Patent Application
20250074929
The present invention relates to a reactivity-imparting compound, a method for producing a reactivity-imparting compound, and a layered body.
Priority is claimed on Japanese Patent Application No. 2020-185196, filed on Nov. 5, 2020, and Japanese Patent Application No. 2021-145578, filed on Sep. 7, 2021, the contents of which are incorporated herein by reference.
Composite materials consisting of different materials bonded together, for example, a layered body with a metal film formed on an inorganic base material or a polymer base material, are used in circuit boards for cellular phones, vehicle members, or the like.
In layered bodies, poor adhesion between materials causes delamination between the materials. For this reason, improvement in adhesion is an important property for layered bodies. Techniques for improving adhesion between materials include, for example, a technique for forming unevenness on the surface of a base material. A portion of the metal film penetrates into the unevenness on the surface of the base material, which exerts an anchor effect and improves adhesion.
However, for example, if the surface of a base material for circuit boards is uneven, the transmission distance of signals becomes longer, resulting in transmission loss. For this reason, it is difficult to use the technique for forming unevenness on the surface of a base material for circuit board applications.
As a technique for improving adhesion strength without forming unevenness on a surface, there is a technique for introducing hydroxyl groups into a substrate through corona discharge treatment. However, because the corona discharge treatment may degrade a base material and introduces only a small number of hydroxyl groups, improvement in adhesion is limited.
As another technique for improving adhesion strength without forming unevenness on a surface, there is a technique for reacting a compound capable of imparting reactivity to the surface of a base material with the surface of the base material. For example, organofunctional silane compounds have been developed to improve the performance of a layered bodies such as polymeric material glass and metals. This method uses a coupling agent, that is, a bifunctional molecule, which reacts with both a polymeric material and a bonding target (for example, a metal) to form a covalent bond. Specifically speaking, silane coupling agents are organofunctional silane monomers which have binary reactivity. This property allows a functional group at one end of a molecule to be hydrolyzed to form a silanol which then enables bonding through condensation or the like with similar functional groups on glass or the like or OH groups on metal oxides. At the other end of the silane molecule, there is a functional group capable of reacting with an organic substance such as an amino group or a mercapto group. In this manner, silane coupling agents are known as very useful molecules that covalently bond organic materials to other materials.
Patent Document 1 discloses a method for forming a metal film, the method including: a step of providing an agent containing a specific compound on the surface of a base body; and a step of providing a metal film on the surface of a compound through a wet-type plating method, in which the compound is a compound having an OH group or an OH-producing group, an azide group, and a triazine ring in one molecule, and in which the base body is composed of a polymer. Molecules having azide groups are irradiated with ultraviolet light to produce nitrenes from the azide groups, and the produced nitrenes react with the surface of a base material, whereby high adhesion can be obtained.
However, there is currently a demand for a method that provides higher adhesion than the technique of Patent Document 1. In addition, in the technique of Patent Document 1, since the molecules having azide groups are irradiated with short-wavelength ultraviolet light, there has been a problem in that the base material deteriorates and the adhesion is reduced.
The present invention has been made in consideration of the above-described problems, and an object of the present invention is to provide a reactivity-imparting compound that inhibits photodegradation of a base material and provides high adhesion, a method for producing a reactivity-imparting compound, and a layered body.
In order to solve the problems, the present invention proposes the following means.
<1> A reactivity-imparting compound according to one embodiment of the present invention includes, in one molecule: a silane coupling moiety represented by Formula (1) below; and a diazirine group.
[In Formula (1), * represents an adjacent carbon atom, and R1, R2, and R3 each represents a hydrogen atom or an alkyl group and may be the same as or different from each other.]
<2> The reactivity-imparting compound according to <1> above may be a compound represented by Formula (2) below.
[In Formula (2), X represents a triazine ring or a benzene ring, Z1, Z2, and Z3 each represents any one of O, NH, S, or CH2, m1, m2, and m3 each represents an integer of 1 to 10, Y1, Y2, and Y3 are each the silane coupling moiety or a diazirine group represented by Formula (3) or (11) above, at least one of Y1, Y2, and Y3 is the silane coupling moiety, and at least one of Y1, Y2, and Y3 is the diazirine group; in Formula (3) above, * represents an adjacent carbon atom and R4 is an arbitrary functional group; and in Formula (11) above, * represents an adjacent carbon atom, R5 is an arbitrary functional group, and A is an arylene group or a divalent heterocyclic group.]
<3> In the reactivity-imparting compound according to <2>, the X may be a triazine ring.
<4> In the reactivity-imparting compound according to <2> or <3>, Z1, Z2, and Z3 each may be NH or O.
<5> The reactivity-imparting compound according to <4> above may be a compound represented by Formula (4) below.
<6> The reactivity-imparting compound according to <4> above may be a compound represented by Formula (12) below.
<7> The reactivity-imparting compound according to <4> above may be a compound represented by Formula (13) below.
<8> The reactivity-imparting compound according to <4> above may be a compound represented by Formula (14) below.
<9> A method for producing a reactivity-imparting compound according to one embodiment of the present invention includes: a diazirine group-imparting step of reacting a compound containing a trihalogenated triazine ring with a compound containing a hydroxyl group and a diazirine group to obtain a diazirine group-imparted compound to which one or more diazirine groups are imparted; and a silane coupling moiety-imparting step of reacting the diazirine group-imparted compound with a compound containing an amino group and a silane coupling moiety represented by Formula (6) below.
[In Formula (6), * represents an adjacent carbon atom, and R1, R2, and R3 each represents a hydrogen atom or an alkyl group and may be the same as or different from each other.]
<10> The method for producing a reactivity-imparting compound according to <9>, in which, in the diazirine group-imparting step, two diazirine groups may be imparted.
<11> The method for producing a reactivity-imparting compound according to <9> or <10>, in which a compound of Formula (18) below may be reacted with 3-aminopropyltriethoxysilane to obtain a compound of Formula (4) below.
<12> The method for producing a reactivity-imparting compound according to <9> or <10> above, in which a compound of Formula (20) below may be reacted with 3-aminopropyltriethoxysilane to obtain a compound of Formula (13) below.
<13> The method for producing a reactivity-imparting compound according to <9>, in which, in the diazirine group-imparting step, one diazirine group may be imparted.
<14> The method for producing a reactivity-imparting compound according to <9> or <13>, in which a compound of Formula (15) below may be reacted with 3-aminopropyltriethoxysilane to obtain a compound of Formula (12) below.
<15> The method for producing a reactivity-imparting compound according to <9> or <13> above, in which a compound of Formula (17) below may be reacted with 3-aminopropyltriethoxysilane to obtain a compound of Formula (14) below.
<16> A layered body according to one aspect of the present invention includes: a first base material; a reactivity-imparting compound layer which is provided on the first base material and composed of the reactivity-imparting compound according to any one of <1> to <8> above; and a second base material provided on the reactivity-imparting compound layer.
According to the above-described aspects of the present invention, it is possible to provide a reactivity-imparting compound that inhibits photodegradation of a base material and provides high adhesion, a method for producing a reactivity-imparting compound, and a layered body.
Hereinafter, reactivity-imparting compounds according to embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.
