Triazine silane compounds and their use as adhesion promoters

Abstract

The present invention relates to a specific triazinesilane compound, its oligomer, a mixture containing said compound and / or said oligomer, and respective storage and working solutions.Furthermore, the present invention relates to a synthesis method for said specific triazinesilane compound, and the use of said working solution as a surface treatment liquid.

Description

[Technical Field]

[0001] The present invention relates to specific triazinesilane compounds, their oligomers, mixtures containing the compounds and / or the oligomers, and storage and working solutions thereof. The present invention also relates to a synthesis method for the specific triazinesilane compounds and the use of the working solutions as surface treatment solutions.

[0002] The present invention further relates to a method for increasing the adhesive strength between a metal, metal alloy, or metal oxide surface and an organic material surface, the method comprising, as a main step, contacting at least a portion of the metal, metal alloy, or metal oxide with a specific triazine silane compound, a specific triazine silane oligomer, or a mixture containing the compound and / or the oligomer. The present invention further relates to the use of the specific triazine silane compound, the specific triazine silane oligomer, or the mixture in the method for increasing adhesive strength, as well as to the reduction of wedge-shaped spaces between a metal, metal alloy, or metal oxide surface and an organic material surface. Wedge-shaped spaces can also be seen in the formation of halos, which typically form at the interface between a substrate and a laminate after a desmear process of a structured sample. [Background technology]

[0003] Heteroaromatic silane compounds are frequently used in the manufacture of electronic components, in particular in surface treatment solutions for treating metal surfaces and surfaces of organic materials, for example as preparations for further processing steps.

[0004] US2016 / 0368935A1 relates to an azole silane compound, a surface treatment liquid using the azole silane compound, a surface treatment method, and uses thereof.

[0005] JP2018016865A discloses a triazole surface treatment agent containing a silane compound.

[0006] The article "Corrosion protection of copper with 3-glycidoxypropyltrimethoxysilane-based sol-gel coating through 3-amino-5-mercapto-1,2,4-triazole doping," Journal of Research on Chemical Intermediates, Vol. 42, No. 2, pp. 1315-1328, 2015, discloses a study on corrosion protection of copper in a neutral medium by forming a sol-gel coating on the copper surface. It discloses that a 3-glycidoxypropyltrimethoxysilane-based sol-gel coating on copper doped with 3-amino-5-mercapto-1,2,4-triazole forms a thiolate bond to the copper.

[0007] JPH06279461A refers to a surface treatment agent for improving rust prevention on metal surfaces, particularly for copper foils used in copper-clad laminates for printed circuits. The agent is an azole silane obtained by reacting 1H-1,2,4-triazole-3-thiol with 3-glycidoxypropyltrimethoxysilane at 80-200°C.

[0008] The article "Recovery of rhodium-containing catalysts by silica-based chelating ion exchangers containing N and S donor atoms," Journal of Inorganica Chimica Acta 315 (2001), pp. 183-190, discloses 4-amino-3-methyl-1,2,4-triazole-5-thione attached to the bifunctional spacer (3-glycidoxypropyl)trimethoxysilane before immobilization on silica.

[0009] WO2019 / 243180 discloses azole silane compounds, their synthesis, and their respective uses in solutions and surface treatments.

[0010] WO2020 / 178146 discloses the use of an azole silane compound in a method for increasing the adhesive strength between the surface of a metal, metal alloy or metal oxide and the surface of an organic material.

[0011] JP2016169300A (JP6436819B2) discloses silicon-free 2,4-diamine-substituted triazines.

[0012] 2,4,6-Triamine-substituted triazines are disclosed in Chem. Eur. J. 2009, 15, pp. 6279-6288 and JP2017002402A (JP6370836B2). Their use in epoxy resins is disclosed in JP6392273.

[0013] Due to the structural diversity of triazinesilane compounds, the majority of such compounds must be produced on demand and are typically not readily available as standard commercial products. Therefore, simple and efficient synthetic methods are desirable.

[0014] Typically, triazinesilane compounds readily polymerize in the presence of water by forming silicon-oxygen-silicon bonds. This is often undesirable immediately after the compound's synthesis. While polymerization may be desirable for end-use applications, there is usually a need to solubilize the newly synthesized compound in a solvent to prevent excessive and / or premature polymerization of the monomers, but also to enable further processing of the compound. Furthermore, it is desirable to have a sufficiently high concentration of each triazinesilane compound in such a solvent in order to economically transport them to another manufacturing site. In fact, the solubility of known triazinesilane compounds in typically available / desired solvents is often insufficient.

[0015] Furthermore, in many cases, the synthesis of heteroaromatic silane compounds involves the generation of educts, including halides, such as chlorides, bromides, and iodides. Such halides are often released during synthesis, thereby contaminating the resulting synthesis product. This typically requires additional purification steps to remove the halides and their respective salts. However, such additional steps significantly increase the risk of water contamination and premature polymerization. Furthermore, such purification steps often adversely affect the overall yield of the final heteroaromatic silane compound. In some cases, such compounds are not purified, and as a result, the halides and their respective salts remain with the heteroaromatic silane compound. However, in many applications, working with heteroaromatic silane compounds containing halides is completely undesirable. In other cases, while halides are generally tolerated, it is undesirable to utilize heteroaromatic silane compounds containing unlimited amounts of halides.

[0016] Adhesion strength refers to the physical and chemical strength by which the adhesive layer bonds to the metal substrate.

[0017] Another aspect related to adhesive strength is the avoidance of wedge space formation. This means that during typical subsequent processes, such as lamination and curing, laser treatment, desmearing, and reduction, wedge-shaped structures form at the interface between the substrate and the laminate. These so-called wedge spaces are undesirable because they promote delamination of the laminate. Wedge spaces are often already evident as halos around drill holes, indicating chemical diffusion to the substrate. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] US2016 / 0368935A1 [Patent Document 2] JP2018016865A [Patent Document 3] JPH06279461A [Patent Document 4] WO2019 / 243180 [Patent Document 5] WO2020 / 178146 [Patent Document 6] JP2016169300A [Patent Document 7] JP6436819B2 [Patent Document 8] JP2017002402A [Patent Document 9] JP6370836B2 [Patent Document 10] JP6392273 [Non-patent literature]

[0019] [Non-Patent Document 1] "Corrosion protection of copper with 3-glycidoxypropyltrimethoxysilane-based sol-gel coating through 3-amino-5-mercapto-1,2,4-triazole doping," Journal of Research on Chemical Intermediates, Vol. 42, No. 2, pp. 1315-1328, 2015 [Non-patent document 2] “Recovery of rhodium-containing catalysts by silica-based chelating ion exchangers containing N and S donor atoms,” Journal of Inorganica Chimica Acta 315 (2001), pp. 183-190 [Non-patent document 3] Chem. Eur. J. 2009, 15, pp. 6279-6288 Summary of the Invention [Problem to be solved by the invention]

[0020] Therefore, the first object of the present invention is to provide a triazinesilane compound with increased solubility in a suitable solvent, based on the above-mentioned problems. The second object of the present invention is to provide a simple and efficient synthesis method, which does not release halides and their salts, respectively, so that the need for additional purification steps can be avoided.

[0021] As mentioned above, it was an additional task to provide a method that does not exhibit the drawbacks related to adhesive strength and wedge space and halo formation. [Means for solving the problem]

[0022] The first object mentioned above is to provide a compound of formula (I)

[0023] [ka]

[0024] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; E is -S- and -NH-(CH2) m -NH-, Z is

[0025] [ka]

[0026] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. This problem is solved by the triazine silane compound of the formula:

[0027] The second object is to provide a compound of formula (II)

[0028] [ka]

[0029] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; Z is

[0030] [ka]

[0031] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. The above-mentioned problem is solved by a synthesis method for a triazine silane compound.

[0032] A synthesis method comprising the steps of: (i) Formula (III)

[0033] [ka]

[0034] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; m is an integer ranging from 2 to 12; o is an integer ranging from 2 to 12) obtaining a compound of formula (I), (ii) a silane compound selected from the following group: (ii-a) Silane compound of formula (IV)

[0035] [ka]

[0036] and (ii-b) Silane compound of formula (V) OCN-(CH2) n -Si(OR)3 (V) (In formula (IV) or (V), R is (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents C1 to C5 alkyl; n is an integer ranging from 1 to 12) obtaining a step of (iii) reacting said intermediate of formula (III) with said silane compound in a solvent, resulting in a compound of formula (II) as defined above; and (iv) optionally hydrolyzing the compound of formula (II) obtained in step (iii) so that at least one of R is (CH2-CH2-O) m -Z, m=0 and Z=H A synthesis method comprising:

[0037] Independent experiments have shown that the above-mentioned synthesis method produces triazinesilane compounds with improved solubility and stability in specific solvents. Furthermore, the above synthesis method utilizes a halogen-free educt. Therefore, no halide ions are released during synthesis in each solvent. This is highly desirable because a specific amount of each halide can be added, even if the halide ions are needed for further use, so that the total concentration is accurately known.

