JP2018172759A - Surface treatment liquid and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment liquid that has improved adhesion between a metal unroughened or slightly roughened and an insulation resin layer, has improved chemical resistance to an agent such as plating solution, to suppress haloing.SOLUTION: A surface treatment liquid containing a specific azole silane compound and a specific azole compound is brought into contact with a metal surface, to solve the problem.SELECTED DRAWING: None

Description

  The present invention relates to a metal surface treatment liquid and use thereof.

In recent years, in order to cope with the higher frequency of printed wiring boards, metal circuits (for example, copper circuits) have been subjected to no roughening treatment (no roughening treatment) or low roughening treatment. In such a printed wiring board, ensuring the adhesion between the metal circuit and the insulating resin layer is a problem.
In addition, in order to reduce the thickness of multilayer printed wiring boards in order to reduce the size and thickness of electronic devices and electronic parts, it is necessary to reduce the thickness of insulating resin layers between layers (for example, layers made of insulating resins such as solder resist and prepreg). It is conceivable that when the insulating resin layer becomes thinner, the oxygen permeability increases, and when the resin is heated and cured, the surface of the circuit (conductive pattern) of the metal wiring layer (for example, a conductive part made of metal such as copper or copper alloy) is formed. Since the oxide is formed and dissolved during the plating process, haloing (the oxide between the metal wiring layer and the insulating resin layer is eroded to generate a void) is likely to occur.

  Patent Documents 1 to 4 describe inventions related to a surface treatment agent for improving the adhesion between a metal surface and a resin material. In these documents, a technique is proposed in which a surface treatment agent containing a novel azolesilane compound is brought into contact with a metal surface, and an insulating resin layer is formed through a chemical conversion film formed from the treatment agent.

Japanese Patent Laying-Open No. 2015-92020 Japanese Patent Laying-Open No. 2015-143395 JP, 2006-56449, A JP, 2006-125143, A

  However, although these techniques improve the adhesion between the metal and the resin, there is a problem that haloing occurs due to the thinning of the insulating resin layer.

  Therefore, the present invention improves the adhesion between the metal to be subjected to no roughening treatment (no roughening treatment) or low roughening treatment and the insulating resin layer, and is not affected by chemicals such as a plating solution, that is, An object of the present invention is to provide a surface treatment liquid capable of suppressing haloing.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have treated the metal surface with a surface treatment liquid containing both a specific azolesilane compound and a specific azole compound. As a result, the present invention has been completed.

That is, the present invention is as described in the following <1> to <14>.
<1> characterized in that it contains at least one azole silane compound represented by the following chemical formula (I) and at least one selected from the group consisting of azole compounds represented by chemical formulas (II) to (XIV). Metal surface treatment liquid.

(In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH _3. Y represents —NH— or —S—. R represents —CH ₃ or —CH _2. CH represents _3. m represents an integer of 1 to 12, and n represents an integer of 0 or 1 to 3).

(In formulas (II) to (XIV), X ^{1 to} X ⁴³ each independently represents a hydrogen atom, an amino group, a mercapto group, an alkyl group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms. Represents.)

<2> The metal surface treatment solution according to <1>, containing 0.0001 to 5% by mass of the azolesilane compound.
<3> The metal surface treatment solution according to <1> or <2>, wherein the azole compound is contained in an amount of 0.0001 to 5% by mass.
<4> The metal surface treatment solution according to any one of <1> to <3>, further comprising at least one selected from the group consisting of an acid, an alkali, and an organic solvent. .
<5> The metal surface treatment solution according to any one of <1> to <4>, wherein the metal is copper or a copper alloy.

<6> A metal treatment method, wherein the metal surface treatment solution according to any one of <1> to <4> is brought into contact with a metal surface.
<7> The metal processing method according to <6>, wherein the metal is copper or a copper alloy.

<8> A printed wiring board comprising a step of bringing a metal surface treatment liquid according to any one of <1> to <4> into contact with a metal surface to form a chemical conversion film. Manufacturing method.
<9> The method for producing a printed wiring board according to <8>, wherein the metal is copper or a copper alloy.

<10> A method for adhering a metal and a resin material, wherein a chemical conversion film is formed by bringing the metal surface treatment liquid according to any one of <1> to <4> into contact with the surface of the metal. And the said metal and the said resin material are adhere | attached through the said chemical film, The adhesion method of the metal and resin material characterized by the above-mentioned.
<11> The method for adhering a metal and a resin material according to <10>, wherein the metal is copper or a copper alloy.

