Branched triazolyl compound for aluminum surface adhesive, aluminum surface adhesive, resin composition, and cured resin

Abstract

The invention discloses a branched triazolyl compound for an aluminum surface adhesive, the aluminum surface adhesive, a resin composition and a resin hardened material, and relates to the technical field of adhesives. The general formula of the branched triazolyl compound for the aluminum surface adhesive is as shown in the formula (1): # imgabs0 # formula (1). A cured film prepared from the resin composition added with the branched triazolyl compound has good adhesion to an aluminum or aluminum alloy base material, and the problem of separation of the cured film from the aluminum or aluminum alloy base material can be remarkably improved.

Description

Technical Field

[0001] This application relates to the technical field of adhesives, and particularly relates to a branched triazolyl compound for aluminum surface adhesives, an aluminum surface adhesive, a resin composition, and a resin cured product. Background Art

[0002] Currently, polyimide (PI) resins, polybenzoxazole (PBO) resins, etc. with excellent heat resistance and adhesion have been widely used in surface protective films, interlayer insulating films, and cured films of semiconductor components in electronic devices. To ensure the reliability of semiconductor packaging, the adhesion between the cured film permanently remaining in the device and 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 from the contacting substrate, resulting in poor reliability of the device at best and short-circuit burning of the device at worst. Among the substrates in contact with the cured film, copper and aluminum account for a very large proportion.

[0003] However, the adhesion between the cured film and the surface of aluminum or aluminum alloy substrates (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 oxidizes and passivates very quickly, and it is difficult for general adhesives to form a strong complexation or van der Waals force similar to that with the copper surface on the aluminum oxide surface. In recent years, as the redistribution in semiconductor packaging has developed towards miniaturization, the adhesion between the cured film and the aluminum surface is a problem that must be solved. The actual solution is generally to increase the usage amount of azole-based and purine-based adhesives, but this will affect the lithography window and storage stability of the composition, and the adhesive in the composition may even precipitate during refrigerated transportation due to too high a concentration. Another method is to chemically modify the existing adhesives, but with little effect. Therefore, there is an urgent need to develop a composition that can have good adhesion to aluminum or aluminum alloy surfaces. Summary of the Invention

[0004] In view of this, this application provides a branched triazolyl compound for aluminum surface adhesives, an aluminum surface adhesive, a resin composition, and a resin cured product, aiming to improve the technical problem that the existing adhesives are not suitable for adhesion to aluminum surfaces.

[0005] In a first aspect, an embodiment of this application provides a branched triazolyl compound for aluminum surface adhesives, and the general formula of the branched triazolyl compound is shown in (1): Formula (1); Among them, A is an organic group with 0 to 50 carbon atoms; R1 is selected from at least one of O, N, hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; R2 and R3 are each 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, hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; n is an integer from 2 to 4; Z is a triazole residue having the structure of the following formula (2): Formula (2).

[0006] It should be noted that the inventors have found through research that when n is 1 in formula (1), there is almost no bonding effect on the aluminum surface.

[0007] In some embodiments of the present application, A is an organic group with 0 to 20 carbon atoms; and / or R1 is selected from at least one of O, a divalent hydrocarbon group with 1 to 6 carbon atoms, a substituted hydrocarbon group, a hydrocarbon oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group; and / or R2 and R3 are each independently selected from at least one of a hydrogen atom, a monovalent hydrocarbon group with 1 to 10 carbon atoms, a substituted hydrocarbon group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group; and / or R4 is selected from at least one of H, a monovalent hydrocarbon group with 1 to 10 carbon atoms, a substituted hydrocarbon group, a hydrocarbon oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group.

[0008] In some embodiments of the present application, A includes at least one of the following structures:

[0009] Among them, 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, and a heterocyclic group; an integer of 1 ≤ n1 ≤ 4; an integer of 2 ≤ n2 ≤ 4; an integer of 2 ≤ n3 ≤ 4; X1 includes at least one of the following structures .

[0010] In some embodiments of the present application, R1 includes at least one of the following structures: .

[0011] In some embodiments of the present application, the branched triazolyl compound includes at least one of the compounds represented by the following formulas (3) to (12):

[0012] 。

[0013] The second aspect of the present application provides a resin composition, which includes a resin matrix and the branched triazolyl compound described above.

[0014] In some embodiments of the present application, the mass percentage of the branched triazolyl compound to the resin matrix is greater than 0.1% and less than or equal to 5%; and / or The resin composition is a negative photosensitive resin composition; and / or The resin matrix includes at least one of a polyimide precursor resin, a polyimide resin, an acrylate resin, an epoxy resin, a polybenzoxazole precursor resin, a polybenzoxazole resin, a benzocyclobutene resin, and a silicone resin; and / or The resin composition further includes at least one of a photoinitiator, a polymerization inhibitor, a silicone substrate adhesive, a thermal crosslinking agent, and a photo crosslinking agent.