[0038] The present invention specifically refers to the specific triazine silane compounds defined above. In many cases, the triazine silane compounds of the present invention in which Y represents NH and N(NH), preferably NH, are preferred. In other cases, the triazine silane compounds of the present invention in which Y represents S are preferred. In both cases, nitrogen-containing Y is preferred compared to S Y.

[0039] X is NH2, NH(NH2), NH(CH2) o represents NH2, SH, SCH3 or OCH3, where o is an integer ranging from 2 to 12, preferably NH2, NH(NH2), NH(CH2) o Preferred are triazine silane compounds of the present invention wherein o is NH2, SH or SCH3, where o is an integer ranging from 2 to 12, more preferably NH2.

[0040] Formula (VI)

[0041] [ka]

[0042] (In the formula, m is an integer ranging from 2 to 10; n is an integer ranging from 1 to 10, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. The triazine silane compounds of the present invention, which are compounds of the formula:

[0043] Formulas (VIa) and (VIb)

[0044] [ka]

[0045] The compound of formula (I) is particularly preferred.

[0046] Alternatively, formula (VII)

[0047] [ka]

[0048] (In the formula, m is an integer ranging from 2 to 10; n is an integer ranging from 1 to 10, R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. The triazine silane compounds of the present invention, which are compounds of the formula:

[0049] Formula (VIIa)

[0050] [ka]

[0051] The compound of formula (I) is particularly preferred.

[0052] In the context of this invention, the term "independently" (or similar phrases) in conjunction with a variable indicates that the selected feature for such variable in a first compound is independent of the selected feature for the same variable in a second compound, and when a compound contains at least two occurrences of the same variable, they are selected independently of each other and may therefore be different. This principle applies equally to other "independently" terms.

[0053] The present invention also refers to oligomers of the triazine silane compounds of the present invention. Thus, the present invention relates to oligomers of the triazine silane compounds of the present invention, which are prepared by reacting, in the presence of water, with the compound represented by formula (II):

[0054] [ka]

[0055] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; Z is

[0056] [ka]

[0057] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. The term also refers to triazine silane oligomers obtained by reacting two triazine silane compounds according to the formula (II) (preferably the compounds of formula (II) described throughout the text, which are particularly preferred) with one another so that the triazine silane oligomer contains at least one silicon-oxygen-silicon moiety. This reaction is sometimes also called oligomerization.

[0058] The oligomerization referred to above requires at least a small amount of water for hydrolysis to form at least some OH groups on various silicon atoms. Preferably, the triazine silane oligomers are obtained by reacting the triazine silane compounds with each other in the presence of at least 2 wt.-% water, based on the total mass of each reaction composition.

[0059] In the context of the present invention, the term "triazine silane oligomer" includes a combination of at least two monomers, i.e., the reaction of at least two triazine silane compounds of the present invention with each other. Furthermore, this term includes up to 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 monomers. Preferred triazine silane oligomers of the present invention are those in which the oligomer is selected from the group consisting of triazine silane dimers, triazine silane trimers, triazine silane tetramers, triazine silane pentamers, triazine silane hexamers, triazine silane heptamers, and triazine silane octamers. More preferred are triazine silane oligomers of the present invention are those in which the oligomer is selected from the group consisting of triazine silane dimers, triazine silane trimers, and triazine silane tetramers. The latter alternatively means that preferred triazine silane oligomers of the present invention contain one, two, or three silicon-oxygen-silicon moieties, respectively.

[0060] A wide variety of oligomers of the present invention can be formed based on the triazine silane compounds of the present invention, and therefore, the oligomers of the present invention are best and properly described by reacting them with one another.

[0061] In the context of the present invention, the term "at least" in combination with a particular value represents (and is interchangeable with) this value or more. For example, the above-mentioned "at least one silicon-oxygen-silicon moiety" represents (and is interchangeable with) "one or more silicon-oxygen-silicon moieties." Most preferably, "at least one" represents (and is interchangeable with) "one, two, three, or more than three."

[0062] The oligomer has the formula (VIII)

[0063] [ka]

[0064] [In the formula, R is independently (CH2-CH2-O) p - represents T, p is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; T represents H or C1 to C5 alkyl; k is 1, 2 or 3, preferably 1 or 2; M independently represents a group of formula (II-I)

[0065] [ka]

[0066] (In formula (II-I), X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH, SH, SCH and OCH, preferably NH; Z is

[0067] [ka]

[0068] is selected from the group consisting of m is an integer ranging from 2 to 12, preferably ranging from 2 to 8, more preferably ranging from 2 to 6, even more preferably ranging from 3 to 4, and most preferably n is 3; n is an integer ranging from 1 to 12, preferably ranging from 1 to 8, more preferably ranging from 2 to 6, even more preferably ranging from 3 to 4, and most preferably n is 3; o is an integer ranging from 2 to 12) represents the part of Most preferred are oligomers of the invention which are compounds of the formula:

[0069] In the above moiety of formula (VIa), the dashed line represents the covalent bond connecting the entire moiety to the silicon atom depicted in formula (VIII).

[0070] In only some cases are the triazine silane oligomers of the present invention more preferred where k is an integer ranging from 1 to 7, preferably ranging from 1 to 5. However, most preferably, k is 1, 2 or 3, preferably 1 or 2.

[0071] Preferably, the oligomers of the present invention are homo-oligomers, meaning that preferably identical monomers are combined with each other to form the oligomer.

[0072] Alternatively, in the oligomers of the present invention, it is preferred that at least all of the moieties that do not form the silicon-oxygen-silicon backbone (i.e., the triazine moieties and the ether moieties connecting the triazine moieties to the silicon atoms) are identical in chemical formula, and in such cases, M is preferably not independently defined.

[0073] The triazine silane compound of the present invention and the triazine silane oligomer of the present invention can be present as a mixture. Alternatively, more than one compound or more than one oligomer can be present as a mixture. Typically, an organic solvent promotes solubility. Therefore, the present invention provides (a) - one or more triazine silane compounds according to the invention (described throughout the text, preferably as preferred), and / or one or more triazine silane oligomers according to the invention (mentioned throughout the text, preferably as preferred), (b) - one or more organic solvents It also refers to mixtures comprising, preferably consisting of:

[0074] Preferably the mixtures of the present invention are substantially free, preferably free, of halide ions.

[0075] In the context of the present invention, the term "substantially free" of an object (e.g., a compound, material, etc.) means that the object does not affect the intended purpose of the invention and is not present at all or present only in a very small and inconsistent amount (magnitude). For example, such an object may be added or used unintentionally, for example, as an unavoidable impurity. "Substantially free" preferably means 0 (zero) ppm to 50 ppm, preferably 0 ppm to 25 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, and most preferably 0 ppm to 1 ppm, relative to the total mass of the mixture (as defined for said mixture). 0 ppm means that the respective object is completely absent, which is most preferred. This principle also applies to other embodiments of the present invention, such as the storage solution of the present invention (see the following text) and the working solution of the present invention (also see the following text).

[0076] In the mixture, the total amount of the triazine silane compounds of the present invention and the oligomers of the present invention combined is in the range of 5 wt.-% to 30 wt.-%, preferably 8 wt.-% to 28 wt.-%, more preferably 12 wt.-% to 26 wt.-%, even more preferably 15 wt.-% to 24 wt.-%, and most preferably 17 wt.-% to 22 wt.-% based on the total mass of the mixture. Preferably, the mixture is substantially free of, preferably free of, any other triazine silane compounds and triazine silane oligomers, respectively, not according to the present invention.

[0077] Highly preferred are mixtures of the present invention, wherein the mixture is substantially free, preferably free, of water.Thus, preferred are mixtures of the present invention, wherein the one or more triazine silane compounds according to the present invention are substantially free, preferably free, of -SiOH groups.

[0078] Preferred are mixtures of the invention, wherein the one or more organic solvents comprise a solvent selected from the group consisting of acetone, 1,3-dioxolane, acetonitrile, 1,4-dioxane, methanol, ethanol, 1-propanol, 2-propanol, t-butanol, prop-2-en-1-ol, ethyl lactate, ethylene glycol monomethyl ether acetate, N,N-dimethylformamide, 2-butoxyethanol, di(propylene glycol) methyl ether, tetrahydrofurfuryl alcohol, N-methyl-2-pyrrolidone, 2-(2-methoxyethoxy)ethanol, gamma-butyrolactone, ethylene glycol, propylene glycol, dipropylene glycol, epsilon-caprolactone, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, tetrahydrothiophene-1-oxide, diethylene glycol monobutyl ether acetate, propylene carbonate, sulfolane, glycerol, and mixtures thereof.