<12> A printed wiring board including a metal wiring layer and an insulating resin layer made of a resin material, and an azolesilane compound represented by the following chemical formula (I) between the metal wiring layer and the insulating resin layer And a chemical conversion film derived from at least one selected from the group consisting of azole compounds represented by the following chemical formulas (II) to (XIV):

(In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH _3. Y represents —NH— or —S—. R represents —CH ₃ or —CH _2. CH represents _3. m represents an integer of 1 to 12, and n represents an integer of 0 or 1 to 3).

(In formulas (II) to (XIV), X ^{1 to} X ⁴³ each independently represents a hydrogen atom, an amino group, a mercapto group, an alkyl group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms. Represents.)

<13> A printed wiring board including a metal wiring layer and an insulating resin layer made of a resin material, wherein the metal constituting the metal wiring layer and the resin material are described in <10> or <11>. A printed wiring board, which is bonded by a bonding method between a metal and a resin material.

<14> An electronic device comprising the printed wiring board according to <12> or <13>.

  The surface treatment liquid of the present invention contains both the azole silane compound and the azole compound, so that the surface of the metal is not roughened or the adhesion between the metal wiring layer and the insulating resin layer that is subjected to low roughening treatment. The chemical resistance of the metal wiring layer against chemicals such as a plating solution can be improved and haloing can be suppressed without impairing the resistance. Therefore, the finely patterned metal circuit can be suitably used as a treatment liquid when adhering to the insulating resin layer.

  Hereinafter, the present invention will be described in detail.

  The metal surface treatment liquid of the present invention (hereinafter also simply referred to as “surface treatment liquid”) includes at least one azolesilane compound represented by the following chemical formula (I) and chemical formulas (II) to (XIV) described later. And at least one selected from the group consisting of azole compounds represented by) as a component of the surface treatment liquid.

(Azole silane compound)
The azole silane compound contained in the metal surface treatment liquid of the present invention is an azole silane compound represented by the following chemical formula (I) (hereinafter also referred to as “specific azole silane compound”). This specific azole silane compound may contain 1 type individually, and may contain it in combination of 2 or more type.

(In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH _3. Y represents —NH— or —S—. R represents —CH ₃ or —CH _2. CH represents _3. m represents an integer of 1 to 12, and n represents an integer of 0 or 1 to 3).

  Since the specific azole silane compound is a substance having an azole ring, it has a metal rust prevention function that is a characteristic of the azole compound, and also has a function to enhance adhesion between different materials that are the characteristics of the silane compound. , Demonstrate the adhesion function between metal and resin material.

  The azole silane compound (specific azole silane compound) represented by the chemical formula (I) includes azole silane compounds represented by the chemical formulas (I-1) to (I-4).

(In formulas (I-1) to (I-4), X, Y, R and m are the same as described above.)

That is, the azole silane compound represented by the chemical formula (I-1) (hereinafter also referred to as azole silane compound (I-1)) is an azole silane compound (tri) in which n is 0 in the chemical formula (I). Alkoxy).
Similarly, an azole silane compound represented by the chemical formula (I-2) (hereinafter also referred to as an azole silane compound (I-2)) is an azole silane compound when n is 1, and the chemical formula (I-3) ) (Hereinafter also referred to as azole silane compound (I-3)) is an azole silane compound in the case where n is 2, an azole silane compound (I-4) ( Hereinafter, the azole silane compound (I-4) is also an azole silane compound when n is 3.

  The azole silane compounds (I-2) to (I-4) are species produced by hydrolysis of the azole silane compound (I-1) present in the surface treatment liquid. Together with the azole silane compound (I-1), it is suitable as a component of the silane coupling agent. Further, the azole silane compounds (I-2) to (I-4) can be used by being extracted from the surface treatment liquid by removing volatile components from the surface treatment liquid, for example.

