Surface treatment method, surface treatment agent, method for producing a bond, method for producing a material having a conductive coating, method for producing a material having a coating film formed thereon, and compound

Abstract

To provide a surface treatment method.SOLUTION: An embodiment of the invention is a surface treatment method that forms a conjugate of two substances by interface molecular binding and includes a step for coating one substance with a solution containing one or more kinds of compounds α to set the compounds α on the surface of at least one substance. The compound α is a compound α1 having one or more groups selected from the group consisting of a benzene ring, an alkoxysilyl group, an azido group, an azido sulfonyl group, and a diazomethyl group in one molecule, or a compound α2 obtained by hydrolysis condensation of a hydrolyzable silane compound containing the compound α1.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a surface treatment method, a surface treatment agent, a method for producing a bond, a method for producing a material having a conductive coating, a method for producing a material having a coating film formed thereon, and a compound. [Background technology]

[0002] Compounds having two or more functional groups can form chemical bonds by utilizing the properties of each functional group, and are therefore useful as interfacial molecular bonding agents for interface molecular bonding (IMB), which involves placing a compound at the interface between two substances to bond the two substances through chemical bonds.

[0003] For example, Patent Document 1 describes a method for bonding polymeric substances A and B, which includes the steps of placing a specific interfacial molecular binder on the surface of substance A, irradiating the surface of substance A with ultraviolet light, placing substance B opposite the surface of substance A, and applying force to substances A and B to bond substances A and B. The interfacial molecular binder disclosed in Patent Document 1 is a compound having an azide group, an alkoxysilyl group, and a triazine ring in one molecule, such as 2,4-diazido-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine (hereinafter referred to as "IMB-P").

[0004] Furthermore, Patent Document 2 describes a method for forming a metal film, which includes a step of providing a specific interfacial molecular binder on the surface of a polymeric substance, and a step of providing a metal film on the surface of the substance by a wet plating technique. The interfacial molecular binder disclosed in Patent Document 2 is the same as that disclosed in Patent Document 1.

[0005] Furthermore, Patent Document 3 describes a surface treatment method in which a specific interfacial molecular binder is applied to the surface of a material for the purpose of bonding with resin or metal foil, etc. The interfacial molecular binder disclosed in Patent Document 3 is a compound having an amino group, an alkoxysilyl group, and a triazine ring in one molecule, such as 6-((3-triethoxysilyl)propylamino)-2,4-bis((2-amino)ethylamino)-1,3,5-triazine (hereinafter referred to as "IMB-A").

[0006] Patent Document 4 discloses a bonding laminate in which a specific interfacial molecular binder is disposed on one side of a thermoplastic resin layer, and describes that the interfacial molecular binder is a general compound having an azide group and a group that generates a silanol group by hydrolysis. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 5083926 [Patent Document 2] Patent No. 4936344 [Patent Document 3] Patent No. 5729852 [Patent Document 4] Patent No. 6674594 Summary of the Invention [Problem to be solved by the invention]

[0008] The IMB-P described in Patent Documents 1 and 2 requires irradiation with short-wavelength ultraviolet light, which degrades materials such as resins, during surface treatment using a photochemical reaction. Furthermore, IMB-P is poorly soluble in water, necessitating the use of a flammable solvent such as ethanol. IMB-A described in Patent Document 3 is readily soluble in water and generally suitable for bonding applications, but unsuitable for plating applications. Furthermore, the interfacial molecular bonding agent specifically discussed in the examples of Patent Document 4 is limited to IMB-P. Therefore, the water solubility of the general interfacial molecular bonding agents described in Patent Document 4, their compatibility with various materials such as resins, metals, glass, and ceramics, their suitability for applications such as bonding, plating, and coating, and their photoreaction characteristics are completely unknown. For these reasons, there is a need for new interfacial molecular bonding agents suitable for forming bonds between two materials, surface treatment methods using such interfacial molecular bonding agents, and methods for manufacturing such bonds.

[0009] An object of the present invention is to provide a new compound that undergoes chemical reactions related to surface treatment and interfacial molecular bonding by irradiation with ultraviolet light, or by low-temperature heat treatment alone without ultraviolet light irradiation.A further object of the present invention is to provide a surface treatment agent that is a solution of the above-mentioned compound, and a surface treatment method using such a surface treatment agent.A further object of the present invention is to provide a method for producing a bonded body, a method for producing a material having a conductive coating, and a method for producing a material having a coating film formed thereon. [Means for solving the problem]

[0010] One aspect of the present invention is a surface treatment method comprising a step of applying a solution containing one or more compounds α to the surface of at least one substance, with the aim of forming a bond between two substances through interfacial molecular bonding. The compound α is compound α1 having, in one molecule, a benzene ring, an alkoxysilyl group, and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group, and a diazomethyl group, or compound α2 obtained by hydrolysis and condensation of a hydrolyzable silane compound containing the compound α1.

[0011] Another aspect of the present invention is a surface treatment agent used in the above-mentioned surface treatment method, which is a solution containing one or more compounds α.

[0012] Another aspect of the present invention is a method for producing a conjugate by bonding substance A and substance B, the method comprising: a surface treatment step of treating the surface of substance A or the surfaces of both substances by the above-mentioned surface treatment method; an arrangement step of placing the treated surface of substance B or the surface of substance B opposite the surface of substance A on which compound α is present; and a bonding step of applying force to at least one of substance A and substance B to integrally bond the two substances.

[0013] Another aspect of the present invention is a method for producing a material having a conductive coating, comprising: a surface treatment step of applying an agent containing the compound α to a surface of a material by the above-described surface treatment method; and a coating formation step of applying a conductive coating to the surface of the material on which the compound α is present by electroless plating, vapor deposition, or coating.

[0014] Another aspect of the present invention is a method for producing a substance having a coating film formed thereon, the method comprising: a surface treatment step of applying an agent containing the compound α to the surface of a substance by the surface treatment method; and a coating film formation step of forming a coating film on the surface of the substance where the compound α is present.

[0015] Another aspect of the present invention is a compound α1 represented by the following formula (1) or (2), or a hydrolysis condensation product α2 obtained by hydrolysis condensation of a hydrolyzable silane compound containing the above compound α1: [ka] In formula (1), R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. 2 are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. 1 is an azide group, an azidosulfonyl group, or a diazomethyl group. 1represents a single bond, an ester group, an ether group, a thioether group, an amide group, a urethane group, a urea group, -NHR 3 -, or a group represented by the following formula (3a) or (3b): 3 is an alkyl group having 1 to 6 carbon atoms. Z 1 is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more of -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. m is an integer of 1 to 3. R 1 , X 1 , Y 1 and Z 1 When there are a plurality of R, they each independently satisfy the above definition. 1 At least one of the groups is an alkoxy group having 1 to 12 carbon atoms. In formula (2), multiple R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group, and a plurality of R 4 , R 5 and R 6 At least one of R is an alkoxy group having 1 to 12 carbon atoms. 7 are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. 2 is an azide group, an azidosulfonyl group, or a diazomethyl group. 2 are each independently a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more groups selected from -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. [ka] In formula (3a), R 8 is a hydrogen atom or a methyl group. [Effects of the Invention]

[0016] According to one aspect of the present invention, a new compound can be provided in which a chemical reaction involving surface treatment and interfacial molecular bonding can proceed by irradiation with ultraviolet light, or by low-temperature heat treatment alone without ultraviolet light irradiation. According to another aspect of the present invention, a surface treatment agent that is a solution of the compound described above, and a surface treatment method using such a surface treatment agent can be provided. According to other aspects of the present invention, a method for producing a bonded body, a method for producing a material having a conductive coating, and a method for producing a material having a coating film formed thereon can be provided. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is an overall flow diagram according to one embodiment of the present invention using an electroless plating process. [Figure 2] FIG. 2 is a detailed flow diagram of the pretreatment step in FIG. [Figure 3] FIG. 3 is a detailed flow diagram of the post-treatment process in FIG. [Figure 4] FIG. 4 is a detailed flow diagram of the electroless plating process in FIG. [Figure 5] 5A and 5B are overall flow diagrams according to one embodiment of the present invention using a thermocompression bonding process or a coating film forming process, respectively. [Figure 6] FIG. 6 is an explanatory diagram of the structures of various conjugates produced by a production method according to one embodiment of the present invention. [Figure 7] FIG. 7 is a table showing the results of the peel test. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, embodiments of the present invention will be described in detail. It should be understood that the present invention is not limited to the embodiments described below, but also includes various modifications that are implemented within the scope of the present invention.

[0019] <Surface treatment method> A surface treatment method according to one embodiment of the present invention is a surface treatment method comprising a step of applying a solution containing one or more compounds α to the surface of at least one substance, with the aim of forming a bond between two substances through an interfacial molecular bond, wherein the compound α is compound α1 having, in one molecule, a benzene ring, an alkoxysilyl group, and one or more groups selected from the group consisting of an azide group, an azide sulfonyl group, and a diazomethyl group, or compound α2 obtained by hydrolysis and condensation of a hydrolyzable silane compound containing compound α1. The interfacial molecular bond refers to the bonding of the two substances by chemically bonding each substance to the compound through a chemical reaction via a certain compound at the interface between the two substances, or the bond resulting from this bonding.

[0020] According to this surface treatment method, a surface treatment capable of forming interfacial molecular bonds can be performed by irradiation with ultraviolet rays or by only low-temperature heat treatment without ultraviolet irradiation.

[0021] (Step of providing compound α on the surface of at least one material) In this process, compound α is provided on the surface of at least one material by applying a solution containing one or more compounds α. "Applying" a solution containing compound α to a material means "adhering" or "bringing the solution containing compound α to the surface of the material in a state of contact," and includes not only brushing, but also "adhering" or "bringing the solution to the surface of the material in a state of contact" by methods such as dripping, spraying, spin coating, rolling, inkjet printing, and immersion. Note that after "application," a step of drying the surface of the material on which compound α is present may be added.

[0022] (material) The two substances subjected to the surface treatment method may be made of the same material or different materials. Each substance may be made of multiple materials. Each substance may have a coating or the like formed on its surface. Each substance may be part of an object made of multiple materials. Examples of materials that make up each substance include plating bases, resin materials, conductors such as metals, elastomers, glass, ceramics, etc.

[0023] The plating substrate may be, for example, a Pd catalyst.