[0079] Highly preferred are mixtures of the present invention, wherein the one or more organic solvents comprise a solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, t-butanol, di(propylene glycol) methyl ether, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

[0080] In some cases, highly preferred are mixtures of the present invention, wherein the one or more organic solvents are selected from the group consisting of glycol ethers, preferably di(propylene glycol) methyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

[0081] In the context of the present invention, the inventive mixtures as defined above are preferably the direct result of the respective synthetic procedure, e.g. the inventive synthetic method (see below for further details).

[0082] Furthermore, the mixture according to the present invention (described throughout, preferably described as preferred) is preferred, in which all the triazinesilane compounds according to the present invention (described throughout, preferably described as preferred) and all the triazinesilane oligomers according to the present invention (described throughout, preferably described as preferred) account for at least 51 mol-%, preferably at least 60 mol-%, more preferably at least 70 mol-%, most preferably at least 80 mol-%, and most preferably at least 90 mol-% of all compounds containing at least one silicon atom in the mixture.The above also preferably applies to the storage solution according to the present invention (see the following text) and the working solution according to the present invention (see the following text), respectively.

[0083] The present invention provides (a) - one or more triazine silane compounds according to the invention (described throughout the text, preferably as preferred), and - optionally one or more triazine silane oligomers according to the invention (described throughout the text, preferably as preferred), (b) - optionally water; (c) - one or more water-miscible organic solvents and provided that when water is present, the pH is 9 or greater.

[0084] Preferably, the preservative solutions of the present invention are substantially free, preferably free, of halide ions, and only in some cases are halide ions present, preferably by deliberate addition of halide ions, preferably chloride ions.

[0085] Preservative solutions of the present invention are preferred in which the total amount of all triazine silane compounds according to the present invention (described throughout the text, preferably as preferred) and all triazine silane oligomers according to the present invention (described throughout the text, preferably as preferred) combined is in the range of 0.2 wt.-% to 30 wt.-%, preferably in the range of 0.5 wt.-% to 28 wt.-%, more preferably in the range of 0.7 wt.-% to 25 wt.-%, even more preferably in the range of 0.8 wt.-% to 22 wt.-%, and most preferably in the range of 0.9 wt.-% to 20 wt.-%, based on the total weight of the preservative solution.

[0086] The storage solutions described above optionally contain water.Preferred storage solutions of the present invention are those in which the storage solution is alkaline and the water is present in a total amount ranging from 10 wt.-% to 80 wt.-%, preferably from 15 wt.-% to 78 wt.-%, more preferably from 20 wt.-% to 76 wt.-%, even more preferably from 33 wt.-% to 74 wt.-%, and most preferably from 38.6 wt.-% to 70 wt.-%, based on the total mass of the storage solution.

[0087] The preservation solution contains one or more water-miscible organic solvents. Such organic solvents promote the required solubility of the respective triazinesilane compounds and their oligomers, especially when they are present in relatively higher concentrations (e.g., up to and approximately 15 wt.-%, see above). Therefore, preservation solutions of the present invention are preferred in which the one or more water-miscible organic solvents are present in a total amount ranging from 5 wt.-% to 89.5 wt.-%, preferably from 10 wt.-% to 84.2 wt.-%, more preferably from 14 wt.-% to 79 wt.-%, even more preferably from 18 wt.-% to 65.5 wt.-%, and most preferably from 24 wt.-% to 59 wt.-%, based on the total weight of the preservation solution.

[0088] In many cases, a stock solution of the present invention in which the total weight of water is less than the total weight of all water-miscible organic solvents is preferred.

[0089] As mentioned above, the storage solution is alkaline when water is present. In the context of the present invention, this means a pH of 9 or higher. Storage solutions of the present invention are preferred in which the solution has a pH of 9.6 or higher, preferably in the range of 10.5 to 14, more preferably in the range of 11 to 14, and most preferably in the range of 12 to 14. If the pH is significantly lower than pH 9, the solubility of the triazine silane compound and its oligomers decreases even to the point of undesirable precipitation. Acidic pH is not suitable for storage purposes, since precipitation has been observed at such pH in many cases where the concentration of the present triazine silane compound and its corresponding oligomer is relatively high. It is known from WO 2019 / 243180 that undesirable phase separation and decomposition of the azole silane compound is frequently observed when the pH is significantly higher than 13. In contrast, this triazine silane solution exhibits good phase stability at high pH values.

[0090] Furthermore, the triazine silane solution exhibits good stability, i.e., it does not exhibit phase separation or decomposition over a wide temperature window. Specifically, such solutions are stable from -5°C to 50°C.

[0091] In the context of the present invention, pH is referenced to a temperature of 25°C.

[0092] In the alkaline preservative solutions of the present invention, the alkaline pH is preferably achieved by utilizing at least one alkaline hydroxide, most preferably sodium hydroxide.

[0093] The alkaline pH not only allows for a relatively high concentration of the triazine silane compound and its oligomer in the storage solution, but also allows the triazine silane compound of the present invention to be more firmly maintained in a monomeric state, significantly reducing the formation of the triazine silane oligomer of the present invention. However, if such oligomers are formed in the alkaline storage solution of the present invention, they are typically rapidly hydrolyzed to form the monomeric form due to the alkaline pH. This is desirable in the storage solution of the present invention.

[0094] A stock solution of the present invention is preferred, in which the total mass of all triazine silane compounds according to the present invention is higher than the total mass of all triazine silane oligomers according to the present invention in said solution.

[0095] In some cases, preferred are stock solutions of the invention in which Z is H and p is 0 for at least 80 wt.-%, preferably at least 90 wt.-%, and most preferably at least 95 wt.-% of the total mass of all triazine silane compounds according to the invention. This means that in the stock solution the triazine silane compounds are mostly present in their hydrolyzed form containing SiOH groups.

[0096] The storage solutions mentioned above are particularly suitable for transporting and / or storing one or more triazinesilane compounds of the present invention. However, for utilizing said compounds, for example, as surface treatment liquids in the manufacture of electronic components, respective working solutions are preferred. Thus, the present invention further relates to working solutions having a pH in the range of 2 to 14, The solution is (a) - one or more triazine silane compounds according to the invention (described throughout the text, preferably as preferred), and / or one or more triazine silane oligomers according to the invention (mentioned throughout the text, preferably as preferred), (b) - optionally water; (c) - one or more water-miscible organic solvents; In the working solution, the total amount of all triazine silane compounds according to the invention (described throughout the text, preferably described as preferred) and all triazine silane oligomers according to the invention (described throughout the text, preferably described as preferred) is 10 wt.-% or less, based on the total mass of the working solution.

[0097] Particularly preferred are working solutions of the invention, provided that they comprise at least one triazine silane oligomer according to the invention (described throughout the text, preferably as preferred), which is particularly preferred for freshly prepared working solutions.

[0098] The above term "10 wt.-% or less" does not include 0 wt.-%, meaning that said total amount is always >0 wt.-%, preferably at least 0.1 wt.-%.

[0099] Preferred working solutions of the present invention are those in which the combined total amount of all triazine silane compounds according to the present invention (described throughout the text, preferably as preferred) and all triazine silane oligomers according to the present invention (described throughout the text, preferably as preferred) is in the range of 0.1 wt.-% to 6 wt.-%, preferably in the range of 0.2 wt.-% to 5 wt.-%, more preferably in the range of 0.3 wt.-% to 4 wt.-%, even more preferably in the range of 0.4 wt.-% to 3.7 wt.-%, and most preferably in the range of 0.5 wt.-% to 3.5 wt.-%, based on the total weight of the working solution.

[0100] Independent experiments have shown that the individual presence of one or more triazine silane compounds according to the present invention and one or more triazine silane oligomers according to the present invention fluctuates over time. In a freshly prepared working solution, the total mass of the triazine silane compounds according to the present invention is typically higher than the total mass of the triazine silane oligomers according to the present invention. However, as the working solution is used over time, the total mass of the triazine silane oligomers increases significantly, sometimes even to the point where the total mass of the triazine silane oligomers exceeds the total mass of the triazine silane compounds. Furthermore, handling of the working solution according to the present invention also affects the total mass of the compounds and oligomers, respectively. For example, significant drag-out during use of the working solution and the corresponding replenishment of fresh working solution typically leads to a steady state in terms of the triazine silane compounds versus the triazine silane oligomers.

[0101] Most preferably, the working solution of the present invention comprises: one or more triazine silane compounds according to the invention (mentioned throughout the text, preferably as preferred), and - containing one or more triazine silane oligomers according to the invention (described throughout the text, preferably as preferred). Therefore, the respective working solutions containing at least one compound and at least one oligomer are most preferred.

[0102] The working solutions of the present invention have a pH in the range of 2 to 14. Preferred are working solutions of the present invention having a pH in the range of 3 to 14, more preferably in the range of 4.0 to 13.5.

[0103] Preferred working solutions of the invention are those in which water is present in a total amount ranging from 5 wt.-% to 90 wt.-%, preferably in a total amount ranging from 10 wt.-% to 85 wt.-%, more preferably in a total amount ranging from 15 wt.-% to 80 wt.-%, relative to the total mass of the working solution.

