Compound, surface treatment agent, surface treatment method, and method for producing metal-resin composite

Abstract

Compound (A) has a substituent Q bonded to a carbon atom of the 1,3,5-triazine ring 1 To substituent Q 6 . Substituent Q 1 To substituent Q 6 At least one of them is X and at least one of them is Y. 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 2 R is a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. 51 and R 52 is a divalent organic group. a is an integer from 1 to 3,

Description

Technical Field

[0001] The present application relates to a compound, a surface treatment agent, a surface treatment method, and a method for producing a metal-resin composite. Background Art

[0002] In the manufacture of electronic parts or various molded bodies, metals, ceramics, resins, etc. are bonded to each other, and the bonding between metals and various components is sought. For example, in the manufacturing process of printed circuit boards, resin materials such as etching resists, plating resists, solder resists, and prepregs are bonded to the surface of metal layers or metal circuits to seek high adhesion between metals and resins.

[0003] In order to improve the adhesion between metal and resin, etc., there is a known method of surface treating metal. For example, Patent Document 1 describes that: using a compound in which a Si-OH generating group (specifically, an alkoxysilyl group) is bonded to an amino group of melamine via an alkylene group, the metal is surface treated to form a coating on the metal surface, thereby improving the adhesion between the metal and various components.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent document 1: International Publication No. 2013 / 186941. Summary of the invention

[0007] When a metal is surface treated with a solution containing the compound described in Patent Document 1 to form a coating and bonded to a resin or the like, a significant decrease in adhesion occurs when an accelerated degradation test is performed. The purpose of the present application is to provide a compound that can be appropriately used as a surface treatment agent for metals, and a surface treatment agent formed using the compound.

[0008] One embodiment of the present application is a compound represented by the following general formula (A).

[0009]

[0010] In the general formula (A), Q 1 To Q 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, the following X or the following Y, Q 1 To Q 6 Among them, at least one is X and at least one is Y.

[0011]

[0012]

[0013] R 51 is an alkylene group having 1 to 12 carbon atoms which may contain a heteroatom. 52 It is an alkylene group having 1 to 12 carbon atoms which may contain heteroatoms; or a divalent organic group having carbon atoms and nitrogen atoms in the main chain and having 20 or less atoms constituting the main chain, wherein a part of the main chain of the divalent organic group constitutes a part of a 1,3,5-triazine ring, or a carbon atom of the 1,3,5-triazine ring is bonded to a nitrogen atom in the main chain. 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 2 is a hydrogen atom, or a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. a is an integer from 1 to 3. 3 is a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and the above X.

[0014] The compounds of general formula (A) can be roughly divided into: 1 X, Q 3 A compound of the following general formula (1) wherein Y, X and Y are bonded to different nitrogen atoms; and Q 1 X, Q 2 It is a compound of the following general formula (2) wherein Y, X and Y are bonded to the same nitrogen atom.

[0015]

[0016] In the general formula (1), Q 5 It can be X, Y or a hydrogen atom, preferably X or Y. Q 2 , Q 4 and Q 6 It may be a hydrogen atom.

[0017] In the general formula (2), Q 3 , Q 4 , Q 5 and Q 6 It may be a hydrogen atom.

[0018] One embodiment of the present application is a surface treatment agent comprising the compound. The surface treatment agent contains the compound and a solvent. By contacting the surface treatment agent with the surface of the metal component, the metal component can be surface treated to form a coating. The surface treated metal component has excellent adhesion to the resin. As the metal component, copper or copper alloy materials can be cited.

[0019] The surface of a metal component is treated with a surface treatment agent containing the compound of the present application, thereby improving the adhesion between the metal component and the resin. By bonding the surface-treated metal component to the resin, a metal-resin composite having excellent adhesion at the interface between the metal component and the resin component can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic cross-sectional view showing one embodiment of a surface-treated metal member.

[0021] Figure 2 Schematic cross-sectional view showing one embodiment of a metal-resin composite.

[0022] The description of the reference numerals is as follows:

[0023] 10: Surface treatment of metal components

[0024] 11:Metal components

[0025] 12: Lamination

[0026] 20: Resin components

[0027] 50: Metal-resin composite. DETAILED DESCRIPTION

[0028] [Structure of the compound]

[0029] The compound of the present application is a melamine derivative represented by the following general formula (A). Melamine is a 1,3,5-triazine ring having amino groups (-NH 2 ) compounds, by substituting the hydrogen atoms of the amino groups, a melamine derivative can be obtained.

[0030]

[0031] Q in the general formula (A) 1 To Q 6 Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, the following X or the following Y.

[0032]

[0033]

[0034] In X and Y, R 51 and R 52 is a divalent organic group. 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 2 is a hydrogen atom, or a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. a is an integer of 1 to 3.

[0035] In Y, R 3 is a monovalent organic group selected from the group consisting of a hydrogen atom, an amino group, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and the above X.

[0036] The compound of the present application is characterized in that the substituent Q bonded to the nitrogen atom in the general formula (A) 1 To substituent Q 6 At least one of them is X and at least one of them is Y. By having X and Y in the same molecule, the film is excellent in the formation property on the surface of metal or the like, and the film formed by the compound tends to be suppressed from deteriorating even in a high temperature and high humidity environment.

[0037] In the compound represented by the general formula (A) (hereinafter sometimes referred to as "compound (A)"), Q 1 To Q 6 In the compound (A), at least two Xs may be present, or at least two Ys may be present. At least two Xs may be the same or different. At least two Ys may be the same or different. In the compound (A), X and Y may be bonded to the same nitrogen atom, or X and Y may be bonded to different nitrogen atoms.

[0038] X is a group having an alkoxysilyl group and / or a silanol group at the terminal, 1 In the case of a hydrogen atom, -Si-OR 1 is a silanol group, in R 1 In the case of an alkyl group, -Si-OR 1 is an alkoxysilyl group. The alkoxysilyl group generates a silanol group by hydrolysis. From the perspective of the safety of the compound, R 1 In terms of film forming properties and improved adhesion, a is preferably 2 or more, and a is particularly preferably 3. 1 ) a (R 2 ) 3-aA dialkoxymonoalkylsilyl group or a trialkoxysilyl group is preferred, and a trialkoxysilyl group is particularly preferred.

[0039] In R 1 In the case of an alkyl group, -Si-OR 1 The compound represented by the general formula (A) is condensed by hydrolysis to form a coating film. 1 , preferably an alkyl group having a carbon number of 6 or less. Examples of the alkyl group having a carbon number of 6 or less include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl, among which methyl or ethyl is preferred.

[0040] When a in X is 1 or 2, R 2 , preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms are as described above, among which a methyl group or an ethyl group is preferred.