[0024] Examples of the resin material include thermoplastic resin and thermosetting resin. Examples of thermoplastic resins include general-purpose resins, engineering resins, and super-engineering resins. Examples of general-purpose resins include polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene (AS), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), and cycloolefin polymer (COP). Examples of engineering resins include polyamide (PA), polyacetal (POM), polycarbonate (PC), polyphenylene ether (PPE (modified PPO)), polybutylene terephthalate (PBT), ultra-high molecular weight polyethylene (U-PE), and polyvinylidene fluoride (PVDF). Examples of super engineering resins include polysulfone (PSU), polyethersulfone (PES), polyphenylene sulfide (PPS), polyarylate (PAR), polyamideimide (PAI), polyetherimide (PEI), polyetheretherketone (PEEK), polyimide (PI), liquid crystal polymer (LCP), and polytetrafluoroethylene (PTFE). Examples of thermosetting resins include phenolic resin (PF), epoxy resin (EP), melamine resin (MF), urea resin (UF), unsaturated polyester resin (UP), alkyd resin, polyurethane (PUR), and thermosetting polyimide (PI). Thermosetting resins are available in various commercial forms, including C-stage (cured) sheets such as polyimide (PI), B-stage (uncured) sheets such as build-up sheets, prepregs, die-bond sheets, and anisotropic conductive sheets (ACF), and A-stage materials such as conductive or insulating compounds, pastes, and inks.

[0025] Examples of conductors include metals such as copper, silver, gold, nickel, aluminum, and silicon, as well as graphite, CNT (carbon nanotubes), and CNF (carbon nanofibers).

[0026] Examples of elastomers include natural rubber, synthetic rubber, urethane rubber, silicone rubber, and fluororubber.

[0027] Examples of glass include ordinary soda glass (white plate glass, etc.), borosilicate glass, lead glass, flint glass, optical glass, and quartz glass.

[0028] Examples of ceramics include aluminum oxide, zirconium oxide, aluminum nitride, silicon carbide, silicon nitride, forsterite, steatite, cordierite, sialon, barium titanate, lead zirconate titanate, ferrite, mullite, and mica.

[0029] The shapes of the two substances are not particularly limited, but the substance on whose surface the compound α is provided (the substance to which a solution containing one or more compounds α is applied; the substance to which the surface treatment is performed) is preferably a non-particulate substrate. 3 That is, the volume of the substance on which the compound α is provided is less than 1 mm 3 More than 1cm is preferable. 3In addition, in the case of a substance on whose surface the compound α is provided, the surface area of ​​one separable substance is preferably 1 mm 2 It is preferable that it is 1cm or more. 2 More preferably, the above is the case. Specific shapes of the substance on whose surface compound α is provided include, for example, a plate, a sheet, a film, a tube, a column, a thread, an amorphous mass, and any other shape formed into a predetermined shape. By performing surface treatment on a substance of such a relatively large size, a bond between two substances can be efficiently obtained.

[0030] (Compound α) Compound α is compound α1 having, in one molecule, a benzene ring, an alkoxysilyl group, and one or more groups selected from the group consisting of an azide group, an azide sulfonyl group, and a diazomethyl group, or compound α2 obtained by hydrolysis and condensation of a hydrolyzable silane compound containing compound α1. Two or more types of compound α can be used, and compound α1 and compound α2 can also be used in combination.

[0031] An alkoxysilyl group refers to a group in which an alkoxy group (oxyhydrocarbon group) is bonded to a silicon atom. An alkoxy group refers to a group in which a hydrocarbon group is bonded to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a vinyloxy group, a phenoxy group, and a benzyloxy group. The number of alkoxy groups bonded to the silicon atom may be 1, 2, or 3, and 3 is preferred. In the alkoxysilyl group, a group other than an alkoxy group may be bonded to the silicon atom, and examples of such a group include an alkyl group, a phenyl group, a hydroxy group, and a hydrogen atom. As the alkoxy group, an alkoxy group having 1 to 3 carbon atoms is preferred, and a methoxy group, an ethoxy group, and a propoxy group are more preferred. Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, and a tribenzyloxysilyl group.

[0032] The alkoxysilyl group contained in compound α can form a chemical bond of the "-Si-OM- type" with inorganic material M, such as a metal, through a chemical reaction. Furthermore, the azide group, azidosulfonyl group, or diazomethyl group contained in compound α can form a chemical bond of the "-NC- type" or other type with organic material M, such as a resin, through a chemical reaction. Here, "chemical bond" refers to a covalent bond, an ionic bond, a bond due to intermolecular forces, or the like, and preferably refers to a covalent bond or an ionic bond. Therefore, whether the substance is organic or inorganic, when compound α is applied to the surface of the substance by coating, if the above-mentioned chemical reaction occurs through heat treatment or ultraviolet irradiation treatment, compound α will be strongly chemically bonded to the substance and supported on the surface of the substance. Furthermore, compound α typically contains an alkoxysilyl group, azide group, azidosulfonyl group, or diazomethyl group that has not yet formed a chemical bond with the substance, making the surface of the substance suitable for forming a strong chemical bond with other substances.

[0033] Compound α is preferably a compound in which one or more groups selected from the group consisting of an azide group, an azide sulfonyl group, and a diazomethyl group are directly bonded to a benzene ring. When an azide group or the like is directly bonded to a benzene ring, the reaction rate of the reaction in which a nitrogen molecule (N2) is eliminated from the azide group or the like by UV irradiation or heat treatment is higher than when the azide group or the like is not directly bonded to the benzene ring. Furthermore, an azide group or the like directly bonded to a benzene ring is characterized by a sufficiently high photolysis reaction rate, even with long-wavelength UV light, compared to an azide group or the like directly bonded to a triazine ring, such as compound IMB-P. That is, in the case of a triazine ring, the photolysis reaction rate has a peak in a certain wavelength range centered on a specific wavelength of short-wavelength UV light, whereas in the case of a benzene ring, the photolysis reaction rate has a peak in a similar wavelength range centered on a specific wavelength of longer-wavelength UV light. Therefore, by using compound α in which an azide group or the like is directly bonded to a benzene ring, it is possible to perform surface treatment efficiently even when irradiating the material to be surface treated (e.g., fluororesin) with long-wavelength ultraviolet light that does not significantly deteriorate the material.

[0034] (Compound α1) The compound α1 is preferably a compound represented by the following formula (1) or (2).

[0035] [ka]

[0036] In formula (1), R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. 2 are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. 1 is an azide group, an azidosulfonyl group, or a diazomethyl group. 1 represents a single bond, an ester group, an ether group, a thioether group, an amide group, a urethane group, a urea group, -NHR 3 -, or a group represented by the following formula (3a) or (3b): 3 is an alkyl group having 1 to 6 carbon atoms. Z 1 is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more of -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. m is an integer of 1 to 3. R 1 , X 1 , Y 1 and Z 1 When there are a plurality of R, they each independently satisfy the above definition. 1 At least one of the groups is an alkoxy group having 1 to 12 carbon atoms.

[0037] In formula (2), multiple R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group, and a plurality of R 4 , R 5 and R 6At least one of R is an alkoxy group having 1 to 12 carbon atoms. 7 are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. 2 is an azide group, an azidosulfonyl group, or a diazomethyl group. 2 are each independently a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more groups selected from -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms.

[0038] [ka]

[0039] In formula (3a), R 8 is a hydrogen atom or a methyl group.

[0040] R 1 , R 4 , R 5 and R 6 Examples of the alkyl group having 1 to 12 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. R 1 , R 4 , R 5 and R 6 Examples of the alkoxy group having 1 to 12 carbon atoms represented by the formula include the alkoxy groups described above. R 2 and R 7 Examples of the halogen represented by the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. R 2 and R 7 The monovalent organic group represented by the formula (I) includes a monovalent hydrocarbon group, an alkoxy group, -Y 1 -Z 1 -Si-R 1 3(Y 1 , Z 1 and R 1 is Y in equation (1). 1 , Z 1 and R 1) and a group represented by -COO-N-(-Z 2 -SiR 4 R 5 R 6 )2(Z 2 , R 4 , R 5 and R 6 is Z in equation (2) 2 , R 4 , R 5 and R 6 and the like), and a group represented by the formula (14) described below. R 3 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0041] The preferred forms of the compound represented by formula (1) are as follows: R 1 As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable, an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkoxy group having 1 to 3 carbon atoms is even more preferable. R 2 is preferably a hydrogen atom. X 1 As X, an azide group and an azidosulfonyl group are preferred. 1 is Y 1 It is preferably bonded at the para or meta position to the group containing the above. Y 1 As the alkyl group, an amide group is preferred, and an amide group represented by *-CONH- (* indicates the bonding site to the benzene ring) is more preferred. Z 1 As the alkylene group, an alkylene group having 2 to 12 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable. m is preferably 3.

[0042] The preferred forms of the compound represented by formula (2) are as follows: R 4 , R 5 and R 6As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable, an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkoxy group having 1 to 3 carbon atoms is even more preferable. R 7 is preferably a hydrogen atom. X 2 As X, an azide group and an azidosulfonyl group are preferred. 2 is -COO-N-(-Z 2 -SiR 4 R 5 R 6 It is preferred that the bond is at the para or meta position relative to the group represented by 2. Z 2 As the alkylene group, an alkylene group having 2 to 12 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable.

[0043] The compound α1 is also preferably a compound represented by the following formula (11), (12) or (13) (hereinafter generally referred to as "IMB-K").

[0044] [ka]

[0045] In formulas (11) to (14), X 10 , X 11 and X 12 are each independently an azide group, an azidosulfonyl group, or a diazomethyl group. 11 and E 12 are each independently >C=O, a methylene group, or an alkylene group having 2 to 12 carbon atoms. 11 , Y 12 , Y 13 and Y 14 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or -J 13 -Si(OA 10 ) 3-k (R 10 ) k It is a group represented by J 11 , J 12 and J 13are each independently a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing an oxygen atom (—O—) between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. 15 -R 15 or -OA 15 Y is a group represented by the formula: 16 -R 16 or -OA 16 A is a group represented by the formula: 10 , A 15 and A 16 are each independently an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a hydrogen atom. 10 , R 15 and R 16 are each independently an alkyl group having 1 to 4 carbon atoms or a benzyl group. k is an integer of 0 or more and 2 or less. Q 10 is a hydrogen atom or an organic group represented by formula (4). In formulas (11) and (12), Y 11 and Y 12 and at least one of Y contains an oxygen atom. 15 and Y 16 and at least one of them contains an oxygen atom. In formula (13), the group X bonded to the benzene ring 11 and X 12 are each independently bonded to the para or meta position.

[0046] (Method for synthesizing compound α1) The synthesis method of compound α1 is not particularly limited, but for example, it can be obtained by reacting a silane coupling agent A having an alkoxysilyl group and a reactive group a other than an alkoxysilyl group with a compound B having a reactive group b capable of bonding with the reactive group a, a benzene ring, and one or more groups selected from the group consisting of an azide group, an azide sulfonyl group, and a diazomethyl group, by a known method. Examples of combinations of the reactive group a and the reactive group b include combinations of an isocyanate group, an epoxy group, an amino group, etc., with a carboxy group.