A reactivity-imparting compound according to the present embodiment includes, in one molecule: a silane coupling moiety represented by Formula (1) below; and a diazirine group. * in Formula (1) below represents an adjacent carbon atom.
The reactivity-imparting compound according to the present embodiment includes one or more silane coupling moieties. Silane coupling moieties are moieties that produce silanol groups through hydrolysis. Produced silanol groups react with metals of a metal layer in a layered body and improve adhesion. That is, the adhesion with respect to the metal layer is improved by adsorbing the reactivity-imparting compound according to the present embodiment on the surface of a base material and producing silanol groups. The adhesion with respect to the metal layer is improved as the number of silane coupling moieties in the reactivity-imparting compound increases. In a case where the adhesion with respect to the metal layer is low, the number of silane coupling moieties is preferably increased.
R1, R2, and R3 in the silane coupling moiety in Formula (1) above each represents a hydrogen atom or an alkyl group. R1, R2, and R3 may be the same as or different from each other. Examples of alkyl groups for R1, R2, and R3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Alkyl group for R1, R2, and R3 preferably is a methyl group or an ethyl group.
The reactivity-imparting compound according to the present embodiment includes one or more diazirine groups. Diazirine groups are chemically stable, and produce carbenes with emission of long-wavelength ultraviolet rays. Carbenes are highly reactive and can form covalent bonds with molecules near the carbenes. For this reason, after applying the reactivity-imparting compound according to the present embodiment to the surface of a base material or after adsorbing the reactivity-imparting compound on the surface of the base material by immersing the base material in a solution of the reactivity-imparting compound, light can be emitted to form covalent bonds between the base material and the reactivity-imparting compound. Accordingly, high adhesion can be obtained between the base material and the reactivity-imparting compound according to the present embodiment. Furthermore, since carbenes can provide higher adhesion than nitrenes produced from azide groups, higher adhesion than a reactivity-imparting compound in the related art in which an azide group is used can be obtained. In addition, since diazirine groups have an absorption band on a longer wavelength side than azide groups and diazomethyl groups producing carbenes, photodegradation of a resin can be suppressed. The adhesion with respect to the base material is improved as the number of diazirine groups in the reactivity-imparting compound increases. The number of diazirine groups is preferably increased in a case where, for example, a less adhesive base material is used.
The reactivity-imparting compound is preferably a compound represented by Formula (2) below.
X in Formula (2) above represents a triazine ring or a benzene ring. X functions as a spacer between a silane coupling moiety and a diazirine group. In addition, in X in Formula (2) above, the bonding position between Z1, Z2, and Z3 can be adjusted to adjust the positional relationship between a silane coupling moiety related to adsorption with a metal layer of a layered body and a diazirine group related to adsorption with a base material of the layered body. Accordingly, the adhesion between the base material and the metal layer can be adjusted. X is preferably a triazine ring for ease of production and to adjust the positional relationship between a diazirine group and a silane coupling moiety. The triazine ring may be any of 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine, but 1,3,5-triazine is particularly preferable. In a case where X in Formula (2) above is a benzene ring, the bonding position between Z1, Z2, and Z3 is not particularly limited, but bonding at positions 1, 3, and 5 is preferable. In the case where X is a benzene ring, moieties other than Z1, Z2, and Z3 are not particularly limited, and may be a hydrogen atom or may be an arbitrary functional group such as a hydroxyl group or a methyl group.
Z1, Z2, and Z3 in Formula (2) above are each preferably any one of O, NH, S, or CH2. Z1, Z2, and Z3 are each preferably O or NH for ease of production and chemical stability, for example. Z1, Z2, and Z3 may be the same as or different from each other.
An integer of m1, m2, or m3 represents the length of a spacer between a silane coupling moiety and a diazirine group. By adjusting the numbers of m1, m2, and m3, the contact frequency between the base material and a diazirine group and the contact frequency between the metal layer and a silane coupling moiety can be adjusted. m1, m2, or m3 in Formula (2) above are preferably integers of 1 to 10. m1, m2, or m3 are preferably integers of 1 to 6. The integers of m1, m2, or m3 may be the same as or different from each other.
Y1, Y2, and Y3 are each a silane coupling moiety represented by Formula (1) above or a diazirine group represented by Formula (3) or (11) below. At least one of Y1, Y2, and Y3 is a silane coupling moiety represented by Formula (1) above. In Formula (2) above, the number of silane coupling moieties is 1 or 2. Since the reactivity-imparting compound represented by Formula (2) above has at least one silane coupling moiety, the adhesion between the reactivity-imparting compound and the metal layer can be improved. For better adhesion with respect to the metal layer, the number of silane coupling moieties is set to 2.
At least one of Y1, Y2, and Y3 is a diazirine group (diazirine-containing group) represented by Formula (3) or (11) below. In Formula (2) above, the number of diazirine groups is 1 or 2. Since the reactivity-imparting compound represented by Formula (2) above has at least one silane coupling moiety, one or more strong covalent bonds can be formed between the reactivity-imparting compound and the base material. For this reason, the reactivity-imparting compound according to the present embodiment has excellent adhesion with respect to the base material. For better adhesion with respect to the metal layer, the number of diazirine groups is set to 2. * in Formula (3) below represents an adjacent carbon atom. R4 in Formula (3) below is not particularly limited and is an arbitrary functional group. Since the presence of diazirine groups near a terminal increases the contact frequency with the base material, R4 is preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group. In particular, R4 is preferably a trifluoromethyl group or a pentafluoroethyl group to improve the photoreaction efficiency.
* in Formula (11) below represents an adjacent carbon atom. R5 in Formula (11) below is not particularly limited and is an arbitrary functional group. Since the presence of diazirine groups near a terminal increases the contact frequency with the base material, R5 is preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group. In particular, R5 is preferably a trifluoromethyl group or a pentafluoroethyl group to improve the photoreaction efficiency. Ain Formula (11) below is an arylene group or a divalent heterocyclic group. Some or all hydrogen atoms in the arylene group or divalent heterocyclic group may be substituted with halogen atoms, alkyl groups, and the like.
Examples of arylene groups for Ain Formula (11) below 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.
Examples of divalent heterocyclic groups for A in Formula (11) below include a divalent group excluding two hydrogen atoms out of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting a heterocyclic ring such as furan, thiophene, and pyridine.
Specific examples of Formula (2) above include N2,N4-bis(2-(3-methyl-3H-diazirin-3-yl)ethyl)-N6-((3-triethoxysilyl)propyl)-1,3,5-triazine-2,4,6-triamine represented by Formula (5) below, 4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine represented by Formula (4) below, 6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine represented by Formula (12) below, N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine represented by Formula (13) below, and N2,N4-bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine represented by Formula (14) below.
Since the reactivity-imparting compound according to the present embodiment has a silane coupling moiety and a diazirine group which is a photoreactive nitrogen-functional group, the diazirine group is photolyzed by light (at a wavelength around 360 nm) to produce carbenes (two-carbonated carbon which has six valence electrons and no charge) which are highly reactive chemical species. These carbene moieties form covalent bonds with the surface of a base material of a layered body. After the formation of covalent bonds, the silane coupling moiety of the reactivity-imparting compound is immobilized on the surface of the base material. The silane coupling moiety forms silanol groups through hydrolysis with water contained in a solvent or the like. Accordingly, the base material can be imparted with reactivity that enables bonding with other materials (for example, a metal layer) via silanol groups.