[0041] Y has an amino group (-NH 2 ). The presence of two amino groups directly bonded to the carbon atoms of the 1,3,5-triazine ring helps improve the bonding properties between components, and tends to suppress degradation of the coating in a high temperature and high humidity environment and maintain high adhesion.

[0042] The compound (A) has a molecular weight of 380 or more in its structure. The molecular weight of the compound (A) may be 400 or more or 420 or more. When the molecular weight of the compound (A) is too large, the solubility in the solvent or the film forming property tends to be reduced, so the molecular weight of the compound (A) is preferably 2000 or less, more preferably 1500 or less, and may also be 1200 or less or 1000 or less.

[0043] Compound (A) having at least one X and at least one Y is generally classified into a compound in which X and Y are bonded to different nitrogen atoms (sometimes described as "compound (1)") and a compound in which X and Y are bonded to the same nitrogen atom (sometimes described as "compound (2)").

[0044] <Compound (1)>

[0045] In the general formula (A), the compound in which X and Y are bonded to different nitrogen atoms is represented by the following general formula (1).

[0046]

[0047] In the general formula (1), Q 2 , Q 4 , Q 5 and Q 6Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, X or Y.

[0048] In the general formula (1), Q 5 It is preferably X or Y. That is, the compound (1) is preferably a compound represented by the following general formula (11) or (12).

[0049]

[0050] In the general formula (11) and the general formula (12), Q 2 It is preferably a hydrogen atom or X. Q 4 and Q 6 Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or X, and is preferably a hydrogen atom or X.

[0051] In the general formula (11) and the general formula (12), Q 2 is X or a hydrogen atom, Q 4 and Q 6 The compounds containing hydrogen atoms are represented by the following general formula groups.

[0052]

[0053] In the general formula (1), Q 5 and Q 6 It can be a hydrogen atom. In the general formula (1), Q 5 and Q 6 The compound containing a hydrogen atom is represented by the following general formula (13).

[0054]

[0055] In the general formula (13), Q 2 Preferably, a hydrogen atom or X, Q 4 It is preferably a hydrogen atom or X. In the general formula (13), Q 2 is X or a hydrogen atom, and Q 4 The compounds where X is a hydrogen atom or X are represented by the following general formula groups.

[0056]

[0057] In the general formula (A), Q 1 X, Q 3In the case where Y, X and Y are bonded to different nitrogen atoms, the compounds of formula (132) and formula (134) are equivalent to compound (1). 3 Y, Q 4 As long as X, X and Y are bonded to the same nitrogen atom, the compounds of the general formula (132) and the general formula (134) are also equivalent to the compound (2).

[0058] From the viewpoint of film formation on the metal surface, interlayer adhesion and durability of the film, the number of X and Y in compound (1) is 1 or 2, and preferably, the number of either or both of X and Y is 2. Among the above, preferred are structures of general formula (111), general formula (121), general formula (122) and general formula (133).

[0059] R in X 51 is a linking group to which the nitrogen atom of the amino group of melamine or the silicon atom of the silane group is linked, and is an alkylene group having 1 to 12 carbon atoms which may contain a heteroatom. When compound (1) contains two or more Xs, R in each X is 51 Can be the same or different.

[0060] R 51 It may be a straight chain or may have a branch. 51 The number of atoms in the main chain (the number of atoms between the nitrogen atom of the amino group of melamine and the silicon atom of the silane group) is preferably 1 to 12, more preferably 2 to 12.

[0061] R 51 It may be an alkylene group or a heteroalkylene group containing atoms other than carbon (heteroatoms) in the main chain. The heteroalkylene group may contain an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, an amino group, an imino group, etc. 51 Preferably, it is a straight-chain alkylene or heteroalkylene group having 1 to 12 carbon atoms, and more preferably, it is a straight-chain alkylene group having 1 to 12 carbon atoms. 51 In the case of a linear alkylene group, the carbon number is preferably 1 to 8, more preferably 2 to 6. 51 Specific examples of the branched alkylene group include an isopropylene group, an isobutylene group, and an isopentylene group.

[0062] The R in the Y 3 is a hydrogen atom, an amino group, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or X. 3 , preferably a hydrogen atom, as R other than a hydrogen atom 3 , preferably an alkyl group having 1 to 6 carbon atoms, phenyl, benzyl, amino, X, or the like.

[0063] The R in the Y 52 is a linking group that links the nitrogen atoms of the amino groups of two adjacent melamine skeletons and is a divalent organic group. When compound (1) contains two or more Ys, R in each Y is 52 Can be the same or different.

[0064] R 52 It may be a straight chain or may have branches. 52 May contain ring structures. 52 The number of atoms constituting the main chain (the number of atoms between the nitrogen atoms of the amino groups of the two melamine skeletons) is preferably 1 to 20.

[0065] R 52 For example, it is an alkylene group having 1 to 12 carbon atoms which may contain a heteroatom. The alkylene group having 1 to 12 carbon atoms which may contain a heteroatom may be an alkylene group or a heteroalkylene group containing atoms other than carbon atoms (heteroatoms) in the main chain. The heteroalkylene group may contain an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, an amino group, an imino group, etc. 52 It can be a linear alkylene or heteroalkylene having 1 to 12 carbon atoms. When the heteroalkylene contains a nitrogen atom (amino group) in the main chain, R 52 A branched structure in which an alkyl group is bonded to a nitrogen atom of a heteroalkylene group may also be included.

[0066] As mentioned above, R 52 It may contain a ring structure. 52 Examples of the ring structure include: a divalent organic group having 20 or less atoms constituting the main chain, wherein the atoms constituting the main chain are part of the ring structure; and a ring structure outside the main chain is bonded to a nitrogen atom of the main chain. The ring structure is preferably a 1,3,5-triazine ring.

[0067] R, which is an atom constituting the main chain and is a part of the ring structure 52 Examples of R include: a melamine skeleton, wherein a portion of the main chain constitutes a portion of a 1,3,5-triazine ring. 52 Examples of the compounds include compounds represented by the following general formula (125).

[0068]

[0069] R in the general formula (125) 3 , Q 2 , Q 4 , Q 6 and X and R 3 , Q 2 , Q 4 , Q 6 Same as X, multiple R3 , Q 2 , Q 4 , Q 6 and X may be the same or different. 3 , Q 2 , Q 4 and Q 6 Preferred is a hydrogen atom.

[0070] The structure of general formula (125) is an example of the structure of general formula (12), wherein Y 1 and Y 2 Equivalent to the two Ys in the general formula (12). 1 In the figure, the ethylene group R is surrounded by the dotted line. 521 Equivalent to the divalent organic group R in Y 52 .Y 2 The part R surrounded by the dotted line 522 Equivalent to the divalent organic group R in Y 52 . R 522 -CCN-[C=NC]-NCC- constitutes the main chain, and [C=N-C] as a part thereof becomes a constituent element of the 1,3,5-triazine ring.