[0047] Examples of the silane coupling agent A include 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, bis(3-aminopropyl)diethoxysilane, and bis(3-aminopropyl)dimethoxysilane.

[0048] Examples of compound B include azidobenzoic acid, azidosulfonylbenzoic acid, diazomethylbenzoic acid, 3-(4-azidophenyl)propionic acid, chlorides of these carboxylic acids, azidoaniline, and azidophenol.

[0049] (Compound α2) Compound α2 obtained by hydrolysis and condensation of a hydrolyzable silane compound containing compound α1 has a structural unit A derived from compound α1. Compound α2 may be obtained by another synthesis method as long as its structure is the same as that of the compound obtained by hydrolysis and condensation of a hydrolyzable silane compound containing compound α1. Compound α2 is preferably a silsesquioxane compound. Compound α2 preferably has at least one of an alkoxysilyl group and a hydroxysilyl group, and more preferably has a hydroxysilyl group.

[0050] Examples of the structural unit A include a structural unit represented by the following formula (4): The structural unit represented by the following formula (4) is a structural unit derived from a compound α1 represented by formula (1) in which m is 3.

[0051] [ka]

[0052] In formula (4), R 1 , R 2 , X 1 , Y 1 and Z 1 is R in Eq. (1) 1 , R 2 , X 1 , Y 1 and Z 1 a is an integer from 0 to 2.

[0053] R in equation (4) 1 , R 2 , X 1 , Y 1 and Z 1 Specific examples of R in formula (1) 1 , R 2 , X 1 , Y 1 and Z 1 The specific example is the same as that of the formula (4). 1 is preferably a hydroxy group or an alkoxy group, more preferably a hydroxy group, from the viewpoint of reactivity, etc. a is preferably 1.

[0054] The lower limit of the content of the structural unit A relative to all structural units in the compound α2 is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%, while the upper limit of this content is preferably 90 mol%, more preferably 80 mol%, and even more preferably 70 mol%.

[0055] Compound α2 preferably has a structural unit B containing an amino group (—NH2). When compound α2 has the structural unit B, there is an advantage that the water solubility of compound α2 is improved. Examples of hydrolyzable silane compounds that provide the structural unit B include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0056] The lower limit of the content of the structural unit B relative to all structural units in the compound α2 is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%, while the upper limit of this content is preferably 90 mol%, more preferably 80 mol%, and even more preferably 70 mol%.

[0057] The compound α2 may have a structural unit C other than the structural unit A and the structural unit B. Examples of hydrolyzable silane compounds that provide the structural unit C include compounds represented by the following formula (C).

[0058] [ka]

[0059] In formula (C), R d is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an organic group having a reactive group, and a plurality of R d may be the same or different. e is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a plurality of R e may be the same or different, and x represents an integer of 0 to 3. Furthermore, these alkyl groups, alkenyl groups, and aryl groups may be either unsubstituted or substituted, and can be selected depending on the properties.

[0060] R d and R e Specific examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, an n-decyl group, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-glycidoxypropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a [(3-ethyl-3-oxetanyl)methoxy]propyl group, a 3-mercaptopropyl group, and a 3-isocyanatopropyl group. dSpecific examples of the alkenyl group represented by R include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. d and R e Specific examples of the aryl group represented by R include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a p-methoxyphenyl group, a 1-(p-hydroxyphenyl)ethyl group, a 2-(p-hydroxyphenyl)ethyl group, a 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl group, and a naphthyl group. e A specific example of the acyl group represented by the formula (I) is an acetyl group.

[0061] In formula (C), when x=0 it is a tetrafunctional silane, when x=1 it is a trifunctional silane, when x=2 it is a difunctional silane, and when x=3 it is a monofunctional silane.

[0062] Specific examples of the hydrolyzable silane compound represented by formula (C) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltriethoxysilane. Propyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, p-methoxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,Examples of suitable silanes include trifunctional silanes such as 4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic acid; bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, and (3-glycidoxypropyl)methyldiethoxysilane; and monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane.

[0063] The hydrolyzable silane compounds may be used alone or in combination of two or more.

[0064] The weight average molecular weight (Mw) of the compound α2 is not particularly limited, but is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000, in terms of polystyrene measured by GPC (gel permeation chromatography).

[0065] (Method for synthesizing compound α2) Compound α2 can be obtained by (i) hydrolysis and condensation of a hydrolyzable silane compound containing compound α1, or (ii) a method of obtaining a hydrolyzed condensate of a hydrolyzable silane compound by reacting a compound having structural unit B with "a compound X having a reactive group capable of bonding with an amino group, a benzene ring, and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group, and a diazomethyl group" (e.g., azidobenzoic acid, azidosulfonylbenzoic acid, diazomethylbenzoic acid, etc.). In the above method (ii), the amino group in structural unit B reacts with compound X to form structural unit A.

[0066] A general method can be used for the hydrolysis and condensation to obtain compound α2. For example, a solvent, water, and optionally a catalyst are added to a hydrolyzable silane compound, and the mixture is heated and stirred at 50 to 150°C for approximately 0.5 to 100 hours. During stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be removed by distillation, if necessary.

[0067] The catalyst to be added as needed is not particularly limited, but acid catalysts and base catalysts are preferably used. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, ion exchange resins, etc. Specific examples of base catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having an amino group, ion exchange resins, etc. The amount of catalyst added is preferably 0.01 to 10 parts by mass per 100 parts by mass of the hydrolyzable silane compound.

[0068] From the viewpoint of storage stability of the solution containing compound α2, it is preferable that the solution after hydrolysis and condensation does not contain a catalyst, and the catalyst can be removed as necessary. There are no particular limitations on the removal method, but preferred examples include water washing and / or treatment with an ion exchange resin. Water washing is a method in which the solution is diluted with an appropriate hydrophobic solvent, then washed several times with water, and the resulting organic layer is concentrated using an evaporator. Treatment with an ion exchange resin is a method in which the solution is brought into contact with an appropriate ion exchange resin.

[0069] The solvent used in the hydrolysis condensation reaction is not particularly limited, but a compound having an alcoholic hydroxyl group is preferably used. The compound having an alcoholic hydroxyl group is not particularly limited, but a compound having a boiling point of 110 to 250°C under atmospheric pressure is preferably used.

[0070] Specific examples of compounds having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, etc. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

[0071] Other solvents may be used together with the compound having an alcoholic hydroxyl group. Examples of other solvents include esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, and acetylacetone, ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol dimethyl ether, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0072] (Specific examples of compound α) More specifically, the compound α can include compounds represented by the following formula (15), (16), (17), (18a), (18b), (18c) or (19).

[0073] [ka]

[0074] [ka]

[0075] The compound represented by formula (19) is a silsesquioxane compound composed of 1, m, and n units of the three types of structural units shown in formula (19) bonded together, where X is an azide group, 1 is an integer of 0 or greater, m is an integer of 1 or greater, and n is an integer of 0 or greater. a , R b and R c are each independently a hydrogen atom, a hydroxy group, an alkoxy group, or -O-. f is a hydrogen atom, a hydroxy group, an alkoxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an organic group having a reactive group, and a plurality of R f may be the same or different. These alkyl, alkenyl, and aryl groups may be either unsubstituted or substituted, and can be selected depending on the properties. The compound represented by formula (19) ("IMB-4KP") is water-soluble, for example, when l:m:n = 1:1:0. In general, this compound is water-soluble except when the ratio l / (m+n) is close to 0 (e.g., less than 0.2 or less than 0.1). That is, from the viewpoint of water solubility, the lower limit of the ratio l / (m+n) is preferably 0.2, more preferably 0.5, and even more preferably 1. The upper limit of the ratio l / (m+n) is preferably 5, more preferably 2.

[0076] (Solution: Surface treatment agent) A solution containing one or more compounds α is a so-called surface treatment agent. That is, a surface treatment agent according to one embodiment of the present invention is a surface treatment agent used in the surface treatment method, and is a solution containing one or more compounds α. The surface treatment agent (a solution containing one or more compounds α) may be, for example, a primer treatment agent for performing a primer treatment on a non-particulate substrate.

[0077] The solution (surface treatment agent) contains a solvent. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellosolve, and carbitol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, octane, decane, dodecane, and octadecane; esters such as ethyl acetate, methyl propionate, and methyl phthalate; ethers such as tetrahydrofuran (THF), ethyl butyl ether, anisole, and propylene glycol monomethyl ether acetate (PGMEA); and water. The solvents exemplified for use in hydrolysis and condensation can also be used. Among these, alcohols, ethers, and water are preferred. The solvents can be used alone or in combination.

[0078] The solution may contain components other than compound α and the solvent. Examples of such components include surfactants. However, the content of compound α relative to the total solid content (all components other than the solvent) in the solution is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The content of compound α relative to the total solid content in the solution may be 100% by mass.

[0079] The surface treatment agent can be used as a plating surface treatment agent, a plating pretreatment agent, a painting pretreatment agent such as a pretreatment agent for difficult-to-paint materials, an insert molding agent, etc. The surface treatment agent can also be used as a surface treatment agent for producing assemblies such as semiconductor packages, power modules, electromagnetic wave shields, lithium battery electrodes, lithium battery components, automotive components, printed wiring boards, LED modules, waveguides, various circuit boards (high-speed transmission boards, heat sink circuit boards, flexible copper-clad laminates (FCCLs), ceramic circuit boards, built-up boards, conductive circuits, etc.), electronic devices, metal-resin bonding materials or sealing materials (metal-resin bonding materials or sealing materials for electronic devices, conductive circuits, foods, cosmetics, pharmaceuticals, etc.).

[0080] (Other processes, etc.) The surface treatment method preferably further comprises, before the step of providing the compound α on the surface of at least one of the materials, a step of subjecting the at least one material to one or more pretreatments selected from the group consisting of cleaning treatment, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, and itro treatment. Such pretreatments can further enhance the adhesion of the bonded structure.

[0081] The surface treatment method preferably further comprises a step of irradiating the compound α present on the surface of at least one of the materials with ultraviolet light after the step of providing the compound α on the surface of at least one material. The azide group (-N3) and the like are decomposed by the action of ultraviolet light, releasing nitrogen molecules (N2). The remaining N atoms are activated, and a strong chemical bond is formed between the C atoms and the N atoms on the surface of the material. Therefore, the compound α supported on the surface of the material undergoes a photochemical reaction and forms a chemical bond with the surface by ultraviolet irradiation. At this time, ultraviolet irradiation can be performed by selecting an ultraviolet wavelength that is less likely to deteriorate the material, such as by irradiating ultraviolet light from an LED light source. The azide group of the compound α also undergoes a chemical reaction in response to ultraviolet irradiation, releasing nitrogen molecules (N2), forming a strong chemical bond with the material. Specifically, irradiation is preferably performed using an ultraviolet lamp with a wavelength range of 230 to 300 nm, preferably 240 to 280 nm.

