Reactive imparting compound, method for producing reactive imparting compound, and layer substrate

Abstract

Disclosed is a reactive imparting compound which contains, within one molecule, a silane coupling group represented by the following formula (1) and a bisaziridine group.[Chemical Formula 1]

Description

Technical Field

[0001] This application relates to reactive imparting compounds, reactive imparting compounds, and layer substrates.

[0002] This application claims priority to Japanese Application 2020-185196, filed November 5, 2020, and Japanese Application 2021-145578, filed September 7, 2021, the entire contents of which are incorporated herein by reference. Background Technology

[0003] Composite materials made by bonding different materials, such as layer substrates with metal films formed on inorganic or polymer substrates, can be used in circuit boards for mobile phones or vehicle parts.

[0004] In a multilayer substrate, poor adhesion between materials can lead to separation. Therefore, improving adhesion is a crucial performance characteristic in multilayer substrates. One technique for improving adhesion is forming irregular shapes on the substrate surface. By embedding a portion of a metal film into these irregular shapes on the substrate surface, an anchoring effect is created, thereby improving adhesion.

[0005] However, for example, if the surface of the substrate used for a circuit board is uneven, the signal transmission distance becomes longer, resulting in transmission loss. Therefore, it is difficult to utilize techniques that form irregular shapes on the substrate surface when used for circuit boards.

[0006] Introducing hydroxyl groups into a substrate via corona discharge is a technique that improves adhesion without creating irregular shapes on the substrate surface. However, corona discharge treatment can degrade the substrate and introduces relatively few hydroxyl groups, thus limiting its effectiveness in improving adhesion.

[0007] The technique of enabling reactivity to react with the surface of a substrate is another way to improve adhesion without forming irregular shapes on the surface. For example, a silane compound with organic functional groups is being developed to improve the adhesion of polymeric materials to laminated substrates such as glass or metal. This method involves using a coupling agent, i.e., a bifunctional group, to react with both the polymeric material and the adhesive target (e.g., a metal), forming a covalent bond. Specifically, silane coupling agents belong to the class of silane monomers with organic functional groups and possess bifunctionality. This property allows the functional group at one end of the molecule to hydrolyze to form a silanol, which is then bonded by condensation with similar functional groups on glass or OH groups on metal oxides. The other end of the silane molecule contains functional groups such as amino or mercapto groups that can react with organic matter. Therefore, silane coupling agents are considered very useful as molecules for bonding organic substances with other materials via covalent bonds.

[0008] Patent Document 1 discloses a method for forming a metal film, characterized by the following steps: depositing an agent containing a specific compound on the surface of a substrate; and depositing a metal film on the surface of the compound using a wet plating technique; wherein the compound is a compound having an OH group or OH-generating group, an azide group, and a triazine ring within one molecule, and the substrate is composed of a polymer. Irradiating the molecule containing the azide group with ultraviolet light causes the azide group to generate a nitrous group, which then reacts with the substrate surface, thereby achieving high adhesion.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent No. 4936344 Invention Summary

[0012] The problem the invention aims to solve

[0013] However, there is a need for a method that can achieve higher adhesion compared to the technology in Patent Document 1. Furthermore, in the technology of Patent Document 1, the irradiation of molecules with azide groups with short-wavelength ultraviolet light leads to substrate degradation and reduced adhesion.

[0014] This application was made in view of the above-mentioned problems, and its object is to provide a reactive imparting compound, a method for preparing the reactive imparting compound, and a layer substrate, wherein the reactive imparting compound can reduce the photodegradation of the substrate and obtain high adhesion.

[0015] To address the aforementioned problems, this application proposes the following technical means.

[0016] <1> This application provides a reactive-giving compound containing, within one molecule, a silane coupling group and a diazinon group represented by the following formula (1).

[0017] Chemical (1)

[0018]

[0019] In formula (1), * represents an adjacent carbon atom, R 1 R 2 R 3 R represents a hydrogen atom or an alkyl group. 1 R 2 R 3 They can be the same or different.

[0020] <2> In the above <1> The reactive compounds described herein can be compounds represented by the following formula (2).

[0021] [Chemistry 2]

[0022]

[0023] [Chemistry 3]

[0024]

[0025] [Chemistry 4]

[0026]

[0027] In formula (2), X represents a triazine ring or a benzene ring, and Z represents a triazine ring or a benzene ring. 1 Z 2 and Z 3 Y represents any one of O, NH, S, or CH2, m1, m2, and m3 represent integers between 1 and 10. 1 Y 2 and Y 3 It is the silane coupling group, or the bisacrididine group represented by formula (3) or (11), Y 1 Y 2 and Y 3 At least one of them is the silane coupling group, Y 1 Y 2 and Y 3 At least one of them is the bisacrylidine group, where * in formula (3) represents an adjacent carbon atom, R 4 It is any functional group, and in the formula (11), * represents an adjacent carbon atom, R 5 It can be any functional group, where A is an aryl or divalent heterocyclic group.

[0028] <3> exist <2> In the reactive compound described herein, X may be a triazine ring.

[0029] <4> In the above <2> or <3> In the reactive-endowing compound described herein, the Z 1 Z 2 and Z 3 It can be NH or O.

[0030] <5> In the above <4> The reactive compounds described herein can be compounds represented by the following formula (4).

[0031] [Chemistry 5]

[0032]

[0033] <6> In the above <4> The reactive compounds described herein may be compounds represented by the following formula (12).

[0034] [Chemistry 6]

[0035]

[0036] <7> In the above <4> The reactive compounds described herein may be compounds represented by the following formula (13).

[0037] [Chemistry 7]

[0038]

[0039] <8> In the above <4> The reactive compounds described herein may be compounds represented by the following formula (14).

[0040] [Chemistry 8]

[0041]

[0042] <9> One aspect of this application discloses a method for preparing a reactive-donating compound, comprising: a bisacrididin group-donating step, wherein a compound containing a trihalogenated triazine ring is reacted with a compound containing a hydroxyl group and a bisacrididin group to obtain a bisacrididin group-donated compound having one or more bisacrididin groups; and a silane coupling group-donating step, wherein the bisacrididin group-donated compound is reacted with a compound containing an amino group and a silane coupling group represented by the following formula (6).

[0043] [Chemistry 9]

[0044]

[0045] In formula (6), * represents an adjacent carbon atom; R 1 R 2 and R 3 Indicates a hydrogen atom or an alkyl group; R 1 R 2 and R 3 They can be the same or different.

[0046] <10> exist <9> In the method for preparing the reactive compound described herein, two of the bisacrididine groups may be imparted in the bisacrididine group imparting step.

[0047] <11> exist <9> or <10> In the method for preparing the reactive compound described herein, the compound represented by formula (18) can be reacted with 3-aminopropyltriethoxysilane to obtain the compound represented by formula (4).

[0048] [Chemistry 10]

[0049]

[0050] [Chemistry 11]

[0051]

[0052] <12> In the above <9> or <10> In the method for preparing the reactive compound described herein, the compound represented by formula (20) below can be reacted with 3-aminopropyltriethoxysilane to obtain the compound represented by formula (13) below.

[0053] [Chemistry 12]

[0054]

[0055] [Chemistry 13]

[0056]

[0057] <13> exist <9> In the method for preparing the reactive compound described herein, a bisacrididine group may be imparted in the bisacrididine group imparting step.

[0058] <14> exist <9> or <13> In the method for preparing the reactive compound described herein, the compound represented by formula (15) below can be reacted with 3-aminopropyltriethoxysilane to obtain the compound represented by formula (12) below.

[0059] [Chemistry 14]

[0060]

[0061] [Chemistry 15]

[0062]

[0063] <15> exist <9> or <13> In the method for preparing the reactive compound described herein, the compound represented by formula (17) can be reacted with 3-aminopropyltriethoxysilane to obtain the compound represented by formula (14).

[0064] [Chemistry 16]

[0065]

[0066] [Chemistry 17]

[0067]

[0068] <16> One aspect of this application provides a layered substrate, comprising: a first substrate; and a reactive compound layer disposed on the first substrate, wherein the layer comprises the above-described... <1> to <8> The reactive imparting compound constitutes the reactive imparting compound layer as described in any one of the following; and the second substrate is disposed on the reactive imparting compound layer.

[0069] Invention Effects

[0070] According to the above aspects of this application, a reactive imparting compound, a method for preparing the reactive imparting compound, and a layer substrate can be provided, wherein the degradation of the substrate is controlled and the adhesion is improved. Attached Figure Description

[0071] Figure 1 This is a schematic cross-sectional view of a substrate with a reactive compound-converted layer, as shown in some embodiments of this application.

[0072] Figure 2 The optical absorption spectrum of the reactive compound is shown in some embodiments of this application.

[0073] Figure 3 The optical absorption spectra of the compounds are based on the reactivity shown in some comparative examples of this application.

[0074] Figure 4 The optical absorption spectrum of the reactive compound is shown in Example 1 of this application.

[0075] Figure 5 The optical absorption spectrum of the reactive compound is shown in Example 2 of this application.

[0076] Figure 6 This is a graph showing the change in the optical absorption spectrum of the reactive-donating compound when exposed to light, as shown in Reference Example 1 of this application.

[0077] Figure 7 This is a graph showing the change in the optical absorption spectrum of the reactive-donating compound when exposed to light, as shown in Reference Example 2 of this application. Specific Implementation

[0078] The reactive compounds according to embodiments of this application will now be described. However, this application is not limited to the following embodiments.

[0079] (Reactivity-imparting compounds)

[0080] In this embodiment, the reactivity-enhancing compound contains a silane coupling group and a diacrylidine group in one molecule, represented by the following formula (1). In the following formula (1), * represents an adjacent carbon atom.