[0071] As the divalent organic group R constituting Y 52 The example in which the main chain atoms of R constitute part of the ring structure has been described for the structure of the general formula (125). 52 The examples where the atoms in the main chain of R are part of the ring structure are not limited thereto. 52 It may contain more than two ring structures, or a structure formed by linking more than two melamine skeletons. 52 In the case of containing melamine skeleton, in R 52 The nitrogen atom of melamine does not necessarily need to be bonded to X. For example, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, etc. may also replace R in the general formula (125). 522 X is bonded to the nitrogen atom of melamine.

[0072] R is a ring structure outside the main chain that is bonded to the nitrogen atom of the main chain. 52 Examples of such a compound include a 1,3,5-triazine ring in which the carbon atom is bonded to the nitrogen atom of the main chain. 52 Examples of compounds include compounds represented by the following general formula (135).

[0073]

[0074] R in the general formula (135)3 , Q 2 , Q 4 , Q 5 , Q 6 and X and R 3 , Q 2 , Q 4 , Q 5 , Q 6 Same as X. 3 It is preferably a hydrogen atom. 2 , Q 4 , Q 5 and Q 6 It is preferably a hydrogen atom, or X or Y.

[0075] Y in the general formula (135) is equivalent to Y in the general formula (1), and the portion R enclosed by the dotted line is 523 Equivalent to the divalent organic group R in Y 52 . R 523 -CCNCC- constitutes the main chain, which is bonded to the carbon atoms of the 1,3,5-triazine ring through the nitrogen atoms of the main chain, thus forming a part of the melamine skeleton.

[0076] R as a divalent organic group 52 Examples of compounds having a ring structure outside the main chain have been described with respect to the structure of the general formula (135), but R 52 Compounds having a ring structure outside the main chain are not limited thereto. 52 It may be a divalent organic group in which the main chain and the ring structure outside the main chain are indirectly bonded via a divalent organic group such as an alkylene group. 52 It may have two or more ring structures outside the main chain, and may also contain two or more melamine skeletons. 52 In the case of containing a melamine skeleton, the nitrogen atoms not involved in the bond with the main chain (nitrogen atoms outside the ring that are bonded to the carbon atoms at the 4-position and the 6-position of the triazine ring in the general formula (135)) may be bonded to atoms other than hydrogen atoms. For example, in the general formula (135), R 523 The 2-NH 2 Independently, one or two of the two hydrogen atoms may be substituted by an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, X or Y, etc.

[0077] <Compound (2)>

[0078] In the general formula (A), the compound in which X and Y are bonded to the same nitrogen atom is represented by the following general formula (2).

[0079]

[0080] In the general formula (2), Q 3 , Q 4 , Q 5 and Q 6 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, X or Y. The details of X and Y are the same as those described for the compound (1).

[0081] In the general formula (2), Q 3 , Q 4 , Q 5 and Q 6 A hydrogen atom is preferred. That is, the compound (2) is preferably a compound represented by the following general formula (21).

[0082]

[0083] When X and Y in the general formula (21) are specifically described, it can be rewritten as the following general formula (22).

[0084]

[0085] R in the general formula (22) 1 , R 2 ,a,R 3 , R 51 With R 52 The details are as described above.

[0086] Regarding compound (1), as described above, R 52 A linking group that links the nitrogen atoms of the amino groups of two adjacent melamine skeletons is preferably an alkylene group having 1 to 12 carbon atoms that may contain heteroatoms; or a divalent organic group having carbon atoms and nitrogen atoms in the main chain and having 20 or less atoms constituting the main chain, wherein a part of the main chain of the divalent organic group constitutes a part of the ring structure, or a ring structure outside the main chain is bonded to a nitrogen atom in the main chain. 52 Typically, it is a straight-chain alkylene group, and specific examples thereof include ethylene, propylene, butylene, pentylene, and hexylene. 52 It may be a heteroalkylene group. 52 When a ring structure is included, the ring structure is preferably a 1,3,5-triazine ring.

[0087] In the general formula (22), as R 52 Examples of compounds containing a ring structure outside the main chain include 52 The main chain nitrogen atom of the compound is bonded to the carbon atom of the 1,3,5-triazine ring.52 Examples of compounds include compounds represented by the following general formula (225).

[0088]

[0089] R in the general formula (225) 1 , R 2 ,a,R 3 and R 51 Same as above. Y in general formula (225) is equivalent to Y in general formula (21), and the part R surrounded by the dotted line is 525 With the divalent organic group R in Y 52 Quite. 525 -CCNCC- constitutes the main chain, which is bonded to the carbon atoms of the 1,3,5-triazine ring through the nitrogen atoms of the main chain, thus forming a part of the melamine skeleton.

[0090] R as a divalent organic group 52 Examples of compounds having a ring structure outside the main chain have been described with respect to the structure of the general formula (225), but R 52 The compound having a ring structure outside the main chain is not limited thereto, and may include various chemical structures as described above with respect to the compound (1).

[0091] Compound (1) is as described above, R 3 is a hydrogen atom, an amino group, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or X. 3 , preferably a hydrogen atom. 3 , preferably an alkyl group having 1 to 6 carbon atoms, phenyl, benzyl, amino, X, etc. As R in the general formula (22) 3 Specific examples of the compound represented by X include Compound 2I in Examples described below, but are not limited thereto.

[0092] [Methods for synthesizing compounds]

[0093] The synthesis method of the compound is not particularly limited. In terms of reactivity and high yield, a method using a reaction of a chlorine atom of a 1,3,5-triazine derivative in which a chlorine atom is bonded to any one or more of the carbon atoms at positions 2, 4, and 6 of 1,3,5-triazine is preferred. A compound in which a nitrogen atom is bonded to a carbon atom of a triazine ring can be obtained by reacting a chlorine atom bonded to a carbon atom of a 1,3,5-triazine ring with an amino group (dehydrochlorination condensation).

[0094] <Synthesis of Compound (1)>

[0095] As shown in the following scheme 1, 51 -Si(OR 1 ) a (R 2 ) 3-a and a 1,3,5-triazine derivative (61) in which a chlorine atom is a substituent on a carbon atom, and a hydrogen atom of an amino group of melamine is replaced by an aminoalkyl-R 52 -NH 2 The reaction of the substituted melamine derivative (71) can yield a compound of the general formula (121) having one X and two Ys.

[0096]

[0097] As shown in the following Scheme 2, a compound of the general formula (111) having two Xs and one Y can be obtained by reacting a 1,3,5-triazine derivative (62) with a melamine derivative (71).