[0082] Preferably, the surface treatment method further comprises a step of heat-treating the compound α present on the surface of at least one of the materials after the step of providing the compound α on the surface of at least one of the materials. The azide group (-N3) or the like is decomposed by heating, releasing nitrogen molecules (N2). The remaining N atoms or the like become activated, and a strong chemical bond is formed between the C atoms or the like on the surface of the material and the N atoms or the like. Therefore, the compound α supported on the surface of the material and the surface undergo a chemical reaction by the heat treatment, forming a chemical bond. The heat treatment temperature is preferably 70°C or higher and 150°C or lower. In one embodiment, the heat treatment temperature may be 80°C or higher and 120°C or lower, and more preferably 90°C or higher and 110°C or lower. The ultraviolet irradiation treatment and the heat treatment may be used in combination. When the ultraviolet irradiation treatment and the heat treatment are used in combination, either one may be performed first, or they may be performed simultaneously. Furthermore, the ultraviolet irradiation treatment and the heat treatment may be repeatedly applied, with or without being combined with other treatments such as a cleaning treatment.

[0083] The surface treatment method preferably further includes a step of providing a compound β on the surface of at least one of the substances prior to the step of providing the compound α on the surface of the at least one of the substances, and the compound β is preferably a compound having, in one molecule, a functional group capable of forming a chemical bond with at least one of the substances through a chemical reaction and a functional group capable of forming a chemical bond with the compound α through a chemical reaction.

[0084] By using compound β as an intermediary, the types and ratios of functional groups of compound α appearing on the surface of the substance carrying compound α can be controlled, and the adhesive strength of the bonded body formed by laminating, plating, film-forming, or the like with another substance after the surface treatment can be increased.

[0085] Examples of compound β include amine-based aliphatic silane coupling agents such as 3-(triethoxysilyl)propylamine, amine-based aromatic silane coupling agents such as IMB-A, azide-based aliphatic silane coupling agents such as (3-azidopropyl)triethoxysilane, azide-based aromatic silane coupling agents such as IMB-P and IMB-K, thiol-based aliphatic silane coupling agents such as 3-(triethoxysilyl)propanethiol, and thiol-based aromatic silane coupling agents such as 6-(3-triethoxysilylpropylamino)-1,3,5-triazine-2,4-dithiol monosodium salt (hereinafter referred to as "IMB-N"). Compound β may be the same as compound α.

[0086] The surface treatment method preferably includes a step of providing compound α on the surface of at least one material, followed by a step of providing compound β on the surface of the first material. Preferably, compound β is a compound having, within one molecule, a functional group capable of chemically bonding with compound α through a chemical reaction and a functional group capable of chemically bonding with the other material through a chemical reaction. Even with this method, the presence of compound β can control the type and proportion of functional groups of compound β appearing on the surface of the material carrying compound α, thereby enhancing the adhesion strength of the bonded structure formed by laminating, plating, or film-forming the other material after the surface treatment. Specific examples of compound β used in this case include the same compounds as those described above. Furthermore, compound β may be the same as compound α.

[0087] The surface treatment method further includes a step of providing compound α on the surface of at least one substance, in which the compound α is provided on the surface of one substance and compound β is provided on the surface of the other substance. Preferably, the compound β is a compound having, within one molecule, a functional group capable of chemically bonding with the compound α through a chemical reaction and a functional group capable of chemically bonding with the other substance through a chemical reaction. By providing compound α on the surface of one substance and compound β on the other substance, the adhesive strength of the bond formed after the surface treatment can be increased. Specific examples of the compound β used in this case include the same compounds as those described above. Furthermore, compound β may be the same as compound α.

[0088] A surface treatment method according to another embodiment of the present invention includes a step of applying an agent containing compound α to the surface of a coating film of a material on which a coating film has been formed, by the surface treatment method according to one embodiment of the present invention. In this way, the surface treatment method according to one embodiment of the present invention can also be applied to the surface of a coating film of a material on which a coating film has been formed.

[0089] <Method of manufacturing the conjugate> A method for producing a conjugate according to one embodiment of the present invention is a method for producing a conjugate by bonding substances A and B, and includes the following steps: a surface treatment step of treating the surface of substance A or the surfaces of both substances by the surface treatment method according to one embodiment of the present invention; an arrangement step of placing the treated surface of substance B or the surface of substance B opposite the surface of substance A on which compound α is present; and a bonding step of applying force to at least one of substance A and substance B, thereby bonding the two substances together.

[0090] According to this method for producing a conjugate, a conjugate can be produced in which both substances are strongly chemically bonded via compound α. In the bonding step, a force is applied in the direction in which substance A and substance B face each other (the direction in which substance A and substance B come into close contact with each other). The same applies to the bonding steps in other embodiments.

[0091] In the method for producing the bonded body, the bonding step is preferably carried out at a temperature of 40° C. or higher and 350° C. or lower, and more preferably at a temperature of 90° C. or higher and 250° C. or lower. By carrying out the bonding step at such a temperature, a more strongly bonded bonded body can be obtained.

[0092] A method for producing a bonded body according to another embodiment of the present invention includes a surface treatment step in which the surface of a coating film formed on substance A is treated using a surface treatment method according to one embodiment of the present invention; an arrangement step in which the surface of substance B is arranged opposite the surface of the coating film; and a bonding step in which force is applied to at least one of substance A and substance B to bond the two substances together.

[0093] A method for producing a bonded body according to another embodiment of the present invention includes a surface treatment step of treating the surface of substance B using a surface treatment method according to one embodiment of the present invention, an arrangement step of arranging the surface of a coating film of substance A, on which a coating film has been formed, facing the surface of substance B, and a bonding step of applying force to at least one of substance A and substance B to bond the two substances together.

[0094] <Method of manufacturing a material having a conductive coating> A method for producing a material having a conductive coating according to one embodiment of the present invention includes a surface treatment step of applying an agent containing the compound α to the surface of the material by the surface treatment method according to one embodiment of the present invention, and a coating formation step of applying a conductive coating to the surface of the material on which the compound α is present by electroless plating, vapor deposition, or coating.

[0095] According to this method for producing a material having a conductive coating, it is possible to produce a material having a conductive coating in which the material and the conductive coating are firmly chemically bonded via compound α. One example of a method for providing a conductive coating by coating is to apply a conductive paste to the surface of a material containing compound α, and then heat the paste to sinter and harden it, thereby forming a conductive coating on the surface. Examples of conductive pastes that can be used include low-temperature sintering silver paste, silver nanopaste, and silver nanoink.

[0096] <Method for manufacturing a material with a coating film> A method for producing a substance having a coating film formed thereon according to one embodiment of the present invention includes a surface treatment step of applying an agent containing compound α to the surface of the substance by the surface treatment method according to one embodiment of the present invention, and a coating film formation step of forming a coating film on the surface of the substance on which compound α is present.

[0097] According to the method for producing a material having a coating film formed thereon, it is possible to produce a material having a coating film formed thereon, in which the material and the coating film are firmly chemically bonded via compound α. Here, examples of methods for forming a coating film include film formation by thermal curing of a liquid material, film formation by ultraviolet (UV) curing of a liquid material, film formation by moisture curing of a liquid material, film formation by drying of a solvent in a liquid material, film formation by room temperature curing caused by mixing of materials, and film formation by room temperature curing caused by contact of a liquid material with air.

[0098] <Compound> A compound according to one embodiment of the present invention is a compound α1 represented by the above formula (1) or (2), or a hydrolysis condensation product α2 obtained by hydrolysis condensation of a hydrolyzable silane compound containing the above compound α1. The specific form of the compound is as described above.

[0099] <Surface treatment agent> A surface treatment agent according to one embodiment of the present invention includes the compound according to one embodiment of the present invention. Specific forms of the surface treatment agent are as described above.

[0100] Hereinafter, as one embodiment of the present invention, a method for manufacturing a material having a conductive coating, a method for manufacturing a bonded body using a thermocompression bonding process, a method for manufacturing a material having a coating formed thereon, and the resulting bonded body will be specifically described.

[0101] <1. Overall flow of the manufacturing method for a material having a conductive coating> 1 is an overall flow diagram of a method for producing a material having a conductive coating according to one embodiment of the present invention. This embodiment, in which a conductive coating is formed on a material using electroless plating, is composed of a surface treatment step Sst in which a surface treatment is performed on the surface of the material, and a coating formation step Sc in which a conductive coating is formed on the surface of the surface-treated material.

[0102] <1-1. Surface treatment process Sst (when electroless plating is used)> The surface treatment process Sst includes a degreasing and cleaning process S1, a pre-treatment process S2, an IMB supporting process (also simply referred to as the "supporting process") S3, a post-treatment process S4, step S5 for determining whether or not to repeat processes S3 and S4, and a post-IMB heat treatment process S6.

[0103] The degreasing and cleaning step S1 is a step of cleaning the substance using a solvent, etc. For example, the substance is immersed in a solvent such as acetone or ethanol, subjected to ultrasonic cleaning, and then dried.

[0104] The pretreatment step S2 is a step of pretreating the substance. As shown in Fig. 2, the pretreatment step S2 includes a main pretreatment step S21 and a post-pretreatment cleaning step S22 in which the substance that has been subjected to the main pretreatment step is immersed in a cleaning solvent such as a silicon cleaner or an acid cleaner and ultrasonically cleaned.

[0105] In the main pretreatment step S21, one or more treatments selected from the group consisting of plasma treatment in which the substance is treated with plasma such as oxygen plasma or atmospheric plasma, corona discharge treatment in which the surface of the substance is irradiated with corona discharge, acid treatment, alkali treatment, ultraviolet irradiation treatment, itro treatment in which the surface of the substance is exposed to the combustion flame of combustion gas mixed with a coupling agent such as a silane coupling agent, and defluorination treatment in which the substance is immersed in an alkali metal solution to defluorinate.

[0106] The IMB supporting treatment step S3 is a step for performing treatment for interface molecular bonding (IMB). Interface molecular bonding generally refers to a technique in which a compound (assumed to be compound α) is interposed at the interface between two substances (substance A and substance B), and a chemical reaction is performed to chemically bond substance A to compound α, and substance B to compound α, thereby chemically bonding substances A and B via compound α. Here, the chemical bond is preferably a covalent bond or an ionic bond.