[0015] In some embodiments of the present application, 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%.

[0016] In some embodiments of the present application, by mass parts, the resin composition includes Resin matrix 100 parts; Branched triazyl compound 0.5 parts to 2 parts; Photoinitiator 0.5 parts - 5 parts; Polymerization inhibitor 0.5 parts - 5 parts; Photo crosslinking agent 0.5 parts - 8 parts; Silicone substrate adhesive 0.5 parts to 8 parts; Thermal crosslinking agent 0.5 parts to 8 parts.

[0017] The third aspect of the present application provides a resin cured product, which is obtained by curing the resin composition.

[0018] Beneficial effects: The general formula of the branched triazolyl compound used as an aluminum surface adhesive in the present application is as shown in (1): Formula (1); Among them, A is an organic group having 0 to 50 carbon atoms; 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, and a heterocyclic group; R2 and R3 are each 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 hydrocarbon oxy 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 to 4; Z is a triazole residue having the structure of the following formula (2): Formula (2). The cured film prepared from the resin composition added with the dendritic triazole-based compound in the present application has good adhesion to an aluminum or aluminum alloy substrate, and can significantly improve the problem of separation between the cured film and the aluminum or aluminum alloy substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0020] Figure 1 It is a schematic diagram of a multi-layer redistribution line (RDL) structure provided by an embodiment of the present application; Figure 2 It is a schematic diagram of a cut surface of a multi-layer redistribution line (RDL) structure provided by an embodiment of the present application; Figure 3 It is a schematic diagram of an evaluation criterion for evaluating the separation degree between the cured film of the resin composition and the RDL in the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] The experimental examples described in the present application are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art without creative efforts belong to 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.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0023] In the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0024] In the present application, "at least one" means one or more, and "a plurality" means two or more. "One or more", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can each represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can each be single or plural.

[0025] The various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be construed as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub - ranges and single values within that 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., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, and this applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0026] All along, polyimide (PI) resins, polybenzoxazole (PBO) resins, etc. with excellent heat resistance and adhesion have been widely used in surface protective films, interlayer insulating films, cured films, etc. of semiconductor elements in electronic devices. To ensure the reliability of semiconductor packaging, the adhesion between the cured film permanently remaining in the device and 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 from the contacting substrate, resulting in poor reliability of the device at best and short - circuit burning of the device at worst. Among the substrates in contact with the cured film, copper and aluminum account for a very large proportion.

[0027] Regarding the adhesion problem between the cured film and the copper surface, there are many solutions. In some related technologies, urea - and thiourea - containing adhesion agents are added. In other related technologies, self - synthesized triazole - based copper adhesion agents are added. However, the additives added in the above - mentioned representative patents are all for the adhesion between the cured film and the copper surface. The main function of this additive is to increase the adhesion between the cured film and the copper surface and inhibit the discoloration of the copper surface during curing.

[0028] However, the adhesion between the cured film and the surface of aluminum or aluminum alloy substrate (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 oxidizes and passivates very quickly, and it is difficult for general adhesives to form strong complexation or van der Waals forces with the aluminum oxide surface similar to those with the copper surface. In recent years, the redistribution in semiconductor packaging has been developing towards miniaturization, and the adhesion between the cured film and the aluminum surface is a problem that must be solved. The actual solution is generally to increase the usage 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 with little effect. Therefore, there is an urgent need to develop a composition with good adhesion to aluminum or aluminum alloy surface.

[0029] In view of this, an embodiment of the present application provides a branched triazole-based compound for an aluminum surface adhesive, and the general formula of the branched triazole-based compound is shown in (1): Formula (1); Wherein, A is an organic group with 0 to 50 carbon atoms; R1 is selected from at least one of O (oxygen atom), N (nitrogen atom), hydrocarbon group, substituted hydrocarbon group, hydrocarbonoxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; R2 and R3 are each independently selected from at least one of H, hydrocarbon group, substituted hydrocarbon group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; R4 is at least one of H (hydrogen atom), O, N, hydrocarbon group, substituted hydrocarbon group, hydrocarbonoxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; n is an integer from 2 to 4; Z is a triazole residue having the following structure (2): (2).

[0030] It should be noted that in addition to carbon (C) atoms, the organic group A may also include heteroatoms such as Si (silicon atom), O, N, and S (sulfur atom). Further, the organic group A is an organic group with 0 to 20 carbon atoms.

[0031] Specifically, the organic group A includes but is not limited to at least one of the following structures:

[0032] 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, and heterocyclic group; 1 ≤ n1 ≤ 4 is an integer; 2 ≤ n2 ≤ 4 is an integer; 2 ≤ n3 ≤ 4 is an integer; X1 includes at least one of the following structures .