[0098]

[0099] By using with -N[R 51 -Si(OR 1 ) a (R 2 ) 3-a ] 2 By replacing the 1,3,5-triazine derivative (61) in Scheme 1 with a 1,3,5-triazine derivative (63) having a chlorine atom as a substituent, a compound of the general formula (122) having two Xs and two Ys can be obtained as shown in the following Scheme 3.

[0100]

[0101] By using the following 1,3,5-triazine derivative (64) instead of the 1,3,5-triazine derivative (61) in the above scheme 1, a compound of the general formula (125) can be obtained.

[0102]

[0103] The reaction of the 1,3,5-triazine derivative (61) to the 1,3,5-triazine derivative (64) with the melamine derivative (71) is carried out, for example, in the presence of chlorine at a temperature of about 20° C. to 200° C.

[0104] 1,3,5-triazine derivatives (61) to (63) having a hydrolyzable silyl group and a chlorine atom as a substituent can be synthesized by the method described in WO2013 / 186941, for example. Specifically, compounds (61) and (62) can be obtained by reacting cyanuric chloride with an aminosilane compound such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. Furthermore, compound (63) can be obtained by reacting cyanuric chloride with an aminosilane compound such as bis[3-(trimethoxysilyl)propyl]amine and bis[3-(triethoxysilyl)propyl]amine.

[0105] Compound (64) can be synthesized by reacting compound (61) with ethylenediamine as shown in the following Scheme 4. In this reaction, by making the amount of compound (61) more than 2 times the molar amount of ethylenediamine, the formation of trimers or higher polymers can be suppressed.

[0106]

[0107] By using a diamine having a different chain length, such as diaminopropane, diaminobutane, diaminopentane, or hexamethylenediamine, instead of ethylenediamine, the chain length between the nitrogen atoms of two adjacent melamine skeletons can be changed.

[0108] The hydrogen atoms of the amino groups of melamine are replaced by aminoalkyl-R 52 -NH 2 The substituted melamine derivatives can be prepared by reacting 2-chloro-4,6-diamino-1,3,5-triazine with diamine (H 2 NR 52 -NH 2 In this reaction, the amount of diamine is set to be excessively greater than the amount of 2-chloro-4,6-diamino-1,3,5-triazine, thereby suppressing the formation of multimers.

[0109]

[0110] <Formation of Compound (2)>

[0111] As shown in the following Scheme 6, by reacting 2-chloro-4,6-diamino-1,3,5-triazine with an aminosilane compound (81), a compound of the general formula (22) in which X and Y are bonded to the same nitrogen atom can be obtained.

[0112]

[0113] From the viewpoint of improving the reaction yield, in the reaction of Scheme 6, the amount of 2-chloro-4,6-diamino-1,3,5-triazine is preferably set to an excess of 2 molar times the amount of the aminosilane compound (81). 3 When the terminal primary amino group (-NH 2 ) undergoes dehydrochlorination condensation with 2-chloro-4,6-diamino-1,3,5-triazine, the other hydrogen atom of the amino group has low acidity and is restricted by steric hindrance, so it hardly reacts with 2-chloro-4,6-diamino-1,3,5-triazine. Therefore, even if the amount of 2-chloro-4,6-diamino-1,3,5-triazine is excessive, side reaction products are hardly generated.

[0114] As R 3 Specific examples of aminosilane compounds (81) having a hydrogen atom include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(6-aminohexylamino)propyltrimethoxysilane, 3-(6-aminohexylamino)propyltriethoxysilane, 8-(2-aminoethylamino)octyltrimethoxysilane, 8-(2-aminoethylamino)octyltriethoxysilane, 3-(2-aminoethylamino)isobutyltrimethoxysilane, and 3-(2-aminoethylamino)isobutyltriethoxysilane.

[0115] R in the aminosilane compound (81) 3 It is not limited to a hydrogen atom, and may be an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group, etc. 3 It may also contain a hydrolyzable silyl group. 3 Specific examples of the aminosilane compound (81) containing a hydrolyzable silyl group include N,N′-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine.

[0116] As aminosilane compounds, there can be used a hydrolyzable silane group and a terminal amino group (-NHR 3 ) between the aminosilane compound (82) and 2-chloro-4,6-diamino-1,3,5-triazine to obtain a compound of the general formula (225).

[0117]

[0118] Specific examples of the aminosilane compound (82) include 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane and 3-[2-(2-aminoethylamino)ethylamino]propyltriethoxysilane.

[0119] The reaction of the aminosilane compound (81) or (82) with 2-chloro-4,6-diamino-1,3,5-triazine is carried out in the presence of a base such as triethylamine at a temperature of about 20°C to 200°C.

[0120] [Surface treatment agent]

[0121] The compound (A) can be used as a surface treatment agent for metal components or resin components. For example, a surface treatment agent can be prepared by dissolving the compound (A) in a solvent. The solvent is not particularly limited as long as it can dissolve the compound (A), and water, dimethyl sulfoxide, alcohols such as ethanol or isopropanol, amides such as N-methyl-2-pyrrolidone or N,N-dimethylformamide, esters, ethers, cellosolves such as butyl cellosolve, ketones, aromatic hydrocarbons, etc. can be used. The solvent can be a mixed solvent. As water, water from which ionic substances or impurities are removed is preferred, for example, ion exchange water, pure water, ultrapure water, etc. can be preferably used.

[0122] The concentration of the compound (A) in the surface treatment agent is not particularly limited, but is preferably about 0.01% by weight to 60% by weight, or 0.05% by weight to 50% by weight, 0.1% by weight to 30% by weight, 0.5% by weight to 25% by weight, or 1% by weight to 20% by weight, from the viewpoint of both film formation on the metal surface and stability of the solution. The molar concentration of the compound (A) in the surface treatment agent is, for example, about 0.1mmol / L to 1500mmol / L, or 1mmol / L to 1000mmol / L, 5mmol / L to 500mmol / L, or 10mmol / L to 300mmol / L.

[0123] The surface treatment agent may contain a plurality of compounds (A). When a plurality of compounds (A) are contained, the total concentration is preferably within the above range.

[0124] The surface treatment agent may contain various additives in addition to the compound (A) and the solvent. Examples of the additives include metal ions such as copper ions or salts thereof, complexing agents, surfactants, stabilizers, silane coupling agents, pH adjusters, and the like.

[0125] [Surface treatment of metal components]

[0126] The surface treatment agent is brought into contact with the surface of the metal member, and the solvent is dried and removed as necessary, thereby Figure 1 As shown, a coating 12 is formed on the surface of the metal member 11. By providing the coating 12 formed of the compound (A) on the surface of the metal member 11, the adhesion between the metal member and the resin is improved.

