Reactivity-imparting compound and laminate

Abstract

To provide a reactivity-imparting compound capable of suppressing photodegradation of a substrate, having excellent storage stability, and demonstrating superior adhesion stability in high-temperature and high-humidity conditions.SOLUTION: According to the present disclosure, the reactivity-imparting compound comprises, in one molecule, reactive functional groups and diazirine groups, wherein the reactive functional group is one or more selected from the group consisting of SH group, SNa group, and amino group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a reactivity imparting compound and a laminate. [Background technology]

[0002] Composite materials in which different materials are bonded together, such as laminates in which a metal film is formed on an inorganic or polymer substrate, are used in circuit boards for mobile phones, vehicle components, and the like.

[0003] In a laminate, if the adhesion between materials is low, peeling occurs between the materials. Therefore, improving adhesion is an important characteristic of a laminate. One technique for improving the adhesion between materials is, for example, forming irregularities on the surface of the substrate. When part of the metal film penetrates into the irregularities on the surface of the substrate, an anchor effect is exerted, improving adhesion.

[0004] However, for example, if the surface of a substrate for a circuit board is uneven, the signal transmission distance increases and transmission loss occurs, making it difficult to use a technique for forming unevenness on the surface of a substrate for circuit board applications.

[0005] One technique for improving adhesion without forming surface irregularities is to introduce hydroxyl groups onto the substrate using corona discharge treatment, but corona discharge treatment can cause deterioration of the substrate and only introduces a small number of hydroxyl groups, so there is a limit to how much adhesion can be improved.

[0006] Another technique for improving adhesion without creating surface irregularities involves reacting the substrate surface with a compound that can impart reactivity to the substrate surface. For example, organofunctional silane compounds have been developed to improve the performance of laminates between polymeric materials and glass or metals. This method uses a coupling agent, i.e., a bifunctional molecule, that reacts with both the polymeric material and the bonding target (e.g., metal) to form a covalent bond. Specifically, silane coupling agents are organofunctional silane monomers that possess bifunctionality. This property allows the functional group at one end of the molecule to hydrolyze, forming a silanol, which then bonds with similar functional groups on glass or OH groups on metal oxides through condensation. The other end of the silane molecule contains a functional group, such as an amino group or a mercapto group, that can react with organic materials. Thus, silane coupling agents are known to be highly useful molecules for covalently bonding organic materials to other materials.

[0007] As a technique for improving adhesion without forming irregularities on the surface, Patent Document 1 discloses a method for forming a metal film, which includes a step of applying an agent containing a specific compound to the surface of a substrate, and a step of applying a metal film to the surface of the compound by a wet plating technique, wherein the compound has an OH group or an OH-yielding group, an azide group, and a triazine ring in one molecule, and the substrate is constructed using a polymer.

[0008] In the technology of Patent Document 1, a molecule having an azide group is irradiated with ultraviolet light to generate a nitrene from the azide group, and the generated nitrene reacts with the surface of the substrate, thereby achieving high adhesion.

[0009] However, the technology of Patent Document 1 has the problem that the substrate deteriorates and adhesion decreases because short-wavelength ultraviolet light is irradiated onto molecules having an azide group. As a technology that can suppress substrate deterioration and improve adhesion, Patent Document 2 discloses a reactivity-imparting compound that has, in one molecule, a silane coupling moiety represented by a specific formula and a diazirine group. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Patent No. 4936344 [Patent Document 2] International Publication No. 2022 / 097644 Summary of the Invention [Problem to be solved by the invention]

[0011] Currently, there is a demand for a reactivity-imparting compound that has higher storage stability than the reactivity-imparting compound disclosed in Patent Document 2 and that has excellent adhesion stability under high-temperature and high-humidity environments.

[0012] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a reactivity-imparting compound and a laminate that suppress photodegradation of a substrate, have excellent storage stability, and have excellent adhesion stability under high-temperature and high-humidity environments. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention proposes the following means. (1) The reactivity imparting compound of the first aspect of the present invention is A reactive functional group and a diazirine group; and The reactive functional group is at least one selected from the group consisting of an SH group, an SNa group, and an amino group. (2) Aspect 2 of the present invention is the reactivity imparting compound of Aspect 1, It may be a compound represented by the following formula (1). [ka] [ka] [ka] [ka] [ka] [In the above formula (1), Z 1 represents a triazine ring or a benzene ring, and Q 1 , Q 2 , and Q 3 At least one of Q is the reactive functional group or the first structure represented by the formula (2), 1 , Q 2 , and Q 3 At least one of the above is a second structure represented by the above formula (3), and * in the above formula (2) represents an adjacent carbon atom, and X 1 represents O, NH, or S; m1 represents an integer of 1 to 10; Y 1 represents an SH group, an SNa group, or an amino group, * in the above formula (3) represents an adjacent carbon atom, and X 2 represents O, NH, or S; m2 represents an integer of 1 to 10; Y 2 is a third structure represented by the above formula (4) or a fourth structure represented by the above formula (5), in which * represents an adjacent carbon atom, and R 1 is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group, * in the above formula (5) represents an adjacent carbon atom, Ar is an arylene group, a divalent heterocyclic group, or a methylene group, and R 2 is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group. (3) Aspect 3 of the present invention is the reactivity imparting compound of Aspect 2, Said Z 1 may be a triazine ring. (4) A fourth aspect of the present invention is the reactivity imparting compound of the second or third aspect, X 1 and X 2 may be NH or O. (5) A fifth aspect of the present invention is the reactivity imparting compound of the fourth aspect, It may be a compound represented by the following formula (6). [ka] (6) A sixth aspect of the present invention is the reactivity imparting compound of the fourth aspect, It may be a compound represented by the following formula (7). [ka] (7) In a seventh aspect of the present invention, the reactivity imparting compound of the fourth aspect may be a compound represented by the following formula (8). [ka] (8) Aspect 8 of the present invention is the reactivity imparting compound of aspect 4, It may be a compound represented by the following formula (9). [ka] (9) The laminate of the ninth aspect of the present invention is A first substrate; a reactivity-imparting compound layer provided on the first substrate and composed of the reactivity-imparting compound according to any one of aspects 1 to 8; a second substrate provided on the reactivity imparting compound layer; Equipped with. [Effects of the Invention]

[0014] According to the above-described aspects of the present invention, it is possible to provide a reactivity imparting compound and a laminate that suppress photodegradation of a substrate, have excellent storage stability, and have excellent adhesion stability under high-temperature and high-humidity environments. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a cross-sectional view of a laminate using a reactivity imparting compound according to an example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0016] The reactivity imparting compound and the laminate according to the embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

[0017] (Reactivity-imparting compound) The reactivity imparting compound according to this embodiment has a reactive functional group and a diazirine group in one molecule, and the reactive functional group is one or more selected from the group consisting of an SH group, an SNa group, and an amino group.