[0104] In order to sufficiently solubilize the inventive triazine silane compounds and inventive triazine silane oligomers in the working solution, one or more water-miscible organic solvents are present in the solution, preferably in a total amount ranging from 5 wt.-% to 90 wt.-%, more preferably from 10 wt.-% to 85 wt.-%, and even more preferably from 15 wt.-% to 80 wt.-%, based on the total weight of the working solution.

[0105] As mentioned above, in the context of the present invention, the triazine silane compound of the present invention and the triazine silane oligomer of the present invention are initially halide-free.This means that, on the one hand, the compound and oligomer do not contain halide atoms themselves, respectively, because no educt containing halogen atoms is used, and on the other hand, no halide ions are present in the immediate synthesis environment.However, in some cases, it is preferred that the working solution of the present invention contains a precisely defined amount of halide ions.Therefore, in some cases, (d) - Preferred are working solutions of the invention which further comprise halide ions, preferably chloride ions.

[0106] In other cases, however, the working solutions of the present invention are substantially free, preferably free, of chloride ions, and more preferably substantially free, preferably free, of halide ions.

[0107] One or more water-miscible organic solvents are present in both the storage solution of the present invention and the working solution of the present invention. The one or more water-miscible organic solvents are selected from the group consisting of C1 to C4 alcohols, ethers, glycol ethers and mixtures thereof, preferably - C1 to C3 alcohols, cyclic and acyclic ethers, such as diethyl ether, tetrahydrofuran, 1,4-dioxane and mixtures thereof, preferably 1,4-dioxane, tetrahydrofuran and mixtures thereof; - HO-(CH2-CH2-O) p -T (In the formula, p is 1, 2, 3 or 4, preferably 1 or 2; T represents C1 to C5 alkyl, preferably C3 to C5 alkyl; and mixtures thereof, more preferably more preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof; Preferred is a storage solution according to the present invention (described throughout, and preferably described as preferred) or a working solution according to the present invention (described throughout, and preferably described as preferred) comprising a water-miscible organic solvent selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof.

[0108] The water-miscible organic solvents defined above equally apply to the synthetic methods of the present invention (see text below).

[0109] In each case, glycol ethers are preferred over alcohols. Glycol ethers typically provide improved stabilization compared to the alcohols. Furthermore, alcohols generally exhibit lower flash points compared to glycol ethers, making them potentially dangerous from a fire hazard perspective. A relatively high flash point is usually desirable to prevent ignition. Thus, glycol ethers typically exhibit desirable solubility, stability, and safety. This principle preferably applies equally to the mixtures of the present invention, the stock solutions of the present invention, and the synthetic methods of the present invention (see the following text).

[0110] Preferably, all of the triazine silane compounds (described throughout, preferably as preferred) according to the present invention and all of the triazine silane oligomers (described throughout, preferably as preferred) according to the present invention represent at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, even more preferably at least 93 wt.-%, most preferably at least 95 wt.-%, and most preferably at least 98 wt.-% of the total weight of all triazine silane compounds and oligomers in the storage solution (described throughout, preferably as preferred) according to the present invention or the working solution (described throughout, preferably as preferred) according to the present invention. Most preferably, no other triazine silane compounds or oligomers other than those according to the present invention are present. This means that the absolute total amount of triazine silane compounds and triazine silane oligomers combined (as defined in the preceding sentence) is very preferably the case, provided that no other triazine silane compounds and triazine silane oligomers are present in the storage solution of the invention and the working solution of the invention, respectively.

[0111] Further preferred are storage solutions (described throughout, preferably referred to as preferred) and working solutions (described throughout, preferably referred to as preferred) according to the present invention, in which all triazine silane compounds (described throughout, preferably referred to as preferred) according to the present invention and all triazine silane oligomers (described throughout, preferably referred to as preferred) according to the present invention represent at least 51 mol-% of all compounds containing at least one silicon atom in the storage solution and working solution, respectively, preferably at least 60 mol-%, more preferably at least 70 mol-%, most preferably at least 80 mol-%, and even most preferably at least 90 mol-%.

[0112] The present invention also relates to a synthesis method for the triazine silane compounds of formula (II).

[0113] Formula (II)

[0114] [ka]

[0115] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; Z is

[0116] [ka]

[0117] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O)p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. A synthesis method for a triazine silane compound of the formula: (i) Formula (III)

[0118] [ka]

[0119] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; m is an integer ranging from 2 to 12) obtaining a compound of formula (I), (ii) a silane compound selected from the following group: (ii-a) Silane compound of formula (IV)

[0120] [ka]

[0121] , and (ii-b) Silane compound of formula (V) OCN-(CH2) n -Si(OR)3 (V) (In formula (IV) or (V), R is (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents C1 to C5 alkyl; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12) obtaining a step of (iii) reacting said intermediate of formula (III) with said silane compound in a solvent, resulting in a compound of formula (II) as defined above; and (iv) optionally hydrolyzing the compound of formula (II) obtained in step (iii), so that at least one of R is (CH2-CH2-O) m -Z, m=0 and Z=H A synthesis method comprising:

[0122] What has been said above with respect to the inventive triazinesilane compounds (preferably those described as preferred), e.g. with respect to the highly preferred inventive triazinesilane compounds, preferably also applies to the inventive synthesis method.

[0123] The synthesis of compounds of formula (III) obtained in step (i) is known in the literature.

[0124] Formula (III)

[0125] [ka]

[0126] The synthesis of the compound of formula (I) preferably comprises the following steps: (Ai) Formula (IX)

[0127] [ka]

[0128] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; o is an integer ranging from 2 to 12; Hal is selected from Cl, Br and I, preferably Hal is Cl. a step of obtaining a triazine compound of formula (I), (A-ii) Diamine H2N(CH2) m obtaining NH2; (A-iii) Reacting the triazine compound with the diamine in a solvent to form a compound represented by formula (III)

[0129] [ka]

[0130] a step of producing an intermediate of (A-iv) Optionally isolating / purifying the intermediate of formula (III) Includes:

[0131] A preferred synthesis is the synthesis of a compound of formula (IIIa)

[0132] [ka]

[0133] The synthesis of the compound of formula (I) is carried out by the following steps: (Ai) Formula (IXa)

[0134] [ka]

[0135] a step of obtaining a triazine compound of formula (I), (A-ii) a step of obtaining the diamine HN(CH)NH, i.e., 1,4-diaminobutane; (A-iii) Reacting the triazine compound with the diamine in a solvent to form a compound represented by formula (IIIa)

[0136] [ka]

[0137] a step of producing a compound of formula (I) (A-iv) Optionally isolating / purifying the intermediate of formula (IIIa) Includes:

[0138] Step (iv) is optional and includes the presence of at least some water to hydrolyze the compound obtained in step (iii) of the process of the present invention. Preferably, such water is added in an additional step, e.g., step (iv), after step (iii). If such a compound is desired (m=0 and Z=H), step (iv) is not optional.

[0139] Highly preferred is a synthesis method of the present invention wherein in step (iii) the solvent comprises an organic solvent, more preferably one or more organic solvents, most preferably one or more water-miscible organic solvents.

[0140] In many cases, in step (iii), the solvent is selected from the group consisting of C1 to C4 alcohols, glycol ethers, and mixtures thereof; Preferably - C1 to C3 alcohols, - HO-(CH2-CH2-O) p -T (In the formula, p is 1, 2, 3 or 4, preferably 1 or 2; T represents C1 to C5 alkyl, preferably C3 to C5 alkyl; and mixtures thereof, more preferably more preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof; Preferred in the synthesis method of the present invention is one or more solvents selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof.

[0141] Generally, glycol ethers are preferred over the alcohols defined above (see text above for reasons), and therefore each of the synthetic methods of the present invention is preferred.

[0142] In step (iii), the synthesis method of the present invention (described in detail previously) is preferred, wherein the solvent is substantially free, preferably free, of water.

[0143] Preferably, in step (iii), the solvent is one or more organic solvents, and after step (iii) of the process of the invention, a mixture according to the invention is obtained (see above text for mixture). What has been said above with respect to the mixture of the invention also applies to the synthesis process of the invention.

[0144] In the preferred synthesis method of the present invention, the total molar ratio of the compound of formula (III) to the compound of formula (IV) or (V) is in the range of 1:0.7 to 1:1.3, preferably in the range of 1:0.80 to 1:1.2, more preferably in the range of 1:0.9 to 1:1.2, and most preferably in the range of 1:0.95 to 1:1.05. If the total molar ratio is significantly higher than 1:1.3, the synthesis product is not sufficiently stable. If the total molar ratio is significantly lower than 1:0.7, too much unreacted educt is present in the synthesis product, which is undesirable because the desired chemical species is a triazinesilane compound containing triazine and silane moieties. This principle applies equally to the mixture of the present invention, the stock solution of the present invention, and the working solution of the present invention.