A conventionally well-known compound which contains an azide group and a triazine ring is photolyzed to produce highly reactive chemical species (nitrenes) from the azide group moiety. Here, the reactivity-imparting compound of the present embodiment that produces carbenes can be activated by longer-wavelength light than the compound producing nitrenes derived from the azide group moiety.
In addition, the reactivity-imparting compound of the present embodiment which has a diazirine group has higher bonding strength than the conventional compound having an azide group. For example, in a case where a resin to which the reactivity-imparting compound of the present embodiment is imparted is metal-plated, the metal is less likely to peel off than with the conventional compound having an azide group. The reactivity-imparting compound of the present disclosure can be applied to resin-to resin bonding, such as bonding between silicone resins, in addition to resin-to-metal bonding. In addition, the reactivity-imparting compound of the present disclosure can also be applied to, for example, bonding between a resin and an inorganic material such as ceramics or quartz.
The reactivity-imparting compound of the present embodiment can be appropriately produced, for example, through a method for introducing a silane coupling moiety and a diazirine group into a compound with 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. The trihalogenated triazine ring refers to a triazine ring in which three hydrogen atoms are substituted with halogens, Chlorine is preferable as a substituted halogen. Examples of compounds with a trihalogenated triazine ring include cyanuric chloride, 3,5,6-trichloro-1,2,4-triazine, and 4,5,6-trichloro-1,2,3-triazine.
A method for producing a reactivity-imparting compound according to the present embodiment includes: a diazirine group-imparting step of reacting a compound containing a trihalogenated triazine ring with a compound containing a hydroxyl group and a diazirine group to obtain a diazirine group-imparted compound; and a silane coupling moiety-imparting step of reacting the diazirine group-imparted compound with a compound containing an amino group and a silane coupling moiety represented by Formula (6) below. * in Formula (6) below represents an adjacent carbon atom. Here, an example in which cyanuric chloride obtained by chlorinating 1,3,5-triazine is used as a compound with a trihalogenated triazine ring will be described, but the same reaction can be used for compounds with other trihalogenated triazine rings to obtain the reactivity-imparting compound according to the present embodiment.
In the diazirine group-imparting step, cyanuric chloride is reacted with a compound containing a hydroxyl group and a diazirine group to obtain a diazirine group-imparted compound. Examples of compounds containing a hydroxyl group and a diazirine group include 2-(3-methyl-3H-diazirin-3-yl)ethanol, 2-(3-butyl-3H-diazirin-3-yl)ethanol, 2-(3-pentyl-3H-diazirin-3-yl)ethanol, and (4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanol.
Synthesis using 2-(3-methyl-3H-diazirin-3-yl)ethanol will be described below. In a case of imparting one diazirine group, for example, a reaction of Formula (7) below is exemplified. Base in Formula (7) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. 2,4-Dichloro-6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine of Formula (15) below can be obtained through the reaction of Formula (7) below.
Synthesis using (4-(3-(trifluoromethyl)-31H-diazirin-3-yl)phenyl)methanol will be described below. In a case of imparting one diazirine group, for example, a reaction of Formula (16) below is exemplified. Base in Formula (16) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. 2,4-Dichloro-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine of Formula (17) below can be obtained through the reaction of Formula (16) below. The temperature during the reaction is, for example, room temperature (20° C. to 30° C.).
In a case of imparting two diazirine groups, for example, a reaction of Formula (8) below is exemplified. Base in Formula (8) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. 2-Chloro-4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine of Formula (18) below can be obtained through the reaction of Formula (8) below. The number of diazirine groups imparted to a triazine ring can be controlled by the reaction temperature during imparting of the diazirine groups. The temperature during a reaction is set, for example, to room temperature in a case where only one diazirine group is imparted, and to 40° C. to 50° C. in a case where two diazirine groups are imparted. The reaction temperature can be set appropriately.
In a case where two diazirine groups are imparted using (4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanol, the reaction is as shown in Formula (19) below. Base in Formula (19) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. 2-Chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine of Formula (20) below can be obtained through the reaction of Formula (19) below. The number of diazirine groups imparted to a triazine ring can be controlled by the reaction temperature or the formulation proportion during imparting of the diazirine groups.
In the silane coupling moiety-imparting step, the diazirine group-imparted compound obtained in the above-described diazirine group-imparting step is reacted with the compound containing an amino group and a silane coupling moiety represented by Formula (6) above. The reactivity-imparting compound according to the present embodiment can be obtained through this silane coupling moiety-imparting step.
R1, R2, and R3 in the silane coupling moiety in Formula (6) above each represents a hydrogen atom or an alkyl group. R1, R2, and R3 may be the same as or different from each other. Examples of alkyl groups for R1, R2, and R3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Alkyl groups for R1, R2, and R3 preferably include a methyl group and an ethyl group.
Examples of compounds containing an amino group and a silane coupling moiety represented by Formula (6) above include 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
An example of a reaction of 2,4-dichloro-6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine synthesized in Formula (7) above with 3-aminopropyltriethoxysilane is shown in Formula (9) below. Base in Formula (9) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. 6-(2-(3-Methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine of Formula (12) above can be obtained through the reaction of Formula (9) below.
An example of a reaction of 2-chloro-4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine synthesized in Formula (8) above with 3-aminopropyltriethoxysilane is shown in Formula (10) below. Base in Formula (10) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. 4,6-Bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine of Formula (4) above can be obtained through the reaction of Formula (10) below.
An example of a reaction of 2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine synthesized in Formula (16) above with 3-aminopropyltriethoxysilane is shown in Formula (21) below. Base in Formula (21) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. N2,N4-bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine of Formula (14) above can be obtained through the reaction of Formula (21) below.
An example of a reaction of 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine synthesized in Formula (19) above with 3-aminopropyltriethoxysilane is shown in Formula (22) below. Base in Formula (22) below represents a base, and diisopropylethylamine, pyridine, triethylamine, and the like can be used. N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine of Formula (13) above can be obtained through the reaction of Formula (22) below
An example of a layered body in which the reactivity-imparting compound according to the present embodiment is used will be described below. As shown in
Examples of the base material 1 include inorganic materials such as ceramics, and a resin. The form of the base material 1 is not particularly limited, and may be a plate shape or a granular shape. The base material 1 is an example of a first base material.
The resins may be curable resins (for example, a thermosetting resin, a photocurable resin, and an electron beam-curable resin), thermoplastic resins, fiber-reinforced resins, rubber (vulcanized rubber), and other materials with a coating film or the like containing such polymers on the surface. Specific examples of resins include acrylonitrile-butadiene-styrene (ABS) resin. ABS resin is used for vehicle components and the like, and is used for layered bodies having a portion where ABS and a metal are bonded together through metal plating on the surface of ABS. In addition, examples of resins for circuits include an epoxy resin, a polyimide resin, a liquid crystal polymer, a cycloolefin polymer (COP), a fluorine resin, and polyphenylene sulfide (PPS).