[0018] The reactivity imparting compound according to this embodiment has one or more reactive functional groups. The reactive functional groups are one or more selected from the group consisting of an SH group, an SNa group, and an amino group. The reactive functional groups improve adhesion to the coating layer in the laminate.

[0019] When the reactive functional group is a thiol group (SH group) or an SNa group, adhesion to Au, Ag, Cu, rubber, etc. is improved. Therefore, when improving adhesion to metals such as Au, Ag, and Cu, resins such as rubber, ceramics, etc., SH groups and SNa groups are preferred as reactive functional groups. Furthermore, thiol groups and SNa groups have excellent storage stability, facilitating long-term storage of the reactivity-imparting compound. The presence of thiol groups and SNa groups can improve the solubility of the reactivity-imparting compound in basic aqueous solutions. This allows the use of water, which has a low environmental impact, as a solvent. When improving adhesion to Au, Ag, Cu, and rubber, it is preferable that the total number of thiol groups and SNa groups in the reactivity-imparting compound is two. Furthermore, thiol groups and SNa groups also have the ability to support catalysts used in plating, thereby improving plating adhesion.

[0020] When the reactive functional group is an amino group, it becomes easier to support Pd or the like, which serves as a catalyst for forming the plating. This makes it easier to form a plating layer with high adhesion. Therefore, when forming a plating, the reactive functional group is preferably an amino group. To further improve adhesion to the plating layer, it is preferable that the total number of amino groups in the reactivity-imparting compound is two. Furthermore, since amino groups have excellent storage stability, the reactivity-imparting compound can be easily stored for a long period of time. When the reactivity-imparting compound has an amino group, the solubility of the reactivity-imparting compound in an acidic aqueous solution is improved. This makes it possible to use water, which has a low environmental impact, as a solvent.

[0021] The reactivity imparting compound according to this embodiment has one or more diazirine groups. The diazirine group is chemically stable, and generates carbene upon irradiation with ultraviolet light or heating. The carbene is highly reactive and can form a covalent bond with a molecule in the vicinity of the carbene. Therefore, after applying the reactivity imparting compound according to this embodiment to the surface of a substrate, a covalent bond can be formed between the substrate and the reactivity imparting compound by irradiating the substrate with light or heating. This allows for high adhesion between the substrate and the reactivity imparting compound according to this embodiment.

[0022] Furthermore, carbenes can provide higher adhesion than nitrenes generated from azide groups, resulting in higher adhesion than reactivity-imparting compounds using azide groups. Furthermore, diazirine groups have absorption bands at longer wavelengths than azide groups and diazomethyl groups that generate carbene, thereby suppressing photodegradation of resins. Adhesion to substrates improves as the number of diazirine groups in the reactivity-imparting compound increases. When using substrates with poor adhesion, it is preferable to set the total number of diazirine groups in the reactivity-imparting compound to 2.

[0023] The diazirine group generates a highly reactive structure (carbene) at a lower temperature than the azide group and the diazomethyl group. Therefore, by incorporating a thermally reactive functional group (e.g., a thiol group) into the reactivity-imparting compound, it can be used as a thermally reactive molecular bonding agent.

[0024] The structure between the reactive functional group and the diazirine group in the reactivity imparting compound functions as a molecular bonding agent at the monomolecular level as long as the reactive functional group and the diazirine group are connected via a covalent bond. Therefore, the structure of the reactivity imparting compound is not particularly limited as long as all bonds between at least the reactive functional group and the diazirine group are covalent bonds.

[0025] The reactivity-imparting compound is not particularly limited as long as it has a reactive functional group and a diazirine group in one molecule, and the reactive functional group is one or more selected from the group consisting of an SH group, an SNa group, and an amino group. The reactivity-imparting compound is preferably a compound represented by the following formula (1). The total number of reactive functional groups and diazirine groups in the reactivity-imparting compound is preferably 3.

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] In the above formula (1), Z 1 represents a triazine ring or a benzene ring. 1 Z in the above formula (1) functions as a spacer between the reactive functional group and the diazirine group. 1The bonding position of the reactive functional group and the diazirine group can be adjusted, thereby adjusting the adhesion between the substrate and the metal layer. In order to facilitate the production and adjust the positional relationship between the diazirine group and the reactive functional group, Z 1 The triazine ring may be any of 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine, with 1,3,5-triazine being particularly preferred.

[0032] Z in the above formula (1) 1 If is a benzene ring, Q 1 , Q 2 , and Q 3 The bonding positions of X and Q are not particularly limited, but are preferably 1-, 3-, and 5-positions. 1 , Q 2 , and Q 3 The other portion is not particularly limited and may be a hydrogen atom or any functional group.

[0033] Q in the above formula (1) 1 , Q 2 and Q 3 At least one of the structures Q contains a reactive functional group (reactive structure). 1 , Q 2 , Q 3 , and Q 4 At least one of the reactive functional groups is preferably the reactive functional group described above or the second structure represented by the formula (2) above. The reactive structures in the reactivity-imparting compound may be the same or different. In the formula (2) above, * represents an adjacent carbon atom, and X 1 represents O, NH, or S, and m1 represents an integer of 1 to 10. X 1 is preferably O or NH in terms of chemical stability. The integer m1 represents the length of the spacer between the reactive functional group and the diazirine group. By adjusting the number of m1, the frequency of contact between the metal layer and the reactive functional group can be adjusted. In the above formula (2), m1 is preferably an integer of 1 to 10. Y 1is an SH group, an SNa group, or an amino group. When there are two reactive structures, Y in the reactive structure 1 may be the same or different, but are preferably the same in order to improve adhesion to metals and resins such as rubber.

[0034] Q in the above formula (1) 1 , Q 2 , and Q 3 At least one of the structures Q contains a diazirine group (diazirine structure). 1 , Q 2 , and Q 3 At least one of the above is preferably a third structure represented by the above formula (3). In the above formula (3), * represents an adjacent carbon atom, and X 2 represents O, NH, or S. X 2 is preferably O, NH, or CH2 in terms of chemical stability. m2 is an integer of 1 to 10. The integer m2 represents the length of the spacer between the reactive functional group and the diazirine group. By adjusting the number of m2, the frequency of contact between the substrate and the diazirine group can be adjusted. Y in the above formula (3) 2 is the third structure represented by the above formula (4) or the fourth structure represented by the above formula (5). When there are two diazirine structures, Y 2 may be the same or different.