[0145] Preferred is a synthesis method according to the invention, wherein in step (iii) the temperature is in the range of from 50°C to 90°C, preferably in the range of from 60°C to 85°C.

[0146] In the synthesis method of the present invention, in step (i), the triazine compound of formula (III) is preferably obtained as a suspension. This means that the triazine compound of formula (III) is preferably suspended in at least one solvent, so that the triazine compound and the at least one solvent form the suspension. Therefore, it is preferred that the at least one solvent is one or more organic solvents, preferably one or more water-miscible organic solvents. It is highly preferred that the at least one solvent used to form the suspension is the same as the solvent used in step (iii). Most preferably, the triazine compound of formula (III) is selected from the group consisting of C1 to C4 alcohols, glycol ethers, and mixtures thereof, preferably - C1 to C3 alcohols, cyclic and acyclic ethers, such as diethyl ether, tetrahydrofuran, 1,4-dioxane and mixtures thereof, preferably 1,4-dioxane, tetrahydrofuran and mixtures thereof; - HO-(CH2-CH2-O) p -T (In the formula, p is 1, 2, 3 or 4, preferably 1 or 2; T represents C1 to C5 alkyl, preferably C3 to C5 alkyl; and mixtures thereof, more preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof, most preferably It is suspended in one or more solvents selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

[0147] In step (iii), the synthesis method of the present invention is preferred, wherein the reacting step is carried out for 1 hour to 48 hours, preferably 3 hours to 30 hours, more preferably 5 hours to 24 hours.

[0148] The present invention also relates to the specific use of the above-mentioned working solution of the invention (described throughout the text, preferably described as preferred) as a surface treatment liquid for treating preferably metal surfaces and / or surfaces of organic materials, preferably both metal surfaces and organic materials involved in the manufacture of electronic components.

[0149] Due to the method according to the present invention, the adhesion strength (e.g., peel strength) between the metal and the organic material can be increased without using any etching cleaning step. However, in some cases, especially when the surface roughness of the metal surface does not affect the quality of the circuit, an additional etching cleaning step can be performed. In this case, the adhesion strength between the metal and the organic material can be increased even further.

[0150] The contacting step in step (ii) may be applied as a dip coating, which means that the solution is prepared in the form of a bath into which the copper, copper alloy or copper oxide is immersed.

[0151] Alternatively, step (ii) may be applied as a spray application, meaning that the solution is transferred into a spray dispenser and then sprayed onto the copper, copper alloy or copper oxide.

[0152] Alternatively, step (ii) may be applied as a coating application, such as bar coating, spin coating and curtain coating.

[0153] The process according to the invention is preferably carried out at a temperature of from 5°C to 60°C, more preferably from 10°C to 40°C, even more preferably from 20°C to 30°C.

[0154] Preferred is the method according to the present invention, which, before carrying out step (ii), further comprises the following step: (ia) contacting at least a portion of said metal, metal alloy or metal oxide with an etching cleaning solution, preferably an etching cleaning solution containing one or more acids and / or one or more oxidizing agents, more preferably an etching cleaning solution containing a mixture of an inorganic acid and a peroxide (preferably a mixture of sulfuric acid and hydrogen peroxide).

[0155] According to the present invention, this is preferred when the oxidizing agent is a peroxide, more preferably when the peroxide is hydrogen peroxide.

[0156] According to the present invention, it is preferred if the etching cleaning solution comprises a corrosion inhibitor in addition to the acid and / or one or more oxidizing agents.

[0157] A preferred method according to the invention further comprises, before carrying out step (ii), the following step: (ib) contacting at least a portion of said metal, metal alloy or metal oxide with a (preferably second) etching cleaning solution. In the case where step (ib) is carried out after step (ia), the etching cleaning solution used is the second etching cleaning solution. In the case where step ib is carried out without a previous etching cleaning step, the etching cleaning solution used is the first etching cleaning solution.

[0158] According to the present invention, the second etching cleaning solution comprises an iron(III) salt or iron(III) complex, more preferably the second etching cleaning solution comprises iron(III) sulfate (Fe2(SO4)3), iron(III) chloride (FeCl3), iron(III) bromide (FeBr3), iron(III) nitrate (Fe(NO3)3), iron(III) acetate (Fe(OC(O)CH3)3), (Fe(OH)3), or a mixture thereof, and even more preferably the second etching cleaning solution comprises iron(III) sulfate (Fe2(SO4)3). The ferric ion is preferably contained in a concentration ranging from 1 to 100 g / l, preferably from 1 to 50 g / l, more preferably from 1 to 30 g / l.

[0159] Alternatively, according to the present invention, the second etching cleaning solution comprises an inorganic acid, more preferably the second etching cleaning solution comprises sulfuric acid, hydrochloric acid or a mixture thereof, and even more preferably the second etching cleaning solution comprises sulfuric acid.

[0160] According to the present invention, the second etching cleaning solution preferably comprises an acid, preferably sulfuric acid, in addition to an iron(III) salt or iron(III) complex.

[0161] According to the present invention, typical metal, metal alloy or metal oxide removal during step ia is less than 2 μm, preferably removal is from 0.1 μm to 1.5 μm, more preferably removal is from 0.2 μm to 1.2 μm, even more preferably removal is from 0.4 μm to 1.1 μm, and most preferably removal is from 0.5 μm to 1.0 μm, resulting in an average surface roughness Ra of at most 100 nm.

[0162] According to the invention, typical removal of metal, metal alloy or metal oxide during step ib is less than 20 nm, resulting in an average surface roughness Ra of at most 10 nm, preferably at most 5 nm.

[0163] Preferred is a process according to the invention, which, before carrying out step (ii), further comprises the following step: (ic) contacting at least a portion of said metal, metal alloy or metal oxide with a solution, preferably a sodium hydroxide solution, which is preferred when the solution contains a metal-complexing agent.

[0164] In some embodiments of the invention, this is preferred when the solution used in step ic further contains sodium chlorite. The use of sodium chlorite in the solution used in step ic is especially preferred when no iron(III) salt or iron(III) complex is used in step ib or when step ib is not performed in the process according to the invention.

[0165] The order of steps (ia), (ib) and (ic) can be varied. The method according to the invention can be carried out in the following order: (ia), (ib), (ic) or (ia), (ic), (ib) or (ib), (ia), (ic) or (ib), (ic), (ia) or (ic), (ia), (ib) or (ic), (ib), (ia). The order (ia), (ib), (ic) is preferred. It is also possible that in the method according to the invention none of steps (ia), (ib), (ic) are carried out, or one or two of them are carried out.

[0166] Preferred is a method according to the present invention, wherein the organic material applied in step (iii) is an organic polymer.

[0167] A method according to the invention is preferred, wherein the organic material applied in step (iii) is by laminating the organic material to at least the contacting areas of the metal, metal alloy or metal oxide.

[0168] Preferred is a method according to the present invention, which comprises, after step (iii), an additional step: (iv) subjecting the substrate and the organic material to a heat treatment at a temperature in the range of from 142°C to 420°C, preferably in the range of from 145°C to 300°C, more preferably in the range of from 150°C to 220°C.

[0169] Preferred is a process according to the invention, wherein after step (ii), after step (ia), after step (ib) and / or after step (ic) a step of rinsing at least part of the metal, metal alloy or metal oxide is carried out, the metal, metal alloy or metal oxide preferably being rinsed with water. This is preferred if the water used in the rinsing step after step (ii) has a pH value in the range from 4 to 10, preferably in the range from 5 to 9, more preferably in the range from 6 to 8, most preferably in the range from 6.5 to 7.5.

[0170] Preference is given to the process according to the invention, wherein after step (ii), after step (ia), after step (ib) and / or after step (ic) a step of drying at least part of the metal, metal alloy or metal oxide is carried out.

[0171] The method according to the invention is preferred, in which the metal, metal alloy or metal oxide is copper, aluminum, titanium, nickel, tin, iron, silver, gold, an alloy comprising at least one of the aforementioned metals (or an alloy comprising only the aforementioned metals), or a metal oxide of at least one of the aforementioned metals. The method according to the invention is especially preferred, in which the metal is copper, the metal alloy contains copper, and the metal oxide is or contains copper oxide.