[0081] [Chemistry 18]

[0082]

[0083] The reactive compound in this embodiment contains one or more silane coupling groups. The silane coupling groups are hydrolyzed to generate silanol groups. The resulting silanol groups react with the metal in the metal layer of the substrate to improve adhesion. That is, by adsorbing the reactive compound in this embodiment onto the substrate surface to generate silanol groups, the adhesion to the metal layer is improved. The more silane coupling groups in the reactive compound, the better the adhesion to the metal layer. If the adhesion to the metal layer is low, it is preferable to increase the number of silane coupling groups.

[0084] The R of the silane coupling group in formula (1) above 1 R 2 and R 3 Represents a hydrogen atom or an alkyl group. R 1 R 2 and R 3 They can be the same or different. As R... 1 R 2 and R 3 Alkyl groups, for example, include: methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. As R 1 R 2 and R 3 The alkyl group represented is preferably methyl or ethyl.

[0085] The reactive compound in this embodiment contains one or more bisacrididine groups. The bisacrididine groups are chemically stable and generate carbenes by irradiation with long-wavelength ultraviolet light. Carbenes are highly reactive and can form covalent bonds with nearby molecules. Therefore, by coating the reactive compound of this embodiment onto the substrate surface or immersing the substrate in a solution of the reactive compound, the reactive compound is adsorbed onto the substrate surface. Subsequently, by irradiation with light, covalent bonds can be formed between the substrate and the reactive compound. Thus, high adhesion between the substrate and the reactive compound of this embodiment can be obtained. Furthermore, since carbenes exhibit higher adhesion than nitrite groups generated from azide groups, higher adhesion than conventional reactive compounds containing azide groups can be obtained. Additionally, since bisacrididine groups have an absorption band at longer wavelengths compared to azide groups and diazomethyl groups that generate carbenes, photodegradation of the resin can be suppressed. The more bisacrididine groups in the reactive compound, the stronger the adhesion to the substrate. When using substrates containing low adhesion, it is preferable to increase the number of bisacrylidine groups.

[0086] The reactivity-imparting compound is preferably a compound represented by the following formula (2).

[0087] [Chemistry 19]

[0088]

[0089] In formula (2) above, X represents a triazine ring or a benzene ring. X acts as a spacer between the silane coupling group and the bisacrididine group. The position of X in formula (2) above can be adjusted by changing its position relative to Z. 1 Z 2 and Z 3 The binding position of the silane coupling group and the bisacrididine group is adjusted by modifying the positional relationship between the silane coupling group and the metal layer of the substrate, and the bisacrididine group is related to the adsorption of the substrate of the substrate. Therefore, the adhesion between the substrate and the metal layer can be adjusted. To facilitate the preparation and adjustment of the positional relationship between the bisacrididine group and the silane coupling group, X is preferably a triazine ring. The triazine ring can be any one of 1,2,3-triazine, 1,2,4-triazine and 1,3,5-triazine, and 1,3,5-triazine is particularly preferred. When X in the above formula (2) is a benzene ring, it is related to Z 1 Z 2 and Z 3 There are no special restrictions on the binding position, but it is preferred to bind at positions 1, 3, and 5. When X is a benzene ring, Z 1 Z 2 and Z 3 There are no special restrictions on the parts other than hydrogen atoms, which can be any functional groups such as hydroxyl, methyl, etc.

[0090] Z in equation (2) above 1 Z 2 and Z 3 Preferably, it is any one of O, NH, S, or CH2. Based on the ease of production and chemical stability, Z... 1 Z 2 and Z 3 O or NH is preferred. 1 Z 2 and Z 3 They can be the same or different.

[0091] Integers m1, m2, and m3 represent the spacing length between the silane coupling group and the bisacrylidine group. By adjusting the quantities of m1, m2, and m3, the contact frequency between the substrate and the bisacrylidine group, as well as the contact frequency between the metal layer and the silane coupling group, can be adjusted. In the above formula (2), m1, m2, and m3 are preferably integers from 1 to 10. m1, m2, and m3 are preferably integers from 1 to 6. m1, m2, and m3 can be the same or different.

[0092] Y 1 Y 2 and Y 3 It can be a silane coupling group represented by formula (1) above or a bisacrylidine group represented by formula (3) or (11) below. 1 Y2 and Y 3 At least one of them is a silane coupling group represented by formula (1) above. In formula (2) above, the number of silane coupling groups is one or two. The reactivity-enhancing compound shown in formula (2) above contains at least one or more silane coupling groups, which can improve the adhesion of the reactivity-enhancing compound to the metal layer. If it is desired to further improve the adhesion to the metal layer, the number of silane coupling groups is set to two.

[0093] Y 1 Y 2 and Y 3 At least one of them is a bisacrididine group (a group containing a bisacrididine group) represented by formula (3) or (11) below. In formula (2) above, the number of bisacrididine groups is 1 or 2. Since the reactive compound represented by formula (2) contains at least one bisacrididine group, one or more strong covalent bonds can be formed between the reactive compound and the substrate. Therefore, the reactive compound in this embodiment has excellent adhesion to the substrate. When it is desired to further improve the adhesion to the substrate, the number of bisacrididine groups is set to 2. In addition, * in formula (3) below represents an adjacent carbon atom. R in formula (3) below 4 There are no special restrictions; any functional group is acceptable. Because the presence of the bisacrylidine group near the end increases the contact frequency with the substrate, therefore, R... 4 Preferably, it contains hydrogen atoms, methyl, ethyl, trifluoromethyl, or pentafluoroethyl. Particularly preferred is R. 4 When the methyl or pentafluoroethyl form is used, the photoreaction efficiency can be improved.

[0094] In equation (11) below, * represents an adjacent carbon atom. In equation (11) below, R... 5 There are no special restrictions and it can be any functional group. Because the presence of the bisacrylidine group near the end increases the frequency of contact with the substrate, therefore, R 5 Preferably, it is a hydrogen atom, methyl, ethyl, trifluoromethyl, or pentafluoroethyl. In particular, when R... 5 When R is trifluoromethyl or pentafluoroethyl, the photoreaction efficiency can be improved, therefore R 5 Preferred to be trifluoromethyl or pentafluoroethyl. In formula (11) below, A is an arylene or a divalent heterocyclic group. Some or all of the hydrogen atoms in the arylene or divalent heterocyclic group may be substituted with halogen atoms, alkyl groups, etc.

[0095] In formula (11) below, the arylene group of A may include 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,6-naphthylene, and similar groups.

[0096] As a divalent heterocyclic group of A in the following formula (11), examples include divalent groups obtained by removing two hydrogen atoms from the hydrogen atoms that are directly bonded to the carbon atoms or heteroatoms that constitute heterocycles such as furan, thiophene, and pyridine.

[0097] [Chemistry 20]

[0098]

[0099] [Chemistry 21]

[0100]

[0101] As a specific embodiment of the above formula (2), for example, N represented by the following formula (5) can be listed. 2 N 4 -bis(2-(3-methyl-3H-bisacrididin-3-yl)ethyl)-N 6 -((3-triethoxysilyl)propyl)-1,3,5-triazine-2,4,6-triamine, 4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine represented by formula (4) below, and 6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-triazine represented by formula (12) below. 2 N 4 -bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine, N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine represented by formula (13) below, and N-represented by formula (14) below. 2 N 4 -bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-bisacryl-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine, etc.

[0102] [Chemistry 22]

[0103]

[0104] [Chemistry 23]

[0105]

[0106] [Chemistry 24]

[0107]

[0108] [Chemistry 25]

[0109]

[0110] [Chemistry 26]

[0111]

[0112] (Reactivity imparts a function to a compound)

[0113] The reactivity-imparting compound contains a diacrylidine group and a silane coupling group, which are photoreactive nitrogen-containing functional groups. Therefore, the diacrylidine group is decomposed by light (wavelength approximately 360 nm) to generate a carbene (a double-coordinated carbon with six valence electrons and no charge), which is a highly reactive chemical substance. The carbene site forms a covalent bond with the substrate surface of the laminate. After covalent bonding, the silane coupling group of the reactivity-imparting compound is fixed to the substrate surface. The silane coupling group is hydrolyzed with water contained in a solvent to form a silanol group. Therefore, the substrate can be endowed with reactivity that allows it to bond with other materials (e.g., metal layers) via the silanol group.

[0114] Conventionally known compounds containing azido groups and triazine rings are photodecomposed, with the azido groups generating highly reactive chemicals (nitrite groups). Compared to compounds that generate nitrite groups from azido groups, the carbene-generating reactivity-enhancing compound of this embodiment can be activated by longer wavelengths of light.

[0115] Furthermore, compared to conventional compounds containing azide groups, the reactive compound containing bis(aziridine) groups in this embodiment exhibits higher adhesive strength. For example, when metal plating is performed on a resin coated with the reactive compound, the reactive compound in this embodiment is less likely to cause metal peeling compared to existing compounds containing azide groups. In addition to its use in bonding resins to metals, the reactive compound disclosed in this application can also be applied to resin-to-resin bonding, such as bonding silicone resins to each other. Furthermore, the reactive compound of this application can also be applied to the bonding of resins to inorganic materials such as ceramics and quartz.

[0116] (Methods for manufacturing reactive compounds)

[0117] The reactivity-imparting compounds in this embodiment can be prepared, for example, by adding a silane coupling group and a bisacrididine group to a compound containing a triazine ring or a benzene ring. A trihalogenated triazine ring is used as an example, but it can also be prepared by a chemical reaction of a benzene ring. A trihalogenated triazine ring refers to a triazine ring in which three hydrogen atoms are replaced by a halogen. The halogen is preferably chlorine. Compounds containing a trihalogenated triazine ring include cyanuric chloride, 3,5,6-trichloro-1,2,4-triazine, and 4,5,6-trichloro-1,2,3-triazine.