[0035] In the above formula (4), * represents an adjacent carbon atom, and R 1 is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group. 1 is preferably a trifluoromethyl group or a pentafluoroethyl group, since the photoreaction efficiency is improved.

[0036] In the above formula (5), * represents an adjacent carbon atom, Ar represents an arylene group or a divalent heterocyclic group, and R 2 is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group. 2is preferably a trifluoromethyl group or a pentafluoroethyl group, since the photoreaction efficiency is improved.

[0037] Examples of the arylene group for Ar in the above formula (5) include a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, and a 2,6-naphthylene group.

[0038] Examples of the divalent heterocyclic group of Ar in the following formula (5) include divalent groups in which two hydrogen atoms have been removed from the hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting a heterocycle such as furan, thiophene, or pyridine.

[0039] Z 1 Specific examples of the reactivity-imparting compound of formula (1) above when Z is a triazine ring and the reactive functional group is an SH group or an SNa group include a compound represented by formula (6) below and 2,4-dimercapto-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine monosodium salt represented by formula (7) below. 1 Specific examples of the reactivity-imparting compound of formula (1) above when R is a triazine ring and the reactive functional group is an amino group include a compound represented by formula (8) below and 2,4-di(2-aminoethylamino)-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine represented by formula (9) below. For improving adhesion to Au, Ag, Cu, and rubber, 2,4-dimercapto-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine monosodium salt represented by formula (7) below is preferred. For improving adhesion to plating layers using a catalyst such as Pd, 4-di(2-aminoethylamino)-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine represented by formula (9) below is preferred.

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] (Action of reactivity-imparting compound) The reactivity imparting compound according to this embodiment has a diazirine group, which is a photo- and thermally reactive nitrogen functional group, and a reactive functional group. The diazirine group is photodecomposed by light (at a wavelength of approximately 360 nm) to generate a highly reactive chemical species, carbene (a carbon atom with six valence electrons and no charge). This carbene moiety forms a covalent bond with the substrate surface of the laminate. After forming the covalent bond, the reactive functional group of this reactivity imparting compound is fixed to the surface of the substrate (e.g., a resin substrate). This imparts reactivity that allows bonding with other materials (e.g., a metal layer) via the reactive functional group.

[0045] Furthermore, the diazirine group of the reactivity imparting compound according to this embodiment thermally decomposes at approximately 80°C to 180°C, generating a highly reactive carbene. This carbene moiety forms a covalent bond with the substrate surface of the laminate. Conventionally, copper foil and a resin substrate have been bonded by heating to near the melting point of the resin and then hot pressing. However, in the case of the reactivity imparting compound of the present disclosure, a covalent bond can be formed at or below the melting point of the resin constituting the substrate, allowing bonding without deforming the substrate.

[0046] Furthermore, the reactivity imparting compound having a diazirine group of this embodiment has higher bonding strength than conventional compounds having an azide group, and when a resin substrate to which reactivity has been imparted with the reactivity imparting compound is metal-plated, the reactivity imparting compound of this embodiment can suppress metal peeling more effectively than conventional compounds having an azide group.

[0047] The reactivity imparting compound according to this embodiment has excellent storage stability because the reactive functional group is one or more selected from the group consisting of an SH group, an SNa group, and an amino group. Furthermore, the reactivity imparting compound according to this embodiment has one or more reactive functional groups selected from the group consisting of an SH group, an SNa group, and an amino group, so water can be used as a solvent. Therefore, the reactivity imparting compound according to this embodiment can reduce the environmental impact.

[0048] (Method of producing reactivity-imparting compound) The reactivity imparting compound of this embodiment can be appropriately produced, for example, by introducing a reactive functional group and a diazirine moiety into a compound having a triazine ring or a benzene ring. Here, a trihalogenated triazine ring will be described as an example, but a benzene ring can also be synthesized using a chemical reaction. A trihalogenated triazine ring refers to a triazine ring in which three hydrogen atoms are substituted with halogen atoms. Chlorine is preferred as the substituted halogen atom. Examples of compounds having a trihalogenated triazine ring include cyanuric chloride, 3,5,6-trichloro-1,2,4-triazine, and 4,5,6-trichloro-1,2,3-triazine.

[0049] The method for producing the reactivity imparting compound according to this embodiment includes a diazirine group imparting step of reacting a compound having a trihalogenated triazine ring with a compound having a functional group (halogen reactive group) reactive with a halogeno group and a diazirine group to obtain a diazirine group imparting compound, and a reactive functional group imparting step of reacting the diazirine group imparting compound with a compound having a reactive functional group. Here, an example is described in which cyanuric chloride in which 1,3,5-triazine is chlorinated is used as the compound having a trihalogenated triazine ring, but the reactivity imparting compound according to this embodiment can also be obtained by a similar reaction in the case of compounds having other trihalogenated triazine rings.

[0050] <Diazirine Group Addition Step> In the diazirine group-imparting step, cyanuric chloride is reacted with a compound having a halogen-reactive group and a diazirine group to obtain a diazirine group-imparted compound. Examples of the compound having a hydroxyl group, a halogen-reactive group such as an amine hydrochloride, and a diazirine group include 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamine hydrochloride.

[0051] The synthesis using 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamine hydrochloride is described below. For example, the reaction is as shown in the following formula (10). In the following formula (10), DIPEA represents N,N-diisopropylethylamine. A base other than N,N-diisopropylethylamine may be used in the reaction of the following formula (10). In the reaction of the following formula (10), for example, pyridine, triethylamine, etc. can be used instead of N,N-diisopropylethylamine. In the reaction of the following formula (10), 4,6-dichloro-2-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine can be obtained as a diazirine group-imparting compound.

[0052] [ka]

[0053] <Reactive Functional Group Addition Step> In the reactive functional group imparting step, the diazirine group imparting compound obtained in the diazirine group imparting step is reacted with a compound having a halogen-reactive group and a reactive functional group. The reactive functional group of the compound having a halogen-reactive group and a reactive functional group may be protected with a protecting group. The reactive functional group imparting step can be used to obtain the reactivity imparting compound according to this embodiment. If the reactive functional group is protected with a protecting group, the reactivity imparting compound according to this embodiment can be obtained by deprotecting the reactive functional group after the reactive functional group imparting step (deprotection step).

[0054] Examples of compounds having an amino group and a reactive functional group include 2-tert-butoxycarbonylaminoethylamine and sodium hydrogen sulfide.