[0127] The coating 12 is formed by adsorption of the compound (A) on the metal surface. The compound (A) has at least four primary amino groups (-NH 2 ), this primary amino group is easily coordinated to the metal. 1 Since the compound (A) is hydrolyzable and condensable, it can form covalent bonds between molecules when adsorbed on the metal surface. Therefore, it is believed that the compound (A) has excellent film-forming properties on the metal surface and the film deteriorates less in a high temperature and high humidity environment, which helps improve the bonding properties between components.

[0128] As a metal component, the surface of the copper foil (electrolytic copper foil, rolled copper foil) used in electronic parts, decorations, and building materials such as semiconductor wafers, electronic substrates, and lead frames, or the surface of copper films (electroless copper films, electrolytic copper films), or the copper materials of various purposes such as linear, rod-shaped, tubular, and plate-shaped can be exemplified. In particular, the surface treatment agent has excellent film formation properties on the surface of copper or copper alloy. Therefore, as a metal component, copper foil, copper films, and copper materials are preferably used. The surface of the metal component can be smooth or roughened. By forming a film by surface treatment of the roughened metal component, the adhesion of the metal component to the resin can be further improved sometimes.

[0129] The surface treatment of the metal member is performed, for example, under the following conditions.

[0130] Generally, the surface of the metal component is cleaned by acid or the like. In addition to cleaning, corona discharge treatment, plasma discharge treatment, ultraviolet irradiation, acid treatment, alkali treatment, water vapor treatment, etc. can also be performed. Then, the surface treatment agent is brought into contact with the metal component. For example, the metal component is immersed in the treatment solution and the immersion treatment is performed for about 2 seconds to 30 minutes. The solution temperature at this time is preferably about 10°C to 50°C, and more preferably about 15°C to 35°C. During the immersion treatment, shaking can be performed as needed. As a method for bringing the surface treatment agent into contact with the metal component, in addition to the immersion method, a coating method such as a spray method, a rod coating method, a spin coating method, a comma coating method, and an inkjet method can also be used. After the surface treatment agent is brought into contact with the metal component, the remaining solution attached to the metal surface is removed, thereby obtaining a surface-treated metal component 10 having a coating 12 on the surface of the metal component 11.

[0131] As a method for removing the remaining solution attached to the metal surface, drying, washing, etc. can be cited. For washing the remaining surface treatment agent formed by the solution attached to the metal surface, water or an aqueous solution can generally be used. As a cleaning solution, a dilute acid or alkaline aqueous solution can also be used. As a dilute acid, for example, sulfuric acid or hydrochloric acid of about 0.1% to 6% by weight can be used. As an alkali, a NaOH aqueous solution or a KOH aqueous solution of about 0.1% to 5% by weight can be used. As a cleaning solution, an organic solvent can be used.

[0132] exist Figure 1 In the embodiment, the coating 12 is formed only on one side of the plate-shaped metal member 11, but the surface treatment may be performed on both sides of the metal member to form the coating on both sides of the metal member. The coating is preferably formed on the entire surface of the joint with the resin. The surface treatment of the metal member is not limited to the dipping method, and a suitable coating method such as a spray method or a rod coating method may be selected.

[0133] [Metal-resin composite]

[0134] By bonding the resin member 20 to the surface of the surface treated metal member 10 on which the coating 12 is formed, a Figure 2 The metal-resin composite 50 shown. Figure 2 In the embodiment, the resin member (resin layer) 20 is laminated on only one surface of the plate-shaped metal member 11 via the coating film 12 , but the resin members may be bonded to both surfaces of the metal member.

[0135] Before forming the resin component on the coating, the wettability of the coating surface may be improved or the treatment may be performed in response to the storage environment. As the treatment of the coating surface, cleaning treatment, corona discharge treatment, plasma discharge treatment, ultraviolet irradiation, acid treatment, alkali treatment, water vapor treatment, etc. may be listed. Furthermore, before forming the resin component on the coating, heating and other treatments may also be performed. Since the coating formed by the surface treatment agent containing compound (A) is less deteriorated by heating, even before the formation of the resin component or when the resin component is formed, the high adhesion between the metal and the resin can be exerted.

[0136] The surface treated metal member 10 and the resin member 20 may be joined by lamination, lamination, coating, injection molding, transfer molding, etc. After the resin layer is formed, the resin may be cured by heating or irradiation with active light.

[0137] The resin constituting the resin member is not particularly limited, and examples thereof include thermoplastic resins such as acrylonitrile / styrene copolymer resin (AS resin), acrylonitrile / butadiene / styrene copolymer resin (ABS resin), fluororesin, polyamide, polyethylene, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, and liquid crystal polymer; or thermosetting resins such as epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide-triazine resin, modified polyphenylene ether, and cyanate ester; or ultraviolet curing resins such as ultraviolet curing epoxy resin and ultraviolet curing acrylic resin, etc. These resins may be denatured by functional groups, and may also be reinforced by glass fiber, aromatic polyamide fiber, other fibers, etc.

[0138] Since the coating formed on the metal surface using the surface treatment agent containing the compound (A) has excellent adhesion to the metal and the resin, the resin member 20 can be directly bonded to the coating 12 provided on the surface of the metal member without intervening other layers. That is, by using the surface treatment agent containing the compound (A), a coating is formed only on the surface of the metal member, and the resin member is directly bonded thereto, so that a metal-resin composite with high adhesion can be obtained.

[0139] [Example]

[0140] The following examples of the present application are combined with comparative examples for explanation. In addition, the present application is not limited to the following examples.

[0141] [Synthesis of intermediate compounds]

[0142] <Synthesis Example 1: Synthesis of 2,4-diamino-6-(6-aminohexylamino)-1,3,5-triazine>

[0143] 380.4 parts by weight of hexamethylenediamine and 59.5 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine were added to a reaction vessel (a four-necked flask equipped with a stirring blade, a thermometer, and a reflux cooling tube), and the atmosphere in the reaction vessel was replaced with nitrogen. The temperature was raised to 110°C over 1 hour, and then stirred for 3 hours. The reaction solution was concentrated under reduced pressure, dissolved in methanol, filtered, and purified by reprecipitation with tetrahydrofuran. After that, it was washed with 9% ammonia water and dried under reduced pressure to obtain the following compound (80.5 parts by weight; yield 87.5%).

[0144]

[0145] <Synthesis Example 2: Synthesis of 2,4-diamino-6-(2-(2-aminoethyl sulfide)ethylamino)-1,3,5-triazine>

[0146] 246.0 parts by weight of 2,2'-thiobis(ethylamine) and 119.0 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine were added to the reaction container, and the atmosphere in the reaction container was replaced with nitrogen. The temperature was raised to 110° C. over 1 hour, and then stirred for 3 hours. The reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography (developing solvent: methanol) to obtain the following compound (82.8 parts by weight; yield 44.2%).