[0118] The method for producing the reactive-donating compound in this embodiment includes: a bisacrididin group-donating step, in which a compound containing a trihalogenated triazine ring is reacted with a compound containing a hydroxyl group and a bisacrididin group to obtain a bisacrididin group-donated compound doped with one or more bisacrididin groups; and a silane coupling group-donating step, in which the bisacrididin group-donated compound is reacted with a compound containing an amino group and a silane coupling group represented by the following formula (6). In the following formula (6), * represents an adjacent carbon atom. Here, the compound containing a trihalogenated triazine ring may be cyanuric chloride, wherein 1,3,5-triazine is chlorinated. In this case, the reactive-donating compound in this embodiment can be prepared by reacting other compounds containing a trihalogenated triazine ring.

[0119] [Chemistry 27]

[0120]

[0121] <Bisacrididine group donation steps>

[0122] In the bisacrididin group-donating step, cyanuric chloride is reacted with a compound containing a hydroxyl group and a bisacrididin group to obtain a bisacrididin group-donated compound. Examples of compounds containing a hydroxyl group and a bisacrididin group include: 2-(3-methyl-3H-bisacrididin-3-yl)ethanol, 2-(3-butyl-3H-bisacrididin-3-yl)ethanol, 2-(3-pentyl-3H-bisacrididin-3-yl)ethanol, and (4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)phenyl)methanol, etc.

[0123] The synthesis using 2-(3-methyl-3H-bisacrididin-3-yl)ethanol is described below. When a bisacrididin group is given, the reaction of formula (7) below can be cited as an example. In formula (7) below, base represents a base, such as diisopropylethylamine, pyridine, triethylamine, etc. In the reaction of formula (7) below, 2,4-dichloro-6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine represented by formula (15) below can be obtained.

[0124] [Chemistry 28]

[0125]

[0126] [Chemistry 29]

[0127]

[0128] The synthesis using (4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)phenyl)methanol is described below. When a bisacrididin group is given, the reaction of formula (16) below can be cited as an example. In formula (16) below, base represents a base, such as diisopropylethylamine, pyridine, triethylamine, etc. In the reaction of formula (16) below, 2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine represented by formula (17) below can be obtained. The temperature during the reaction is, for example, room temperature (20°C to 30°C).

[0129] [Chemistry 30]

[0130]

[0131] [Chemistry 31]

[0132]

[0133] When two bisacrididine groups are given, the reaction of formula (8) below can be cited as an example. In formula (8) below, "base" represents a base, such as diisopropylethylamine, pyridine, triethylamine, etc. In the reaction of formula (8) below, 2-chloro-4,6-bis(2-(3-methyl-3H-bisacrididine-3-yl)ethoxy)-1,3,5-triazine represented by formula (18) below can be obtained. The number of bisacrididine groups given to the triazine ring can be controlled by the reaction temperature when giving the bisacrididine groups. For example, when only one bisacrididine group is given, the reaction temperature is set to room temperature, and when two bisacrididine groups are given, the reaction temperature is set to 40-50°C. The reaction temperature can be set appropriately.

[0134] [Chemistry 32]

[0135]

[0136] [Chemistry 33]

[0137]

[0138] When two bis-acrylidine groups are substituted using (4-(3-(trifluoromethyl)-3H-bis-acryl-3-yl)phenyl)methanol, the bis-acrylidine group substitution reaction is shown in formula (19) below. In formula (19), "base" represents a base, which can be diisopropylethylamine, pyridine, triethylamine, etc. In the reaction of formula (19), 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-bis-acryl-3-yl)benzyl)oxy)-1,3,5-triazine, as represented by formula (20), can be obtained. The number of bis-acrylidine groups substituted to the triazine ring can be controlled by the reaction temperature during bis-acrylidine group substitution.

[0139] [Chemistry 34]

[0140]

[0141] [Chemistry 35]

[0142]

[0143] <Silane coupling group donation steps>

[0144] In the silane coupling group donation step, the bisacrididine group-donating compound obtained in the above-described bisacrididine group donation step is reacted with a compound containing an amino group and the silane coupling group represented by formula (6) above. The reactive donation compound in this embodiment can be obtained through this silane coupling group donation step.

[0145] The R of the silane coupling group represented in formula (6) above 1 R 2 and R 3 Represents a hydrogen atom or an alkyl group. R 1 R 2 and R 3 They can be the same or different. As R... 1 R 2 and R 3 Alkyl groups, for example, include: methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. As R 1 R 2 and R 3 The alkyl group represented is preferably methyl or ethyl.

[0146] Examples of compounds containing an amino group and a silane coupling group represented by the above formula (6) include: 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

[0147] The reaction process of 2,4-dichloro-6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine synthesized from the above formula (7) with 3-aminopropyltriethoxysilane is shown in the following formula (9). In the following formula (9), base represents a base, and diisopropylethylamine, pyridine, triethylamine, etc. can be used. Through the reaction of the following formula (9), 6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N of the above formula (12) can be obtained. 2 N 4 -bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine.

[0148] [Chemistry 36]

[0149]

[0150] The reaction process of 2-chloro-4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine synthesized from formula (8) above with 3-aminopropyltriethoxysilane is shown in formula (10) below. In formula (10) below, base represents a base, such as diisopropylethylamine, pyridine, triethylamine, etc. 4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine represented by formula (4) above can be obtained through the reaction in formula (10) below.

[0151] [Chemistry 37]

[0152]

[0153] The reaction process of 2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-bis(acryl-3-yl)benzyl)oxy)-1,3,5-triazine synthesized from the above formula (16) with 3-aminopropyltriethoxysilane is shown in the following formula (21). In the following formula (21), base represents a base, such as diisopropylethylamine, pyridine, triethylamine, etc. Through the reaction of the following formula (21), N represented by the above formula (14) can be obtained. 2 N 4 -bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-bisacryl-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine.

[0154] [Chemistry 38]

[0155]

[0156] The reaction process of 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine synthesized from the above formula (19) with 3-aminopropyltriethoxysilane is shown in the following formula (22). In the following formula (22), base represents a base, and diisopropylethylamine, pyridine, triethylamine, etc. can be used. Through the reaction of the following formula (22), N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine represented by the above formula (13) can be obtained.

[0157] [Chemistry 39]

[0158]

[0159] (Layer substrate)

[0160] The following describes embodiments of layered substrates made using the reactive imparting compounds described in the embodiments of this application. For example... Figure 1 As shown, according to an embodiment of this application, the layer substrate 100 includes a substrate (first substrate) 1, a reactive compound layer 2, and a metal layer (second substrate) 3. Each part will be described below.

[0161] (Substrate)

[0162] Examples of substrate 1 include inorganic materials such as ceramics, or resins. The shape of substrate 1 is not particularly limited; it can be plate-shaped or granular. Substrate 1 is an example of a first substrate.

[0163] The resin can be a curable resin (e.g., thermosetting resin, photocurable resin, electron beam curable resin), thermoplastic resin, fiber-reinforced resin, rubber (vulcanized rubber), or other materials with a coating containing the above-mentioned polymers on the surface. Acrylonitrile butadiene styrene (ABS) resin is a specific example of a resin. ABS resin is used in vehicle parts as a substrate for bonding ABS to metal by metallization of the surface. Furthermore, as resins for circuit applications, examples include epoxy resin, polyimide resin, liquid crystal polymer, cyclic olefin polymer (COP), fluoropolymer, and polyphenylene sulfide (PPS).

[0164] When the substrate 100 is used as a printed circuit board, it needs to withstand heat loads during wiring and soldering processes. Furthermore, when the substrate 100 is used in movable parts of electronic products, sufficient mechanical strength is required. Therefore, a polyimide resin with excellent properties in terms of heat resistance, mechanical strength, and dimensional stability is preferred.

[0165] Inorganic materials used as substrate 1 include, for example, materials containing silicon oxide. Furthermore, electronic device components and circuit boards include substrates containing various inorganic and organic materials, and are used as layer substrates by forming circuits on their surfaces through metal plating or the like.

[0166] For purposes such as improving mechanical strength, the resin of substrate 1 may also contain inorganic particles such as talc, lubricants, antistatic agents, etc.

[0167] When the substrate 100 is used as a substrate for a printed circuit board, its thickness is not particularly limited. For example, when the substrate 1 is used as a flexible wiring substrate, the thickness of the substrate 1 is preferably between 1 μm and 200 μm. If the thickness of the substrate 1 is less than 1 μm, its mechanical strength may be insufficient, so a thickness less than 1 μm is not a preferred thickness. The thickness of the substrate 1 is more preferably 3 μm or more. Furthermore, if the film thickness exceeds 200 μm, the bending processability may decrease, so a thickness exceeding 200 μm is not a preferred thickness. The thickness of the substrate 1 is more preferably 150 μm or less.

[0168] When the substrate 100 is used as a substrate for a printed circuit board, the arithmetic mean roughness Ra of the substrate 1 is, for example, 0.01 to 1 μm. If the arithmetic mean roughness Ra is between 0.01 μm and 1 μm, it is also possible to accommodate circuit miniaturization. Furthermore, if the arithmetic mean roughness Ra is 0.2 μm or less, transmission loss in the high-frequency region can be reduced. The arithmetic mean roughness Ra can be measured according to JIS B 0601:2013.

[0169] (Reactivity imparted to compound layer 2)

[0170] A reactive compound layer 2 is disposed on the substrate 1 and is composed of the reactive compound in this embodiment. Here, "disposed on the substrate 1" includes not only disposing the reactive compound layer 2 on the substrate 1 in contact, but also disposing an intermediate layer between the substrate 1 and the reactive compound layer 2. Furthermore, it also includes disposing the reactive compound layer 2 on a portion of the surface of the substrate 1.