[0055] An example of the reaction between 4,6-dichloro-2-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine synthesized by the above formula (10) and 2-tert-butoxycarbonylaminoethylamine is shown in the following formula (11). In the following formula (11), DIPEA represents N,N-diisopropylethylamine. A base other than N,N-diisopropylethylamine may be used in the reaction of the following formula (11). In the reaction of the following formula (11), for example, pyridine, triethylamine, etc. can be used instead of N,N-diisopropylethylamine. 2,4-di(2-tert-butoxycarbonylaminoethylamino)-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine can be obtained through the reaction of the following formula (11).

[0056] [ka]

[0057] An example of the reaction of 4,6-dichloro-2-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine synthesized by the above formula (10) with sodium hydrogen sulfide is shown in the following formula (12). Through the reaction of the following formula (12), 2,4-dimercapto-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine monosodium salt can be obtained.

[0058] [ka]

[0059] <Deprotection process> The amino group of 2,4-di(2-tert-butoxycarbonylaminoethylamino)-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine obtained by the reaction of the above formula (11) is protected. When the reactive functional group is protected with a protecting group, a reactivity-imparting compound can be obtained by deprotection. The deprotection method can be appropriately selected depending on the type of protecting group. For example, when the amino group is protected with a tert-butoxycarbonyl (Boc) group, it can be deprotected with trifluoroacetic acid (TFA), as in the reaction of the following formula (13). This allows the reactivity-imparting compound of this embodiment to be obtained.

[0060] [ka]

[0061] (Laminate) A laminate using the reactivity imparting compound according to this embodiment will now be described. As shown in Fig. 1, a laminate 100 according to this embodiment of the present invention includes a substrate (first substrate) 10, a reactivity imparting compound layer 20, and a coating layer (second substrate) 30. Each layer will be described below.

[0062] (base material) The material of the substrate 10 may be an inorganic material such as ceramics or glass, or a resin. The form of the substrate 10 is not particularly limited, and may be a plate or granular shape. The substrate 10 is an example of a first substrate.

[0063] The resin of the substrate 10 may be a curable resin (e.g., thermosetting resin, photocurable resin, or electron beam curable resin), a thermoplastic resin, a fiber-reinforced resin, rubber (vulcanized rubber), or other material having a coating containing such a polymer on its surface. Specific examples of resins include acrylonitrile butadiene styrene (ABS) resin. ABS resin is used for vehicle components and is used as a laminate in which ABS and metal are bonded together by metal plating on the surface. Resins used for circuit boards include epoxy resin, polyimide resin, fluorine-based resin, polyphenylene ether resin (PPE), cycloolefin polymer (COP), polypropylene (PP), polyphenylene sulfide (PPS), and liquid crystal polymer. However, resins with low dielectric constants and dielectric loss tangents are used for high-speed communications.

[0064] When the laminate 100 is used as a high-frequency printed wiring board, COP, PP, PPE, fluorine-based resin, liquid crystal polymer, or the like, which have small dielectric properties (dielectric constant, dielectric loss tangent), are desirable. However, if wiring is formed on the surface while it remains smooth, there is a problem with adhesion to metal. However, by using the reactivity-imparting compound according to this embodiment, it is possible to improve adhesion to metal even when the surface is smooth.

[0065] An example of the inorganic insulating material of the substrate 10 is a material containing silicon oxide. In addition, components of electronic devices and circuit boards include substrates containing various inorganic and organic materials, and can be used as laminates by forming circuits on the surface by metal plating or the like.

[0066] When the substrate 10 is made of resin, it may contain inorganic particles such as talc, a lubricant, an antistatic agent, etc., depending on the purpose of improving the mechanical strength, etc.

[0067] When the laminate 100 is used as a printed wiring board, its thickness is not particularly limited. However, for example, when the substrate 10 is used as a flexible wiring board, the thickness of the substrate 10 is preferably 1 μm or more and 200 μm or less. If the thickness of the substrate 10 is less than 1 μm, the mechanical strength of the substrate 10 may be insufficient, which is not preferred. The thickness of the substrate 10 is more preferably 3 μm or more. Furthermore, if the thickness of the film exceeds 200 μm, the foldability may decrease, which is not preferred. The thickness of the substrate 10 is more preferably 150 μm or less.

[0068] When the laminate 100 is used as a printed wiring board, the arithmetic mean roughness Ra of the substrate 10 is, for example, 0.01 to 1 μm. If the arithmetic mean roughness Ra is between 0.01 μm and 1 μm, it can accommodate miniaturized circuits. Furthermore, if the arithmetic mean roughness Ra is 0.2 μm or less, transmission loss in the high frequency range can be reduced. The arithmetic mean roughness Ra can be measured in accordance with JIS B 0601:2013.

[0069] (Reactivity imparting compound layer 20) The reactivity imparting compound layer 20 is provided on the substrate 10 and is composed of the reactivity imparting compound according to this embodiment. Here, "provided on the substrate 10" not only means providing the reactivity imparting compound layer 20 so as to be in contact with the surface of the substrate 10, but also includes providing an intermediate layer between the substrate 10 and the reactivity imparting compound layer 20. It also includes providing the reactivity imparting compound layer partially on the surface of the substrate 10.

[0070] The thickness of the reactivity imparting compound layer 20 is not particularly limited as long as it covers the entire surface of the substrate 10. The thickness of the reactivity imparting compound layer 20 may be, for example, equal to or greater than the thickness of a single molecule (a monomolecular layer or greater) of the reactivity imparting compound that constitutes the reactivity imparting compound layer 20. The upper limit of the thickness of the reactivity imparting compound layer 20 is not particularly limited, but is, for example, 400 nm or less.

[0071] (covering layer) The coating layer 30 is provided on the reactivity imparting compound layer 20. The coating layer 30 is made of, for example, a metal, a resin, an inorganic insulating material, etc. Examples of metals for the coating layer 30 include Au, Ag (silver), Sn (tin), Cu (copper), and copper alloys. Examples of resins for the coating layer 30 include rubber, liquid crystal polymer, epoxy resin, and silicone resin. Examples of inorganic insulating materials for the coating layer 30 include ceramics, glass, and quartz. When the laminate 100 is a printed circuit board, the metal constituting the covering layer 30 is preferably Cu or a Cu alloy, which has high conductivity, from the viewpoint of power loss and transmission loss. The covering layer 30 only needs to cover at least a portion of the base material 10, and its shape is not limited to a layer. The covering layer 30 is an example of a second base material.

[0072] The thickness of the coating layer 30 is not particularly limited, but is, for example, 0.1 μm to 50 μm. More preferably, the thickness of the coating layer 30 is 2 μm to 10 μm. If the thickness of the coating layer 30 is 0.1 μm to 50 μm, sufficient mechanical strength can be obtained.