[0147]

[0148] <Synthesis Example 3: Synthesis of 2,4-diamino-6-(2-(2-(2-aminoethoxy)ethoxy)ethylamino)-1,3,5-triazine>

[0149] 303.3 parts by weight of 1,2-bis(2-aminoethoxy)ethane and 119.0 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine were added to the reaction container, and the atmosphere in the reaction container was replaced with nitrogen. The temperature was raised to 110° C. over 1 hour, and the mixture was stirred for 3 hours. Thereafter, the mixture was purified in the same manner as in Synthesis Example 2 to obtain the following compound (93.7 parts by weight; yield 44.6%).

[0150]

[0151] <Synthesis Example 4: Synthesis of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine>

[0152] 393.6 parts by weight of ethylenediamine and 59.5 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen. The temperature was raised to 110°C over 1 hour, and stirred for 3 hours. The reaction solution was concentrated under reduced pressure, and the excess diamine was distilled off, dissolved in 9% ammonia water, filtered, and purified by reprecipitation with methanol and tetrahydrofuran. The filtrate was dried under reduced pressure to obtain the following compound (62.9 parts by weight; yield 91.0%).

[0153]

[0154] <Synthesis Example 5: Synthesis of 2,4-diamino-6-(2-(2-aminoethylmethylamino)ethylamino)-1,3,5-triazine>

[0155] 239.9 parts by weight of 2,2'-diamino-N-methyldiethylamine and 119 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine were added to the reaction container, and the atmosphere in the reaction container was replaced with nitrogen. The temperature was raised to 110° C. over 1 hour, and the mixture was stirred for 3 hours. Thereafter, the mixture was purified in the same manner as in Synthesis Example 2 to obtain the following compound (81.5 parts by weight; yield 44.1%).

[0156]

[0157] <Synthesis Example 6: Synthesis of 2,4-dichloro-6-(3-(triethoxysilylpropyl)amino)-1,3,5-triazine>

[0158] According to the description of Examples in WO2013 / 186941, the following compounds were synthesized.

[0159]

[0160] <Synthesis Example 7: Synthesis of 2,4-dichloro-6-(3-(diethoxymethylsilyl)propyl)amino-1,3,5-triazine>

[0161] According to the description of WO2013 / 186941, the following compounds were synthesized.

[0162]

[0163] <Synthesis Example 8: Synthesis of 2,4-dichloro-6-(bis(3-triethoxysilylpropyl)amino)-1,3,5-triazine>

[0164] According to the description of WO2013 / 186941, the following compounds were synthesized.

[0165]

[0166] <Synthesis Example 9: Synthesis of 2-chloro-4,6-bis(3-(triethoxysilylpropyl)amino)-1,3,5-triazine>

[0167] According to the description of WO2013 / 186941, the following compounds were synthesized.

[0168]

[0169] <Synthesis Example 10: Synthesis of N,N'-bis(4-(2-chloro-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine)-yl)-ethylenediamine>

[0170] In a four-necked flask equipped with a stirring blade, a thermometer and a dropping funnel, 300 parts by weight of tetrahydrofuran and 191.3 parts by weight of 2,4-dichloro-6-(3-(triethoxysilylpropyl)amino)-1,3,5-triazine were placed, the reaction vessel was substituted with nitrogen, and the temperature was adjusted to 30°C. A mixture of 47.5 parts by weight of triethylamine, 14.1 parts by weight of ethylenediamine and 100 parts by weight of tetrahydrofuran was added dropwise to the solution over a period of 2 hours, and then stirred for 2 hours. After cooling to 0°C, the mixture was allowed to stand, and filtered after decantation. The filtrate was concentrated using a rotatory evaporator. After that, the following compound (135.0 parts by weight; yield 79%) was obtained by purification using silica gel column chromatography (developing solvent: chloroform).

[0171]

[0172] [Synthesis of Compounds for Surface Treatment Agents]

[0173] According to the following synthesis examples, the compounds shown in Tables 1 to 5 were synthesized. Compounds 101, 102 and 103 were synthesized according to the examples described in WO2013 / 186941. Compound 108: 3-(2-aminoethylamino)propyltrimethoxysilane was a commercially available product.

[0174] The compounds obtained by synthesis were analyzed by liquid chromatography mass spectrometry (LC / MS), and the m / z of the proton addition product and the sodium addition ion corresponding to the target compound (see [M+H] in Tables 1 to 5) was determined. + and [M+Na] + The target compound is confirmed by detecting ions with a value of . In the synthesis of the intermediate compound, the target compound is also confirmed to be synthesized by LC / MS analysis of the purified compound.

[0175] <Synthesis Example 21: Synthesis of Compound 1A>

[0176] 300 parts by weight of dimethyl sulfoxide and 80.5 parts by weight of 2,4-diamino-6-(6-aminohexylamino)-1,3,5-triazine were added to a reaction container (a four-necked flask equipped with a stirring blade, a thermometer, and a reflux cooling tube), and the reaction container was substituted with nitrogen, and the temperature was raised to 70°C. After adding a mixture of 66.0 parts by weight of 2,4-dichloro-6-(3-(triethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran to this solution, it was stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 39.8 parts by weight of triethylamine was added and stirred for 30 minutes. After that, 50 parts by weight of tetrahydrofuran was added, filtered, and the filtrate was concentrated by a rotary evaporator, and then dried under reduced pressure. Dimethyl sulfoxide was added to the product to obtain a solution containing 15% by weight of compound 1A.

[0177] <Synthesis Example 22: Synthesis of Compound 1B>

[0178] 300 parts by weight of dimethyl sulfoxide and 82.8 parts by weight of 2,4-diamino-6-(2-(2-aminoethyl sulfide)ethylamino)-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen and heated to 70°C. A mixture of 66.7 parts by weight of 2,4-dichloro-6-(3-(triethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran was added to the solution, and stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 40.2 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 18% by weight of Compound 1B.

[0179] <Synthesis Example 23: Synthesis of Compound 1C>

[0180] 300 parts by weight of dimethyl sulfoxide and 31.5 parts by weight of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen and heated to 70°C. After adding a mixture of 103.0 parts by weight of 2-chloro-4,6-bis(3-(triethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran to this solution, it was stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 20.7 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 13% by weight of Compound 1C.

[0181] <Synthesis Example 24: Synthesis of Compound 1D>

[0182] 300 parts by weight of dimethyl sulfoxide and 62.9 parts by weight of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen and heated to 70°C. After adding a mixture of 68.7 parts by weight of 2,4-dichloro-6-(3-(triethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran to this solution, it was stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 41.4 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 15% by weight of Compound 1D.