[0171] There is no particular limitation on the thickness of the reactive compound layer 2; it only needs to cover the entire surface of the substrate 1. The thickness of the reactive compound layer 2 can be, for example, more than one molecule (more than a monolayer) of the reactive compound constituting the reactive compound layer 2. There is no particular upper limit on the thickness of the reactive compound layer 2; for example, it can be below 400 nm.

[0172] (Metal layer)

[0173] A metal layer 3 is disposed on the reactive compound layer 2. The metal layer 3 is composed of silver, tin, copper, copper alloys, etc. When the substrate 100 is used as a substrate for a printed circuit board, considering power loss and transmission loss, the metal constituting the metal layer 3 is preferably copper or a copper alloy with high conductivity. The metal layer is an example of a second substrate.

[0174] The thickness of the metal layer is not particularly limited, for example, it is between 0.1 μm and 50 μm. More preferably, the thickness of the metal layer is between 2 μm and 10 μm. Sufficient mechanical strength can be obtained if the thickness of the metal layer is between 0.1 μm and 50 μm.

[0175] The layer substrate 100 of this embodiment has been described above. In this embodiment, an example using a metal layer 3 as the second substrate is given, but the second substrate of this application is not limited to a metal layer 3. For example, a resin substrate containing liquid crystal polymers, epoxy resins, silicone resins, etc., can be used instead of a metal layer as the second substrate. Alternatively, an inorganic substrate containing ceramics, quartz, etc., can be used instead of a metal layer as the second substrate. Furthermore, while an example using a metal layer as the second substrate is given in this embodiment, the shape of the second substrate is not limited to a layered structure, as long as the first substrate and the second substrate can be bonded by a reactive compound. The combination of the first substrate and the second substrate of the layer substrate of this application can be, for example, a combination of resin and inorganic materials such as ceramics, a combination of resin and metal, a combination of inorganic materials such as ceramics and metal, or a combination of the same or different types of resins.

[0176] (Layer substrate manufacturing method)

[0177] The following describes the manufacturing method of the layer substrate in this embodiment, but the manufacturing method of the layer substrate in this embodiment is not limited to the following method.

[0178] In manufacturing the substrate of this embodiment, firstly, a reactive compound layer 2 containing the reactive compound of this embodiment is formed on a substrate (first substrate) 1. The method for forming the reactive compound layer 2 is not particularly limited. For example, the reactive compound layer 2 can be formed by coating a solution containing the reactive compound onto the surface of the substrate 1. Alternatively, the reactive compound layer 2 can be formed by immersing the substrate 1 in a solution containing the reactive compound.

[0179] When using a solution containing a reactive compound, water, organic solvents, etc., can be appropriately selected as the solvent. Specifically, the solvent can be water, alcohol, ketone, aromatic hydrocarbon, ester, ether, etc. The reactive compound can be dispersed in the solvent without dissolving. When using a solution, the solvent in the solution can evaporate through natural drying or heating.

[0180] An amplifying agent can be added to a solution containing a reactive compound. Other compounds that aid adhesion, such as silane coupling agents, can be used as amplifying agents, such as benzophenone.

[0181] After forming a reactive compound layer 2 on substrate 1, a carbene is generated from the bisacrididine group of the reactive compound by applying energy. Through the reaction of the carbene with substrate 1, a high degree of adhesion can be achieved between the reactive compound layer 2 and substrate 1.

[0182] As a method of applying energy, energy can be applied, for example, by irradiating with light. The diacaridine group in the reactive compound of this embodiment is activated by reaction over a wide range of wavelengths, but to suppress photo-induced degradation, the irradiation light is preferably on the longer wavelength side. Specifically, wavelengths between 300 nm and 450 nm are preferred. Existing light irradiation devices can be used appropriately for light irradiation. In this case, the substrate 1 on which the reactive compound layer 2 is formed can be heated before irradiation to enhance the activation effect.

[0183] After applying energy to the reactive compound layer 2 to improve the adhesion between the substrate 1 and the reactive compound layer 2, a metal layer (second substrate) 3 is formed. The metal layer 3 can be formed by plating or the like. As a plating method, dry plating (evaporation or sputtering) and wet plating methods can be appropriately selected, or both methods can be used together. When forming the metal layer 3, it is preferable to use wet plating such as electroless plating or electroplating to form a metal thin film. Before forming the metal layer 3, a pretreatment step of conventionally known plating steps can be appropriately applied. In addition, when forming a resin substrate or an inorganic substrate, etc., as the second substrate on the reactive compound layer 2, known methods can be used.

[0184] Example

[0185] The embodiments of this application will be described below. The conditions in the embodiments are examples of conditions adopted to confirm the feasibility and effectiveness of this application, and are not limited to these examples. Various conditions may be adopted as long as they can achieve the purpose of this application without departing from the spirit of this application.

[0186] (Test conditions)

[0187] The following instruments and reagents were used in the synthesis of the samples and the analysis of the synthesized samples.

[0188] Analytical instruments

[0189] Nuclear magnetic resonance spectrometer: JEOL JNM-ECA500 nuclear magnetic resonance measurement device (500MHz)

[0190] Mass spectrometer: JEOL JMS-700 mass spectrometer

[0191] • Reagents: Commercially available reagents were used, and purified using standard methods as needed. 2-(3-methyl-3H-bisacrididin-3-yl)ethanol was purchased from Shigematsu Chemical. (4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)phenyl)methanol was purchased from Tokyo Chemical Industry.

[0192] Various reaction solvents: dried and purified using conventional methods as needed.

[0193] Silica gel: Wako Gel C-200 (Wako Pure Chemicals), Silica gel 60N (Kanto Chemicals)

[0194] The method used to synthesize the sample will be described below.

[0195] (Example 1)

[0196] In a 10 mL flask equipped with a side arm, under an argon atmosphere, add anhydrous THF (1.1 mL), 2-(3-methyl-3H-bisacryl-3-yl)ethanol (0.39 mL, 4.07 mmol, 2.50 eq.), and diisopropylethylamine (0.54 mL, 4.07 mmol, 2.50 eq.), and cool to 0 °C. Add cyanuric chloride (0.307 g, 1.63 mmol, 1.00 eq.) dissolved in anhydrous THF (0.72 mL), and stir the mixture in a dark environment for 1 hour. After heating to room temperature (20–30 °C), stir in a dark environment for 16 hours. After stirring, add water, and extract the mixture with diethyl ether. Dry the organic layer with anhydrous sodium sulfate, filter, remove the solvent, and vacuum dry to obtain a yellow crude liquid (0.654 g). The crude product was purified by silica gel column chromatography using hexane:chloroform = 1:1 as the elution solvent to obtain 2,4-dichloro-6-(2-(3-methyl-3H-bisacryl-3-yl)ethoxy)-1,3,5-triazine (0.292 g, 1.18 mmol, 72%), which was a yellow liquid.

[0197] The nuclear magnetic resonance and mass spectrometry results of compound (2,4-dichloro-6-(2-(3-methyl-3H-bisacryl-3-yl)ethoxy)-1,3,5-triazine are shown below.

[0198] 1 H NMR (500MHz, CDCl3): δ1.14 (s, 3H, CH3), 1.88 (t, J=6.6Hz, 2H, CH2), 4.43 (t, J=6.6Hz, 2H, CH2);

[0199] 13 C NMR (126MHz, CDCl3): δ20.1, 23.7, 33.6, 65.4, 170.8, 172.7;

[0200] FAB-MS: m / z 248 [(M+H)] + ].

[0201] Then, 2,4-dichloro-6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine (0.500 g, 2.02 mmol, 1.00 eq.) was placed in a 50 mL side-ended flask under an argon atmosphere. Anhydrous 1,4-dioxane (10.1 mL), 3-aminopropyltriethoxysilane (0.86 mL, 3.69 mmol, 1.83 eq.), and diisopropylethylamine (0.81 mL, 4.76 mmol, 2.36 eq.) were added, the mixture was heated to 65 °C, and stirred in a light-protected environment for 3 hours. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a colorless crude liquid (1.04 g). The crude product was purified by silica gel column chromatography using chloroform:ethyl acetate (3:1) as the elution solvent to obtain 6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-methyl as described in Example 1. 2 N 4 -Bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine (0.476 g, 0.770 mmol, 38%) is a colorless liquid.

[0202] The resulting compound is 6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N 2 N 4 The nuclear magnetic resonance and mass spectrometry results of bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine are shown below.

[0203] 1 ¹H NMR (500 MHz, CDCl₃): δ 0.66 (brt, 4H, CH₂), 1.09 (s, 3H, CH₃), 1.23 (t, J = 6.9 Hz, 18H, CH₃), 1.67 (brs, 4H, CH₂), 1.77 (brs, 2H, CH₂), 3.33 and 3.40 (each brs, total 4H, CH₂), 3.82 (q, J = 6.9 Hz, 12H, CH₂), 4.13 and 4.20 (each brs, total 2H, CH₂), 5.14 and 5.24 (brs, 2H, NH); 13 C NMR (126MHz, CDCl3): δ7.75, 18.4, 20.1, 23.0, 24.1, 34.1, 43.3, 58.5, 61.4, 16.3, 170.0;

[0204] HR-FAB-MS: C 25 H 52 N7O7Si2[(M+H) +The calculated m / z value is 618.3467; the measured value is 618.3471.