[0073] (Method of manufacturing laminate) A method for producing the laminate according to this embodiment will be described below, but the method for producing the laminate according to this embodiment is not limited to the following method.

[0074] When producing the laminate according to this embodiment, first, a reactivity imparting compound layer 20 made of the reactivity imparting compound according to this embodiment is formed on a substrate (first substrate) 10. The method for forming the reactivity imparting compound layer 20 is not particularly limited. For example, the reactivity imparting compound layer 20 may be formed by applying a solution containing the reactivity imparting compound to the surface of the substrate 10. Alternatively, the reactivity imparting compound layer 20 may be formed by immersing the substrate 10 in a solution containing the reactivity imparting compound.

[0075] When a solution containing a reactivity-imparting compound is used, the solvent can be appropriately selected from water, an organic solvent, etc. Specifically, the solvent may be water, an alcohol, a ketone, an aromatic hydrocarbon, an ester, an ether, etc. The reactivity-imparting compound may be dispersed in the solvent without dissolving. When a solution is used, the solvent in the solution may be dried by air drying, heating, etc.

[0076] A reactivity amplifier may be added to the solution containing the reactivity-imparting compound. Examples of the reactivity amplifier include compounds that contribute to other bonds, such as silane coupling agents, and photosensitizers, such as benzophenone.

[0077] After forming the reactivity imparting compound layer 20 on the substrate 10, energy is applied to generate carbene from the diazirine group of the reactivity imparting compound. This carbene reacts with the substrate 10, resulting in high adhesion between the reactivity imparting compound layer 20 and the substrate 10.

[0078] An example of a means for providing energy is irradiation with light. The diazirine group of the reactivity imparting compound of this embodiment is activated in response to a wide range of wavelengths, but to suppress deterioration due to light, it is preferable that the light be on the long wavelength side. Specifically, a wavelength of 300 nm or more is preferable, and a wavelength of 400 nm or less is preferable. For light irradiation, an existing light irradiation device can be appropriately used. In this case, the substrate 10 on which the reactivity imparting compound layer 20 has been formed may be heated before irradiation to enhance the activation effect.

[0079] Another method for applying energy is to carry out a heat treatment. By carrying out a heat treatment at about 80°C to 180°C (preferably 80 to 100°C), carbene is generated from the diazirine group of the reactivity imparting compound. The heating temperature for the heat treatment is preferably 80°C or higher and lower than the melting point of the substrate 10. By heating at a temperature of 80°C or higher and lower than the melting point of the substrate 10, the reactivity imparting compound can be bonded to the substrate 10 while suppressing deformation of the substrate.

[0080] Energy is applied to the reactivity-imparting compound layer 20 to improve the adhesion between the substrate 10 and the reactivity-imparting compound layer 20, and then the coating layer 30 is provided. The coating layer 30 may be provided by plating or the like, or by bonding a metal foil, metal plate, or the like. In the case of bonding, the same reactivity-imparting compound may be applied to the surface of the metal plate or foil that will be bonded to the substrate 10, and energy may be applied to achieve adhesion. As the plating method, a dry plating method (vapor deposition or sputtering) or a wet plating method may be appropriately selected, or both may be used in combination. When forming the metal coating layer 30, it is preferable to use wet plating such as electroless plating or electroplating. Before forming the coating layer 30, a conventionally known pretreatment process for plating may be performed.

[0081] When the coating layer 30 (second substrate) is foil- or plate-shaped, the coating layer 30 may be subjected to a surface treatment such as corona discharge treatment, followed by application of the reactivity imparting compound according to this embodiment to form a second reactivity imparting compound layer (not shown). Surface treatment such as corona discharge treatment can introduce hydrophilic groups into the surface of the second substrate. When carbene is generated from the diazirine group in the reactivity imparting compound, it reacts with the hydrophilic group, thereby bonding the coating layer 30 and the reactivity imparting compound. Substrates with hydrophilic groups do not require surface treatment. By doing this, a first substrate provided with a reactivity imparting compound layer and a second substrate provided with a second reactivity imparting compound layer can be bonded by bonding and heating the reactivity imparting compound layer and the second reactivity imparting compound layer, forming a laminate 100. For example, if the reactivity imparting compound has a thiol group, the thiol group can be oxidized by heat treatment to form a disulfide, thereby bonding the reactivity imparting compound layer and the second reactivity imparting compound layer. [Example]

[0082] Next, examples of the present invention will be described, but the conditions in the examples are merely examples adopted to confirm the feasibility and effects of the present invention, and the present invention is not limited to these examples. Various conditions can be adopted in the present invention as long as they do not deviate from the gist of the present invention and the object of the present invention is achieved.

[0083] (Test conditions) The following instruments and reagents were used for the synthesis of samples and the analysis of the synthesized samples. ·Analytical equipment Nuclear magnetic resonance spectrum: JEOL JNM-ECA500 NMR measurement device (500 MHz) Bruker AVANCEIII500 NMR measurement device (500 MHz) Mass spectrum: JEOL JMS-700 MS measurement device Differential scanning calorimetry: Shimadzu DSC-60A Plus differential scanning calorimetry instrument UV / visible absorption spectrum: JASCO V-700 UV-visible absorption analyzer ·reagent Various reagents: Commercially available reagents were used and purified by standard methods as necessary. Various reaction solvents: dried and purified by standard methods as necessary. Silica gel: Wako-gel C-200 (Wako Pure Chemical Industries, Ltd.),

[0084] The synthesis method of the sample will be explained below.

[0085] (Synthesis of intermediates) Cyanuric chloride (2.00 g, 10.8 mmol) and 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamine hydrochloride (2.71 g, 10.8 mmol, 1.0 eq.) were placed in a 300 mL recovery flask, and acetonitrile (100 mL) and water (60 mL) were added. After cooling to 0 °C, N,N-diisopropylethylamine (DIPEA) (5.5 mL, 32.3 mmol, 3.0 eq.) was added dropwise. After stirring at 0 °C for 4 hours in the dark, the reaction solution was added with cooled water (60 mL) and allowed to stand for 15 minutes. The precipitate was filtered off by suction filtration and dried under reduced pressure to obtain the intermediate (4,6-dichloro-2-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine) (3.37 g, 9.28 mmol, yield 86%) as a white solid.