In the practice of the present invention, it is preferable to use the azolesilane compound (I-1) as a raw material when preparing the surface treatment liquid.
Examples of the azole silane compound (I-1) include, for example,
3-trimethoxysilylmethylthio-1,2,4-triazole, 3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, 3- [3- (triethoxysilyl) propylthio] -1 , 2,4-triazole, 3- [6- (triethoxysilyl) hexylthio] -1,2,4-triazole, 3- [12- (trimethoxysilyl) dodecylthio] -1,2,4-triazole, 3, -Methyl-5- [2- (triethoxysilyl) ethylthio] -1,2,4-triazole, 3-methyl-5- [4- (trimethoxysilyl) butylthio] -1,2,4-triazole, 3 -Methyl-5- [10- (trimethoxysilyl) decylthio] -1,2,4-triazole, 3-amino-5-triethoxysilylmethylthio-1,2, -Triazole, 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, 3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4 -Triazole, 3-amino-5- [12- (trimethoxysilyl) dodecylthio] -1,2,4-triazole, 3-amino-5- [3- (triethoxysilyl) propylthio] -1,2,4 -Triazole, 3-mercapto-5- [2- (trimethoxysilyl) ethylthio] -1,2,4-triazole, 3-mercapto-5- [5- (trimethoxysilyl) pentylthio] -1,2,4 -Triazole, 3-mercapto-5- [8- (trimethoxysilyl) octylthio] -1,2,4-triazole, 3-methylthio-5- [3- (trime Xylyl) propylthio] -1,2,4-triazole, 3-methylthio-5- [10- (trimethoxysilyl) decylthio] -1,2,4-triazole, 3-methylthio-5- [4- (triethoxy) Silyl) butylthio] -1,2,4-triazole (when Y is —NH—),
2-trimethoxysilylmethylthio-1,3,4-thiadiazole, 2- [6- (trimethoxysilyl) hexylthio] -1,3,4-thiadiazole, 2- [8- (triethoxysilyl) octylthio] -1 , 3,4-thiadiazole, 5-methyl-2- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole, 5-methyl-2- [5- (trimethoxysilyl) pentylthio] -1 , 3,4-thiadiazole, 5-methyl-2- [12- (triethoxysilyl) dodecylthio] -1,3,4-thiadiazole, 2-amino-5- [3- (trimethoxysilyl) propylthio] -1 , 3,4-thiadiazole, 2-amino-5- [8- (trimethoxysilyl) octylthio] -1,3,4-thiadiazole, 2-amino 5- [2- (triethoxysilyl) ethylthio] -1,3,4-thiadiazole, 2-amino-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole, 2-mercapto- 5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole, 2-mercapto-5- [5- (trimethoxysilyl) pentylthio] -1,3,4-thiadiazole, 2-mercapto- 5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole, 2-mercapto-5- [10- (triethoxysilyl) decylthio] -1,3,4-thiadiazole, 2-methylthio- 5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole, 2-methylthio-5- [4- (trimethoxysilane) L) butylthio] -1,3,4-thiadiazole, 2-methylthio-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole, and 2-methylthio-5- [8- (tri Ethoxysilyl) octylthio] -1,3,4-thiadiazole (when Y is —S—)
Etc.

  The azole silane compound (I-1) can be synthesized, for example, by the method described in JP-A-2006-56449.

  The specific azole silane compound used in the practice of the present invention is, among the above, 3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, 3- [3- (triethoxysilyl) propylthio]. -1,2,4-triazole, 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, 3-amino-5- [3- (triethoxysilyl) propylthio] Preferred are -1,2,4-triazole and 3-methylthio-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole.

<Hydrolysis of azole silane compound>
As described above, the azolesilane compound (I-1) is hydrolyzed when contacted with water, and this hydrolysis mode is shown in Scheme (A).
In this scheme (A), the silyl group of the azole silane compounds (I-1) to (I-3) is hydrolyzed, that is, the trialkoxysilyl group is gradually dialkoxyhydroxysilyl group. , Dihydroxyalkoxysilyl groups, and trihydroxysilyl groups are shown. In addition, X of group shown by Chemical formula (e) is an integer showing the number of repeating units.

In general, it is known that a substance having an alkoxysilyl group in the molecule acts as a silane coupling agent.
For example, taking adhesion between copper and a resin material as an example, the azole silane compound used in the practice of the present invention has an azole ring and an alkoxysilyl group (—Si—OR) in the molecule, and the azole ring is Interacts with resin and copper to form chemical bonds.
In addition, the alkoxysilyl group is hydrolyzed and converted to a hydroxysilyl group (—Si—OH), and this hydroxysilyl group chemically bonds with copper oxide scattered on the surface of copper.
Therefore, when the surface treatment liquid of the present invention is brought into contact with copper, a chemical conversion film derived from the azole silane compound represented by the chemical formula (I) is formed on the surface of the copper by bonding with an azole ring or a hydroxysilyl group. Thus, when an insulating resin layer made of a resin material is formed on the surface of this chemical conversion film, the adhesion between copper and the resin material is improved compared to the case where an insulating resin layer is formed directly on the surface of copper. Can be increased.