In a case where the layered body 100 is used as a printed wiring board, a thermal load is applied to the layered body 100, for example, through soldering of wiring. In addition, in a case where the layered body 100 is used as a movable part of an electronic product, sufficient mechanical strength is required. For this reason, a polyimide resin having excellent properties in terms of heat resistance, mechanical strength, and dimensional stability is preferable.
Examples of inorganic materials for the base material 1 include materials containing silicon oxide. In addition, electronic device components and circuit boards include a substrate containing various inorganic and organic materials, and a circuit is formed on its surface through metal plating and the like to use the formed body as a layered body.
A resin of the base material 1 may contain inorganic particles such as talc, a lubricant, an antistatic agent, and the like depending on the purpose such as improvement in mechanical strength.
In a case where the layered body 100 is used as a printed wiring board, the thickness thereof is not particularly limited. However, in a case where the base material 1 used is a flexible wiring board, the thickness of the base material 1 is preferably 1 μm to 200 μm, for example. In a case where the thickness of the base material 1 is less than 1 μm, there is a probability that the mechanical strength of the base material 1 will be insufficient, which is not preferable. The thickness of the base material 1 is more preferably 3 μm or more. In addition, if the thickness of the film exceeds 200 μm, the bendability may deteriorate, which is not preferable. The thickness of the base material 1 is more preferably 150 μm or less.
In a case where the layered body 100 is used as a printed wiring board, the arithmetic average roughness Ra of the base material 1 is, for example, 0.01 to 1 μm. If the arithmetic average roughness Ra is 0.01 μm to 1 μm, it is possible to cope with miniaturization of circuits. In addition, if the arithmetic average roughness Ra is 0.2 μm or less, the transmission loss in a high-frequency region can be reduced. The arithmetic average roughness Ra can be measured in accordance with JIS B 0601:2013.
The reactivity-imparting compound layer 2 is provided on the base material 1 and is composed of the reactivity-imparting compound according to the present embodiment. Here, the expression “provided on the base material 1” means not only providing the reactivity-imparting compound layer 2 so as to be in contact with the surface of the base material 1, but also providing an intermediate layer between the base material 1 and the reactivity-imparting compound layer 2. In addition, the expression also includes partially providing the reactivity-imparting compound layer on the surface of the base material 1.
The thickness of the reactivity-imparting compound layer 2 is not particularly limited as long as the reactivity-imparting compound layer covers the entire surface of the base material 1. The thickness of the reactivity-imparting compound layer 2 may be, for example, thicker than or equal to the thickness of a single molecule of a reactivity-imparting compound constituting the reactivity-imparting compound layer 2 (thicker than or equal to a monomolecular layer). The upper limit of the thickness of the reactivity-imparting compound layer 2 is not particularly limited but is, for example, 400 nm or thinner.
The metal layer 3 is provided on the reactivity-imparting compound layer 2. The metal layer 3 is made of silver, tin, copper, and copper alloys. In a case where the layered body 100 is a printed substrate, metals forming the metal layer 3 are preferably copper and copper alloys with high conductivity from the viewpoints of power loss and transmission loss. The metal layer is an example of a second base material.
The thickness of the metal layer is not particularly limited but is, for example, 0.1 μm to 50 μm. The thickness of the metal layer is more preferably 2 μm to 10 μm. Sufficient mechanical strength can be obtained if the thickness of the metal layer is 0.1 μm to 50 μm.
The layered body 100 according to the present embodiment has been described above. In the present embodiment, the metal layer 3 has been described as an example of the second base material, but the second base material of the present invention is not limited to the metal layer 3. For example, a resin base material made of a liquid crystal polymer, an epoxy resin, and a silicone resin may be used as the second base material instead of the metal layer. In addition, an inorganic base material made of ceramic, quartz, and the like may be used as the second base material instead of the metal layer. In addition, in the present embodiment, an example of using a metal layer as the second base material has been given. However, the shape of the second base material is not limited to the layer shape as long as the first base material is bonded to the second base material via the reactivity-imparting compound. Combinations of the first base material and the second base material of the layered body of the present disclosure may include, for example, a combination of a resin and an inorganic material such as ceramics, a combination of a resin and a metal, a combination of a metal and an inorganic material such as ceramics, and a combination of the same or different kinds of resins.
Hereinafter, a method for producing the layered body according to the present embodiment will be described, but is not limited to the following method.
When producing the layered body according to the present embodiment, the reactivity-imparting compound layer 2 consisting of the reactivity-imparting compound according to the present embodiment is first formed on the base material (first base material) 1. The method for forming the reactivity-imparting compound layer 2 is not particularly limited. For example, a solution containing a reactivity-imparting compound may be applied to the surface of the base material 1 to form the reactivity-imparting compound layer 2. Alternatively, the base material 1 may be immersed in a solution containing a reactivity-imparting compound to form the reactivity-imparting compound layer 2.
In a case where a solution containing a reactivity-imparting compound is used, water, an organic solvent, and the like can be appropriately selected as a solvent. Specifically, water, alcohol, ketones, aromatic hydrocarbons, esters, ethers, and the like may be used. A reactivity-imparting compound may be dispersed in a solvent without being dissolved. In a case where a solution is used, a solvent in the solution may be volatilized through natural drying, heating, or the like.
An amplification agent may be added to a solution containing a reactivity-imparting compound. Examples of amplification agents include: compounds, such as a silane coupling agent, contributing to other bonding; and photosensitizers such as benzophenone.
After the reactivity-imparting compound layer 2 is formed on the base material 1, energy is applied to produce carbenes from a diazirine group of the reactivity-imparting compound. By reacting these carbenes with the base material 1, high adhesion is obtained between the reactivity-imparting compound layer 2 and the base material 1.
As a means for applying energy, irradiation with light can be performed, for example. The diazirine group of the reactivity-imparting compound of the present embodiment is activated by reacting with a wide range of wavelengths. Long-wavelength light is preferable to suppress deterioration due to light. Specifically, a wavelength of 300 nm or longer is preferable, and a wavelength of 450 nm or shorter is preferable. An existing light irradiation device can be appropriately used for light irradiation. At this time, the base material 1 on which the reactivity-imparting compound layer 2 is formed may be heated before the irradiation to enhance the effect of the activation.
After applying energy to the reactivity-imparting compound layer 2 to improve adhesion between the base material 1 and the reactivity-imparting compound layer 2, a metal layer (second base material) 3 is provided. The metal layer 3 may be provided through plating or the like. As the plating method, a dry plating (vapor deposition or sputtering) technique and a wet plating technique can be appropriately selected, and both may be used in combination. When forming the metal layer 3, wet plating such as electroless plating or electroplating is preferably used to form a metal thin film. A pretreatment step for a conventionally well-known plating process can be appropriately applied before the formation of the metal layer 3. In addition, in a case of forming a resin base material, an inorganic base material, or the like on the reactivity-imparting compound layer 2 as a second base material, a well-known method can be used.
Next, examples of the present invention will be described. However, the conditions in the examples are merely condition examples employed for confirming the feasibility and effect of the present invention, although the present invention is not limited to these condition examples. The present invention can adopt various conditions as long as the gist of the present invention is not deviated from and the object of the present invention is achieved.
The following instruments and reagents were used to analyze synthesis of samples and synthesized samples.