[0086] The results of nuclear magnetic resonance spectroscopy and mass spectroscopy of the obtained intermediate are shown below. 1 H NMR(500MHz,DMSO-d6):δ 4.56(d,J=6.3Hz,2H,benzyl-H),7.27(d,J=8.6Hz,2H,benzene-H),7.44(d,J=8.6Hz,2H,benzene-H),9.63(t,J=6.3Hz,NH); 13 C NMR (126MHz, DMSO-d6): δ 28.0(q,J=39.7Hz),43.5,121.9(q,J=275Hz),126.5,126.6,128.2,140.1,165.7,168.7,169.6; 19 F NMR(471MHz,DMSO-d6):δ -64.5; FAB-MS m / z 363 [(M+H) + ]

[0087] (Synthesis of reactivity imparting compound of Example 1) The intermediate (0.496 g, 1.37 mmol) was placed in a 50 mL three-neck flask and purged with argon. After adding anhydrous THF (10 mL), 2-tert-butoxycarbonylaminoethylamine (3.2 mL, 20 mmol, 15 eq.) was added dropwise, followed by N,N-diisopropylethylamine (DIPEA) (0.69 mL, 4.1 mmol, 3.0 eq.). After stirring for 15 hours at room temperature in the dark, water was added to the reaction solution, which was then extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was dried under reduced pressure to yield a crude yellow liquid (1.09 g). The crude product was separated and purified by silica gel column chromatography using chloroform:ethyl acetate = 1:10 as a developing solvent to obtain 2,4-di(2-tert-butoxycarbonylaminoethylamino)-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine (0.706 g, 1.16 mmol, yield 85%) as a yellow liquid.

[0088] The results of nuclear magnetic resonance spectroscopy and mass spectroscopy of the reactivity imparting compound of Example 1 obtained are shown below. 1 H NMR(500MHz,CDCl3):δ 1.43(s,18H,C(CH3)3),3.28(brs,4H,CH2),3.42(brs,4H,CH2),4.56(brs,2H,benzyl -H),5.45(brs,5H,NH),7.15(d,J=7.5Hz,2H,benzene-H),7.34(brs,2H,benzene-H); 13 C NMR(126MHz,CDCl3):δ 28.36(q,J=40.7Hz),28.42,40.8,41.1,44.1,79.3,122.2(q,J=275Hz),126.7,127.7,127.9,141.5,156.3,166.1,166.5; 19 F NMR (471 MHz, CDCl3): δ -65.3; HR-FAB-MS m / z calculation for C 26 H38 F3N 10 O4[(M+H) + ]:611.3030; Found:611.3027

[0089] (Synthesis of reactivity imparting compound of Example 1A) The reactivity imparting compound (0.596 g, 0.976 mmol) from Example 1 was placed in a 50 mL three-neck flask and purged with argon. Anhydrous dichloromethane (15 mL) was added, and the mixture was cooled to 0°C. Trifluoroacetic acid (1.5 mL, 20 mmol, 20 eq.) was then added dropwise. After stirring for 2 hours at 0°C in the dark, the solvent and excess trifluoroacetic acid were removed under reduced pressure. The solid residue was washed with diethyl ether, dissolved in water, and made basic (pH > 10) by the addition of aqueous sodium hydroxide (1 mol / L) in small portions. Extraction was performed with dichloromethane, and the organic layer was washed with water and then with saturated brine. This organic layer was dried over anhydrous sodium sulfate and filtered, and then the solvent was removed under reduced pressure. The residue was dried under reduced pressure to obtain the reactivity imparting compound of Example 1A (2,4-di(2-aminoethylamino)-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine) (0.368 g, 0.897 mmol, yield 92%) as a yellow solid.

[0090] The results of nuclear magnetic resonance spectroscopy and mass spectroscopy of the resulting reactivity imparting compound of Example 1A are shown below. 1 H NMR(500MHz,CDCl3):δ 1.62(brs,4H,NH2),2.83(brs,4H,CH2),3.37(brs,4H,CH2),4.56(brs,2H,benzyl-H), 5.48(brs,3H,NH),7.13(d,J=7.9Hz,2H,benzene-H),7.26(d,J=7.9Hz,2H,benzene-H); 13 C NMR (126MHz, CDCl3): δ 28.4(q,J=40.6Hz),41.6,43.4,44.0,122.2(q,J=275Hz),126.6,127,7(2C),141.9,166.2,166.5; 19 F NMR (471 MHz, CDCl3): δ -65.3; HR-FAB-MS m / z calculation for C 16 H 22 F3N 10 [(M+H) + ]:411.1981; Found:411.1980

[0091] (Synthesis of reactivity imparting compound of Example 2) The intermediate (0.300 g, 0.826 mmol) was placed in a 50 mL side-arm flask and purged with argon. Anhydrous ethanol (10 mL) was added, followed by the dropwise addition of a solution of sodium hydrogen sulfide (0.131 g, 2.34 mmol, 2.8 eq.) in anhydrous ethanol (5 mL). After stirring at room temperature for 3 hours in the dark, the reaction solution was suction filtered to recover the filtrate. The solvent was removed from the filtrate under reduced pressure, and the residue was dried under reduced pressure to yield 2,4-dimercapto-6-{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine monosodium salt (0.310 g, 0.815 mmol, 99% yield) as a white solid.

[0092] The results of nuclear magnetic resonance spectroscopy and mass spectroscopy of the reactivity imparting compound of Example 2 obtained are shown below. 1 H NMR(500MHz,DMSO-d6):δ 4.53(d,J=6.3Hz,2H,benzene-H),7.25(d,J=8.3Hz,2H,benzene-H),7.40(d,J=8.3Hz,2H,benzene-H),7.83(brt,1H,NH),11.5(brs,1H,SH); 13 C NMR(126MHz,DMSO-d6):δ 28.1(q,J=40.9Hz),"42.9,122.0(q,J=275Hz),126.1,126.5,128.0,141.9,156.5,178.2,182.9; 19 F NMR(471MHz,DMSO-d6):δ -64.5; HR-FAB-MS m / z calculation for C 12 H8F3N6NaS2[(M+H)+]:381.0180;Found 381.0175

[0093] (Synthesis of Intermediate 2) A 200 mL recovery flask was charged with cyanuric chloride (1.00 g, 5.42 mmol) and 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamine hydrochloride (3.03 g, 12.1 mmol, 2.2 eq.) and placed under an argon atmosphere. Acetonitrile (50 mL) and water (30 mL) were added, followed by the dropwise addition of N,N-diisopropylethylamine (DIPEA) (2.8 mL, 16.5 mmol, 3.0 eq.). After stirring at room temperature for 4 hours in the dark, water was added to the reaction solution and the mixture was allowed to stand for 15 minutes. The precipitate was filtered off by suction filtration and dried under reduced pressure at 40 °C to obtain intermediate 2 (6-chloro-2,4-bis{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine (2.07 g, 3.82 mmol, 70%)) as a white solid.