[0205] (Example 2)

[0206] In a 10 mL flask equipped with a side arm, under an argon atmosphere, add anhydrous THF (1.1 mL), 2-(3-methyl-3H-bisacrididin-3-yl)ethanol (0.39 mL, 4.07 mmol, 2.50 eq.), and diisopropylethylamine (0.54 mL, 4.07 mmol, 2.50 eq.), and cool to 0 °C. Add cyanuric chloride (0.308 g, 1.63 mmol, 1.00 eq.) dissolved in anhydrous THF (0.72 mL), and stir the mixture in a dark environment for 1 hour. The temperature is then raised to 40 °C, and stirred in a dark environment for 17 hours. After stirring, water is added, and the mixture is extracted with diethyl ether. The organic layer is dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a crude yellow liquid (0.582 g). The crude product was purified by silica gel column chromatography using hexane:chloroform = 1:1 as the elution solvent to obtain 2-chloro-4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine (0.227 g, 0.728 mmol, 45%), which was a yellow liquid.

[0207] The nuclear magnetic resonance spectrum and mass spectrometry results of the obtained compound 2-chloro-4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine are shown below.

[0208] 1 H NMR (500MHz, CDCl3): δ1.13 (s, 6H, CH3), 1.85 (t, J=6.4Hz, 4H, CH2), 4.37 (t, J=6.4Hz, 4H, CH2);

[0209] 13 C NMR (126MHz, CDCl3): δ20.2, 23.8, 33.8, 64.4, 171.9, 172.9;

[0210] FAB-MS: m / z 312[(M+H)] + ].

[0211] Then, 2-chloro-4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine (0.396 g, 1.27 mmol, 1.00 eq.) was placed in a 50 mL side-ended flask under an argon atmosphere. Anhydrous 1,4-dioxane (8.5 mL), 3-aminopropyltriethoxysilane (0.34 mL, 1.46 mmol, 1.15 eq.), and diisopropylethylamine (0.33 mL, 1.94 mmol, 1.53 eq.) were added, the mixture was heated to 65 °C, and stirred in a light-protected environment for 3 hours. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a crude yellow liquid (0.645 g). The crude product was purified by silica gel column chromatography using chloroform:ethyl acetate = 4:1 as the elution solvent to obtain the product of Example 2, 4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine (0.501 g, 1.01 mmol, 80%), which is a yellow liquid.

[0212] The nuclear magnetic resonance and mass spectrometry results of the obtained compound (4,6-bis(2-(3-methyl-3H-bisacryl-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine) are shown below.

[0213] 1 H NMR (500MHz, CDCl3): δ0.67 (t, J=7.6Hz, 2H, CH2), 1.10 (s, 3H, CH3), 1.11 (s, 3H, CH 3), 1.23 (t, J = 6.9Hz, 9H, CH3), 1.71 (quint, J = 7.6Hz, 2H, CH2), 1.79 (t, J = 6.3Hz, 2 H, CH2), 1.81 (t, J=6.3Hz, 2H, CH2), 3.44 (q, J=7.6Hz, 2H, CH2), 3.83 (q, J=6.9Hz, 6 H, CH2), 4.22 (t, J=6.3Hz, 2H, CH2), 4.28 (t, J=6.3Hz, 2H, CH2), 5.80 (brt, 1H, NH);

[0214] 13 C NMR (126MHz, CDCl3): δ7.73, 18.4, 20.12, 20.14, 22.9, 23.97, 24.01, 33.9, 43.5, 58.5, 62.3, 62.4, 168.1, 171.3, 171.9;

[0215] HR-FAB-MS: C 20 H 37 N8O5Si[(M+H) + The calculated m / z value is 497.2656; the measured value is 497.2652.

[0216] (Example 3)

[0217] Cyanuryl chloride (1.00 g, 5.42 mmol, 1.00 eq.) was placed in a 50 mL flask equipped with a side arm and placed under an argon atmosphere. It was dissolved in anhydrous dichloromethane (9.5 mL) and cooled to 0 °C. (4-(3-(trifluoromethyl)-3H-bisacryl-3-yl)phenyl)methanol (1.17 g, 5.41 mmol, 1.00 eq.) and diisopropylethylamine (1.01 mL, 5.94 mmol, 1.10 eq.) dissolved in anhydrous dichloromethane (5.4 mL) were added, and the mixture was stirred for 1 hour in the dark. The mixture was then heated to room temperature (20–30 °C) and stirred for 1.5 hours in the dark. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a crude yellow liquid (1.88 g). The crude product was purified by silica gel column chromatography using hexane:chloroform = 1:4 as the elution solvent to obtain 2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine (1.45 g, 3.98 mmol, 73%), which was a yellow liquid.

[0218] The nuclear magnetic resonance spectrum and mass spectrometry results of the obtained compound (2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine are shown below.

[0219] 1 ¹H NMR (500MHz, CDCl₃): δ 5.53 (s, 2H, CH₂), 7.23 (d, J = 8.6Hz, 2H, benzene-H), 7.51 (d, J = 8.6Hz, 2H, benzene-H);

[0220] 13 C NMR (126MHz, CDCl3): δ28.4 (q, J=40.9Hz), 70.7, 122.1 (q, J=275Hz), 127.0, 128.9, 130.0, 135.5, 170.8, 172.8;

[0221] 19 F NMR (471MHz, CDCl3): δ-65.0;

[0222] HR-FAB-MS: C 12 H7Cl2F3N5O[(M+H) + The calculated m / z value is 363.9980; the measured value is 363.9972.

[0223] Then, 2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-bis(acryl-3-yl)benzyl)oxy)-1,3,5-triazine (0.300 g, 0.824 mmol, 1.00 eq.) was placed in a 20 mL flask with a side arm and the atmosphere was set to argon. Anhydrous 1,4-dioxane (6.04 mL), 3-aminopropyltriethoxysilane (0.44 mL, 1.89 mmol, 2.29 eq.), and diisopropylethylamine (0.42 mL, 2.47 mmol, 3.00 eq.) were added, and the mixture was heated to 65 °C and stirred in a dark environment for 3 hours. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate and filtered, then the solvent was removed and the mixture was dried under vacuum to obtain a crude yellow liquid (0.360 g). The crude product was purified by silica gel column chromatography using chloroform:ethyl acetate (4:1) as the elution solvent to obtain product N from Example 3. 2 N 4 -Bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-bisacryl-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine (0.160 g, 0.218 mmol, 26%), is a yellow liquid.

[0224] The obtained compound N 2 N 4 The nuclear magnetic resonance (NMR) and mass spectrometry (MS) results of bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine are shown below.

[0225] 1 ¹H NMR (500 MHz, CDCl₃): δ 0.65 and 0.66 (each brt, total 4H, CH₂), 1.22 (t, J = 6.9 Hz, 18H, CH₃), 1.68 (brs, 4H, CH₂), 3.33 and 3.39 (each brs, total 4H, CH₂), 3.82 (q, J = 6.9 Hz, 12H, CH₂), 5.14, 5.23 and 5.29 (each brs, total 2H, NH), 5.33 (brs, 2H, CH₂), 7.16 (d, J = 6.9 Hz, 2H, benzene-H), 7.43–7.48 (brm, 2H, benzene-H);

[0226] 13 C NMR (126MHz, CDCl3): δ7.75, 18.4, 23.0, 23.1, 28.4 (q, J=40.9Hz), 43.4, 58.5, 66.8, 67.0, 67.2, 1 22.2 (q, J=275Hz), 126.5, 127.9, 128.3, 128.4, 128.5, 138.9, 166.8, 167.3, 167.6, 170.0, 170.4;

[0227] 19 F NMR (471MHz, CDCl3): δ-65.2.

[0228] (Example 4)

[0229] Cyanuryl chloride (1.00 g, 5.42 mmol, 1.00 eq.) was placed in a 50 mL flask equipped with a side arm and placed under an argon atmosphere. It was dissolved in anhydrous dichloromethane (9.5 mL) and cooled to 0 °C. (4-(3-(trifluoromethyl)-3H-bisacryl-3-yl)phenyl)methanol (2.42 g, 11.9 mmol, 2.20 eq.) and diisopropylethylamine (2.02 mL, 11.9 mmol, 2.20 eq.) dissolved in anhydrous dichloromethane (5.4 mL) was added, and the mixture was stirred for 1 hour in the dark. The temperature was raised to room temperature (20–30 °C) and stirred for 16 hours in the dark. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a yellow solid crude product (3.32 g). The crude product was purified by silica gel column chromatography using hexane:chloroform = 1:4 as the elution solvent to obtain 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine (2.46 g, 4.52 mmol, 83%) as a white solid.

[0230] The nuclear magnetic resonance spectrum and mass spectrometry results of the obtained compound 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine are shown below.

[0231] 1 ¹H NMR (500MHz, CDCl₃): δ 5.47 (s, 4H, CH₂), 7.21 (d, J = 8.4Hz, 4H, benzene-H), 7.47 (d, J = 8.4Hz, 4H, benzene-H);

[0232] 13C NMR (126MHz, CDCl3): δ28.4 (q, J=40.9Hz), 69.8, 122.1 (q, J=275Hz), 126.9, 128.7, 129.7, 136.3, 172.0, 173.0;

[0233] 19 F NMR (471MHz, CDCl3): δ-65.0.

[0234] HR-FAB-MS: C 21 H 13 ClF6N7O2[(M+H) + The calculated m / z value is 544.0723; the measured value is 544.0722.

[0235] Then, 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine (0.266 g, 0.489 mmol, 1.00 eq.) was placed in a 20 mL side-ended flask under an argon atmosphere. Anhydrous 1,4-dioxane (5.35 mL), 3-aminopropyltriethoxysilane (0.12 mL, 0.515 mmol, 1.05 eq.), and diisopropylethylamine (0.12 mL, 0.706 mmol, 1.44 eq.) were added, and the mixture was heated to 65 °C and stirred in a light-proof environment for 3 hours. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a crude yellow liquid (0.339 g). The crude product was purified by silica gel column chromatography using chloroform:ethyl acetate = 4:1 as the elution solvent to obtain N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine (0.243 g, 0.333 mmol, 68%), which was a yellow liquid.