[0107] Specifically, the IMB loading treatment step S3 is a step in which a solution containing compound α (surface treatment agent) is applied to the material treated in the pretreatment step S2, thereby carrying out a treatment to load compound α onto the surface of the material. For example, compound α is loaded onto the surface of the material by immersing the material in a solution containing compound α and then drying it. In other words, compound α is provided on the surface of the material, and compound α is present on the surface of the material.

[0108] The post-treatment step S4 is a step of subjecting the substance to at least one of ultraviolet irradiation treatment and heat treatment in order to chemically bond the substance and compound α through a chemical reaction. As shown in Fig. 3, the post-treatment step S4 includes step S41 of determining whether to perform ultraviolet irradiation treatment, step S42 of irradiating the surface of the substance supporting compound α with ultraviolet light having a predetermined wavelength distribution and intensity for a predetermined time if the ultraviolet irradiation treatment is to be performed, step S43 of determining whether to perform heat treatment, step S44 of maintaining the surface of the substance supporting compound α at a predetermined temperature for a predetermined time if the treatment is to be performed, step S45 of determining whether to perform cleaning, and step S46 of cleaning the surface of the substance with a solvent such as ethanol or acetone to remove unreacted compound α and by-products if the cleaning treatment is to be performed.

[0109] Step S5 is a step for determining whether or not repetitive processing is necessary. If repetitive processing is necessary, the IMB loading processing step S3 and post-processing step S4 are repeated. If repetitive processing is not necessary, the post-IMB heat treatment step S5 is performed.

[0110] The post-IMB heat treatment step S6 is a step for chemically bonding the substance and compound α through a chemical reaction, and is a step of performing heat treatment at a predetermined heat treatment temperature and heat treatment time. The heat treatment temperature is preferably 80°C or higher and 250°C or lower, and the heat treatment time is preferably 3 minutes or higher and 60 minutes or lower. Note that if the most recently performed post-treatment step S4 includes the heat treatment step S44 but does not include the cleaning step S46, the heat treatment step S44 is considered to be the post-IMB heat treatment step S5.

[0111] <1-2. Coating formation process Sc (when using electroless plating)> In an embodiment of the present invention in which a conductive coating is formed using electroless plating, the coating formation process Sc includes an electroless plating process S7 and, optionally, an electrolytic plating process S8, as shown in Fig. 1. For example, if a thicker plating film is required, the electroless plating process S7 may be followed by the electrolytic plating process S8 to increase the thickness. Examples of metals that can be electroplated include Cu, Ni, Ag, Pd, Au, Pt, Zn, Cr, Sn, and Bi.

[0112] As shown in FIG. 4, the electroless plating process S7 includes a pre-dip process S71, a catalyst application process S72, an accelerator process S73, an electroless plating process S74, and an annealing process S75.

[0113] In the pre-dip step S71, the material that has undergone the post-IMB heat treatment step S5 is immersed in a pre-dip liquid. Subsequently, in the catalyst application step S72, the material is immersed in a catalyst liquid to apply a catalyst such as Pd. The catalyst liquid is, for example, Cataposit 44 (manufactured by Rohm & Haas Electronic Materials Co., Ltd.). Subsequently, in the accelerator step S73, the material is immersed in an accelerator liquid for accelerator treatment to remove Sn colloids and activate the catalyst. The accelerator liquid is, for example, hydrochloric acid of a predetermined concentration, for example, 0.1 to 10 v / v%.

[0114] Next, in the electroless plating step S74, the material is subjected to electroless plating. The metal to be plated is, for example, Cu, Ni, etc. The formed plating film is chemically bonded to the material through interfacial molecular bonds via compound α carried on the surface of the material. Next, in the annealing step S75, an annealing treatment is performed at a predetermined temperature for a predetermined time. The predetermined temperature and predetermined time are, for example, 90 to 130°C and 3 to 60 minutes. The annealing treatment reduces plating stress and improves peel strength.

[0115] <2. Overall flow of the method for manufacturing a bonded body using thermocompression bonding> Figure 5A is an overall flow diagram of a method for manufacturing a bonded body of two substances A and B according to one embodiment of the present invention. This embodiment, which uses thermocompression bonding to form a bonded body of two substances, includes a surface treatment process Sst in which a surface of at least one substance A is subjected to a surface treatment, a placement process Sp in which the surface of substance B is placed opposite the surface of substance A, and a bonding process Su in which heat and force are applied to at least one of substances A and B to bond the two substances together. The placement process Sp and bonding process Su are collectively referred to as the thermocompression bonding process Shp.

[0116] <2-1. Surface treatment process Sst (when using thermocompression bonding)> In this embodiment, the surface treatment step Sst performed on at least one substance is the same as that in the embodiment shown in Figure 1, so its description will be omitted. Note that the surfaces of both substances may be subjected to surface treatment, or different types of compound α and compound β may be provided on the surfaces of the respective substances by surface treatment, or compound α may be provided on the surface of one substance by surface treatment and then compound β may be provided, or compound β may be provided on the surface of one substance by surface treatment and then compound α may be provided. Furthermore, one or more substances may be substances on whose surfaces a coating film is formed, and the surfaces of the one or more coating films may each be subjected to the surface treatment step Sst.

[0117] <2-2. Placement process Sp> In the placement step Sp, the surface of substance B is placed opposite the surface of substance A that has been subjected to the surface treatment.

[0118] <2-3. Bonding process Su> In the bonding step Su, a predetermined pressure is applied to at least one of substance A and substance B for a predetermined time at a predetermined temperature to bond the two substances. Heating promotes a chemical reaction involving interfacial molecular bonding via compound α, resulting in a strong chemical bond between substance A and substance B. The predetermined time, temperature, and pressure are, for example, 3 to 60 minutes, 90 to 250°C, and 0.1 to 10 MPa. At least one of the substances may be a conductive piece. Examples of the conductive piece include electrolytic thin sheets or rolled thin sheets of various metals, and graphite sheets.

[0119] <3. Overall flow of manufacturing method for material with coating film> Fig. 5B is an overall flow diagram of a method for producing a material having a coating film formed thereon according to one embodiment of the present invention. This embodiment comprises a surface treatment step Sst for performing a surface treatment on the surface of the material, and a coating film formation step Sf for forming a coating film on the surface of the surface-treated material.

[0120] <3-1. Surface treatment process Sst (when forming a coating film)> In this embodiment, the surface treatment step Sst performed on the substance is the same as that in the embodiment shown in FIG. 1, and therefore the description thereof will be omitted.

[0121] <3-2. Paint film formation process Sf> In this embodiment, as shown in FIG. 5B, the coating film formation process Sf includes a coating process S96 in which a liquid material is applied to the surface of the material that has been surface-treated in the surface treatment process Sst, and a curing process S97 in which the liquid material is cured on the surface to form a film. Here, "applying" a liquid material refers to "adhering" or "bringing the liquid material into contact with" the surface of the material, and includes not only extrusion but also brushing, dripping, spraying, spin coating, rolling, inkjet printing, and immersion. Examples of film formation methods include thermal curing of the liquid material, ultraviolet (UV) curing of the liquid material, moisture curing of the liquid material, drying of the solvent in the liquid material, room-temperature curing caused by mixing the materials, and room-temperature curing caused by contact of the liquid material with air. During the film formation process, a chemical reaction involving interfacial molecular bonding via compound α progresses, and the substance and the formed coating film are firmly bonded by chemical bonding. As the liquid material, for example, a liquid resin such as liquid polyimide can be used.

[0122] <4. Combined body> FIG. 6 shows the structures of various conjugates produced by a production method according to one embodiment of the present invention.

[0123] Fig. 6A shows that compound α is provided on the surface of substance A by a surface treatment method according to one embodiment of the present invention, and then substance B is placed opposite the surface of substance A to form a bonded body in which the two substances are bonded by interfacial molecular bonding via compound α. Substance B is placed opposite the surface of substance A by various methods shown in the various aspects of the present invention, such as plating, vapor deposition, sputtering, coating film formation, and bonding.

[0124] Figure (6B) shows that compound α is applied to the surface of substance A by a surface treatment method according to one embodiment of the present invention, and then compound β is applied to the surface of substance A where compound α is present by a method such as ITO treatment, and further substance B is placed opposite the surface of substance A to form a bonded body in which the two substances are bonded by an interfacial molecular bond, which is a chemical bond via compounds α and β. Substance B is placed opposite the surface of substance A by a method such as plating, vapor deposition, sputtering, coating film formation, or bonding.

[0125] Figure (6C) shows that compound β is provided on the surface of substance A by a method such as ITO treatment, and then compound α is provided on the surface of substance A where compound β of substance A is present by a surface treatment method according to one embodiment of the present invention, and further substance B is placed opposite the surface of substance A to form a bonded body in which the two substances are bonded by an interfacial molecular bond, which is a chemical bond via compound β and compound α. Substance B is placed opposite the surface of substance A by a method such as plating, vapor deposition, sputtering, coating film formation, or bonding.

[0126] Figure (6D) shows that compound α is provided on the surface of substance A by a surface treatment method according to one embodiment of the present invention, compound β is provided on the surface of substance B by a method such as ITO treatment, and the surface of substance B is placed opposite the surface of substance A, forming a bonded body in which the two substances are bonded by an interfacial molecular bond, which is a chemical bond via compound α and compound β. Substance B is placed opposite substance A by a method such as bonding.

[0127] Figures (6E) and (6F) are schematic explanatory diagrams showing that when substance A' on which coating film C is formed is regarded as substance A, and the surface of coating film C is regarded as the surface of substance A facing substance B, a bond of the form shown in each of Figures (6A) to (6D) can be formed.

[0128] The combined body can be used as a semiconductor package, a power module, an electromagnetic wave shield, an electrode for a lithium battery, a lithium battery component, an automobile component, a printed wiring board, an LED module, a waveguide, various circuit boards (high-speed transmission boards, heat sink circuit boards, flexible copper-clad laminates (FCCLs), ceramic circuit boards, built-up boards, conductive circuits, etc.), electronic devices, metal-resin bonding materials or sealing materials (metal-resin bonding materials or sealing materials for electronic devices, conductive circuits, foods, cosmetics, pharmaceuticals, etc.), etc. [Example]

[0129] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0130] <Production of compound "IMB-K"> The synthesis methods of various compounds IMB-K according to the present invention will be described below. The synthesized products were identified using a Fourier transform infrared spectrophotometer IRTracer-100 manufactured by Shimadzu Corporation, a nuclear magnetic resonance spectrometer NMR spectrometer Z manufactured by JEOL Ltd., and a gas chromatograph mass spectrometer GCMS-QP2020 NX manufactured by Shimadzu Corporation.