[0033] In some embodiments of the present application, R1 is at least one of O, a divalent hydrocarbon group having 1 to 6 carbon atoms, a substituted hydrocarbon group, a hydrocarbon oxy group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group.

[0034] Specifically, R1 may be at least one of the following structures: 。

[0035] In some embodiments of the present application, R2 and R3 are each independently selected from at least one of a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, a substituted hydrocarbon group, an ester group, an amide group, a sulfonyl group, an aryl group, a substituted aryl group, and a heterocyclic group.

[0036] The branched triazolyl compound in the embodiments of the present application can be added to the resin composition as an aluminum surface adhesive. The added branched triazolyl compound does not aggregate or 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 problem of separation between the cured film and the aluminum or aluminum alloy substrate. The possible principle is that the multi-branched triazole residue can form a coordination effect with the aluminum atom or the alumina surface and form a hydrogen bond with the hydroxyl group on the alumina surface to achieve a strong adhesion effect.

[0037] In some embodiments of the present application, the branched triazolyl compound includes at least one of the compounds represented by the following formulas (3) to (12):

[0038] 。

[0039] The embodiments of the present application further provide a preparation method of a branched triazolyl compound, including the following steps: S10 Provide a first solution, where the first solution includes a solvent and a reagent R2-NH2.

[0040] It should be noted that the R2 group in the reagent has been specifically described in the general formula (1) and will not be elaborated here. Exemplarily, the solvent may be one or more of dichloromethane, tetrahydrofuran, chloroform, acetonitrile, carbon tetrachloride, and toluene.

[0041] In some embodiments of the present application, the step of providing the first solution includes: S11 Dissolve the reagent R2-NH2 in the solvent to obtain a first solution.

[0042] Specifically, taking the reagent R2-NH2 as the metering basis, 1.0 eq of the reagent R2-NH2 is dissolved in one or several solvents of dry dichloromethane, tetrahydrofuran, chloroform, acetonitrile, carbon tetrachloride, toluene with a volume 5-30 times that of the reagent in a nitrogen atmosphere to obtain a first solution.

[0043] S20 Subject the reagent R2-NH2 in the first solution to an azidation reaction to generate R2-N3. 3。

[0044] In some embodiments of the present application, the step of subjecting the reagent R2-NH2 in the first solution to an azidation reaction to generate R2-N3 includes: S21 Sequentially add tert-butyl nitrite (t-BuONO) and trimethylsilyl azide (TMSN3) to the first solution, and react to obtain R2-N3.

[0045] Specifically, under stirring, slowly add 1.0 eq - 2.0 eq of tert-butyl nitrite (t-BuONO) to the first solution, and then cool to -5°C - 0°C. Then slowly dropwise add 1.0 eq - 2.0 eq of trimethylsilyl azide (TMSN3) to the solution cooled to -5°C - 0°C. After the dropping is complete, stir at -5°C - 0°C for 1 h - 3 h, and then slowly rise to room temperature within 1 h - 3 h. Then stir at room temperature for 2 h - 4 h to obtain a crude product solution containing R2-N3. The reaction route is as follows: 。

[0046] S30 Subject R2-N3 to an azide-alkyne cycloaddition reaction with 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 shown in the general formula (1); (13)。

[0047] It should be noted that the groups A, R1, R3, R4 and n in the general formula (13) have been specifically described above and will not be elaborated here.

[0048] Specifically, at room temperature in a nitrogen atmosphere, an aqueous solution of CuSO4 (0.1M - 0.5M) with a dosage of 0.01eq - 0.2eq is added to the crude product solution, followed by the addition of 0.1eq - 0.5eq of sodium ascorbate. Then, the reagent represented by the general formula (13) is slowly added, and the mixture is stirred at 20°C - 50°C for 10h - 30h. After the reaction is completed, water with a volume 5 - 10 times that of the solvent is added, and then ethyl acetate with the same volume as water is added. The mixture is stirred and separated by liquid. The organic phase is washed 3 times with saturated brine, dried over anhydrous magnesium sulfate, filtered to remove solids, and evaporated until slightly less solvent remains. Then, ethyl acetate with a volume 1.0 - 5.0 times that of the R2-N3 reagent is added, and n-hexane with a volume 5 - 20 times that of the R2-N3 reagent is slowly added dropwise at 50 - 60°C. After the dropwise addition, the mixture is refluxed and stirred for 1h - 3h, slowly cooled to room temperature within 3h - 5h, and stirred at room temperature for 3h - 5h. After filtration and drying, a branched triazolyl compound represented by the general formula (1) is obtained. The reaction route is as follows: 。

[0049] An embodiment of the present application also provides an aluminum surface sealant, which includes a branched triazolyl compound, and the general formula of the branched triazolyl compound is as shown in (1): Formula (1).