[0236] The nuclear magnetic resonance (NMR) and mass spectrometry (MS) spectra of the obtained compound N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-bisacrididin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine are shown below.

[0237] 1H NMR (500MHz, CDCl3): δ0.64 (t, J=7.5Hz, 2H, CH2), 1.22 (t, J=6.9Hz, 9H, CH3), 1.69 (quint, J=7.5Hz, 2H, CH2), 3.41 (q, J=7.5Hz, 2H, CH2), 3.82 (q, J=6.9Hz , 6H, CH2), 5.36 (s, 2H, CH2), 5.39 (s, 2H, CH2), 5.91 (t, J=7.5Hz, 1H, NH), 7.18 (d, J=7.9Hz, 4H, benzene-H), 7.43 (d, J=7.9Hz, 2H, benzene-H), 7.46 (d, J=7.9Hz, 2H, benzene-H);

[0238] 13 C NMR (126MHz, CDCl3): δ7.73, 18.4, 22.8, 28.4 (q, J=40.9Hz), 43.5, 58.6, 67.8, 68.1, 122.1 (q, J=275Hz), 126.6, 128.2, 128.5, 128.9, 129.0, 138.0, 168.1, 171.3, 171.9;

[0239] 19 F NMR (471MHz, CDCl3): δ65.1.

[0240] (Refer to Example 1)

[0241] 2,4-Dichloro-6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine (0.110 g, 0.443 mmol, 1.00 eq.) was placed in a 10 mL side-ended flask under an argon atmosphere. Anhydrous 1,4-dioxane (2.21 mL), propylamine (0.08 mL, 0.974 mmol, 2.20 eq.), and diisopropylethylamine (0.23 mL, 1.35 mmol, 3.05 eq.) were added. The mixture was heated to 65 °C and stirred for 3 hours in a dark environment. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a white crude solid (0.152 g). The crude product was purified by silica gel column chromatography using chloroform as the elution solvent to obtain 6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N 2 N 4 -Dipropyl-1,3,5-triazine-2,4-diamine (0.130 g, 0.443 mmol, 100%) is a white solid.

[0242] The resulting compound is 6-(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N 2 N 4 The nuclear magnetic resonance and mass spectrometry results of dipropyl-1,3,5-triazine-2,4-diamine are shown below.

[0243] 1 ¹H NMR (500MHz, CDCl₃): δ 0.95 (t, J = 7.2Hz, 6H, CH₃), 1.09 (s, 3H, CH₃), 1.58 (brsext, 4H, CH₂), 1.74 and 1.78 (brt and brs, total 2H, CH₂), 3.30 and 3.36 (each brs, total 4H, CH₂), 4.13 and 5.07 (each brs, total 2H, NH);

[0244] 13 C NMR (126MHz, CDCl3): δ11.5, 20.2, 23.0, 24.1, 34.1, 42.7, 61.3, 61.4, 166.9, 167.3, 170.3; HR-FAB-MS: C 13 H 24 N7O[(M+H) + The calculated m / z value is 294.2042; the measured value is 294.2044.

[0245] (See Example 2 for reference)

[0246] 2-Chloro-4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-1,3,5-triazine (0.280 g, 0.280 g, 0.898 mmol, 1.00 eq.) was placed in a 20 mL flask with a side arm and the atmosphere was set to argon. Anhydrous 1,4-dioxane (5.58 mL), propylamine (0.09 mL, 1.10 mmol, 1.22 eq.), and diisopropylethylamine (0.23 mL, 1.35 mmol, 1.50 eq.) were added, and the mixture was heated to 65 °C and stirred in a dark environment for 3 hours. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, and then subjected to solvent removal and vacuum drying to obtain a white solid crude product (0.300 g). The crude product was purified by silica gel column chromatography using chloroform as the elution solvent to obtain 4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-propyl-1,3,5-triazine-2-amine (0.291 g, 0.870 mmol, 97%), a white solid.

[0247] The nuclear magnetic resonance and mass spectrometry results of the obtained compound (4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-propyl-1,3,5-triazine-2-amine) are shown below.

[0248] 1 H NMR (500MHz, CDCl3): δ0.96 (t, J=7.2Hz, 3H, CH3), 1.10 (s, 3H, CH3), 1.11 (s, 3H, CH3), 1.61 (sext, J=7.2Hz, 2H, CH2), 1.79 (t, J=6.6Hz, 2 H, CH2), 1.82 (t, J = 6.9Hz, 2H, CH2), 3.40 (q, J = 7.2Hz, 2H, CH2), 4.23 (t, J = 6.6Hz, 2H, CH2), 4.29 (t, J = 6.9Hz, 2H, CH2), 5.65 (brs, 1H, NH);

[0249] 13 C NMR (126MHz, CDCl3): δ11.4, 20.2, 22.8, 24.0, 24.1, 34.0, 42.9, 62.3, 62.5, 168.2, 171.3, 171.9;

[0250] HR-FAB-MS: C 14 H 23 N8O2[(M+H) + The calculated m / z value is 335.1944; the measured value is 335.1948.

[0251] (Comparative Example 1)

[0252] The stirring device and cyanuric chloride (1.00 g, 5.42 mmol) were placed in a 50 mL three-necked flask, followed by the addition of THF (6 mL) and acetonitrile (6 mL) and cooling to -10 °C. Trimethylsilyldiazomethane (2.0 M hexane solution, 3.0 mL, 6.0 mmol) was added, and the mixture was heated to room temperature (20–30 °C) and stirred for 6 hours. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate and filtered, then concentrated using a rotary evaporator and dried under reduced pressure to obtain a brown crude solid. The crude solid was purified by silica gel column chromatography using chloroform:hexane = 4:1 as the eluent to obtain 2,4-dichloro-6-(diazomethyl)-1,3,5-triazine (0.689 g, 3.63 mmol, 67%) as a yellow solid.

[0253] Then, the stirring device and 0.758 g (3.99 mmol) of 2,4-dichloro-6-(diazomethyl)-1,3,5-triazine were placed in a 50 mL three-necked flask under an argon atmosphere. Dry 1,4-dioxane (25 mL) was then added. After adding triethylamine (1.66 mL, 12.0 mmol), 3-aminopropyltriethoxysilane (2.14 mL, 9.18 mmol) was added, and the mixture was stirred at 65 °C for 3 hours. After stirring, water was added, and the mixture was extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated using a rotary evaporator, and dried under reduced pressure to obtain a yellow, viscous, oily crude product. The crude product was purified by silica gel column chromatography using chloroform as the elution solvent to obtain the reactive compound 2,4-bis[(3-triethoxysilylpropyl)amino]-6-diazomethyl-1,3,5-triazine (1.661 g, 2.97 mmol, 74%), which was a yellow viscous oil.

[0254] The nuclear magnetic resonance and mass spectrometry results of the obtained compound 2,4-bis[(3-triethoxysilylpropyl)amino]-6-diazomethyl-1,3,5-triazine are shown below.

[0255] 1 H NMR (500MHz, CDCl3): δ0.66 (t, J=8.4Hz, 4H, CH2), 1.27 (t, J=7.0Hz, 18H, CH3), 1.67 (brs, 4H, C H2), 3.36 (brs, 4H, CH2), 3.82 (q, J=7.0Hz, 12H, CH2), 4.83-5.24 (m, 2H, NH), 5.44 (brs, 1H, CH);

[0256] 13 C NMR (101MHz, CDCl3) δ7.7, 18.3, 23.0, 43.1, 51.5, 58.4, 146.8, 165.1;

[0257] FAB-MSm / z[(M+H) + ]:560.3048

[0258] (Simulation of UV-Vis absorption spectroscopy)

[0259] The following theoretical calculation procedure was used in the simulation of UV-Vis absorption spectra of reactive endowed compounds.

[0260] Theoretical calculation program Gaussian 16, Revision C.01

[0261] UV-Vis absorption spectroscopy simulation method: The reactivity-imparting compound triethoxysilylpropylamino in equation (4) above is simplified to methylamino to obtain a model compound (the model compound obtained by replacing triethoxysilylpropylamino in Example 2 with methylamino). Molecular modeling is performed on this model compound, and the molecular structure is optimized by density functional theory (DFT) calculation. In the DFT calculation, B3LYP is used as the functional and 6-31G(d) is used as the basis function. Using the optimal structure of the obtained model compound, time-correlated density functional theory (TD-DFT) calculation is performed to obtain the simulation results of UV-Vis absorption spectrum. In the TD-DFT calculation, B3LYP is used as the functional and 6-31+G(d,p) is used as the basis function.

[0262] (UV-Vis absorption spectrum)

[0263] Furthermore, the following instruments and reagents were used in the analysis of Examples 1 to 4 and Comparative Example 1.

[0264] Apparatus for measuring ultraviolet-visible absorption spectroscopy: JASCO V-670

[0265] Sample solution: After washing each compound in Examples 1 and 2 and Comparative Example 1 with acetone, weigh and add the solution to a dry 50 mL volumetric flask to make the sample concentration 50 μL. -3 or 2 mmol dm -3 The volume was then adjusted to a final volume using anhydrous ethanol. Anhydrous ethanol was chosen to prevent partial hydrolysis of ethoxysilanes in various compounds.

[0266] Measurement: Place the sample solution in a quartz glass bath (1 cm) that has been washed and dried with acetone, and measure under the following conditions.