[0131] (1) Synthesis of 4-azidobenzoyl chloride (production of raw material) [ka] 2.6 g of 4-azidobenzoic acid (N3C6H4COOH) was dissolved in a mixed solvent of 30 mL of methylene chloride (CH2Cl2) and 0.3 mL of DMF (N,N-dimethylformamide, C3H7NO). Under a nitrogen gas atmosphere, 7.3 g of thionyl chloride (SOCl2) dissolved in 20 mL of methylene chloride was added dropwise at room temperature with stirring. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, low-boiling materials, including methylene chloride, were distilled off to obtain a yellow oil containing 4-azidobenzoic acid chloride (N3C6H4COCl). This oil was used directly in the next reaction without further purification.

[0132] (2) Synthesis of N-(3-triethoxysilylpropyl)-4-azidobenzamide (IMB-4K) [ka]

[0133] 1.8 g of 4-azidobenzoyl chloride (N3C6H4COCl) was dissolved in 15 mL of THF (tetrahydrofuran). Under a nitrogen gas atmosphere, 3.6 g of 3-triethoxysilylpropylamine and 2.1 g of TEA (triethylamine) were dissolved in 20 mL of THF and added dropwise at room temperature with stirring. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the THF-containing solution was distilled off, and the resulting crude product was purified by column chromatography (eluent: acetone / hexane = 85 / 15) to obtain a pale yellow oil in 66% yield (2.4 g). IR, NMR and QCMS analyses confirmed that the product was N-(3-triethoxysilylpropyl)-4-azidobenzamide.

[0134] (3) Synthesis of N-(3-triethoxysilylpropyl)-3-azidobenzamide (IMB-3K) [ka]

[0135] 1.8 g of 3-azidobenzoyl chloride (N3C6H4COCl) was dissolved in 15 mL of THF. Under a nitrogen gas atmosphere, 3.6 g of 3-triethoxysilylpropylamine (H2N(CH2)2Si(OC2H5)3) and 2.1 g of TEA were dissolved in 20 mL of THF and added dropwise at room temperature with stirring. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the THF-containing solution was distilled off, and the resulting crude product was purified by column chromatography (eluent: acetone / hexane = 85 / 15) to obtain a pale yellow oil in 62% yield (2.2 g). Spectroscopic analysis confirmed that the product was N-(3-triethoxysilylpropyl)-3-azidobenzamide.

[0136] (4) Synthesis of N,N-bis(3-triethoxysilylpropyl)-4-azidobenzamide (IMB-4KB) [ka]

[0137] 1.8 g of 4-azidobenzoyl chloride (N3C6H4COCl) was dissolved in 15 mL of THF. Under a nitrogen gas atmosphere, 6 g of bis(3-triethoxysilylpropyl)amine (HN((CH2)3Si(OC2H5)3)2) and 2.1 g of TEA were dissolved in 20 mL of THF and added dropwise at room temperature with stirring. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the THF-containing solution was distilled off, and the resulting crude product was purified by column chromatography (eluent: acetone / hexane = 85 / 15) to obtain a pale yellow oil in 61% yield. Spectroscopic analysis confirmed that the product was N,N-bis(3-triethoxysilylpropyl)-4-azidobenzamide.

[0138] (5) Synthesis of N,N-bis(3-triethoxysilylpropyl)-3-azidobenzamide (IMB-3KB) [ka]

[0139] 1.8 g of 3-azidobenzoyl chloride (N3C6H4COCl) was dissolved in 15 mL of THF. Under a nitrogen gas atmosphere, 6 g of bis(3-triethoxysilylpropyl)amine (HN((CH2)3Si(OC2H5)3)2) and 2.1 g of TEA were dissolved in 20 mL of THF and added dropwise at room temperature with stirring. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the THF-containing solution was distilled off, and the resulting crude product was purified by column chromatography (eluent: acetone / hexane = 85 / 15) to obtain a pale yellow oil in 62% yield. Spectroscopic analysis confirmed that the product was N,N-bis(3-triethoxysilylpropyl)-3-azidobenzamide.

[0140] (6) Synthesis of N,N'-((diethoxysilanediyl)bis(3-propyl-3,1-diyl)bis(4-azidobenzamide) [ka]

[0141] 2.8 g of 4-azidobenzoyl chloride (N3C6H4COCl) was dissolved in 30 mL of THF. Under a nitrogen gas atmosphere, bis(3-aminopropyl)diethoxysilane (2.3 mL) and 2.1 g of TEA were dissolved in 20 mL of THF and added dropwise at room temperature with stirring. The mixture was stirred overnight at room temperature. Stirring was continued for an additional 2 hours to complete the reaction. After the reaction was complete, the THF-containing solution was distilled off, and the resulting crude product was purified by column chromatography (eluent: acetone / hexane = 85 / 15) to obtain a pale yellow oil in 50% yield. The spectrum confirmed that the product was N,N'-((diethoxysilanediyl)bis(3-propyl-3,1-diyl)bis(4-azidobenzamide).

[0142] (7) Production of a silsesquioxane compound (IMB-4KP) represented by the above formula (19) 3-Azidobenzoyl chloride (N3C6H4COCl) was dissolved in THF. Under a nitrogen gas atmosphere, the starting oligomer (Gelest, USA), a hydrolysis condensation product of 3-aminopropyltriethoxysilane, and TEA were dissolved in THF and added dropwise at room temperature with stirring. Stirring was continued to complete the reaction. After the reaction was completed, the solution containing THF was distilled off, and the resulting crude product was purified to obtain the target product. This target product was a silsesquioxane compound represented by formula (19). From the spectrum, it was confirmed that the l, m, and n in formula (19) of the product were in the ratio l:m:n=1:1:0.

[0143] <1. Example of forming a conductive coating on a material by electroless plating> <1-1. Effect of IMB-K in electroless plating on various resin substrates> For each resin substrate shown in the table of Figure 7, a 20 μm thick copper coating was formed according to the flow diagram shown in Figure 1, and adhesion was tested. As shown in the table of Figure 7, in the degreasing and cleaning step S1, acetone or ethanol was used depending on the resin substrate. In the pretreatment step S2, corona discharge treatment or oxygen plasma treatment (100 mL / min, 5 minutes, 200 W) was performed depending on the resin substrate. The post-pretreatment cleaning step S22 was not performed. In the IMB loading treatment S3, the sample was immersed in an ethanol solution of IMB-4K for 30 seconds. In the post-treatment step S4, the sample was exposed to an irradiation energy of 200 mJ / cm from a UV-LED irradiator. 2 The resin substrates were irradiated with ultraviolet light at 100°C. Heat treatment and cleaning were not performed. Steps S3 and S4 were repeated twice. The post-IMB heat treatment process involved holding the resin substrate at 80°C, 110°C, or 125°C for 10 minutes, depending on the resin substrate. After electroless plating step S7 and electrolytic plating step S8, a 20 μm-thick copper coating was obtained. To relieve residual stress from the plating, an annealing treatment was performed at 150°C for 10 minutes. The appearance of the copper coating formed on each resin substrate was observed after electroless plating, electrolytic plating, and annealing. The peel strength of the copper coating was also measured for each resin substrate. A 90° peel strength tester was constructed by attaching a force gauge ZTA-50N to a vertical motorized test stand MX2-500N (manufactured by Imada Co., Ltd.). The peel speed was 50 mm / min. Three samples were prepared for each resin substrate, and measurements were taken on the front and back sides. The maximum and average peel strength values ​​were calculated.

[0144] Without IMB impregnation, electroless copper plating either did not form on any of these resin substrates, or the adhesion strength of the copper coating was extremely weak. However, by performing IMB impregnation prior to electroless plating, a copper coating with good appearance and adhesion was formed. Furthermore, for the fluororesin composite resin substrate of sample #9, we had previously achieved a maximum peel strength of 6.82 N / cm using a process that combined IMB impregnation using IMB-P and electroless plating, but we found that IMB impregnation using IMB-4K and electroless plating could achieve a peel strength that significantly exceeded this.

[0145] <1-2. Effect of IMB-K on electroless plating of COP resin> A 25 μm thick copper coating was formed on a COP sheet material (0.1 mm thick, sample #21) according to the flow diagram shown in Figure 1, and the adhesion was tested. Acetone was used in the degreasing and cleaning step S1. In the pretreatment step S2, oxygen plasma treatment (100 mL / min, 5 min, 200 W) was performed. The post-pretreatment cleaning step S22 was not performed. In the IMB support treatment S3, the sample was immersed in an ethanol solution of IMB-4K for 30 seconds. In the posttreatment step S4, the sample was irradiated with 200 mJ / cm irradiated energy from a UV-LED irradiator. 2 The specimens were irradiated with ultraviolet light at 100°C. Heat treatment and cleaning were not performed. Steps S3 and S4 were not repeated; they were performed only once. In the post-IMB heat treatment process, the specimens were held at 135°C for 15 minutes. After electroless plating step S7 and electrolytic plating step S8, a 25 μm-thick copper coating was obtained. To relieve residual stress from the plating, an annealing treatment was performed at 150°C for 10 minutes. The appearance of the copper coating formed on each resin substrate was observed after electroless plating, electrolytic plating, and annealing. The peel strength of the copper coating was also measured for each resin substrate. Three samples were prepared for each specimen, and measurements were taken for each. The average peel strength was calculated. The appearance of the copper coating was excellent after electroless plating, electrolytic plating, and annealing. The peel strength was 7.27 N / cm.

[0146] As a comparative example, an attempt was made to form a copper coating on a COP sheet material (sample #921) of the same material and thickness using the same process as for sample #21, except that the IMB support process S3 was not performed. However, no electroless copper plating was formed on sample #921, and the copper coating formation failed.

[0147] <1-3. Effect of IMB-K on electroless plating of PI film> A 20 μm-thick copper coating was formed on a PI film (50 μm thick, product name: Kapton, manufactured by DuPont-Toray Co., Ltd., sample #31) according to the flow diagram shown in Figure 1, and the adhesion was tested. Ethanol was used in the degreasing and cleaning step S1. Pretreatment step S2 was not performed. In the IMB coating step S3, the sample was immersed in an ethanol solution of IMB-4K for 30 seconds. Posttreatment step S4 was not performed. Step S3 was performed only once without repetition. In the post-IMB heat treatment step, the sample was held at 110°C for 15 minutes. Subsequently, electroless plating step S7 and electrolytic plating step S8 were performed. In the annealing step S75 of the electroless plating step S7, the sample was held at 110°C for 60 minutes. A 20 μm-thick copper coating was obtained by electrolytic plating. The peel strength of the copper coating on the sample was measured. Three samples were prepared and measurements were performed on each, and the average peel strength was calculated. The peel strength was 4.5 N / cm.