[0050] Among them, the groups A, Z, R1, R2, R3, and R4 have been specifically described above and will not be elaborated here.

[0051] The aluminum surface sealant in the embodiment of the present application includes a branched triazolyl compound. When this aluminum surface sealant is added to a resin composition, the added branched triazolyl compound does not aggregate or crystallize in the resin composition and can be dispersed in the resin composition at a relatively high concentration, keeping the composition in 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 problem of separation between the cured film and the aluminum or aluminum alloy substrate.

[0052] An embodiment of the present application also provides a resin composition, which includes a resin matrix and a branched triazyl compound with the structure shown in the general formula (1). Exemplarily, the resin composition can be a photosensitive resin composition.

[0053] 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 values between any two of the above.

[0054] 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 number of its effective functional groups is too small, and the improvement in the adhesion of the cured film prepared from the resin composition to the aluminum or aluminum alloy substrate is relatively small; if the mass percentage of the branched triazole-based compound to the resin matrix is greater than 5%, it is likely to result in unsatisfactory ambient temperature storage stability of the resin composition.

[0055] 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 values between any two of the above. 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 improve the adhesion performance of the resin composition to the aluminum surface.

[0056] In some embodiments of the present application, by mass, the resin composition comprises 100 parts of resin matrix; 0.1 part to 5 parts of branched triazole-based compound; 0.5 part - 5 parts of photoinitiator; 0.5 part - 5 parts of inhibitor; 0.5 part - 10 parts of photocrosslinking agent; 0.5 part to 10 parts of silicone substrate adhesive; 0.5 part to 10 parts of thermal crosslinking agent.

[0057] The cured product (such as a cured film) formed from the above resin composition has good adhesion to the aluminum surface and can significantly improve the problem of separation between the resin cured film and the aluminum or aluminum alloy substrate.

[0058] In some embodiments of the present application, the resin composition is a negative photosensitive resin composition. Calculated by mass parts, the active ingredients of the negative photosensitive resin composition include: 100 parts of a negative photosensitive resin matrix; 0.7 to 0.9 parts of a branched triamino compound represented by the general formula (1); 0.5 to 1.5 parts of a photoinitiator; 0.5 to 1.5 parts of a polymerization inhibitor; 4 to 6 parts of a photocrosslinking agent; 4 to 6 parts of a silicon substrate adhesive; 3 to 5 parts of a thermal crosslinking agent.

[0059] Furthermore, the negative photosensitive resin composition further includes 10 g to 40 g of a solvent. Exemplarily, the negative photosensitive resin composition further includes 10 g, 20 g, 30 g, 40 g, and values between any two of the above.

[0060] In some embodiments of the present application, the resin matrix includes at least one of a polyimide precursor resin, a polyimide resin, an acrylate resin, an epoxy resin, a polybenzoxazole precursor resin, a polybenzoxazole resin, a benzocyclobutene resin, and a silicone resin.

[0061] In the present application, the photoinitiator is used to initiate a polymerization reaction, and the specific type of the photoinitiator is not limited. Exemplarily, the photoinitiator includes at least one of a radical photoinitiator and an ionic photoinitiator.

[0062] 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 the polymerization inhibitor is not limited. Exemplarily, the polymerization inhibitor includes at least one of a radical scavenging type polymerization inhibitor, an oxidation inhibition type polymerization inhibitor, and an anionic polymerization inhibitor.

[0063] In the present application, the photocrosslinking agent can provide additional crosslinking double bond groups during development, and the specific type of the photocrosslinking agent is not limited. Exemplarily, the photocrosslinking agent includes at least one of a styrene-based photocrosslinking agent, an acrylate-based photocrosslinking agent, a phenolic resin-based photocrosslinking agent, a silicone-based photocrosslinking agent, and an epoxy-based photocrosslinking agent.

[0064] In the present application, a silicon-based substrate adhesive is used to improve the adhesion between the cured product (such as a cured film) of the negative photosensitive resin composition and the silicon material, and the specific type of the silicon-based substrate adhesive is not limited. Exemplarily, the silicon-based substrate adhesive includes but is not limited to at least one of a siloxane adhesive, an epoxy resin adhesive, an acrylate adhesive, and a polyimide adhesive. Specifically, the silicon-based substrate adhesive can be 3-aminopropyltriethoxysilane.

[0065] In the present application, the thermal crosslinking agent can be tetramethoxymethyl glycoluril.

[0066] One or several of the following solvents can be selected for the resin composition and are 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'-dimethylpropyleneurea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropanamide, tetrahydrofuran, dioxane, ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone, 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, etc.