  In this invention, it is preferable that the density | concentration of the specific azole silane compound in a surface treatment liquid is 0.0001-5 mass%. In addition, the density | concentration of a specific azole silane compound is converted into the density | concentration of the trialkoxy azole silane compound (I-1). When the concentration of the specific azolesilane compound is 0.0001% by mass or more, an effect of improving the adhesion between the metal and the resin material is obtained. When the concentration exceeds 5% by mass, the effect of improving the adhesiveness is obtained. Since it is almost flat and the amount of the specific azolesilane compound used is increased, it is not economical. The content of the specific azolesilane compound is more preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and more preferably 4% by mass or less in the surface treatment liquid. 3 mass% or less is still more preferable.

(Azole compound)
The azole compound contained in the metal surface treatment solution of the present invention is at least one selected from the group consisting of azole compounds represented by the following chemical formulas (II) to (XIV) (hereinafter also referred to as “specific azole compounds”). The azole compound. This specific azole compound may contain 1 type independently, and may contain it in combination of 2 or more type.

(In formulas (II) to (XIV), X ^{1 to} X ⁴³ each independently represents a hydrogen atom, an amino group, a mercapto group, an alkyl group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms. Represents.)

  Since the specific azole compound is a substance having an azole ring, it can be formed in a surface treatment solution together with the specific azole silane compound to form a dense chemical conversion film when a metal is treated with the surface treatment solution. This increases the rust prevention property of the metal surface and suppresses haloing, and the adhesion between the metal and the resin material (for example, an insulating resin layer) even if the metal has been subjected to no roughening treatment or low roughening treatment. Can be increased.

The azole compound represented by the chemical formulas (II) to (XIV) will be described.
<Azole compound (pyrrole compound) represented by chemical formula (II)>
Examples of the title pyrrole compound include pyrrole, 1-methylpyrrole, 2-ethylpyrrole, 3-propylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, 1,3,5-trimethylpyrrole, -Aminopyrrole, 2-aminopyrrole, 3-aminopyrrole, 2-mercaptopyrrole, 2- (methylthio) pyrrole, 3- (ethylthio) pyrrole, 3- (isopropylthio) pyrrole and the like.
Among these, it is preferable to use pyrrole, 1-aminopyrrole, 2-aminopyrrole, 3-aminopyrrole, and 2-mercaptopyrrole from the viewpoint of the haloing suppression effect.

<Azole compound represented by chemical formula (III) (pyrazole compound)>
Examples of the title pyrazole compound include pyrazole, 1-methylpyrazole, 1-ethylpyrazole, 1-isopropylpyrazole, 3-methylpyrazole, 4-ethylpyrazole, 4-propylpyrazole, 1,3-dimethylpyrazole, 3, 5-dimethylpyrazole, 1-aminopyrazole, 3-aminopyrazole, 3-amino-5-methylpyrazole, 1,5-diaminopyrazole, 3-amino-5-methylpyrazole, 3-mercapto-1-methylpyrazole, 3 -Mercapto-5-methylpyrazole, 3-amino-5- (methylthio) pyrazole, 4-mercaptopyrazole, 4- (methylthio) pyrazole, 4- (isopropylthio) pyrazole, 4-mercapto-1-propylpyrazole and the like It is done.
Among these, from the viewpoint of the haloing suppression effect, pyrazole, 1-aminopyrazole, 3-aminopyrazole, 3-amino-5-methylpyrazole, 1,5-diaminopyrazole, 3-amino-5-methylpyrazole, 3 It is preferable to use -mercapto-1-methylpyrazole or 3-mercapto-5-methylpyrazole.

<Azole compound (imidazole compound) represented by chemical formula (IV)>
Examples of the title imidazole compound include imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, and 2-isopropylimidazole. 1,2-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 4,5-dimethylimidazole, 2,4,5-trimethylimidazole, 1-aminoimidazole, 2-aminoimidazole, 2-amino-4-methylimidazole, 4-aminoimidazole, 4-amino-2-ethylimidazole, 2-mercaptoimidazole, 2- (methylthio) imidazole, 2- (ethylthio) imidazole, 2- Propylthio) imidazole, 2- (isopropylthio) imidazole, 4-mercapto-imidazole, 4-mercapto-2-methylimidazole, 4- (methylthio) imidazole, 4-amino-5-mercapto-imidazole, and the like.
Among these, from the viewpoint of the haloing suppression effect, imidazole, 2-mercaptoimidazole, 4-mercaptoimidazole, 4-mercapto-2-methylimidazole, 4- (methylthio) imidazole, 4-amino-5-mercaptoimidazole, 2 It is preferable to use -aminoimidazole, 2-amino-4-methylimidazole, 4-aminoimidazole.