[0148] A copper coating was attempted on a PI film (Sample #32) of the same material and thickness as Sample #31 using the same process as Sample #31, except that the film was immersed in an isopropanol solution of IMB-4KP for 30 seconds during IMB loading step S3. A 20 μm-thick copper coating was obtained. The peel strength of the copper coating on the sample was measured. Three samples were prepared and measurements were taken for each. The average peel strength was calculated. The peel strength was 2.0 N / cm.

[0149] <1-4. Effects of various IMB-Ks on electroless plating of COP> A 20 μm thick copper coating was formed on a COP sheet material (0.1 mm thick, sample #41) according to the flow diagram shown in Figure 1, and the adhesion was tested. Acetone was used in the degreasing and cleaning step S1. In the pretreatment step S2, oxygen plasma treatment (100 mL / min, 2 min, 200 W) was performed. The post-pretreatment cleaning step S22 was not performed. In the IMB loading treatment S3, the sample was immersed in an ethanol solution of IMB-4K for 30 seconds. In the post-treatment step S4, the sample was irradiated with 200 mJ / cm of energy from a UV-LED irradiator. 2The specimens were irradiated with ultraviolet light at 100°C. Then, a heat treatment was performed at 125°C for 15 minutes. No cleaning was performed. Steps S3 and S4 were repeated twice. A post-IMB heat treatment step was not performed. A 20 μm thick copper coating was obtained through electroless plating step S7 and electrolytic plating step S8. In electroless plating step S7, an annealing step S75 was performed at 110°C for 60 minutes. After electrolytic plating, the peel strength of the copper coating was measured. Three samples were prepared for each specimen, and measurements were taken for each. The average peel strength was calculated. The peel strength was 6.09 N / cm.

[0150] For COP sheets (samples #42 to #45) of the same material and thickness as sample #41, a 20 μm-thick copper coating was formed using the same process as sample #41, except for the type of IMB-K used in the IMB loading process S3 and whether post-processing step S4 involved heat treatment alone (represented as "H") or both UV irradiation and heat treatment (represented as "UV+H"). Peel strength was then measured. The results are shown below. The UV irradiation conditions in post-processing step S4 were the same as for sample #41, and the heat treatment conditions in post-processing step S4 were 125°C for 15 minutes. Sample IMB agent Post-treatment Peel strength (N / cm) #41 IMB-4KP UV+H 6.09 #42 IMB-3K UV+H 4.78 #43 IMB-3KB UV+H 4.23 #44 IMB-4K H 4.92 #45 IMB-3KB H 4.91

[0151] <2. Example of forming a film on a substrate (substance)> <2-1. Application of silver nanopaste to PI film and the effect of IMB-K> A PI film (sample #51) of the same material and thickness as sample #31 was coated with silver nanopaste and thermally cured to form a conductive coating, according to the flow diagram shown in Figure (5B). The silver nanopaste used was a high-viscosity type (product number: DNS-009P, viscosity: 90–100 Pa·s, silver concentration: 60–70 mass%, standard firing conditions: 120°C for 30 minutes, volume resistivity: 5–10 μΩ·cm) manufactured by Daicel Corporation, diluted five-fold with isopropanol (IPA). In the degreasing and cleaning step S1, sample #51 was subjected to ultrasonic cleaning using ethanol for five minutes. The pretreatment step S2 was not performed. In the IMB loading step S3, the sample was immersed in an IPA solution of IMB-4KP for 10 minutes. The posttreatment step S4 was not performed. Step S3 was performed only once, without repetition. In the post-IMB heat treatment step S6, the sample was held at 100°C for 10 minutes. Subsequently, in the application step S96, the sample was spin-coated with the diluted silver nanopaste (1500 rpm, 20 seconds). Subsequently, in the curing step S97, the sample was heat-treated at 120°C for 30 minutes. After that, a 17 mm-wide cut was made in the conductive coating of the sample, and the sample was fixed with 4 N / cm double-sided tape, and a tape peel test was performed. The conductive coating of sample #51 had adhesion sufficient to withstand the tape peel test.

[0152] A PI film (sample #52) made of the same material and thickness as sample #51 was coated with a conductive coating according to the same process as sample #51, except that the sample was held at 150°C for 10 minutes in post-IMB heat treatment step S6. The adhesiveness of the conductive coating of sample #52 was found to be inferior to that of sample #51. As a comparative example, a PI film (sample #53) of the same material and thickness as sample #52 was coated with a conductive coating according to the same process as sample #52, except that in IMB loading treatment S3, the sample was immersed in an aqueous solution of IMB-A for 10 minutes, and a similar tape peel test was performed. The conductive coating of sample #53 did not have sufficient adhesion to withstand the tape peel test. In addition, PI films (samples #54, #55, and #56) of the same material and thickness as sample #51 were coated with conductive coatings according to the same process as sample #51, except that in IMB loading treatment S3, the samples were immersed in an ethanol solution of IMB-4K, an aqueous solution of IMB-4K, and an aqueous solution of IMB-4K in PGMEA for 10 minutes, respectively, and then subjected to a similar tape peeling test. The conductive coatings of samples #54, #55, and #56 all showed inferior adhesion compared to sample #51. As a comparative example, a PI film (sample #57) of the same material and thickness as sample #51 was coated with a conductive coating according to the same process as sample #51, except that the IMB coating S3 was not performed. The conductive coating of sample #57 showed almost no adhesion.

[0153] These results demonstrate that the IMB loading step S3 is essential when forming a conductive coating on a PI film by applying and curing a conductive paste using the method of the present invention. Furthermore, the post-IMB heat treatment step S6 should be performed at a temperature lower than 150°C, approximately 100°C, for example, 80 to 120°C, or more preferably 90 to 110°C, for a short time of approximately 3 to 10 minutes. Furthermore, by using IMB-4KP as the interfacial molecular bonding agent (IMB agent) in this case, a highly adhesive conductive coating can be formed.

[0154] <2-2. Coating of PI and PAI on silicon wafers and the effects of various IMB-Ks> According to the flow diagram shown in Figure 5B, a PI (UPIA AT, manufactured by Ube Industries, Ltd., solids concentration 18±1%, viscosity 5±1 Pa·s, solvent NMP, thermal curing conditions 350°C 20 minutes) was applied to a silicon wafer (sample #61) and thermally cured to form a film, and the adhesion was tested. In the degreasing and cleaning step S1, the sample was ultrasonically cleaned using ethanol for 5 minutes. The pretreatment step S2 was not performed. In the IMB loading step S3, the sample was immersed in an ethanol solution of IMB-4K for 10 minutes. The posttreatment step S4 was not performed. Step S3 was performed only once without repetition. In the post-IMB heat treatment step S6, the sample was held at 100°C for 3 minutes. Next, in the application step S96, the sample was spin-coated with the above PI (1500 rpm, 20 seconds). Next, in the curing step S97, the sample was heat-treated under the recommended thermal curing conditions for the PI. Then, 1mm wide, 5x5 square cuts were made in the coating film of the sample, and a cross-cut test was performed to confirm the number of adhesions (= 25 - number of peelings). The number of adhesions was 25, and the coating film thickness was 29μm.

[0155] The same silicon wafers as sample #61 (samples #62 to #67) were coated with PI and thermally cured using the same process as sample #61, except that the IMB and solvent used in the IMB deposition process S3 were as follows. The adhesion was then tested. The results are shown below. Sample #67 is a comparative example, and was not subjected to the IMB deposition process S3. (When PI is applied to a silicon wafer) Sample Compound Solvent Film thickness (μm) Number of contacts #61 IMB-4K Ethanol 29 25 #62 IMB-4K Water 25 25 #63 IMB-4K PGMEA 27 25 #64 IMB-4KB Ethanol 33 25 #65 IMB-3K Ethanol 33 25 #66 IMB-3KB Ethanol 25 25 #67 None None 20 0

[0156] In addition, the same silicon wafers (samples #71-73 and #75-77) as samples #61-63 and #65-67 were coated with PAI (HCP-5012-32, Hitachi Chemical Co., Ltd., 30% solids, 3 Pa·s viscosity, NMP / MEK solvent = 80 / 20, cured at 270°C for 20 minutes) instead of PI, and the same process was used to apply and thermally cure the PAI film. After cooling for 15 minutes, the wafers were tested for adhesion. The results are shown below. Sample #77 is a comparative example, and was not subjected to the IMB coating process S3. (When PAI is applied to a silicon wafer) Sample Compound Solvent Film thickness (μm) Number of contacts #71 IMB-4K Ethanol 16 22 #72 IMB-4K Wed 19 25 #73 IMB-4K PGMEA 19 25 #75 IMB-3K Ethanol 16 25 #76 IMB-3KB Ethanol 16 25 #77 None None 20 0

[0157] <2-3. Effect of the combination of ITORO and IMB treatments on the application of PI and PAI to silicon wafers> As in <2-2> above, when applying PI and PAI to silicon wafers, the effect on adhesion was investigated when performing an Itro treatment as a pretreatment step S2. In the Itro treatment, combustion gas was irradiated five times onto the surface of the silicon wafer at a distance of approximately 5 cm from the wafer. The results are summarized below. Ethanol was used as the solvent for both IMB-K and IMB-A. (When PI is applied to a silicon wafer) Sample Compound Itro treatment Film thickness (μm) Number of contacts #81 None None 12 0 #82 No Yes 14 0 #83 IMB-A Yes 13 25 #84 IMB-A None 15 24 #85 IMB-K Yes 11 25 #86 IMB-K None 13 25 (When PAI is applied to a silicon wafer) Sample Compound Itro treatment Film thickness (μm) Number of contacts #91 None None 20 0 #92 No Yes 15 0 #93 IMB-A Yes 19 25 #94 IMB-A None 25 13 #95 IMB-4K Yes 18 25 #96 IMB-4K None 19 25

[0158] These results show that, first, adhesion cannot be ensured by Itro treatment alone without IMB support treatment. Furthermore, by combining Itro treatment with IMB support treatment on silicon wafers, adhesion tends to be improved compared to IMB support treatment alone. Furthermore, whether or not it is combined with Itro treatment, IMB-K tends to have higher adhesion than IMB-A.