[0172] A method according to the present invention, comprising the steps of: (i) providing a substrate, the substrate comprising a metal, a metal alloy, or a metal oxide on at least one surface; (ia) optionally contacting at least a portion of said metal, metal alloy or metal oxide with an etching cleaning solution, preferably an etching cleaning solution containing one or more acids and / or one or more oxidizing agents, more preferably an etching cleaning solution containing a mixture of an inorganic acid and a peroxide, and optionally subsequently rinsing at least a portion of the metal, metal alloy or metal oxide; (ib) optionally contacting at least a portion of said metal, metal alloy or metal oxide with a second etching cleaning solution, the second etching cleaning solution preferably comprising iron (III) sulfate and / or sulfuric acid, and optionally subsequently rinsing (preferably with water) at least a portion of the metal, metal alloy or metal oxide; (ic) optionally contacting at least a portion of said metal, metal alloy or metal oxide with an alkaline solution, and optionally subsequently rinsing at least a portion of the metal, metal alloy or metal oxide (preferably with water); (ii) at least a portion of the metal, metal alloy, or metal oxide, A) Formula (I)

[0173] [ka]

[0174] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; E is -S- and -NH-(CH2) m -NH-, Z is

[0175] [ka]

[0176] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. a triazine silane compound of and / or B) A triazine silane oligomer obtained by reacting triazine silane compounds of formula (I) with each other in the presence of water so that the triazine silane oligomer contains at least one silicon-oxygen-silicon moiety, wherein the compound of formula (I) used in the reaction to form the triazine silane oligomer is: X is H, CH3, NH2, NH(NH2), NH(CH2) o represents NH2, NH(NHU), SH, SCH3, OCH3, NHU or SU, O is an integer ranging from 2 to 12, Y and U have the meanings indicated above, Triazine Silane Oligomer and Optionally, followed by rinsing (preferably with water) at least a portion of the metal, metal alloy or metal oxide; (iii) applying an organic material such that at least a portion of the metal, metal alloy, or metal oxide that was in contact with the triazine silane compound and / or triazine silane oligomer during step (ii) is brought into contact with the applied organic material; and (iv) optionally subjecting the substrate and organic material to a heat treatment at a temperature in the range of 142°C to 420°C, preferably in the range of 145°C to 300°C, more preferably in the range of 150°C to 220°C; Particularly preferred is a method comprising, in this order: Preferably, the metal is copper, the metal alloy contains copper, and the metal oxide is or contains copper oxide.

[0177] Preference is given to a method according to the invention, wherein the substrate is a non-conductive substrate and / or the organic material is a non-conductive organic material, preferably a non-conductive organic polymer. [Brief explanation of the drawings]

[0178] [Figure 1] Photograph depicting halo measurements. [Figure 2] The halo appears as a boundary between the via hole (or clean capture pad), the inner (innermost) and the outer (outermost). DETAILED DESCRIPTION OF THE INVENTION

[0179] The present invention is described by the following embodiments.

[0180] A. Formula (I)

[0181] [ka]

[0182] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; E is -S- and -NH-(CH2) m -NH-, Z is

[0183] [ka]

[0184] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. Triazine silane compound.

[0185] B. E is -NH-(CH2) m -NH-, Formula (II)

[0186] [ka]

[0187] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; Z is

[0188] [ka]

[0189] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. The triazine silane compound of embodiment A has the structure:

[0190] C. X and Y are NH2, NH(NH2), NH(CH2) o The compound of any one of embodiments A to B, wherein X and Y are independently selected from the group consisting of NH2, SH and SCH3, and o is an integer ranging from 2 to 12, preferably X and Y are NH2.

[0191] D. A triazine silane oligomer obtained by reacting the triazine silane compound of any one of embodiments A through C in the presence of water.

[0192] E. (a) - one or more triazine silane compounds according to any one of embodiments A to C, and / or one or more triazine silane oligomers according to embodiment D, (b) - Mixtures containing one or more organic solvents.

[0193] F. (a) - one or more triazine silane compounds according to any one of embodiments A to C, and optionally one or more triazine silane oligomers according to embodiment D, (b) - optionally water; (c) - one or more water-miscible organic solvents 2. A storage solution comprising:

[0194] G. A preservation solution according to embodiment F, in which the combined total amount of all triazine silane compounds according to any one of embodiments A to C and all triazine silane oligomers according to embodiment D (embodiment 4) is in the range of 0.2 wt.-% to 40 wt.-%, preferably in the range of 0.5 wt.-% to 35 wt.-%, more preferably in the range of 0.7 wt.-% to 30 wt.-%, even more preferably in the range of 0.8 wt.-% to 30 wt.-%, and most preferably in the range of 0.9 wt.-% to 25 wt.-%, based on the total weight of the preservation solution.

[0195] H. A working solution having a pH in the range of 2 to 14, wherein the solution (a) - one or more triazine silane compounds according to any one of embodiments A to C, and / or optionally one or more triazine silane oligomers according to embodiment D, (b) - optionally water; (c) - one or more water-miscible organic solvents; The working solution, wherein the combined total amount of all triazine silane compounds according to any one of embodiments A to C and all triazine silane oligomers according to embodiment D is 5 wt.-% or less, based on the total weight of the working solution.

[0196] I. The one or more water-miscible organic solvents are selected from the group consisting of C1 to C4 alcohols, ethers, glycol ethers and mixtures thereof, preferably - C1 to C3 alcohols, diethyl ether, 1,4-dioxane, tetrahydrofuran and mixtures thereof, - HO-(CH2-CH2-O) p -T (In the formula, p is 1, 2, 3 or 4, preferably 1 or 2; T represents C1 to C5 alkyl, preferably C3 to C5 alkyl; and mixtures thereof, more preferably more preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof; A storage solution according to embodiment F or G, or a working solution according to embodiment H, comprising a water-miscible organic solvent selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

[0197] J. Formula (II)

[0198] [ka]

[0199] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3, where o is an integer ranging from 2 to 12; Z is

[0200] [ka]

[0201] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, R is independently (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. A synthesis method for a triazine silane compound of the formula: (i) Formula (III)

[0202] [ka]

[0203] obtaining a compound of formula (I), (ii) a silane compound selected from the following group: (ii-a) Silane compound of formula (IV)

[0204] [ka]

[0205] , and (ii-b) Silane compound of formula (V) OCN-(CH2) n -Si(OR)3 (V) (In formula (IV) or (V), R is (CH2-CH2-O) p - represents T, Independently, p is 0, 1, 2, 3 or 4; T represents C1 to C5 alkyl; n is an integer ranging from 1 to 12) obtaining a step of (iii) reacting said intermediate of formula (III) with said silane compound in a solvent, resulting in a compound of formula (II) as defined above; and (iv) optionally hydrolyzing the compound of formula (II) obtained in step (iii) so that at least one of R is (CH2-CH2-O) m -Z, m=0 and Z=H.

[0206] K. Use of the working solution according to embodiment H as a surface treatment liquid.

[0207] L. A method for increasing the adhesive strength between a metal, metal alloy, or metal oxide surface and an organic material surface, comprising the steps of: (i) providing a substrate, the substrate comprising a metal, a metal alloy, or a metal oxide on at least one surface; (ii) at least a portion of the metal, metal alloy, or metal oxide, A) Formula (II) Formula (I)

[0208] [ka]

[0209] (In the formula, X and Y are NH2, NH(NH2), NH(CH2) o independently selected from the group consisting of NH2, SH, SCH3, and OCH3; E is -S- and -NH-(CH2) m -NH-, Z is

[0210] [ka]

[0211] is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, o is an integer ranging from 2 to 12; R is independently (CH2-CH2-O) p represents -Z, Independently, p is 0, 1, 2, 3 or 4; T represents H or C1 to C5 alkyl. a triazine silane compound of and / or B) Triazine silane oligomers obtained by reacting triazine silane compounds of formula (II) with each other in the presence of water so that the triazine silane oligomer contains at least one silicon-oxygen-silicon moiety. contacting the (iii) applying an organic material such that at least a portion of the metal, metal alloy, or metal oxide that was in contact with the triazine silane compound and / or triazine silane oligomer during step (ii) is brought into contact with the applied organic material. A method comprising, in this order:

[0212] M. The method according to embodiment L, wherein the solution further comprises one or more water-miscible organic solvents.

[0213] N. one or more water-miscible organic solvents selected from the group consisting of C1 to C4 alcohols, ethers, glycol ethers and mixtures thereof, preferably - C1 to C3 alcohols, - HO-(CH2-CH2-O) p -T (In the formula, p is 1, 2, 3 or 4, preferably 1 or 2; T represents C1 to C5 alkyl, preferably C3 to C5 alkyl; and mixtures thereof, more preferably more preferably selected from the group consisting of methanol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and mixtures thereof; The method according to embodiment M, comprising a water-miscible organic solvent selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and mixtures thereof.

[0214] O. The process according to embodiment M or N, wherein a solution of the triazine silane compound and / or triazine silane oligomer of formula (II) is used in step (ii), the solution preferably comprising 5 to 90 wt.-% water, based on the total weight of the solution.

[0215] P. The method according to any one of embodiments M through O, wherein the total amount of triazine silane compound and triazine silane oligomer combined is 5 wt.-% or less, based on the total weight of the solution.

[0216] Q. The method according to any one of embodiments M to P, wherein the solution has a pH in the range of 2 to 14, preferably in the range of 3 to 14, more preferably in the range of 4.0 to 13.5.