Nuclear magnetic resonance spectrum: JEOL JNM-ECA500 NMR measurement device (500 MHz)
Mass spectrometry: JEOL JMS-700 mass spectrometer
Various reagents: Commercially available reagents were used and purified through regular methods as necessary. 2-(3-Methyl-3H-diazirin-3-yl)ethanol was purchased from Amadis Chemical. (4-(3-(Trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanol was purchased from Tokyo Chemical Industry Co., Ltd.
Various reaction solvents: Dried and purified through regular methods as necessary.
Silica gel: Wako-gel C-200 (Wako Pure Chemical Industries, Ltd.), Silica gel 60N (Kanto Chemical Co., Inc.)
Hereinafter, a method for synthesizing samples will be described.
A 10 mL branched flask was placed in an argon atmosphere, and dehydrated THF (1.1 mL), 2-(3-methyl-3H-diazirin-3-yl)ethanol (0.39 mL, 4.07 mmol, 2.50 eq.), and diisopropylethylamine (0.54 mL, 4.07 mmol, 2.50 eq.) were added thereto, and then cooled to 0° C. Cyanuric chloride (0.307 g, 1.63 mmol. 1.00 eq.) dissolved in dehydrated THF (0.72 mL) was added thereto, and the mixture was stirred under a light-shielded condition for 1 hour. After raising the temperature to room temperature (20° C. to 30° C.), the mixture was stirred under a light-shielded condition for 16 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a yellow liquid (0.654 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using hexane and chloroform at 1:1 as a developing solvent to obtain 2,4-dichloro-6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine (0.292 g, 1.18 mmol, 72%) as a yellow liquid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (2,4-dichloro-6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine) are shown below.
1H NMR (500 MHz, CDCl3): δ 1.14 (s, 3H, CH3), 1.88 (t, J=6.6 Hz, 2H, CH2), 4.43 (t, J=6.6 Hz, 2H, CH2);
13C NMR (126 MHz, CDCl3): δ 20.1, 23.7, 33.6, 65.4, 170.8, 172.7;
FAB-MS: m/z 248 [(M+H)+].
Next, 2,4-dichloro-6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine (0.500 g, 2.02 mmol, 1.00 eq.) was added to a 50 mL branched flask and placed in an argon atmosphere. Dehydrated 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 thereto and the temperature was raised to 65° C., and then the mixture was stirred under a light-shielded condition for 3 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a colorless liquid (1.04 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using chloroform and ethyl acetate at 3:1 as a developing solvent to obtain 6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine (0.476 g, 0.770 mmol, 38%) of Example 1 as a colorless liquid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine) are shown below.
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);
13C NMR (126 MHz, CDCl3): δ 7.75, 18.4, 20.1, 23.0, 24.1, 34.1, 43.3, 58.5, 61.4, 16.3, 170.0;
HR-FAB-MS: m/z calcd for C25H52N7O7Si2 [(M+H)+]: 618.3467; Found: 618.3471.
A 10 mL branched flask was placed in an argon atmosphere, and dehydrated THF (1.1 mL), 2-(3-methyl-3H-diazirin-3-yl)ethanol (0.39 mL, 4.07 mmol, 2.50 eq.), and diisopropylethylamine (0.54 mL, 4.07 mmol, 2.50 eq.) were added thereto, and then cooled to 0° C. Cyanuric chloride (0.308 g, 1.63 mmol, 1.00 eq.) dissolved in dehydrated THE (0.72 mL) was added thereto, and the mixture was stirred under a light-shielded condition for 1 hour. After raising the temperature to 40° C., the mixture was stirred under a light-shielded condition for 17 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a yellow liquid (0.582 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using hexane and chloroform at 1:1 as a developing solvent to obtain 2-chloro-4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine (0.227 g, 0.728 mmol, 45%) as a yellow liquid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (2-chloro-4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine) are shown below.
1H NMR (500 MHz, CDCl3): δ 1.13 (s, 6H, CH3), 1.85 (t, J=6.4 Hz, 4H, CH2), 4.37 (t, J=6.4 Hz, 4H, CH2);
13C NMR (126 MHz, CDCl3): δ 20.2, 23.8, 33.8, 64.4, 171.9, 172.9;
FAB-MS: m/z 312 [(M+H)+].
Next, 2-chloro-4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine (0.396 g, 1.27 mmol, 1.00 eq.) was added to a 50 mL branched flask and placed in an argon atmosphere. Dehydrated 1,4-dioxane (8.5 mL), 3-aminopropyltriethoxysilane (0.34 mL, 1.46 mmol, 1M15 eq.), and diisopropylethylamine (0.33 mL, 1.94 mmol, 1.53 eq.) were added thereto and the temperature was raised to 65° C., and then the mixture was stirred under a light-shielded condition for 3 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a yellow liquid (0.645 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using chloroform and ethyl acetate at 4:1 as a developing solvent to obtain 4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine (0.501 g, 1.01 mmol, 80%) of Example 2 as a yellow liquid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine) are shown below.
1H NMR (500 MHz, CDCl3): δ 0.67 (t, J=7.6 Hz, 2H, CH) 1.10 (s, 3H, CH), 1.11 (s, 3H, CH3), 1.23 (t, J=6.9 z, 9H, CH3), 1.71 (quint, J=7.6 z, 2H, CH2), 1.79 (t, J=6.3 z, 2H, CH2), 1.81 (t, J=6.3 Hz, 2H, CH2), 3.44 (q, J=7.6 Hz, 2H, CH2), 3.83 (q, J=6.9 Hz, 6H, CH2), 4.22 (t, J=6.3 Hz, 2H, CH2), 4.28 (t, J=6.3 Hz, 2H, CH2), 5.80 (brt, 1H, NH);
13C NMR (126 MHz, CDCl3): δ 7.73, 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;
HR-FAB-MS: m/z calcd for C20H37N8O5Si [(M+H)+]: 497.2656; Found: 497.2652.
Cyanuric chloride (1.00 g, 5.42 mmol, 1.00 eq.) was added to a 50 mL branched flask and placed in an argon atmosphere. It was dissolved in dehydrated methylene chloride (9.5 mL), and then cooled to 0° C. (4-(3-(Trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanol (1.17 g, 5.41 mmol, 1.00 eq.) dissolved in dehydrated methylene chloride (5.4 mL) and diisopropylethylamine (1.01 mL, 5.94 mmol, 1.10 eq.) were added thereto, and the mixture was stirred under a light-shielded condition for 1 hour. After raising the temperature to room temperature (20° C. to 30° C.), the mixture was stirred under a light-shielded condition for 1.5 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a yellow liquid (1.88 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using hexane and chloroform at 1:4 as a developing solvent to obtain 2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine (1.45 g, 3.98 mmol, 73%) as a yellow liquid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine) are shown below.
1H NMR (500 MHz, CDCl3): δ 5.53 (s, 2H, CH), 7.23 (d, J=8.6 Hz, 2H, benzene-H), 7.51 (d, J=8.6 Hz, 2H, benzene-H);
13C NMR (126 MHz, CDCl3): δ 28.4 (q, J=40.9 Hz), 70.7, 122.1 (q, J=275 Hz), 127.0, 128.9, 130.0, 135.5, 170.8, 172.8;
19F NMR (471 MHz, CDCl3): δ −65.0;
HR-FAB-MS: m/z calcd for C12H7Cl2F3N5O [(M+H)+]: 363.9980; Found: 363.9972.