[0067] Compound Synthesis Example 1 (1) Preparation of a branched triazolyl compound (the compound shown in formula (3))

[0068] Take a 1 L three-necked round-bottom flask. Under a nitrogen atmosphere, dissolve 02-1 (23.53 g, 0.25 mol, 1.0 eq) reagent in 250 ml of dry acetonitrile. With stirring, slowly add tert-butyl nitrite (30.94 g, 0.3 mol, 1.2 eq), cool to 0 °C, and slowly dropwise add azidotrimethylsilane (34.60 g, 0.3 mol, 1.2 eq). After the addition is complete, stir at 0 °C for 1 h, then slowly raise the temperature to room temperature within 1 h, and then stir at room temperature for 3 h to obtain a crude product solution of 03-1, which can be directly used for the next reaction without post-treatment.

[0069] At room temperature under a nitrogen atmosphere, an aqueous solution of CuSO4 (0.135 M, 93 ml, 0.0125 mol, 0.05 eq) was added to the crude product solution of 03, followed by the addition of sodium ascorbate (10.00 g, 0.05 mol, 0.2 eq). 04-1 (20.20 g, 0.07 mol, 0.28 eq) was slowly added while maintaining the internal reaction temperature at no more than 25 °C. The mixture was 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 as the solvent, and then 1.25 L of ethyl acetate was added. The mixture was stirred and separated. The organic phase was washed 3 times with 500 ml of saturated brine, dried over 50 g of anhydrous magnesium sulfate, filtered to remove the solid, and evaporated until slightly less solvent remained (the solvent should not be completely evaporated). Then 100 ml of ethyl acetate was added, and 250 ml of n-hexane was slowly added dropwise at 60 °C. After the addition was complete, the mixture was stirred and refluxed for 1 h, slowly cooled to room temperature within 1 h, and stirred at room temperature for 3 h. It was then filtered and dried under vacuum at 50 °C for 10 h to obtain the target product with the structure of formula (3).

[0070] The NMR test results of the target product are 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, 3.2Hz, 4H), 7.39 (td, J = 14.9, 3.2 Hz, 4H), 4.05 (s, 8H), 3.75 (s, 8H).

[0071] Compound Synthesis Example 2 (1) Preparation of a branched triazolyl compound (the compound shown in formula (4)) The difference from Example 1 is that the reaction substrate 04-1 was changed to 04-2 (23.00 g, 0.092 mol, 0.37 eq), and the dropwise addition amount of n-hexane was changed to 300 ml.

[0072]

[0073] The NMR test results 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).

[0074] Synthesis Example 3 of Compound (1) Preparation of a branched triazolyl compound (compound shown in formula (5)) 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 dropping amount of n-hexane is changed to 350 ml.

[0075]

[0076] The results of NMR 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).

[0077] Synthesis Example 4 of Compound (1) Preparation of a branched triazolyl compound (compound shown in formula (6)) 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).

[0078]

[0079] The results of NMR detection are as follows: 1 H 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).

[0080] Synthesis Example 5 of Compound (1) Preparation of a branched triazolyl compound (compound shown in formula (7)) The difference from 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 dropping amount of n-hexane is changed to 300 ml.

[0081]

[0082] The results of NMR detection are as follows: 1 H NMR (500 MHz, d-DMSO ) δ 8.53 (dd, J J = 15.1, 3.0Hz, 3H), 8.26 (s, 3H), 8.03 (td, J J = 14.9, 2.9 Hz, 3H), 7.93 (dd, J J = 14.9, 3.2Hz, 3H), 7.40 (td, J J = 14.9, 3.3 Hz, 3H), 6.08 (s, 3H), 5.22 (s, 6H).

[0083] Compound Synthesis Example 6 (1) Preparation of a branched triazolyl compound (the compound shown in Formula (8)) The difference from 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 dropping amount of n-hexane is changed to 220 ml.

[0084]

[0085] The results of NMR detection are as follows: 1 H 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).

[0086] Compound Synthesis Example 7 (1) Preparation of a branched triazolyl compound (the compound shown in Formula (9)) The difference from 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 dropping amount of n-hexane is changed to 250 ml.

[0087]

[0088] The results of NMR detection are as follows: 11H 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).

[0089] Compound Synthesis Example 8 (1) Preparation of a branched triazolyl compound (compound represented by formula (10)) The difference from Example 3 is that the reaction substrate 02-1 was changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the dropping amount of n-hexane was changed to 300 ml.

[0090]

[0091] The results of NMR detection are as follows: 1 1H 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).

[0092] Compound Synthesis Example 9 (1) Preparation of a branched triazolyl compound (compound represented by formula (11)) The difference from Example 4 is that the reaction substrate 02-1 was changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the dropping amount of n-hexane was changed to 220 ml.

[0093]

[0094] The results of NMR detection are as follows: 1 1H 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).