[0217] R. Before carrying out step (ii), the following steps: The method according to any of embodiments L through Q, further comprising the step of (ia) contacting at least a portion of the metal, metal alloy, or metal oxide with an etching cleaning solution, preferably an etching cleaning solution containing one or more acids and / or one or more oxidizing agents, more preferably an etching cleaning solution containing a mixture of an inorganic acid and a peroxide.

[0218] S. Before carrying out step (ii), the following steps: The method according to any of embodiments L through R, further comprising (ib) contacting at least a portion of the metal, metal alloy, or metal oxide with a (preferably second) etching cleaning solution, preferably comprising an iron(III) salt or iron(III) complex.

[0219] T. Before carrying out step (ii), the following steps: The method according to any of embodiments L through S, further comprising: (ic) contacting at least a portion of the metal, metal alloy, or metal oxide with a solution.

[0220] U. The method according to any of embodiments L through T, wherein the organic material applied in step (iii) is an organic polymer.

[0221] V. The method according to any of embodiments L through U, wherein the organic material is applied in step (iii) by depositing the organic material onto at least the contacting areas of the metal, metal alloy, or metal oxide.

[0222] W. After step (iii), an additional step: (iv) The method according to any of embodiments L to V, comprising subjecting the substrate and organic material to a heat treatment at a temperature in the range of from 142°C to 420°C, preferably in the range of from 145°C to 300°C, more preferably in the range of from 150°C to 220°C.

[0223] X. The method according to any of embodiments L to W, wherein after step (ii), after step (ia), after step (ib), and / or after step (ic), a step of rinsing at least a portion of the metal, metal alloy, or metal oxide is performed, wherein the metal, metal alloy, or metal oxide is preferably rinsed with water.

[0224] Y. The method according to any of embodiments L through X, wherein after step (ii), after step (ia), after step (ib), and / or after step (ic), a step of drying at least a portion of the metal, metal alloy, or metal oxide is performed.

[0225] Z. The method according to any of embodiments L through Y, wherein the metal, metal alloy, or metal oxide is copper, aluminum, titanium, nickel, tin, iron, silver, gold, an alloy comprising at least one of the foregoing metals, or a metal oxide of at least one of the foregoing metals.

[0226] AA. The method according to any of embodiments L to Z, wherein the contact time in step (ii) is from 5 seconds to 30 minutes, preferably from 7 seconds to 20 minutes, more preferably from 10 seconds to 10 minutes, even more preferably from 12 seconds to 5 minutes, and most preferably from 15 seconds to 120 seconds.

[0227] The present invention is further illustrated by the following non-limiting examples. [Example]

[0228] A) Formula (VI):

[0229] [ka]

[0230] Synthesis of triazinesilane compounds 1) Formula (VIa):

[0231] [ka]

[0232] Synthesis of triazinesilane compounds

[0233] 10.0 g (50.7 mmol) of N2-(4-aminobutyl)-1,3,5-triazine-2,4,6-triamine was suspended in 92.8 ml of diethylene glycol monobutyl ether (DEGBE). The suspension was heated to 80°C. At this temperature, 11.98 g (50.7 mmol) of 3-glycidoxypropyltrimethoxysilane was added. The reaction mixture was held at 80°C for 15 hours.

[0234] After that, a reaction product having a concentration of approximately 20 wt.-% in DEGBE was obtained, and the product thus obtained was used without further purification.

[0235] ESI-MS confirms the formation of compounds containing three methoxy groups attached to the silicon atom. Additionally, compounds containing one, two, or three DEGBE moieties in place of each methoxy group were also identified.

[0236] 2) Formula (VIb):

[0237] [ka]

[0238] Synthesis of triazinesilane compounds

[0239] 21.0 g (106 mmol) of N2-(4-aminobutyl)-1,3,5-triazine-2,4,6-triamine was suspended in 225 ml of diethylene glycol monobutyl ether (DEGBE). The suspension was heated to 80°C. At this temperature, 32.6 g (106 mmol) of [8-(glycidyloxy)-N-octyl]trimethoxysilane was added. The reaction mixture was held at 80°C for 15 hours.

[0240] After that, a reaction product having a concentration of approximately 20 wt.-% in DEGBE was obtained, and the product thus obtained was used without further purification.

[0241] ESI-MS confirms the formation of compounds containing three methoxy groups attached to the silicon atom. Additionally, compounds containing one, two, or three DEGBE moieties in place of each methoxy group were also identified.

[0242] B) Formula (VII):

[0243] [ka]

[0244] Synthesis of triazinesilane compounds

[0245] 2) Formula (VIIa):

[0246] [ka]

[0247] Synthesis of triazinesilane compounds

[0248] 3.0 g (15.2 mmol) of N2-(4-aminobutyl)-1,3,5-triazine-2,4,6-triamine was dissolved in 90 ml of dioxane, and then 3.29 g (15.2 mmol) of (3-isocyanatopropyl)trimethoxysilane was added, and the reaction mixture was heated to 50° C. and held at this temperature for 20 hours.

[0249] 55.08 g of DEGBE was then added and the dioxane was removed by distillation to give the product as a 10 wt.-% (10 w%) solution in DEGBE, which was used without further purification.

[0250] ESI-MS confirms the formation of compounds containing three methoxy groups attached to the silicon atom. Additionally, compounds containing one, two, or three DEGBE moieties in place of each methoxy group were also identified.

[0251] 21.0 g (106 mmol) of N2-(4-aminobutyl)-1,3,5-triazine-2,4,6-triamine was suspended in 225 ml of diethylene glycol monobutyl ether (DEGBE). The suspension was heated to 80°C. At this temperature, 32.6 g (106 mmol) of [8-(glycidyloxy)-N-octyl]trimethoxysilane was added. The reaction mixture was held at 80°C for 15 hours.

[0252] After that, a reaction product having a concentration of approximately 20 wt.-% in DEGBE was obtained, and the product thus obtained was used without further purification.

[0253] ESI-MS confirms the formation of compounds containing three methoxy groups attached to the silicon atom. Additionally, compounds containing one, two, or three DEGBE moieties in place of each methoxy group were also identified.

[0254] C) Sample preparation Samples 1 to 12 (each containing several identical specimens) were prepared as follows: Comparative Example C1 was prepared according to the same method except without step (ii), i.e., no silane was applied.

[0255] Table 1 provides an overview of the reaction steps, which are then described in detail below. Table 2 provides an additional summary.

[0256] [Table 1]

[0257] Step (i): Providing a substrate having a copper surface on at least one surface: Copper foil (150 mm x 75 mm x 35 μm, plated in-house) with a copper surface was used. Under simplified laboratory conditions, copper foil without a substrate was used in the examples.

[0258] For the wedge and halo studies, plated copper panels were used.

[0259] The preparation conditions are as follows: Electrolytically plated copper type: Foil (adhesion test) Panel (wedge-shaped space) Electrolytes: Cupracid AC Plating parameters: 103 minutes 1.5A / dm 2 = 35 μm Cu thickness

[0260] Step (ia): Cleaning the copper surface with an etching cleaning solution: The copper surface of the copper foil was treated with 25 ml / L Hyperflash 25, 50 ml / L H2SO4 50%, and 65 ml / L H2O2 35% at 30°C to achieve an etching depth of 0.5 or 1 μm. After etching cleaning, the etch-cleaned copper surface was rinsed with water for approximately 30 seconds and optionally dried. As a result, an etch-cleaned and rinsed copper surface was obtained.

[0261] Step (ib): Treating the copper surface with an acidic solution: The copper surfaces of all copper foils of Samples 1 to 12 were cleaned using 5 vol% sulfuric acid at room temperature for 20 to 30 seconds.

[0262] Step (ic): treating the copper surface with an alkaline aqueous solution: The copper surfaces of all substrates of Samples 1 to 12 were treated with an alkaline aqueous solution (50°C, 300 seconds). After treatment, the treated copper surfaces of all copper foils were rinsed with cold water for approximately 30 seconds.

[0263] Step (ii): Contacting the copper surface with a silane compound: The copper surfaces of all substrates from Samples 1 to 12 were immersed in a coating solution containing a triazine silane compound and a solvent at 25°C for 60 seconds. When water was present, the pH of the coating solution was 7 (adjusted with sulfuric acid). Details are shown in Table 2.

[0264] The resulting copper surfaces of all the copper foils were then rinsed with water for approximately 30 seconds and dried, resulting in silanized and dried copper surfaces of all the copper foils of Samples 1 to 12.

[0265] Step (ii-a): Annealing step: The copper foils containing the silane-treated copper surfaces of Samples 1 to 12 were then annealed at 130°C for 30 minutes to remove any residual moisture from the surface. These substrates containing copper surfaces were then subjected to a build-up film lamination process (see the following text).

[0266] Step (iii): Applying an organic material to the copper surface of the substrate: In the lamination process, the insulating film (see Table 2) was vacuum laminated onto the copper foil of all samples by using a vacuum laminator in a clean room at room temperature ranging from 20 to 25°C and relative humidity of 50 to 60%.