[0094] The results of nuclear magnetic resonance spectroscopy and mass spectroscopy of the obtained intermediate 2 are shown below. 1 H NMR(500MHz,DMSO-d6):δ 4.42,4.45,4.50(d×3,J=6.3Hz,4H,benzyl-H),7.08,7.24,7.38,7.42(d×4,J=8.5Hz,8H,benzene-H),8.25,8.35,8.39,8.49(t×4,J=6.3Hz,2H,NH); 13 C NMR(126MHz,DMSO-d6):δ 27.9(q,J=40.2Hz),28.0(q,J=39.7Hz),42.9,42.97,43.05,121.9(q,J=275Hz) ,126.0,126.1,126.5,127.9, 128.0,141.6,141.8,165.4,165.8,167.9,168.4; 19 F NMR(471MHz,DMSO-d6):δ -64.7; HR-FAB-MS: m / z calculation for C 21 H 15 35 ClF6N9[(M+H) + ]:542.1043;Found:542.1033.

[0095] (Synthesis of reactivity imparting compound of Example 3) A 50 mL three-neck flask was charged with 6-chloro-2,4-bis{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine (1.00 g, 1.85 mmol) and purged under argon. Anhydrous THF (20 mL) was added, followed by dropwise addition of 2-tert-butoxycarbonylaminoethylamine (2.2 mL, 13.9 mmol, 7.5 eq.). After stirring at room temperature for 15 hours in the dark, the reaction solution was added with water and extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was removed under reduced pressure, and the residue was dried under reduced pressure to yield a crude yellow liquid (1.98 g). The crude product was separated and purified by silica gel column chromatography using chloroform:ethyl acetate=1:10 as a developing solvent, to obtain the reactivity imparting compound of Example 3 (2-(2-tert-butoxycarbonylaminoethylamino)-4,6-bis{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine (1.21 g, 1.82 mmol, 98%)) as a yellow solid.

[0096] The results of nuclear magnetic resonance spectroscopy and mass spectroscopy of the reactivity imparting compound of Example 3 obtained are shown below. 1 H NMR(500MHz,CDCl3):δ 1.40(s,9H,C(CH3)3),3.22(brs,2H,CH2),3.40(brs,2H,CH2),4.53(brs,4H,benzyl-H) ,5.08,5.22,5.33(brs×3,4H,NH),7.13(brs,4H,benzene-H),7.31(brs,4H,benzene-H); 13C NMR (126MHz, CDCl3): δ 28.3(q,J=40.3Hz),28.4,40.6,41.2,44.0,79.3,122.2(q,J=275Hz),126.6,127.7,127.9,141.6,156.4,166.2,166.6; 19 F NMR (471 MHz, CDCl): δ -65.3 HR-FAB-MS: m / z calculation for C 28 H 30 F6N 11 O2 [(M+H) + ]:666.2488;Found:666.2478.

[0097] (Synthesis of reactivity imparting compound of Example 3A) A 50 mL three-neck flask was charged with 2-(2-tert-butoxycarbonylaminoethylamino)-4,6-bis{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine (1.21 g, 1.82 mmol) and purged with argon. Anhydrous dichloromethane (20 mL) was added, and the mixture was cooled to 0 °C. Trifluoroacetic acid (2.1 mL, 27.4 mmol, 15 eq.) was added dropwise. After stirring at room temperature for 2 hours in the dark, the solvent and excess trifluoroacetic acid were removed under reduced pressure. The solid residue was washed with diethyl ether, dissolved in water, and made basic (pH > 10) by the addition of aqueous sodium hydroxide (1 mol / L) in small portions. Extraction was performed with dichloromethane, and the organic layer was washed with water and then with saturated brine. This organic layer was dried over anhydrous sodium sulfate and filtered, and then the solvent was removed under reduced pressure. The residue was dried under reduced pressure to obtain the reactivity imparting compound of Example 3A (2-(2-aminoethylamino)-4,6-bis{4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamino}-1,3,5-triazine (0.678 g, 1.20 mmol, 66%)) as a yellow solid.

[0098] The results of nuclear magnetic resonance spectroscopy and mass spectroscopy of the resulting reactivity imparting compound of Example 3A are shown below. 1H NMR(500MHz,CDCl3):δ 1.63(brs,2H,NH2),2.80(brs,2H,CH2),3.35(q,J=6.0Hz,2H,CH2),4.53(brs,4H,benzy l-H),5.34,5.62(brs×2,3H,NH),7.11(brs,4H,benzene-H),7.31(brs,4H,benzene-H); 13 C NMR(126MHz,CDCl3):δ 28.4(q,J=40.3Hz),41.5,43.2,44.0,122.2(q,J=275Hz),126,6,127.7,127.8,141.7,166.2,166.4; 19 F NMR (471 MHz, CDCl3): δ -65.3; HR-FAB-MS: m / z calculation for C 23 H 22 F6N 11 [(M+H) + ]:566.1964;Found:566.1965.

[0099] (Synthesis of reactivity-imparting compound of Comparative Example 1) N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazin-2-amine was prepared as the reactivity imparting compound of Comparative Example 1. The reactivity imparting compound of Comparative Example 1 was obtained using the method described in Patent Document 2.

[0100] (Experiment to confirm the thermal reactivity of the diazirine group) The thermal reactivity of diazirine, azide, and diazomethyl groups was confirmed by the following method. As model compounds, a compound with an azide group represented by the following formula (14) (comparative compound 1), a compound with a diazomethyl group represented by the following formula (15) (comparative compound 2), and a compound with a diazirine group represented by the following formula (16) (comparative compound 3) were prepared. To confirm the thermal reactivity of these compounds, differential scanning calorimetry (DSC) was performed. Approximately 5 mg of each compound was placed in an aluminum cell, and the top lid was crimped and sealed. Using the prepared sample cell, DSC measurements were performed under conditions of a measurement range of 20 to 300°C and a heating rate of 10°C / min.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] The DSC evaluation results are shown in Table 1. Comparative compound 1, which is solid at room temperature and normal pressure, exhibited an endothermic peak (melting point) with a maximum at 62°C and an exothermic peak (decomposition point) with a maximum at 225°C. Similarly, comparative compound 2, which is solid at room temperature and normal pressure, exhibited an endothermic peak (melting point) with a maximum at 107°C and an exothermic peak (decomposition point) with a maximum at 172°C. On the other hand, comparative compound 3, which is a viscous liquid at room temperature and normal pressure, exhibited only an exothermic peak (decomposition point) with a maximum at 137°C. The thermal decomposition onset temperatures (exothermic peak onset temperatures) of comparative compounds 1 to 3 were 163°C, 121°C, and 98°C, respectively, indicating that comparative compound 3, which has a diazirine group, had the lowest thermal decomposition temperature of approximately 100°C.