[0183] <Synthesis Example 25: Synthesis of Compound 1E>

[0184] 300 parts by weight of dimethyl sulfoxide and 62.9 parts by weight of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen and then heated to 70°C. A mixture of 63.1 parts by weight of 2,4-dichloro-6-(3-(diethoxymethylsilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran was added to the solution, and then stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 41.4 parts by weight of triethylamine was added and stirred for 30 minutes. Thereafter, purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 16% by weight of Compound 1E.

[0185] <Synthesis Example 26: Synthesis of Compound 1F>

[0186] 300 parts by weight of dimethyl sulfoxide and 62.9 parts by weight of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen and heated to 70°C. After adding a mixture of 60.9 parts by weight of 2,4-dichloro-6-(3-(trimethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran to this solution, it was stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 41.4 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 18% by weight of Compound 1F.

[0187] <Synthesis Example 27: Synthesis of Compound 1G>

[0188] 300 parts by weight of dimethyl sulfoxide and 93.7 parts by weight of 2,4-diamino-6-(2-(2-(2-aminoethoxy)ethoxy)ethylamino)-1,3,5-triazine were placed in a reaction container, and the reaction container was substituted with nitrogen and then heated to 70°C. To this solution, a mixture of 67.3 parts by weight of 2,4-dichloro-6-(3-(triethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran was added, and the mixture was stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 40.5 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 20% ​​by weight of Compound 1G.

[0189] <Synthesis Example 28: Synthesis of Compound 1H>

[0190] 300 parts by weight of dimethyl sulfoxide and 62.9 parts by weight of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen and then heated to 70°C. A mixture of 106.7 parts by weight of 2,4-dichloro-6-(bis(3-triethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran was added to the solution, and then stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 41.4 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 18% by weight of Compound 1H.

[0191] <Synthesis Example 29: Synthesis of Compound 1I>

[0192] 300 parts by weight of dimethyl sulfoxide and 62.9 parts by weight of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine were added to the reaction container, and the reaction container was substituted with nitrogen and then heated to 70°C. After adding a mixture of 91.0 parts by weight of 2,4-dichloro-6-(bis(3-trimethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran to this solution, it was stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 41.4 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 15% by weight of Compound 1I.

[0193] <Synthesis Example 30: Synthesis of Compound 1J>

[0194] 300 parts by weight of dimethyl sulfoxide and 62.9 parts by weight of 2,4-diamino-6-(2-aminoethylamino)-1,3,5-triazine were placed in a reaction container, and the reaction container was substituted with nitrogen and then heated to 70°C. To this solution, a mixture of 135.0 parts by weight of N,N'-bis(4-(2-chloro-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine)-yl)-ethylenediamine and 50 parts by weight of tetrahydrofuran was added, and the mixture was stirred at 120°C for 2 hours. After the reaction solution was cooled to 50°C, 41.4 parts by weight of triethylamine was added and stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 19% by weight of Compound 1J.

[0195] <Synthesis Example 31: Synthesis of Compound 1K>

[0196] 300 parts by weight of dimethyl sulfoxide and 81.5 parts by weight of 2,4-diamino-6-(2-(2-aminoethylmethylamino)ethylamino)-1,3,5-triazine were placed in a reaction container, and the reaction container was substituted with nitrogen and then heated to 70° C. To this, a mixture of 66.5 parts by weight of 2,4-dichloro-6-(3-(triethoxysilylpropyl)amino)-1,3,5-triazine and 50 parts by weight of tetrahydrofuran was added, and the mixture was stirred at 120° C. for 2 hours. After the reaction solution was cooled to 50° C., 40.1 parts by weight of triethylamine was added, and the mixture was stirred for 30 minutes. Purification was performed in the same manner as in Synthesis Example 21 to obtain a solution containing 18% by weight of Compound 1K.

[0197] Table 1

[0198]

[0199] Table 2

[0200]

[0201] <Synthesis Example 41: Synthesis of Compound 2A>

[0202] 47.3 parts by weight of 3-(2-aminoethylamino)isobutyltrimethoxysilane, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine and 200 parts by weight of dimethyl sulfoxide were added to the reaction vessel and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and after nitrogen substitution in the reaction vessel, the temperature was raised to 95°C for 1 hour, and then stirred for 6 hours. 600 parts by weight of tetrahydrofuran was added to the reaction solution, and after cooling to room temperature, it was filtered, and the filtrate was concentrated by a rotary evaporator, and then dried under reduced pressure. Dimethyl sulfoxide was added to the product to obtain a solution containing 15% by weight of compound 2A.

[0203] <Synthesis Example 42: Synthesis of Compound 2B>

[0204] 58.5 parts by weight of 8-(2-aminoethylamino)octyltrimethoxysilane, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 18% by weight of Compound 2B.

[0205] <Synthesis Example 43: Synthesis of Compound 2C>

[0206] 44.5 parts by weight of 3-(2-aminoethylamino)propyltrimethoxysilane, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 17% by weight of Compound 2C.

[0207] <Synthesis Example 44: Synthesis of Compound 2D>

[0208] 41.3 parts by weight of 3-(2-aminoethylamino)propyldimethoxymethylsilane, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 18% by weight of Compound 2D.

[0209] <Synthesis Example 45: Synthesis of Compound 2E>

[0210] 62.5 parts by weight of (2-N-benzylaminoethyl)-3-aminopropyltrimethoxysilane, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to a reaction container and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the atmosphere in the reaction container was replaced with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 16% by weight of Compound 2E.

[0211] <Synthesis Example 46: Synthesis of Compound 2F>

[0212] 53.1 parts by weight of 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, 101.9 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 71.0 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 20% ​​by weight of Compound 2F.

[0213] <Synthesis Example 47: Synthesis of Compound 2G>

[0214] 52.9 parts by weight of 3-(2-aminoethylamino)propyltriethoxysilane, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of ethanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 20% ​​by weight of Compound 2G.

[0215] <Synthesis Example 48: Synthesis of Compound 2H>

[0216] 55.7 parts by weight of [3-(6-aminohexylamino)propyl]trimethoxysilane, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to a reaction container and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the atmosphere in the reaction container was replaced with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 18% by weight of Compound 2H.

[0217] <Synthesis Example 49: Synthesis of Compound 2I>

[0218] 76.9 parts by weight of N,N'-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine, 72.8 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 50.8 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95°C over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 17% by weight of Compound 2I.

[0219] Table 3

[0220]

[0221] Table 4

[0222]

[0223] <Synthesis Example 104: Synthesis of Compound 104>

[0224] 44.3 parts by weight of 3-aminopropyltriethoxysilane, 43.7 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 30.6 parts by weight of triethylamine and 20.0 parts by weight of ethanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 16% by weight of Compound 104.