[0267] UV-Vis absorption spectroscopy measurement conditions: bandwidth: 2 nm, scan rate: 200 nm / min, response: fast, data acquisition interval: 1 nm

[0268] Figure 2 This represents the absorption spectrum obtained through simulation. Figure 3 This represents the observed absorption spectrum of Comparative Example 1. For example... Figure 2 and Figure 3As shown, in the absorption spectrum of the model compound containing the bisacrididine group, absorption from the n-π* transition of the bisacrididine group can be observed near 360 nm, while in Comparative Example 1 containing the diazonyl group, no absorption from the n-π* transition of the bisacrididine group is observed near 360 nm. Therefore, according to the simulation of Example 2, since carbene can be generated by irradiation with light on the longer wavelength side compared to the diazonyl group in Comparative Example 1, photodegradation can be suppressed simply by using the reactive-donating compound of this application.

[0269] Figure 4 The spectrum shown is the absorption spectrum of Example 1. Figure 4 (a) indicates a sample concentration of 50 μm. -3 The absorption spectrum at that time Figure 4 (b) indicates a sample concentration of 2 mmol / dm. -3 The absorption spectrum at that time. Additionally... Figure 5 The spectrum shown is the absorption spectrum of Example 2. Figure 5 (a) indicates a sample concentration of 50 μm. -3 The absorption spectrum at that time Figure 5 (b) indicates a sample concentration of 2 mmol / dm. -3 The absorption spectrum at that time. The measurement results are summarized in Table 1 below. λ in Table 1 abs ε represents the light absorption wavelength (nm), and ε represents the molar extinction coefficient (dm). 3 mol -1 cm -1 ). Figure 4 The horizontal axis of (a) and 4(b) represents wavelength (nm), and the vertical axis represents absorbance (in any unit). Figure 5 In (a) and 5(b), the horizontal axis represents wavelength (nm), and the vertical axis represents absorbance (in any unit). For example... Figure 4 As shown in (b) and 5(b), two absorption bands were observed in the ultraviolet region below 400 nm in Examples 1 and 2. Analysis based on simulation results indicated that the absorption band observed near 360 nm was attributed to the absorption from the n-π* transition of the bisacrididine group, i.e., absorption induced by photolysis to generate carbene. This demonstrates that Examples 1 and 2, containing the bisacrididine group, generate carbene upon irradiation with long-wavelength ultraviolet light (UVA), thereby suppressing photodegradation while reacting with the substrate surface. Similarly, in Examples 3 and 4, an absorption peak was also observed near 357 nm.

[0270] [Table 1]

[0271]

[0272] (Photolysis verification experiment 1 of the bisacrididine group)

[0273] Then, experiments were conducted to verify whether the bisacrididine group of Examples 1 and 2 decomposed into carbene under long-wavelength ultraviolet light (UVA) irradiation (wavelength: 365 nm). This was because the 6-(2-(3-methyl-3H-bisacrididine-3-yl)ethoxy)-N 2 N 4 The silane coupling group of -bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine undergoes hydrolysis; therefore, the 6-(2-(3-methyl-3H-bisacryl-3-yl)ethoxy)-N-methyl silane coupling group of Reference Example 1, which is free of silane coupling groups and easily handled, should be used. 2 N 4 -Dipropyl-1,3,5-triazine-2,4-diamine was used for verification experiments. Similarly, 4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-propyl-1,3,5-triazine-2-amine from Reference Example 2 was used instead of 4,6-bis(2-(3-methyl-3H-bisacrididin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine from Example 2 for verification experiments. The measurement conditions are as follows.

[0274] • Apparatus for measuring ultraviolet-visible absorption spectroscopy: JASCO V-670

[0275] • After washing the compound from Reference Example 1 with acetone, the sample solution was weighed and added to a dry 50 mL volumetric flask, then diluted to volume with anhydrous methanol to a sample concentration of 4 mmol / dm³. 3 Then, the compound from Reference Example 2 was washed with acetone and added to a dry 50 mL volumetric flask to achieve a sample concentration of 2 mmol / dm³. 3 Dilute with anhydrous methanol to a final volume.

[0276] • Measurement: Place the sample solution in a quartz glass bath (1 cm) that has been washed and dried with acetone, and measure under the following conditions.

[0277] UV-Vis absorption spectroscopy measurement conditions: bandwidth: 2nm, scan speed: 200nm / min, response: fast, data acquisition interval: 1nm; light source: handheld UV lamp (254nm and 365nm compatible).

[0278] • Irradiation conditions: Wavelength: 365nm, time: 0–40min

[0279] Figure 6 This represents the change in the absorption spectrum of the sample solution in Reference Example 1 under light illumination. Figure 7This represents the change in the absorption spectrum of the sample solution in Reference Example 2 under illumination. The horizontal axis represents wavelength, and the vertical axis represents absorbance (in arbitrary units). Figure 6 and 7 As shown, the longer the irradiation time, the smaller the peak (around 360 nm) of the n-π* transition from the diacrylidine group. This indicates that the diacrylidine group is photolytically decomposed into carbene under light irradiation. Therefore, it can be verified that the diacrylidine group can be decomposed into carbene under light irradiation at a wavelength of 365 nm.

[0280] (Photolysis verification experiment 2 of the bisacrylidine group)

[0281] To verify that the diacaridine group photodecomposes to form carbene, Reference Examples 1 and 2 were dissolved in methanol and irradiated with 365 nm ultraviolet light for 10 minutes. Mass spectrometry analysis was performed on the solutions before and after 10 minutes of irradiation to study the photoreaction products. The measurement conditions are as follows.

[0282] • Measurement equipment: JEOL JMS-700 mass spectrometer

[0283] • Sample solution: Weigh 6 mg of sample and put it into a sample vial, then add 3 mL of anhydrous methanol to prepare the sample solution.

[0284] • Light source: Handheld UV lamp (254nm and 365nm compatible)

[0285] Measurement: A portion of the prepared sample solution was placed into a sample vial without any further processing, serving as the sample before UV irradiation. A portion of the remaining prepared solution was placed into a quartz cuvette, and then the cuvette was irradiated with 365 nm UV light for 10 minutes using a handheld UV lamp. Afterward, this solution was placed into a sample vial, serving as the sample after UV irradiation. Mass spectrometry analysis was then performed.

[0286] In the mass spectrometry (ionization method: electron ionization) of the sample solution of Reference Example 1 before ultraviolet light irradiation, a molecular ion (M) corresponding to the molecular weight of Reference Example 1 at m / z 293 was detected. + On the other hand, in the mass spectrometry of the sample solution after ultraviolet light irradiation, a molecular ion (M0) from the photoreaction product at m / z 297 was detected. + The peak indicates that the photoreaction product was not detected before irradiation. This peak is consistent with the molecular weight 279 of the product generated by the OH insertion reaction of the carbene produced by the photolysis of the bisacrylidine group with the hydroxyl group (OH group) of methanol. This product is 6-(3-methoxybutoxy)-N 2 N 4-Dipropyl-1,3,5-triazine-2,4-diamine. In the mass spectrometry (ionization method: fast atom bombardment ionization) of the sample solution of Reference Example 2 before UV irradiation, a molecular ion peak at m / z 335 was detected. If m / z 335 is considered a protonated molecular ion, the mass number of this peak is 334, consistent with the molecular weight of 334 in Reference Example 2. In the mass spectrometry of the sample solution of Reference Example 2 after UV irradiation, a molecular ion peak at m / z 343 was detected. If m / z 343 is considered a protonated molecular ion, the mass number of this peak is 342, consistent with the molecular weight of 342 of 4,6-bis(3-methoxybutoxy)-N-propyl-1,3,5-triazine-2-amine, which is generated by the OH insertion reaction of the carbene generated from the photolysis of the two diaziridine groups in the molecular structure with the hydroxyl (OH group). Since the product generated by the insertion reaction of carbene with the OH bond of alcohol is a photoreaction product, it can be verified that the bisacrididine group can be decomposed into carbene by irradiation with light of wavelength 365 nm.

[0287] (Fabrication of substrates using reactive compounds and evaluation of peel strength)

[0288] Then, layer substrates were fabricated using the reactive compounds from Examples 1, 2, and 4, and peel strength (adhesion evaluation) was performed. The samples used for evaluation were prepared according to the following procedure.

[0289] "Pre-impregnation solution"

[0290] A pre-impregnation solution was prepared by adding 4.25 g of Cataprep 404A manufactured by Rohm and Haas Electronics Materials Co., Ltd. and 13.2 g of NaCl to 50 mL of distilled water and simultaneously ultrasonically stirring for 10 minutes.

[0291] "Catalyst solution"

[0292] Add 12.5 g of CataPrep 404 (manufactured by Rohm and Haas Electronic Materials Co., Ltd.) to 50 mL of distilled water and sonicate for 10 minutes. After the CataPrep 404 is completely dissolved, add 1.5 mL of Cataposit 44 (manufactured by Rohm and Haas Electronic Materials) to prepare the catalyst solution.

[0293] "Accelerator solution"

[0294] To prepare the accelerator solution, 2.5 g of accelerator-19E manufactured by Rohm and Haas Electronics Materials Co., Ltd. was added to 47.5 mL of distilled water and ultrasonically stirred for 10 minutes.

[0295] Electroless plating solution

[0296] Add 12.5g of Adcapper IW-A (manufactured by Okuno Pharmaceutical Industries Co., Ltd.), 0.75ml of Adcapper C (manufactured by Okuno Pharmaceutical Industries Co., Ltd.), 4ml of Adcapper (manufactured by Okuno Pharmaceutical Industries Co., Ltd.), and 0.15ml of electroless copper RN (manufactured by Okuno Pharmaceutical Industries Co., Ltd.) to 42.6mL of distilled water, and then ultrasonically stir for 10 minutes.