[0159] <2-4. Coating of PAI or PI on PI film and effect of IMB-K> A PI film (sample #101) made of the same material and thickness as sample #31 was coated with PAI and thermally cured according to the flow diagram shown in Figure (5B), forming a coating film, and the adhesion was tested. The same PAI was used as sample #71. In the degreasing and cleaning step S1, the sample was ultrasonically cleaned using ethanol for 5 minutes. The pretreatment step S2 was not performed. In the IMB loading step S3, the sample was immersed in an ethanol solution of IMB-4K for 10 minutes. The posttreatment step S4 was not performed. Step S3 was performed only once, not repeatedly. In the post-IMB heat treatment step S6, the sample was held at 150°C for 10 minutes. Next, in the coating step S96, the sample was spin-coated with the PAI (1500 rpm, 20 seconds). Next, in the curing step S97, the sample was heat-treated under the recommended thermal curing conditions for the PAI. After cooling for 15 minutes, 2 mm wide, 10 x 10 square cuts were made in the coating film of the sample, and the sample was fixed with 5 N / cm double-sided tape to perform a tape peel test.

[0160] For PI films (#102 to #104) of the same material and thickness as sample #101, coatings were formed using the same process as sample #101, except that the compounds used in the IMB loading treatment and the liquid resin applied were as shown below, and adhesion was examined. The results are shown below. Note that ethanol was used as the solvent for all compounds used in the IMB loading treatment. The PI was the same as that applied to sample #61. Sample Coating Compound Film Thickness (μm) Number of contacts #101 PAI IMB-4K 17 100 #102 PAI None 25 100 #103 PI IMB-4K 18 97 #104 No PI 21 86

[0161] These results show that when PAI is applied, adhesion can be ensured even without IMB support treatment, but when PI is applied, sufficient adhesion cannot be ensured without IMB support treatment.

[0162] <2-5. Adhesion test of bonded bodies formed by thermocompression bonding of sheet-like materials and the effect of IMB-K> A PTFE sheet (sample #110) was prepared by thermocompression bonding a metal foil using the manufacturing method shown in Figure (5A), and its peel strength was examined. The PTFE sheet used was manufactured by Nitto Denko (defluorinated, thickness 0.18 mm). The metal foil used was a rolled copper foil with a thickness of 18 μm. In the surface treatment step Sst for the PTFE sheet, the degreasing and cleaning step S1 and the pretreatment step S2 were not performed, and in the IMB loading treatment step S3, a 1% by mass ethanol solution of the compound IMB-4K was applied to a wet thickness of 20 μm. Furthermore, in the post-treatment step S4, irradiation energy of 100 mJ / cm was applied. 2 The heat treatment step S44, the cleaning step S46, and the post-IMB heat treatment step S6 were not performed. Next, in the thermocompression bonding step Shp, rolled copper foil was thermocompression bonded to the surface of the PTFE sheet at a press temperature of 180°C, a press pressure of 8 MPa, and a press time of 10 minutes. After natural cooling, a peel strength test was performed, and a peel strength of 8.0 N / cm was obtained.

[0163] The process for the thermocompression bond was the same as for sample #110, except for the two materials and the compound used in the IBM-supporting process. Two materials were thermocompression bonded together, and a peel strength test was performed. The results are shown below. The thickness of each material was 20 μm or 18 μm. The solvent for compound IMB-4KP was water, and the solvent for the other compounds was ethanol. Sample Substance 1 Substance 2 Compound Peel strength (N / cm) #110 PTFE Cu IMB-4K 8.0 #111 PTFE Cu IMB-3K 7.8 #112 PTFE Cu IMB-4KB 8.0 #113 PTFE Al IMB-4KP 6.5 #114 PI PI IMB-4K 7.2 #115 PI PTFE IMB-4K 8.9 #116 PI Cu IMB-4K 3.9 #117 PI Al IMB-4K 2.1 #118 PI Al None 0.0

[0164] When forming a bonded body by thermocompression bonding, it was found that by performing an IMB support treatment process prior to thermocompression bonding, high peel strength can be achieved for both resin-resin and resin-metal combinations.

[0165] The present invention is not limited to the above-described embodiments and examples, and it goes without saying that the technical scope of the present invention includes various combinations, modifications, design changes, etc., within the scope that do not deviate from the technical idea of ​​the present invention. [Explanation of symbols]

[0166] A: Substance A A' :Substance A' B: Substance B C: Coating film C α: Compound α β: Compound β Sst: Surface treatment process Sc: Coating formation process Shp: Thermocompression bonding process Sf: Paint film formation process

Claims

1. A surface treatment method comprising a step of applying a solution containing one or more compounds α to a surface of at least one substance, for the purpose of forming a bond between two substances through interfacial molecular bonding, The compound α is A compound α1 represented by the following formula (1) or (2): Compound α2 obtained by hydrolysis and condensation of a hydrolyzable silane compound containing the compound α1 The surface treatment method is 【Chemistry 1】 In formula (1), R １ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. ２ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. １ is an azide group or an azidosulfonyl group. １ represents an ester group, an ether group, a thioether group, an amide group, a urethane group, -NHR ３ -, or a group represented by the following formula (3a) or (3b): ３ is an alkyl group having 1 to 6 carbon atoms. １ is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more groups selected from -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. m is an integer of 1 to 3. R １ , X １ , Y １ and Z １ When there are a plurality of R, they each independently satisfy the above definition. １ At least one of the groups is an alkoxy group having 1 to 12 carbon atoms. In formula (2), a plurality of R ４ , R ５ and R ６ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group, and a plurality of R ４ , R ５ and R ６ At least one of the R is an alkoxy group having 1 to 12 carbon atoms. ７ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. ２ is an azide group or an azidosulfonyl group. ２ are each independently a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more groups selected from -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. 【Chemistry 2】 In formula (3a), R ８ is a hydrogen atom or a methyl group.

2. 2. The surface treatment method according to claim 1, wherein the substance on the surface of which the compound α is provided is a non-particulate substrate.

3. Before the step of providing the compound α on the surface of at least one of the materials, 3. The surface treatment method according to claim 1, further comprising a step of subjecting the at least one substance to one or more pretreatments selected from the group consisting of cleaning treatment, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, and itro treatment.

4. After the step of providing the compound α on the surface of at least one of the materials, The surface treatment method according to any one of claims 1 to 3, further comprising the step of irradiating the compound α present on the surface of the substance with ultraviolet light.

5. After the step of providing the compound α on the surface of at least one of the materials, 5. The surface treatment method according to claim 1, further comprising a step of subjecting the compound α present on the surface of the substance to a heat treatment.

6. Before the step of providing the compound α on the surface of at least one of the materials, The method further comprises a step of providing a compound β on the surface of the at least one substance, The compound β is Within one molecule, a functional group capable of chemically bonding to at least one of the substances by chemical reaction; A functional group capable of chemically bonding with the compound α by chemical reaction The surface treatment method according to any one of claims 1 to 5, wherein the compound has the formula:

7. In the step of providing the compound α on the surface of at least one of the materials, the compound α is provided on the surface of one of the materials, and after this step, The method further comprises a step of providing a compound β on the surface of the one material, The compound β is Within one molecule, a functional group capable of chemically bonding to the compound α through a chemical reaction; Functional groups that can chemically bond with other substances through chemical reactions The surface treatment method according to any one of claims 1 to 5, wherein the compound has the formula:

8. In the step of providing the compound α on a surface of at least one of the substances, the compound α is provided on a surface of one of the substances; The method further comprises a step of providing the compound β on the surface of the other material, The compound β is Within one molecule, a functional group capable of chemically bonding to the compound α through a chemical reaction; a functional group capable of chemically bonding with another substance through a chemical reaction; The surface treatment method according to any one of claims 1 to 5, wherein the compound has the formula:

9. A surface treatment agent used in the surface treatment method according to any one of claims 1 to 8, which is a solution containing one or more compounds α according to claim 1.

10. A method for producing a conjugate by bonding substance A and substance B, a surface treatment step of treating the surface of substance A or the surfaces of both substances by the surface treatment method according to any one of claims 1 to 8; an arrangement step of arranging the surface of substance B that has been subjected to the above treatment or a surface of substance B facing the surface of substance A on which compound α is present; a bonding step in which a force is applied to at least one of material A and material B, and the two materials are integrally bonded together; A method for producing a conjugate comprising:

11. The method for producing a bonded body according to claim 10, wherein the bonding step is carried out at a temperature of 40°C or higher and 350°C or lower.

12. a surface treatment step of applying an agent containing the compound α to the surface of a substance by the surface treatment method according to any one of claims 1 to 8; a coating formation step of providing a conductive coating on the surface of the substance on which the compound α is present by electroless plating, vapor deposition or coating; 1. A method for manufacturing a material having a conductive coating, comprising:

13. a surface treatment step of applying an agent containing the compound α to the surface of a substance by the surface treatment method according to any one of claims 1 to 8; a coating film forming step of forming a coating film on the surface of the substance on which the compound α is present; A method for producing a material having a coating film formed thereon, comprising:

14. A surface treatment method comprising a step of applying an agent containing the compound α to a surface of a coating film formed on a substance by the surface treatment method according to any one of claims 1 to 8.

15. a surface treatment step of treating the surface of the coating film of the substance A on which the coating film has been formed by the surface treatment method according to claim 14; a placement step of placing a surface of substance B opposite the surface of the coating film; a bonding step in which a force is applied to at least one of material A and material B, and the two materials are integrally bonded together; A method for producing a conjugate comprising:

16. a surface treatment step of treating the surface of substance B by the surface treatment method according to any one of claims 1 to 8; a positioning step of positioning the surface of the coating film of substance A on which the coating film has been formed, facing the surface of substance B; a bonding step in which a force is applied to at least one of material A and material B, and the two materials are integrally bonded together; A method for producing a conjugate comprising:

17. A compound α1 represented by the following formula (1) or (2), or a hydrolysis condensation product α2 obtained by hydrolysis condensation of a hydrolyzable silane compound containing the compound α1: 【Transformation 3】 In formula (1), R １ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. ２ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. １ is an azide group or an azidosulfonyl group. １ represents an ester group, an ether group, a thioether group, an amide group, a urethane group, -NHR ３ -, or a group represented by the following formula (3a) or (3b): ３ is an alkyl group having 1 to 6 carbon atoms. １ is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more groups selected from -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. m is an integer of 1 to 3. R １ , X １ , Y １ and Z １ When there are a plurality of R, they each independently satisfy the above definition. １ At least one of the groups is an alkoxy group having 1 to 12 carbon atoms. In formula (2), a plurality of R ４ , R ５ and R ６ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group, and a plurality of R ４ , R ５ and R ６ At least one of the R is an alkoxy group having 1 to 12 carbon atoms. ７ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. ２ is an azide group or an azidosulfonyl group. ２ are each independently a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a group containing one or more groups selected from -NH-, -O-, -S-, and -S(O)- at the terminal or between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. 【Chemistry 4】 In formula (3a), R ８ is a hydrogen atom or a methyl group.

18. A surface treatment agent comprising the compound according to claim 17.

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