Next, 2,4-dichloro-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine (0.300 g, 0.824 mmol, 1.00 eq.) was added to a 20 mL branched flask and placed in an argon atmosphere. Dehydrated 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 thereto and the temperature was raised to 65° C., and then the mixture was stirred under a light-shielded condition for 3 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a yellow liquid (0.360 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using chloroform and ethyl acetate at 4:1 as a developing solvent to obtain N2,N4-bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine (0.160 g, 0.218 mmol, 26%) of Example 3 as a yellow liquid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (N2,N4-bis((3-triethoxysilyl)propyl)-6-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2,4-diamine) are shown below.
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);
13C NMR (126 MHz, CDCl3): δ 7.75, 18.4, 23.0, 23.1, 28.4 (q, J=40.9 Hz), 43.4, 58.5, 66.8, 67.0, 67.2, 122.2 (q, J=275 Hz), 126.5, 127.9, 128.3, 128.4, 128.5, 138.9, 166.8, 167.3, 167.6, 170.0, 170.4;
19F NMR (471 MHz, CDCl3): δ −65.2;
Cyanuric chloride (1.00 g, 5.42 mmol, 1.00 eq.) was added to a 50 mL branched flask and placed in an argon atmosphere. It was dissolved in dehydrated methylene chloride (9.5 mL), and then cooled to 0° C. (4-(3-(Trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanol (2.42 g, 11.9 mmol, 2.20 eq.) dissolved in dehydrated methylene chloride (5.4 mL) and diisopropylethylamine (2.02 mL, 11.9 mmol, 2.20 eq.) were added thereto, and the mixture was stirred under a light-shielded condition for 1 hour. After raising the temperature to room temperature (20° C. to 30° C.), the mixture was stirred under a light-shielded condition for 16 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a yellow solid (3.32 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using hexane and chloroform at 1:4 as a developing solvent to obtain 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine (2.46 g, 4.52 mmol, 83%) as a white solid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine) are shown below.
1H NMR (500 MHz, CDCl3): δ 5.47 (s, 4H, CH2), 7.21 (d, J=8.4 Hz, 4H, benzene-H), 7.47 (d, J=8.4 Hz, 4H, benzene-H);
13C NMR (126 MHz, CDCl3): δ 28.4 (q, J=40.9 Hz), 69.8, 122.1 (q, J=275 Hz), 126.9, 128.7, 129.7, 136.3, 172.0, 173.0;
19F NMR (471 MHz, CDCl3): δ −65.0.
HR-FAB-MS: m/z calcd for C21H13ClF6N7O2 [(M+H)+]: 544.0723; Found: 544.0722.
Next, 2-chloro-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine (0.266 g, 0.489 mmol, 1.00 eq.) was added to a 20 mL branched flask and placed in an argon atmosphere. Dehydrated 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 thereto and the temperature was raised to 65° C., and then the mixture was stirred under a light-shielded condition for 3 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a yellow liquid (0.339 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using chloroform and ethyl acetate at 4:1 as a developing solvent to obtain N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine (0.243 g, 0.333 mmol, 68%) as a yellow liquid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (N-((3-triethoxysilyl)propyl)-4,6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)-1,3,5-triazine-2-amine) are shown below.
1H NMR (500 MHz, CDCl3): δ 0.64 (t, J=7.5 Hz, 2H, CH2), 1.22 (t, J=6.9 Hz, 9H, CH3), 1.69 (quint, J=7.5 Hz, 2H, CH2), 3.41 (q, J=7.5 Hz, 2H, CH2), 3.82 (q, J=6.9 Hz, 6H, CH2), 5.36 (s, 2H, CH2), 5.39 (s, 2H, CH2), 5.91 (t, J=7.5 Hz, 1H, NH), 7.18 (d, J=7.9 Hz, 4H, benzene-H), 7.43 (d, J=7.9 Hz, 2H, benzene-H), 7.46 (d, 0.1=7.9 Hz, 2H, benzene-H);
13C NMR (126 MHz, CDCl3): δ 7.73, 18.4, 22.8, 28.4 (q, J=40.9 Hz), 43.5, 58.6, 67.8, 68.1, 122.1 (q, J=275 Hz), 126.6, 128.2, 128.5, 128.9, 129.0, 138.0, 168.1, 171.3, 171.9;
19F NMR (471 MHz, CDCl3): δ −65.1.
2,4-Dichloro-6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine (0.110 g, 0.443 mmol, 1.00 eq.) was added to a 10 mL branched flask and placed in an argon atmosphere. Dehydrated 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 thereto and the temperature was raised to 65° C., and then the mixture was stirred under a light-shielded condition for 3 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a white solid (0.152 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using chloroform as a developing solvent to obtain 6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-dipropyl-1,3,5-triazine-2,4-diamine (0.130 g, 0.443 mmol, 100%) as a white solid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-dipropyl-1,3,5-triazine-2,4-diamine) are shown below.
1H NMR (500 MHz, CDCl3): δ 0.95 (t,J=7.2 Hz, 6H, CH3), 1.09 (s, 3H, CH3), 1.58 (br sext, 4H, CH2), 1.74 and 1.78 (br t and br s, total 2H, CH2), 3.30 and 3.36 (each br s, total 4H, CH2), 4.13 and 5.07 (each br s, total 2H, NH);
13C NMR (126 MHz, CDCl3): δ 11.5, 20.2, 23.0, 24.1, 34.1, 42.7, 61.3, 61.4, 166.9, 167.3, 170.3;
HR-FAB-MS: m/z calcd for C13H24N7O [(M+H)+]: 294.2042; Found: 294.2044.
2-Chloro-4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-1,3,5-triazine (0.280 g, 0.898 mmol, 1.00 eq.) was added to a 20 mL branched flask and placed in an argon atmosphere. Dehydrated 1,4-dioxane (5.58 mL), propylamine (0.09 mL, 110 mmol, 1.22 eq.), and diisopropylethylamine (0.23 mL, 1.35 mmol, 1.50 eq.) were added thereto and the temperature was raised to 65° C., and then the mixture was stirred under a light-shielded condition for 3 hours. After stirring, water was added, and extraction was performed with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, solvent removal and vacuum drying were performed to obtain a white solid (0.300 g) as a crude product. The crude product was separated and purified through silica gel column chromatography using chloroform as a developing solvent to obtain 4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-propyl-1,3,5-triazine-2-amine (0.291 g, 0.870 mmol, 97%) as a white solid.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-propyl-1,3,5-triazine-2-amine) are shown below.
1H NMR (500 MHz, CDCl3): δ 0.96 (t, J=7.2 Hz, 2H, CH3), 1.10 (s, 3H, CH3), 1.11 (s, 3H, CH3), 1.61 (sext, J=7.2 Hz, 2H, CH2), 1.79 (t, J=6.6 Hz, 2H, CH2), 1.82 (t, J=6.9 Hz, 2H, CH2), 3.40 (q, J=7.2 Hz, 2H, CH2), 4.23 (t, J=6.6 Hz, 2H, CH2), 4.29 (t, J=6.9 Hz, 2H, CH2), 5.65 (br s, 1H, NH);
13C NMR (126 MHz, CDCl3): δ 11.4, 20.2, 22.8, 24.0, 24.1, 34.0, 42.9, 62.3, 62.5, 168.2, 171.3, 171.9;
HR-FAB-MS: m/z calcd for C14H23N8O2 [(M+H)+]: 335.1944; Found: 335.1948.