[0267] The vacuum lamination conditions were as follows: 100°C, vacuum: 3 hPa for 30 seconds, pressure: 0.5 MPa for 30 seconds.

[0268] After lamination, a laminated copper surface was obtained.

[0269] [Table 2]

[0270] Adhesion evaluation by peel strength test: For each sample (1 to 12) obtained after lamination, the peel strength was determined: (1) Early period, (2) After 96 hours of HAST (HAST conditions: 130°C, 85% rh, HAST chamber: EHS-221M). (3) After 12 cycles, IR reflow (thermal reliability, simulation of soldering process with temperature peak at 260°C)

[0271] To determine the peel strength, several strips were prepared from each specimen by adhering each copper foil to a rigid board (of the same size as the copper foil) with the rigid board facing the insulating film, resulting in a copper surface with a structurally reinforced insulating film.

[0272] The resulting copper surfaces with structurally reinforced insulating films were then cured in an oven: copper surfaces with GL102 material at 200°C for 90 minutes, and copper surfaces with GX-T31 material at 190°C for 90 minutes.

[0273] Each copper surface with the structurally reinforced insulating film was then sliced ​​into the strips (10 x 100 mm, Bugard drilling / routing).

[0274] The strips were subjected to a peel force tester (Roell Zwick Z010) to assess the peel strength required to delaminate the copper surface from each of the structurally reinforced insulating films (angle: 90°, speed: 50 mm / min). Typically, the higher the peel strength required to avoid delamination, the better the adhesion.

[0275] The peel strengths of Samples 1 through 12 are shown in Table 3 below.

[0276] [Table 3]

[0277] Experiments show that examples of the present invention exhibit good adhesive strength, expressed herein as peel strength.

[0278] Evaluation of halo and wedge spaces Sample preparation: To evaluate halo, copper samples were prepared by adhering each insulating film to a copper panel, resulting in a copper surface with a structurally reinforced insulating film.

[0279] The resulting copper surfaces with structurally reinforced insulating films were then semi-cured in an oven in two steps: copper surfaces with GL102 material at 130°C for 30 minutes, followed by 175°C for 30 minutes; and copper surfaces with GX-T31 material at 100°C for 30 minutes, followed by 170°C for 30 minutes.

[0280] After completing the lamination and semi-curing processes, the copper panels were UV-laser treated to drill blind microvias (BMVs). The substrates then underwent desmearing and reduction conditioning processes. Specifically, these included a sweller treatment under alkaline conditions using Securiganth MV Sweller (Atotech), a permanganate treatment under alkaline conditions using Securiganth MV Etch P (Atotech), and a reduction conditioner treatment under acidic conditions using Securiganth MV Reduction Conditioner (Atotech). After each process, the samples were rinsed with water.

[0281] The laminated materials exhibit thicknesses of ca. 10 μm in the wedge space and halo, and 35 μm in the case where adhesion is investigated.

[0282] measurement: 1) Halo evaluation The substrates were measured by optical microscopy (200x magnification; see Table 4). A photograph depicting the halo measurements can be found in Figure 1.

[0283] The investigated test blind microvias (BMVs) were fabricated as a test grid using laser drilling technology on a surface-treated and Ajinomoto Buildup Film (ABF) laminated test vehicle. Halo data can be obtained after sending the prepared test vehicle through the entire desmear process described above (sweller, permanganate, reducing conditioner).

[0284] Halo measurements are performed by camera (CCD)-assisted light microscopy. For this, the microscope must be operated in epi-illumination mode. All imaging must be performed using the dark field (DF) filter setting. A magnification of approximately 200x is typically used.

[0285] The fully processed test vehicle should be securely placed on the measurement table, with the BMV capture pad set as the optical focus. The CCD exposure time should be adjusted for maximum possible contrast at the edge of the halo. This should make the capture pad appear as bright as possible.

[0286] The visual diameters of the via hole (or clean capture pad), inner (innermost) and outer (outermost) which make the halo appear as boundaries were measured and recorded according to Figure 2. The actual halo value can then be calculated by using the following relationship: 1. External halo (μm) = (outermost diameter (μm) - via hole diameter (μm)) / 2 2. Internal halo (μm) = (internal diameter of halo (μm) - diameter of via hole (μm)) / 2

[0287] Typically, this process can be repeated at least three times with random test vias to minimize statistical reporting.

[0288] [Table 4]

[0289] Experiments show that embodiments of the present invention exhibit good behavior with regard to avoiding the formation of wedge-shaped spaces, expressed here as halo size.

[0290] 2) Evaluation of wedge-shaped spaces Additionally, the substrates were subjected to focused ion beam (FIB) cutting and subsequent scanning electron microscopy (SEM) measurements, which allows for analysis of copper adhesion in the vicinity of blind microvias (BMVs), also known as wedge spaces.

Claims

1. Formula (I) 【Chemistry 1】 (In the formula, X and Y are NH 2 and E is -NH-(CH 2 ) m -NH-, Z is 【Chemistry 2】 is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, R is independently (CH 2 -CH 2 -O) p - represents T, Independently, p is 0, T represents H or C1 to C5 alkyl. Triazine silane compound.

2. (a) - one or more triazine silane compounds according to claim 1, and optionally one or more triazine silane oligomers, (b) - one or more organic solvents A mixture comprising:

3. (a) - one or more triazine silane compounds according to claim 1, and - optionally one or more triazine silane oligomers, (b) - Optionally, water (c) - one or more water-miscible organic solvents 1. A preservative solution comprising:

4. A working solution having a pH in the range of 2 to 14, the solution comprising: (a) - one or more triazine silane compounds according to claim 1, and optionally one or more triazine silane oligomers, (b) - optionally water; (c) - one or more water-miscible organic solvents wherein the total amount of all the triazine silane compounds of claim 1 and all the triazine silane oligomers combined is 5 wt.-% or less based on the total weight of the working solution.

5. 5. The storage solution of claim 3 or the working solution of claim 4, wherein the one or more water-miscible organic solvents comprise a water-miscible organic solvent selected from the group consisting of C1 to C4 alcohols, ethers, glycol ethers, and mixtures thereof.

6. Formula (II) 【Transformation 5】 (In the formula, X and Y are NH 2 and Z is 【Transformation 6】 is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, R is independently (CH 2 -CH 2 -O) p - represents T, Independently, p is 0, T represents H or C1 to C5 alkyl. A synthesis method for a triazine silane compound of the formula: (i) Formula (III) 【Transformation 7】 obtaining a compound of formula (I), (ii) a silane compound selected from the following group: (ii-a) Silane compound of formula (IV) 【Transformation 8】 and (ii-b) Silane compound of formula (V) OCN-(CH 2 ) n -Si(OR) 3 (V) (In formula (IV) or (V), R is (CH 2 -CH 2 -O) p - represents T, Independently, p is 0, T represents C1 to C5 alkyl; n is an integer ranging from 1 to 12) obtaining a step of (iii) reacting the intermediate of formula (III) with said silane compound in a solvent, resulting in the compound of formula (II) as defined above; and (iv) optionally hydrolyzing the compound of formula (II) obtained in step (iii), so that at least one of R is H; A synthesis method comprising:

7. Use of the working solution according to claim 4 as a surface treatment liquid.

8. 1. A method for increasing the adhesive strength between a metal, metal alloy or metal oxide surface and an organic material surface, comprising the steps of: (i) providing a substrate, the substrate comprising a metal, metal alloy, or metal oxide on at least one surface; (ii) at least a portion of the metal, metal alloy, or metal oxide, A) Formula (I) 【Chemistry 9】 (In the formula, X and Y are NH 2 and E is -NH-(CH 2 ) m -NH-, Z is 【Chemistry 10】 is selected from the group consisting of m is an integer ranging from 2 to 12; n is an integer ranging from 1 to 12, R is independently (CH 2 -CH 2 -O) p represents -Z, Independently, p is 0, T represents H or C1 to C5 alkyl. a triazine silane compound of and / or B) triazine silane oligomers obtained by reacting triazine silane compounds of formula (I) with each other in the presence of water so that the triazine silane oligomer contains at least one silicon-oxygen-silicon moiety. contacting the (iii) applying an organic material so that at least a portion of the metal, metal alloy, or metal oxide that was in contact with the triazine silane compound and / or triazine silane oligomer during step (ii) comes into contact with the applied organic material. A method comprising, in this order:

9. The method of claim 8, wherein the solution further comprises one or more water-miscible organic solvents.

10. 10. The method of claim 9, wherein the one or more water-miscible organic solvents comprise a water-miscible organic solvent selected from the group consisting of C1 to C4 alcohols, ethers, glycol ethers, and mixtures thereof.

11. 11. The method according to claim 9, wherein the total amount of the triazine silane compound and the triazine silane oligomer is 5 wt.-% or less based on the total mass of the solution.

12. 12. The method of claim 9, wherein the solution has a pH in the range of 2 to 14.

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