[0225] <Synthesis Example 105: Synthesis of Compound 105>

[0226] 35.9 parts by weight of 3-aminopropyltrimethoxysilane, 43.7 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 30.6 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 18% by weight of Compound 105.

[0227] <Synthesis Example 106: Synthesis of Compound 106>

[0228] 38.7 parts by weight of N-methyl-3-(trimethoxysilyl)propylamine, 43.7 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 30.6 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 16% by weight of Compound 106.

[0229] <Synthesis Example 107: Synthesis of Compound 107>

[0230] 47.1 parts by weight of [3-(butylamino)propyl]trimethoxysilane, 43.7 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine, and 200 parts by weight of dimethyl sulfoxide were added to the reaction container and stirred. 30.6 parts by weight of triethylamine and 20.0 parts by weight of methanol were added to the solution, and the reaction container was substituted with nitrogen. The temperature was raised to 95° C. over 1 hour, and then stirred for 6 hours. Purification was performed in the same manner as in Synthesis Example 41 to obtain a solution containing 18% by weight of Compound 107.

[0231] Table 5

[0232]

[0233] [Preparation of surface treatment agent]

[0234] The surface treatment agent was dissolved in a solvent at a concentration shown in Table 6 or Table 7 to prepare a solution (surface treatment agent). As the solvent, dimethyl sulfoxide (DMSO), a 1:1 mixed solvent of DMSO and methanol, a 1:1 mixed solvent of DMSO and ethanol, or a 2:1 mixed solvent of DMSO and ion exchange water (DIW) can be used.

[0235] [Evaluation of Adhesion]

[0236] An electrolytic copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd.; 3EC-III; thickness 35 μm) was cut into 100 mm×100 mm, and rust-removed by immersion and shaking in a 6.25 wt % sulfuric acid aqueous solution at room temperature for 30 seconds, then washed with water and dried. The treated electrolytic copper foil was used as a test copper foil (test piece).

[0237] After the test piece was immersed in the solution (25°C) shown in Tables 6 and 7 for 180 seconds with shaking, the test piece was taken out of the solution and dried at 60°C. On the surface-treated test piece, a prepreg (FR-4 grade) impregnated with glass cloth epoxy resin was laminated to bond the copper foil to the resin. From the side of the test piece opposite to the resin laminated surface, the copper foil was cut into a rectangular shape of 10 mm wide and 60 mm long, and the copper foil on the cut peripheral part was peeled off. The sample was left to stand for 50 hours under the conditions of 130°C, 85% relative humidity, and 2 atmospheres, and an accelerated degradation test (HAST) was performed. The front end of the copper foil of the sample after HAST was clamped with a clamp, and a 90° peel test was performed according to JIS C6481 and a peeling speed of 50 mm / min over a length of 60 mm to measure the peel strength.

[0238] Tables 6 and 7 show the compositions of the solutions of Examples and Comparative Examples and the results of adhesiveness evaluation.

[0239] Table 6

[0240]

[0241] Table 7

[0242]

[0243] The invention comprises two or more triazine rings and has -NH 2 The peel strengths of Examples 1 to 22 and Examples 41 to 58, which were surface-treated with a compound of, were all 0.20 N / mm or more, and the coatings after the HAST test showed little degradation, indicating excellent adhesion.

[0244] In Comparative Example 10, in which the copper foil was surface treated with Compound 108 as a silane coupling agent that does not contain a triazine ring, the peel strength of the sample in the accelerated degradation test did not reach 0.1 N / mm, and the copper foil and the resin did not adhere. The peel strengths of Comparative Examples 1 to 3, in which the surface was treated with Compound 101 or Compound 102 containing one triazine ring, also did not reach 0.1 N / mm. 2 The peeling force of Comparative Example 4 formed by using Compound 103 was also less than 0.1 N / mm.

[0245] In the case of a -NH group having one triazine ring and having a carbon atom directly bonded to the triazine ring 2In Comparative Examples 5 to 9, in which the copper foil was surface-treated with Compounds 104 to 107, the peel strength of the samples in the accelerated degradation test was higher than that of Comparative Examples 1 to 4. However, the peel strength did not reach 0.10 N / mm, and the bonding properties were insufficient.

Claims

1. A compound, characterized in that It is represented by the following general formula (A): In the general formula (A), Q 1 To Q 6 Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an unsubstituted aryl group having 6 to 25 carbon atoms, an unsubstituted aralkyl group having 7 to 30 carbon atoms, the following X or the following Y; X: R 51 is an alkylene group having 1 to 12 carbon atoms, or a heteroalkylene group having 1 to 12 carbon atoms containing a heteroatom in the main chain; R 52 for: An alkylene group having 1 to 12 carbon atoms, or a heteroalkylene group having 1 to 12 carbon atoms containing a heteroatom in the main chain; or A divalent organic group having a main chain containing carbon atoms and nitrogen atoms and having 20 or less atoms constituting the main chain, wherein the carbon atoms of the main chain of the divalent organic group constitute a part of a 1,3,5-triazine ring or constitute an unsubstituted alkylene group; and the nitrogen atoms of the main chain of the divalent organic group constitute a part of a 1,3,5-triazine ring or are bonded to a carbon atom of the 1,3,5-triazine ring; R 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 2 is a hydrogen atom, or a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms; a is an integer from 1 to 3; R 3 is a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an unsubstituted aryl group having 6 to 25 carbon atoms, an unsubstituted aralkyl group having 7 to 30 carbon atoms, and X; Q of general formula (A) 1 To Q 6 Among them, at least one is X and at least one is Y.

2. The compound according to claim 1, characterized in that In the general formula (A), Q 1 X, Q 3 Y, Q 5 is X, Y or a hydrogen atom.

3. The compound according to claim 2, characterized in that Q 5 is X.

4. The compound according to claim 2, characterized in that Q 5 is Y.

5. The compound according to claim 2, characterized in that In the general formula (A), Q 2 and Q 6 is a hydrogen atom, Q 4 is a hydrogen atom or X.

6. The compound according to claim 1, characterized in that In the general formula (A), Q 1 For X, Q 2 is Y.

7. The compound according to claim 6, characterized in that In the general formula (A), Q 3 , Q 4 , Q 5 and Q 6 A hydrogen atom.

8. A surface treatment agent, characterized in that contain: A compound according to any one of claims 1 to 7; and solvent.

9. A surface treatment method, characterized in that: By bringing the surface treatment agent according to claim 8 into contact with the surface of a metal member, the metal member is surface treated.

10. The surface treatment method according to claim 9, characterized in that: The metal component is copper or a copper alloy.

11. A method for producing a metal-resin composite, characterized in that: The metal member is surface-treated by the surface treatment method according to claim 9, and the resin member is bonded to the surface-treated metal member.

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