A stirrer and cyanuric chloride (1.00 g, 5.42 mmol) were added to a 50 mL three-neck flask, and then, THF (6 mL) and acetonitrile (6 mL) were added thereto and cooled to −10° C. After trimethylsilyldiazomethane (a 2.0 M hexane solution, 3.0 mL, 6.0 mmol) was added thereto, the mixture was heated to room temperature (20° C. to 30° C.) and stirred for 6 hours. After the completion of stirring, water was added thereto, and the mixed solution was extracted with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, the filtrate was concentrated with a rotary evaporator and dried under reduced pressure to obtain a crude product of a brown solid. This crude product was separated and purified through silica gel chromatography using chloroform and hexane at 4:1 as a developing solvent to obtain 2,4-dichloro-6-(diazomethyl)-1,3,5-triazine (0.689 g, 3.63 mmol, 67%) as a yellow solid.
Next, a stirrer and 2,4-dichloro-6-(diazomethyl)-1,3,5-triazine (0.758 g, 3.99 mmol) were added to a 50 mL three-neck flask and placed in an argon atmosphere, and then, dry 1,4-dioxane (25 mL) was added thereto. After triethylamine (1.66 mL, 12.0 mmol) was added thereto, 3-aminopropyltriethoxysilane (2.14 mL, 9.18 mmol) was added thereto, and the mixture was stirred at 65° C. for 3 hours. After the completion of stirring, water was added thereto, and the mixed solution was extracted with diethyl ether. After the organic layer was dried with anhydrous sodium sulfate and filtered, the filtrate was concentrated with a rotary evaporator and dried under reduced pressure to obtain a crude product of a yellow viscous oil. This crude product was separated and purified through silica gel column chromatography using chloroform as a developing solvent to obtain 2,4-bis[(3-triethoxysilylpropyl)amino]-6-diazomethyl-1,3,5-triazine (1.661 g, 2.97 mmol, 74%), which is a reactivity-imparting compound, as a yellow viscous oil.
Results of nuclear magnetic resonance spectrum analysis and mass spectrometry of the obtained compound (2,4-bis[(3-triethoxysilylpropyl)amino]-6-diazomethyl-1,3,5-triazine) are shown below.
1H NMR (400 MHz, CDCl3): δ 0.66 (t, J=8.4 Hz, 4H, CH2), 1.27 (t, J=7.0 Hz, 18H, CH3), 1.67 (br s, 4H, CH2), 3.36 (br s, 4H, CH2), 3.82 (q, J=7.0 Hz, 12H, CH2), 4.83-5.24 (m, 2H, NH), 5.44 (br s, 11H, CH)
13C NMR (101 MHz, CDCl3): δ 7.7, 18.3, 23.0, 43.1, 51.5, 58.4, 146.8, 165.1; FAB-MS: m/z [(M+H)+]: 560.3048
The following theoretical calculation program was used for simulation of a UV-Vis absorption spectrum of a reactivity-imparting compound.
UV-Vis absorption spectrum simulation method: A model compound in which a triethoxysilylpropylamino group of the reactivity-imparting compound of Formula (4) above was simplified to a methylamino group (a model compound in which a triethoxysilylpropylamino group of this Example 2 was substituted with a methylamino group) was molecularly modeled, and the molecular structure was optimized through density functional (DFT) calculations. B3LYP was used as a functional for a DFT calculation, and 6-31G(d) was used as a basis function. Time-dependent density functional (TD-DFT) calculations were performed using the obtained optimum structure of the model compound to obtain UV-Vis absorption spectrum simulation results. B3LYP was used as a functional for a TD-DFT calculation, and 6-31+G(d, p) was used as a basis function.
In addition, the following instruments and reagents were used for the analysis of the obtained Examples 1 to 4 and Comparative Example 1L
UV-Vis absorption spectrum measurement conditions: bandwidth of 2 nm, scanning speed of 200 nm/min, response of Fast, and data acquisition interval of 1 nm
Next, an experiment was conducted to confirm whether or not the diazirine groups of Examples 1 and 2 decompose into carbenes through irradiation with long-wavelength ultraviolet light (UVA) (wavelength of 365 nm). A silane coupling moiety of 6-(2-(3-Methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-bis(3-(triethoxysilyl)propyl)-1,3,5-triazine-2,4-diamine of Example 1 is hydrolyzed, so 6-(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N2,N4-dipropyl-1,3,5-triazine-2,4-diamine of Reference Example 1 which has no silane coupling moiety and is easy to handle was used to conduct the confirmation experiment. Similarly, 4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-propyl-1,3,5-triazine-2-amine of Reference Example 2 was used instead of 4,6-bis(2-(3-methyl-3H-diazirin-3-yl)ethoxy)-N-((3-triethoxysilyl)propyl)-1,3,5-triazine-2-amine of Example 2 to conduct the confirmation experiment. The measurement conditions are as follows.
UV-Vis absorption spectrum measurement conditions: bandwidth of 2 nm, scanning speed of 200 nm/min, response of Fast, and data acquisition interval of 1 nm
To corroborate that carbenes are produced through photolysis of the diazirine group, Reference Examples 1 and 2 were each dissolved in methanol, and photoreaction products were investigated through mass spectrometry of the solutions before and after irradiation with 365 nm ultraviolet light for 10 minutes. The measurement conditions are as follows.
In the mass spectrum of the sample solution of Reference Example 1 before ultraviolet irradiation (ionization method: electron ionization), a molecular ion (M+) peak at m/z 293 which was consistent with the molecular weight of Reference Example 1 was detected. On the other hand, in the mass spectrum of the sample solution after ultraviolet irradiation, a molecular ion (M+) peak at m/z 297 derived from a photoreaction product which was not detected before irradiation was detected. This peak corresponds to a molecular weight of 297 of 6-(3-methoxybutoxy)-N2,N4-dipropyl-1,3,5-triazine-2,4-diamine, which was formed through an OH insertion reaction of carbenes produced through photolysis of the diazirine group with respect to hydroxyl groups (OH groups) of methanol. In the mass spectrum of the sample solution of Reference Example 2 before ultraviolet irradiation (ionization method: fast atom impact ionization), a molecular ion peak at m/z 335 was detected. If m/z 335 is considered to be a protonated molecular ion species, the mass of this peak is 334, which is consistent with a molecular weight of 334 in Reference Example 2. In the mass spectrum of the sample solution of Reference Example 2 after ultraviolet irradiation, a molecular ion peak at m/z 343 was detected. If m/z 343 is considered to be a protonated molecular ion species, the mass of this peak is 342, which is consistent with a molecular weight of 342 of 4,6-bis(3-methoxybutoxy)-N-propyl-1,3,5-triazine-2-amine formed through an OH insertion reaction of carbenes produced through photolysis of two diazirine groups in the molecular structure with respect to hydroxyl groups (OH groups) of methanol. As a photoreaction product, the product of the insertion reaction of the carbenes with respect to the OH bond of the alcohol was detected, and this result corroborated that the diazirine groups can be decomposed into carbenes through light irradiation at a wavelength of 365 nm.