[0095] Compound Synthesis Example 10 (1) Preparation of a branched triazolyl compound (compound represented by formula (12)) The difference from Example 5 is that the reaction substrate 02-1 was changed to 02-2 (23.28 g, 0.25 mol, 1.0 eq), and the dropping amount of n-hexane was changed to 250 ml.

[0096]

[0097] The results of the MRI test 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).

[0098] Composition Example 1 Preparation of negative photosensitive resin composition (1) Preparation of polyimide precursor B-1 Weigh 93.21g (300mmol) of ODPA and add it to a 1L split glass reactor. Rinse the weighing container with 100ml of γ-butyrolactone (GBL) to ensure that all ODPA is transferred to the reactor. Add 78.08g (600mmol) of HEMA and 50ml of GBL mixed solution at room temperature. Adjust the anchor stirring paddle to 150r / min speed. Use a circulating thermostatic cooler to control the system temperature at 25°C. Add 52.2g (660mmol) of pyridine dropwise for one hour. After the addition, add 90ml of GBL. Keep the speed and reaction temperature unchanged and stir for 16h. Lower the reaction system to -15°C, adjust the stirring paddle to 200r / min speed, and uniformly add 86.66g (660mmol) of DCC and 120ml of GBL mixed solution dropwise for one hour. Stir for another 1h after the addition. Add 56.13g (279mmol) ODA to 240ml NMP, heat to 50℃ in N2 atmosphere to dissolve, and add it dropwise to the reaction system at a constant speed within one hour with the stirring paddle at 300r / min. If ODA shows signs of precipitation, it needs to be heated and kept warm to prevent precipitation. After stirring at low temperature for 1h, heat uniformly to 25℃ for 1h, adjust the stirring paddle speed to 400r / min, react at room temperature for 4h, add 20ml ethanol and stir for 1h to quench.

[0099] The reaction solution was filtered after quenching, and the filtrate was immediately poured into 10L methanol for precipitation. The separated block was dissolved in 1.5LGBL and stirred for 5h, then passed through ion exchange resin. The resin solution was collected and dripped into 10L deionized water, and small flake solids were obtained by filtration. The filter cake was washed three times with 1L methanol, filtered and dried, and vacuum dried at 50℃ for 24h to obtain polyimide precursor B-1. (Mn=11542 Mw=20200 PDI=1.75) (2) Preparation of negative photosensitive resin composition Take a 100 ml wide-mouth glass bottle and sequentially add 0.1 g of photoinitiator TR-PBG-305 (Qiangli New Materials), 0.1 g of thermal inhibitor p-methoxyphenol (MEHQ), 0.5 g of photocrosslinker tetraethylene glycol dimethacrylate (TEGDMA), 0.5 g of 3-aminopropyltriethoxysilane, 0.4 g of tetramethoxymethylglycoluril (MX270). Then add 80 mg of the branched triazolyl compound (Formula (3)) prepared in Example 1, and add 20 g of N-methylpyrrolidone (NMP) and shake on a shaker until all components are dissolved. Then add 10.0 g of the synthesized polyimide precursor B-1 to the above solution and continue to shake until completely dissolved. Filter press with a 1.0 μm filter membrane to obtain a negative photosensitive resin composition, and the viscosity measured at 25 °C is 3200 ± 500 cp.

[0100] Composition Example 2 The difference from Composition Example 1 is that a branched triazolyl compound with the structure of Formula (4) is added in the preparation of the negative photosensitive resin composition.

[0101] Composition Example 3 The difference from Composition Example 1 is that a branched triazolyl compound with the structure of Formula (5) is added in the preparation of the negative photosensitive resin composition.

[0102] Composition Example 4 The difference from Composition Example 1 is that a branched triazolyl compound with the structure of Formula (6) is added in the preparation of the negative photosensitive resin composition.

[0103] Composition Example 5 The difference from Composition Example 1 is that a branched triazolyl compound with the structure of Formula (7) is added in the preparation of the negative photosensitive resin composition.

[0104] Composition Example 6 The difference from Composition Example 1 is that a branched triazolyl compound with the structure of Formula (8) is added in the preparation of the negative photosensitive resin composition.

[0105] Composition Example 7 The difference from Composition Example 1 is that a branched triazolyl compound with the structure of Formula (9) is added in the preparation of the negative photosensitive resin composition.

[0106] Composition Example 8 The difference from Composition Example 1 is that a branched triazolyl compound with the structure of Formula (10) is added in the preparation of the negative photosensitive resin composition.

[0107] Composition Example 9 The differences from Composition Example 1: In the preparation of the negative photosensitive resin composition, a branched triazolyl compound having the structure of formula (11) was added.

[0108] Composition Example 10 The differences from Composition Example 1: In the preparation of the negative photosensitive resin composition, a branched triazolyl compound having the structure of formula (12) was added.