[0297] Acrylonitrile-butadiene-styrene resin substrates (ABS substrates) were prepared using ABS substrates (1 mm × 30 mm × 130 μm thickness) manufactured by Mitsubishi Chemical Corporation. The ABS substrates were immersed in ethanol, ultrasonically irradiated for 10 minutes, washed, and dried. After drying, the surface of the ABS substrates was subjected to three corona treatments using a corona discharge device (Corona Master manufactured by Shin-Kuang Electric Co., Ltd., output voltage 12 kV, irradiation distance 0.5 mm). Then, the ABS substrates were immersed in the ethanol solution (concentration 0.1 wt%) of Example 1 or Example 2 for 10 seconds and dried to form a reactive compound-imparting layer. Furthermore, in Example 4, layer substrates without corona discharge treatment and those with corona discharge treatment were prepared, respectively.

[0298] After forming the reactive compound layer, the ABS substrate is irradiated with a high-pressure mercury lamp or an LED lamp. Both the high-pressure mercury lamp and the LED have a dominant wavelength of 365 nm and an illuminance of 17 mW / cm², respectively. 2 and 396mW / cm 2 The irradiance was measured using a UVPF-A2 illuminometer (peak sensitivity 355nm). The irradiation time was 5 minutes. After irradiation, the ABS substrate was immersed in a pre-immersion solution for 1 minute, without washing, and then immersed in a catalyst solution at 50°C for 1 minute, followed by washing with distilled water. After washing, without drying, the ABS substrate was immersed in an accelerator solution for 3 minutes and then washed with distilled water. After washing, the ABS substrate, while wet, was immersed in an electroless plating solution at 32°C for 15 minutes, washed with distilled water and ethanol, and then dried. After drying, the ABS substrate with the copper layer (layer substrate) was annealed at 80°C for 10 minutes. After annealing, it was cooled to room temperature. After cooling, the annealed layer substrate was immersed in a copper sulfate-based electrolytic copper plating solution at a voltage of 15V and a current density of 0.02A / cm².2 The substrate is plated with copper for 60 minutes, washed with distilled water and dried, and then annealed at 80°C for 10 minutes to obtain a layer substrate made using the reactive imparting compounds in each embodiment.

[0299] Peel strength measurement

[0300] A 1 cm wide cut was made in the copper layer portion of the layered substrate formed using the reactive compounds of Examples 1 and 2. The peel strength between the copper layer and the ABS substrate was measured using a adhesion testing machine (IMADA FORCE MEASUREMENT model mX2, manufactured by Imada Corporation) at a tensile speed of 50 mm / min and a tensile angle of 90°. The results are shown in Table 2. Furthermore, the peel strength measurements for Example 4 with and without corona discharge treatment are shown in Table 3.

[0301] [Table 2]

[0302]

[0303] [Table 3]

[0304]

[0305] As shown in Table 2, when irradiated with ultraviolet light using a high-pressure mercury lamp, the substrates composed of the reactive imparting compounds of Examples 1 and 2 all exhibited high peel strength. The reason for this high adhesion is believed to be that the carbene generated in Example 1 or Example 2 undergoes an OH insertion reaction with the hydroxyl groups (OH groups) on the substrate surface generated by corona discharge, forming a covalent bond between the reactive imparting compound and the substrate surface. Furthermore, since few hydroxyl groups are introduced to the substrate surface via corona discharge, it is difficult to directly obtain high adhesion. However, it is confirmed that by combining the reactive imparting compounds from Examples 1 and 2 to the substrate surface through the photoreaction of the diacrylidine group, and imparting a silanol-generating group, a chemical bond is formed between the silanol and the copper layer, thus improving adhesion. When irradiated with an LED lamp, the substrate of Example 2, which contains two diacrylidine groups in its molecule, exhibited higher peel strength than the substrate of Example 1, which contains one diacrylidine group in its molecule. Furthermore, irradiation with a mercury lamp showed higher peel strength than irradiation with an LED lamp. When using a high-pressure mercury lamp with a dominant wavelength of 365 nm and a broad spectrum in the ultraviolet region, carbene is easily generated, resulting in higher photoreaction efficiency between the reactive compound and the substrate. Therefore, high coating adhesion can be obtained regardless of the number of diacrylidine groups within the molecule and the type of reactive compound used. On the other hand, when using an LED lamp with a narrow spectrum centered at 365 nm, carbene is not easily generated, resulting in lower photoreaction efficiency between the reactive compound and the substrate. Therefore, high adhesion can be obtained when using Example 2, which has a large number of diacrylidine groups and a high reactivity with the substrate.

[0306] On the other hand, as shown in Table 3, when the reactive compound of Example 4 was used, the same level of peel strength was observed regardless of whether a high-pressure mercury lamp or an LED lamp was used as the photoreactive light source. Furthermore, high peel strength was observed even without corona treatment. This is because the reactive compound of Example 4 contains a 3-trifluoromethyl-3-phenyldiazepine skeleton, thus increasing the photolysis efficiency of the bisacrididin group, and the resulting carbene can undergo not only OH insertion reactions but also CH insertion reactions.

[0307] Based on the above results, reactive compounds containing bisacrididine groups are considered to be very useful photoreactive molecular binders.

[0308] Industrial applicability

[0309] Since the reactive compound, the method for manufacturing the reactive compound, and the layer substrate of this application can be used in industry to suppress photodegradation of the substrate and obtain high adhesion, it has high industrial applicability.

[0310] Symbol Explanation

[0311] 1. Substrate, 2. Reactive compound layer, 3. Metal layer, 100-layer substrate.

Claims

1. A reactive imparting compound characterized in that, The reactive conferring compound is a compound represented by the following formula (2) wherein, contains a silane coupling group represented by the following formula (1) and a bisaziridine group in one molecule, wherein the number of the silane coupling group is 2, or the number of the bisaziridine group is 2; [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] wherein, The * in the formula (1) indicates adjacent carbon atoms, R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group, R 1 , R 2 and R 3 may be the same or different; In formula (2), X represents a triazine ring or a benzene ring, and Z represents a triazine ring or a benzene ring. 1 Z 2 and Z 3 Y represents any one of O, NH, S, or CH2, m1, m2, and m3 represent integers between 1 and 10. 1 Y 2 and Y 3 It is the silane coupling group, or the bisacrylidine group represented by formula (3) or (11), Y 1 Y 2 and Y 3 At least one of them is the silane coupling group, Y 1 Y 2 and Y 3 At least one of them is the bisacrylidine group; The * in the formula (3) indicates adjacent carbon atoms, R 4 represents a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group or a pentafluoroethyl group; The * in the formula (11) indicates adjacent carbon atoms, R 5 represents a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group or a pentafluoroethyl group, and A is an arylene group or a divalent heterocyclic group.

2. The reactive imparting compound according to claim 1, wherein, The X is a triazine ring.

3. The reactive imparting compound according to claim 1 or 2, wherein, Z 1 , Z 2 , and Z 3 is NH or O.

4. The reactive conferring compound according to claim 3, which is a compound represented by the following formula (4): [Chemical Formula 5] 5. The reactive conferring compound according to claim 3, which is a compound represented by the following formula (12): [Chemical Formula 6] 6. The reactive conferring compound according to claim 3, which is a compound represented by the following formula (13): [Chemical Formula 7] 7. The reactive conferring compound according to claim 3, which is a compound represented by the following formula (14): [Chemical Formula 8] 8. A method for producing a reactive conferring compound, comprising: a bisaziridine group conferring step of reacting a compound containing a trihalogenated triazine ring with a compound containing a hydroxyl group and a bisaziridine group to obtain a bisaziridine group conferring compound to which one or more bisaziridine groups are conferred; a silane coupling group conferring step of reacting the bisaziridine group conferring compound with a compound containing an amino group and a silane coupling group represented by the following formula (6); [Chemical Formula 9] wherein, The * in the formula (6) indicates adjacent carbon atoms; R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group, R 1 , R 2 and R 3 may be the same or different; The compound containing a trihalogenated triazine ring is cyanuric chloride, 3,5,6-trichloro-l,2,4-triazine, 4,5,6-trichloro-l,2,3-triazine; The compound containing a hydroxyl group and a bisaziridine group is 2-(3-methyl-3H-bisaziridine-3-yl)ethanol, 2-(3-butyl-3H-bisaziridine-3-yl)ethanol, 2-(3-pentyl-3H-bisaziridine-3-yl)ethanol, or (4-(3-(trifluoromethyl)-3H-bisaziridine-3-yl)phenyl)methanol; The compound containing an amino group and a silane coupling group represented by the formula (6) is 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane.

9. The method of preparing a reactive conferring compound according to claim 8, wherein, Two of the bisaziridine groups are conferred in the bisaziridine group conferring step.

10. The method of preparing a reactive imparting compound according to claim 8 or 9, wherein, The compound represented by the following formula (18) is reacted with 3-aminopropyltriethoxysilane to obtain a compound represented by the following formula (4): [Chemical Formula 10] [Chemical Formula 11] 11. The method of preparing a reactive imparting compound according to claim 8 or 9, wherein, The compound represented by the following formula (20) is reacted with 3-aminopropyltriethoxysilane to obtain a compound represented by the following formula (13): [Chemical Formula 12] [Chemical Formula 13] 12. The method of preparing a reactive conferring compound according to claim 8, wherein, One of the bisaziridine groups is conferred in the bisaziridine group conferring step.

13. The method of preparing a reactive imparting compound according to claim 8 or 12, wherein, The compound represented by the following formula (15) is reacted with 3-aminopropyltriethoxysilane to obtain a compound represented by the following formula (12): [Chemical Formula 14] [Chemical Formula 15] 14. The method of preparing a reactive imparting compound according to claim 8 or 12, wherein, The compound represented by the following formula (17) is reacted with 3-aminopropyltriethoxysilane to obtain a compound represented by the following formula (14): [Chemical Formula 16] [Chemical Formula 17] 15. A layer substrate, comprising: a first substrate; a reactive property-imparting compound layer provided on the first substrate, composed of the reactive property-imparting compound according to any one of claims 1 to 7; and a second substrate provided on the reactive property-imparting compound layer.

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