[0105] Next, ethanol solutions of comparative compounds 1-3 were heated at 100 °C for 3 hours, and the UV / vis absorption spectra were measured before and after heating. For comparative compounds 1 and 2, the absorption bands derived from the azide group (absorption maximum at 267 nm) and the diazomethyl group (absorption maximum at 270 nm) did not decrease after heating, confirming that thermal decomposition of the azide and diazomethyl groups did not occur under heating conditions at 100 °C. On the other hand, for comparative compound 3, the absorption band derived from the diazirine group (absorption maximum at 362 nm) decreased significantly (89%) after heating, indicating efficient thermal decomposition of the diazirine group under heating conditions at 100 °C. This confirms that the thermal decomposition of comparative compound 3 observed in the DSC measurement was the generation of carbene due to thermal decomposition of the diazirine group. From the comparison of the thermal responsiveness of comparative compounds 1-3, it was confirmed that the diazirine group as a thermally reactive group has a lower thermal decomposition temperature than the azide group or diazomethyl group, and generates carbene at a low temperature of 100°C, making it possible to carry out an efficient thermal reaction.

[0106] [Table 1]

[0107] (Preparation of Laminate Using Reactivity-Providing Compound) Next, laminates using the reactivity-imparting compounds of Example 2 and Comparative Example 1 were produced by the following method.

[0108] A COP substrate (Zeon ZF14-100, 10 mm × 50 mm × 100 μm thick) was prepared as the substrate. The COP substrate was subjected to ultrasonic cleaning with ethanol and then dried. After drying, it was subjected to corona discharge treatment (12 kV, distance from the COP substrate: 0.5 mm, 3 times), immersed for 1 minute in a solution of the reactivity imparting compound of Example 2 (concentration: 2.07 mmol / L, solvent: ethanol) or a solution of the reactivity imparting compound of Comparative Example 1 (concentration: 2.07 mmol / L, solvent: ethanol), dried, and then exposed to light with a mercury lamp for 1 minute. The COP substrate was then washed with ethanol and dried to obtain a COP substrate on which a reactivity imparting compound layer was formed.

[0109] A copper plate (Yamamoto Plating Tester B-60-P05) measuring 20 mm x 30 mm x 0.3 mm thick was prepared as the coating layer. The copper plate was wiped with acetone and then immersed in 0.1% hydrochloric acid for 1 minute. The copper plate was then thoroughly washed with distilled water and dried. After drying, it was subjected to corona discharge treatment (12 kV, 3 times, 0.5 mm distance from the copper plate, 3 times), and then immersed for 10 minutes in a solution of the reactivity imparting compound of Example 2 (concentration 2.07 mmol / L, solvent ethanol) or a solution of the reactivity imparting compound of Comparative Example 1 (concentration 2.07 mmol / L, solvent ethanol), followed by drying. After drying, it was heated in an oven at 110°C for 10 minutes to obtain a copper plate with a reactivity imparting compound layer formed thereon. The copper plate on which the reactivity-imparting compound layer was formed and the COP substrate on which the reactivity-imparting compound layer was formed were subjected to a load of 0.1 kN / cm 2 The laminate was produced by bonding under the conditions of a pressure of 140°C for 30 minutes.

[0110] (HAST test) The obtained laminate of Example 1 and Comparative Example 1 were subjected to an HAST test. The test conditions were 130°C, 85%, and 100 hours.

[0111] "Peel strength measurement of laminated bodies" The peel strength between the copper plate and the COP substrate was measured for the laminates of Example 2 and Comparative Example 1 before and after the HAST test using an adhesion tester (IMADA FORCE MEASUREMENT model mX2 manufactured by IMADA) at a pulling speed of 50 mm / min and a pulling angle of 90°. The results are shown in Table 2.

[0112] [Table 2]

[0113] As shown in Table 2, before the HAST test, the laminate of Comparative Example 1 exhibited a higher peel strength than the laminate of Example 2. However, after the HAST test, the peel strength of the laminate of Comparative Example 1 significantly decreased, whereas the peel strength of the laminate of Example 2 increased. From the above, it was confirmed that the reactivity imparting compound according to this embodiment has excellent adhesive stability under high temperature and high humidity environments. [Industrial Applicability]

[0114] The reactivity imparting compound and laminate of the present invention inhibit photodegradation of the substrate, have excellent storage stability, and exhibit excellent adhesion stability in high-temperature and high-humidity environments, and therefore have high industrial applicability. [Explanation of symbols]

[0115] 10 substrate, 20 reactivity imparting compound layer, 30 coating layer, 100 laminate

Claims

1. A reactive functional group and a diazirine group; and The reactivity-imparting compound, wherein the reactive functional group is at least one selected from the group consisting of an SH group, an SNa group, and an amino group.

2. The reactivity-imparting compound according to claim 1, which is a compound represented by the following formula (1): 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 [In the above formula (1), Z １ represents a triazine ring or a benzene ring, and Q １ , Q ２ , and Q ３ At least one of the reactive functional group and the first structure represented by the formula (2) is １ , Q ２ , and Q ３ At least one of the above is a second structure represented by the formula (3), and * in the above formula (2) represents an adjacent carbon atom, and X １ represents O, NH, or S; m1 represents an integer of 1 to 10; Y １ represents an SH group, an SNa group, or an amino group, * in the above formula (3) represents an adjacent carbon atom, and X ２ represents O, NH, or S; m2 represents an integer of 1 to 10; Y ２ is a third structure represented by the above formula (4) or a fourth structure represented by the above formula (5), in which * represents an adjacent carbon atom, and R １ is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group, * in the above formula (5) represents an adjacent carbon atom, Ar is an arylene group, a divalent heterocyclic group, or a methylene group, and R ２ is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group.

3. Said Z １ The reactivity imparting compound of claim 2, wherein is a triazine ring.

4. The X １ and the X ２ The reactivity imparting compound of claim 2 or 3, wherein is NH or O.

5. The reactivity imparting compound according to claim 4, which is a compound represented by the following formula (6): 【Chemistry 6】

6. The reactivity imparting compound according to claim 4, which is a compound represented by the following formula (7): 【Chemistry 7】

7. The reactivity imparting compound according to claim 4, which is a compound represented by the following formula (8): 【Chemistry 8】

8. The reactivity imparting compound according to claim 4, which is a compound represented by the following formula (9): 【Chemistry 9】

9. A first substrate; a reactivity imparting compound layer provided on the first substrate and composed of the reactivity imparting compound according to claim 1 or 2; a second substrate provided on the reactivity imparting compound layer; A laminate comprising:

Images