[0109] Composition Example 11 The differences from Composition Example 1: In the preparation of the negative photosensitive resin composition, the amount of the branched triazolyl compound having the structure of formula (3) added was changed to 10 mg.

[0110] Composition Example 12 The differences from Composition Example 1: In the preparation of the negative photosensitive resin composition, the amount of the branched triazolyl compound having the structure of formula (3) added was changed to 50 mg.

[0111] Composition Comparative Example 1 The differences from Composition Example 1: In the preparation of the negative photosensitive resin composition, the amount of the branched triazolyl compound having the structure of formula (3) added was changed to 0 mg.

[0112] Composition Comparative Example 2 The differences from Example 1: In the preparation of the negative photosensitive resin composition, the branched triazolyl compound having the structure of formula (3) was replaced with benzimidazole.

[0113] Composition Comparative Example 3 The differences from Example 1: In the preparation of the negative photosensitive resin composition, the branched triazolyl compound having the structure of formula (3) was replaced with guanine.

[0114] Composition Comparative Example 4 The differences from Example 1: In the preparation of the negative photosensitive resin composition, the branched triazolyl compound having the structure of formula (3) was replaced with 8-azaguanine. Composition Experimental Tests (1) Molecular Weight Test The weight-average molecular weight (Mw) of the resin was measured by gel permeation chromatography (in terms of standard polystyrene conversion). The chromatograph used in the measurement was the UltiMate 3000 from Thermo Fisher, the chromatographic column was the Styragel HR3 / 4 DMF from Waters, and the detector was the RI Detector RefractoMax520 from Thermo Fisher.

[0115] (2) Viscosity Test Use a disposable dropper to take 0.5 mL of the resin composition sample and add it to the sample cell of a cone-plate viscometer (BROOKFIELD DV2T RV). Select an appropriate range and control the sample temperature at 25 ± 0.1 °C for viscosity testing.

[0116] (3)Adhesion peel test of the cured film of the composition to the aluminum substrate Use a spin coater to evenly coat the resin composition sample onto a substrate made of PVD aluminum. Place it on a heating stage (NDK-2K) at 120 °C for 3 minutes of soft baking to obtain a soft-baked film with a film thickness of 15 ± 1.5 μm. Then place the film in a vacuum and oxygen-free oven (AMSEMI-HCM-500D) for heat treatment: continuously bake at 140 °C for 30 minutes, then increase the temperature to 350 °C at a heating rate of 3.5 °C / min over 1 hour, and maintain at 350 °C for 1 hour to finally obtain a cured film. Place the cured film in a PCT test chamber for 100 hours of PCT aging test (121 °C, 2 atm saturated steam; ESPEC EHS-222MD). Use a scribing tool (Biuged BGD 502 / 2A) to scribe the cured film after the PCT test into a grid of 10 rows × 10 columns. Finally, use tape (special transparent 3M tape) to conduct a peel test with reference to the cross-cut test of paint and varnish films in national standard GB / T 9286-1998, and record the number of peeled grids as the peeling situation after the PCT test.

[0117] When the number of peeled grids in the adhesion peel experiment is 0, it is regarded as "excellent"; when it is greater than 0 and less than 10, it is regarded as "good"; when it is greater than or equal to 10 and less than 20, it is regarded as "medium"; when it is greater than or equal to 20 and less than 30, it is regarded as "poor"; when it is greater than or equal to 30 to complete peeling, it is regarded as "extremely poor".

[0118] (4)Separation test of the cured film of the resin composition from the aluminum substrate in the redistribution layer (RDL) Apply the resin composition containing the branched triazole-based aluminum adhesion promoter in the aluminum multi-layer redistribution layer (RDL) structure, and Figure 1 Describe the RDL structure. As Figure 1 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 after curing the resin composition in this application, 5 is a reserved Ti seed layer, 6 is a redistribution layer (RDL) metal Al (RDL1), 7 is an interlayer insulating film PI(2) formed by the resin composition in this application, 8 is a reserved Ti seed layer, 9 is an under-bump metal Al (UBM), and 10 is a solder bump.

[0119] Next, a manufacturing method of a multi-layered redistribution layer (RDL) structure will be described. An aluminum substrate 2 for input / output use and a SiN passivation film 3 are fabricated on a silicon chip 1; through spin coating, exposure, and development operations, a patterned interlayer insulating film 4 formed from the resin composition in this application can be fabricated on 3; a Ti seed layer 5 connected to the aluminum substrate 2 is fabricated using a sputtering process, and then a redistribution layer (RDL) metal Al (RDL1) 6 is formed using an evaporation process; the process steps of 3 to 5 are cycled to prepare the structures of 7 to 9; finally, solder bumps 10 are prepared through a ball mounting process. Thus, a multi-layered redistribution structure separated by an interlayer insulating film formed from the resin composition in this application is fabricated.

