to 10 parts; The resin matrix includes at least one of polyimide precursor resin, polyimide resin, acrylate resin, epoxy resin, polybenzoxazole precursor resin, polybenzoxazole resin, benzocyclobutene resin, and silicone resin.

5. The resin composition according to claim 4, wherein The resin composition is a negative photosensitive resin composition.

6. The resin composition according to Claim 5, wherein The mass percentage of the branched triazolyl compound to the resin matrix is greater than or equal to 0.6% and less than or equal to 1%.

7. A resin hardened product, characterized by, The resin hardened product is obtained by hardening the resin composition according to any one of claims 4 to 6.

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