Next, layered bodies were produced using the reactivity-imparting compounds of Examples 1, 2, and 4, and their peel strength evaluation (adhesion evaluation) was performed. Evaluation samples were prepared through the following procedure.
4.25 g of Cataprep 404A manufactured by Rohm and Haas Electronic Materials and 13.2 g of NaCl were added to 50 mL of distilled water while performing ultrasonic agitation for 10 minutes to prepare a pre-dip solution.
12.5 g of Cataprep 404 manufactured by Rohm and Haas Electronic Materials was added to 50 mL of distilled water while performing ultrasonic agitation for 10 minutes. After Cataprep 404 was completely dissolved, 1.5 mL of Cataposit 44 manufactured by Rohm and Haas Electronic Materials was added thereto to prepare a catalyst solution.
2.5 g of Accelerator 19E manufactured by Rohm and Haas Electronic Materials was added to 47.5 mL of distilled water while performing ultrasonic agitation for 10 minutes to prepare a accelerator solution.
2.5 mL of Ad-copper IW-A manufactured by Okuno Chemical Industries Co., Ltd., 0.75 mL, of Ad-copper C manufactured by Okuno Chemical Industries Co., Ltd., 4 mL of Ad-copper manufactured by Okuno Chemical Industries Co., Ltd., and 0.15 mL of Electroless Copper R-N manufactured by Okuno Chemical Industries Co., Ltd. were added to 42.6 mL of distilled water while performing ultrasonic agitation for 10 minutes to prepare an electroless plating solution.
An ABS substrate (1 mm×30 mm×130 μm thick) manufactured by Mitsubishi Chemical Corporation was used as an acrylonitrile-butadiene-styrene resin substrate (ABS substrate). The ABS substrate was immersed in ethanol, irradiated with ultrasonic waves for 10 minutes, washed, and dried. After drying, a corona discharge device (Corona Master manufactured by Shinko Electric & Instrumentation Co., Ltd., voltage output of 12 kV, irradiation distance of 0.5 mm) was used to perform corona treatment three times on the surface of the ABS substrate. Thereafter, the ABS substrate was immersed in an ethanol solution (concentration of 0.1 wt %) of Example 1 or 2 for 10 seconds and dried to form a reactivity-imparting compound layer. Regarding Example 4, layered bodies were produced without and with corona discharge treatment.
The ABS substrate after the reactivity-imparting compound layer was formed was irradiated with light using a high-pressure mercury lamp or an LED lamp. Both the high-pressure mercury lamp and the LED had a dominant wavelength of light of 365 nm and respectively had illuminances of 17 mW/cm2 and 396 mW/cm2 according to the measurement results of an ultraviolet integrated illuminometer UVPF-A2 (peak sensitivity of 355 nm). The irradiation time was 5 minutes. After light irradiation, the ABS substrate was immersed in the pre-dip solution for 1 minute, immersed in the catalyst solution at 50° C. for 1 minute without washing after the immersion, and then washed with distilled water. Thereafter, the ABS substrate was immersed in the accelerator solution for 3 minutes without drying it, and washed with distilled water. After washing, the ABS substrate was immersed in the electroless copper plating solution at 32° C. for 15 minutes while still wet, washed with distilled water and ethanol, and dried. After drying, the ABS substrate (layered body) on which the copper layer was formed was annealed at 80° C. for 10 minutes. After annealing, it was cooled to room temperature. After cooling, the annealed layered body was immersed in a copper sulfate electrolytic copper plating solution, copper-plated at a voltage of 15 V, a current density of 0.02 A/cm2 for 60 minutes, washed with distilled water, dried, and annealed at 80° C. for 10 minutes to obtain a layered body using a reactivity-imparting compound of each example.
A 1 cm wide cut was made in the copper layer portion of the layered body with the reactivity-imparting compounds of Examples 1 and 2, and the peel strength between the copper layer and ABS substrate was measured using an adhesion tester (Imada Force Measurement Model mX2 manufactured by Imada Inc.) under the conditions of a tensile speed of 50 mm/min and a tensile angle of 90°. The obtained results are shown in Table 2. In addition, results of the presence or absence of corona discharge treatment in Example 4 are shown in Table 3.
As shown in Table 2, in a case where irradiation with ultraviolet light was performed using a high-pressure mercury lamp, both layered bodies using Examples 1 and 2 as reactivity-imparting compounds also exhibited a high peel strength. It is thought that carbenes produced in Example 1 or 2 underwent an OH insertion reaction with respect to hydroxyl groups (OH groups) on the substrate surface produced through corona discharge, leading to formation of a covalent bond between the reactivity-imparting compound and the substrate surface, which resulted in high adhesion.
In addition, since the number of hydroxyl groups introduced on the substrate surface through corona discharge is small, it is difficult to obtain high adhesion as it is. However, it was confirmed that adhesion can be improved through bonding the reactivity-imparting compounds of Examples 1 and 2 to the substrate surface via photoreaction of diazirine groups to impart silanol-generating groups and forming a bond between silanol and the copper layer. In a case of using an LED lamp, the layered body using Example 2 having two diazirine groups in the molecule exhibited a higher peel strength than the layered body using Example 1 having one diazirine group in the molecule. In addition, a higher peel strength was exhibited with a mercury lamp than with the LED lamp. When a high-pressure mercury lamp having a broad spectrum in the ultraviolet region with a main wavelength of 365 nm is used, carbenes are likely to be generated and the photoreaction efficiency between the reactivity-imparting compound and the substrate is high, so high plating adhesion can be obtained regardless of the number of diazirine groups in the molecule and regardless of which reactivity-imparting compound is used. On the other hand, in a case of using an LED lamp with a narrow spectrum centered at 365 nm, carbenes are less likely to occur, and the photoreaction efficiency between the reactivity-imparting compound and the substrate is low. Therefore, high adhesion can be obtained by using Example 2 which has more diazirine groups and a higher reaction probability with the substrate.
On the other hand, as shown in Table 3, in a case where the reactivity-imparting compound of Example 4 was used, the same level of peel strength was exhibited regardless of whether a high-pressure mercury lamp or an LED lamp was used as a photoreactive light source. In addition, high peel strength was exhibited even without corona treatment. It is thought that this is because the reactivity-imparting compound of Example 4 had a 3-trifluoromethyl-3-phenyldiazirine skeleton, the photolysis efficiency of the diazirine group was improved, and not only the O—H insertion reaction of the generated carbenes but also a C—H insertion reaction became possible.
Based on the above results, it is thought that the reactivity-imparting compound having a diazirine group is very useful as a photoreactive molecular bonding agent.
According to the reactivity-imparting compound, method for producing a reactivity-imparting compound, and layered body of the present invention, it is possible to suppress photodegradation of a base material and obtain high adhesion, and therefore, the industrial applicability is significant.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-185196 | Nov 2020 | JP | national |
| 2021-145578 | Sep 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/040407 | 11/2/2021 | WO |