[0120] To examine the adhesion between the cured film 7 of the resin composition and the aluminum substrate of the RDL, a cut is made along the center line of the solder bump 10 (as Figure 2 shown), and the separation condition of the bonding interface is observed using a focused ion beam microscope FIB. According to Figure 3 the evaluation criteria shown, the separation degree between the cured film of the resin composition and the RDL is evaluated. As Figure 3 shown, the separation degree between the resin cured film and the RDL is divided into four grades: severe separation, moderate separation, mild separation, and no separation. The more severe the separation, the worse the adhesion.

[0121] Relevant performance tests are conducted on each prepared experimental example, and the test results are shown in Table 2.

[0122] Table 1

[0123] Table 2

[0124] The differences between Composition Examples 1 to 12 and Composition Comparative Example 1 lie in whether the branched triazole-based compound in this application is added to the resin composition, as specifically shown in Table 1. It can be seen from Table 1 and Table 2 that adding the branched triazole-based compound in this application to the resin composition is beneficial to improving the bonding performance, aging resistance, and adhesion performance between the cured film and the aluminum substrate.

[0125] The differences among Composition Examples 1, 11, and 12 lie in the different contents of the branched triazole-based compound in the resin composition. The mass percentage of the branched triazole-based compound to the resin matrix in Example 1 is 0.8%, in Example 11 is 0.1%, and in Example 12 is 0.5%. It can be seen that when the mass percentage of the branched triazole-based compound to the resin matrix in the resin composition is greater than or equal to 0.5%, it is beneficial to improve the adhesion performance, aging resistance, and sealing performance between the obtained cured film and the aluminum substrate.

[0126] The technical solutions provided by the embodiments of the present application have been introduced in detail above. Specific examples are used in this article to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. A branched triazolyl compound for an aluminum surface sealant, characterized in that, The general formula of the branched triazolyl compound is shown in (1): Formula (1); Wherein, A is an organic group having 0 to 50 carbon atoms; R1 is selected from at least one of O, N, hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; R2 and R3 are each independently selected from at least one of H, hydrocarbon group, substituted hydrocarbon group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; R4 is at least one of H, O, N, hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; n is an integer from 2 to 4; Z is a triazole residue having the structure of formula (2) below: Formula (2).

2. The branched triazolyl compound according to claim 1, characterized in that, A is an organic group having 0 to 20 carbon atoms; and / or R1 is selected from at least one of O, a divalent hydrocarbon group having 1 to 6 carbon atoms, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; and / or R2 and R3 are each independently selected from at least one of a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, substituted hydrocarbon group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group; and / or R4 is selected from at least one of H, a monovalent hydrocarbon group having 1 to 10 carbon atoms, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, and heterocyclic group.

3. The branched triazolyl compound according to claim 2, wherein A includes but is not limited to at least one of the following structures: " " represents being connected to H or other organic groups; wherein, R5 is at least one of divalent hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxy group, ester group, amide group, sulfonyl group, aryl group, substituted aryl group, heterocyclic group; an integer of 1≤n1≤4; an integer of 2≤n2≤4; an integer of 2≤n3≤4; X1 includes at least one of the following structures ； And / or, R1 includes at least one of the following structures: .

4. The branched triazolyl compound according to any one of claims 1 to 3, characterized in that, The branched triazolyl compound includes at least one of the compounds shown in the following formulas (3) to (12): 。 5. An aluminum surface sealant, characterized in that, The aluminum surface adhesive includes the branched triazolyl compound according to any one of claims 1 to 4.

6. A resin composition, characterized in that, The resin composition includes a resin matrix and the branched triazolyl compound according to any one of claims 1 to 4.

7. The resin composition according to claim 6, characterized in that, The mass percentage of the branched triazolyl compound to the resin matrix is greater than 0.1% and less than or equal to 5%; and / or The resin composition is a negative photosensitive resin composition; and / or 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; and / or The resin composition further includes at least one of a photoinitiator, a polymerization inhibitor, a silicone substrate adhesive, a thermal crosslinking agent, and a photo crosslinking agent.

8. The resin composition according to claim 7, characterized in that, 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%.

9. The resin composition according to claim 6, characterized in that, By mass parts, the resin composition includes 100 parts of resin matrix; 0.1 part to 5 parts of branched triazyl compound; 0.5 part to 5 parts of photoinitiator; 0.5 part to 5 parts of polymerization inhibitor; 0.5 part to 10 parts of photo crosslinking agent; 0.5 part to 10 parts of silicone substrate adhesive; 0.5 part to 10 parts of thermal crosslinking agent.

10. A resin cured product, characterized in that, The cured resin is obtained by curing the resin composition according to any one of claims 6 to 9.

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