<Azole compound represented by chemical formula (V) or chemical formula (VI) (1,2,4-triazole compound)>
Examples of the title 1,2,4-triazole compound include 1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-ethyl-1,2,4-triazole, and 1-propyl. -1,2,4-triazole, 1-isopropyl-1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-ethyl-1,2,4-triazole, 3-propyl-1 , 2,4-triazole, 3-isopropyl-1,2,4-triazole, 1,3-dimethyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3-ethyl -5-methyl-1,2,4-triazole, 3,5-diethyl-1,2,4-triazole, 3-methyl-5-propyl-1,2,4-triazole, 3,5-diisopropyl-1 , 2, -Triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-amino-5-methyl-1,2 , 4-triazole, 3-amino-5-ethyl-1,2,4-triazole, 3-amino-5-propyl-1,2,4-triazole, 3-amino-5-isopropyl-1,2,4 -Triazole, 3,5-diamino-1,2,4-triazole, 3,5-diamino-1-methyl-1,2,4-triazole, 3,5-diamino-1-ethyl-1,2,4 -Triazole, 3,5-diamino-1-propyl-1,2,4-triazole, 3,5-diamino-1-isopropyl-1,2,4-triazole, 3-mercapto-1,2,4-triazole , 3-Mel Pto-5-methyl-1,2,4-triazole, 5-ethyl-3-mercapto-1,2,4-triazole, 5-propyl-3-mercapto-1,2,4-triazole, 5-isopropyl- 3-mercapto-1,2,4-triazole, 3-mercapto-1-methyl-1,2,4-triazole, 1-ethyl-3-mercapto-1,2,4-triazole, 3-mercapto-4- Methyl-1,2,4-triazole, 4-ethyl-3-mercapto-1,2,4-triazole, 3-mercapto-4-propyl-1,2,4-triazole, 4-isopropyl-3-mercapto- 1,2,4-triazole, 3,5-dimercapto-1,2,4-triazole, 3,5-dimercapto-1-methyl-1,2,4-triazole, 3- (methyl Thio) -1,2,4-triazole, 3- (ethylthio) -1,2,4-triazole, 3- (propylthio) -1,2,4-triazole, 3- (isopropylthio) -1,2, 4-triazole, 1-methyl-3- (methylthio) -1,2,4-triazole, 3-mercapto-5- (methylthio) -1,2,4-triazole, 3,5-bis (methylthio) -1 , 2,4-triazole, 3,5-bis (ethylthio) -1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1- Methyl-1,2,4-triazole, 3-amino-5- (methylthio) -1,2,4-triazole, 3-amino-5- (ethylthio) -1,2,4-triazole, 3-amino- 5- (Pro Ruthio) -1,2,4-triazole, 3-amino-5- (isopropylthio) -1,2,4-triazole, 3-amino-1-methyl-5- (methylthio) -1,2,4- Triazole, 4-amino-5-mercapto-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-1,2,4-triazole, 4-amino-5-ethyl-3-mercapto- 1,2,4-triazole, 4-amino-3- (methylthio) -1,2,4-triazole, 4-amino-3- (ethylthio) -1,2,4-triazole, 4-amino-3- And methyl-5- (methylthio) -1,2,4-triazole.
Among these, 1,2,4-triazole, 3-
Amino-5-mercapto-1,2,4-triazole, 3,5-dimercapto-1,2,
4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-1,2,
It is preferable to use 4-triazole or 3,5-diamino-1,2,4-triazole.

<Azole compound represented by chemical formula (VII) (1,2,3-triazole compound)>
Examples of the title 1,2,3-triazole compound include 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1-ethyl-1,2,3-triazole, and 1-propyl. -1,2,3-triazole, 1-isopropyl-1,2,3-triazole, 4-methyl-1,2,3-triazole, 4-ethyl-1,2,3-triazole, 4-propyl-1 , 2,3-triazole, 4-isopropyl-1,2,3-triazole, 1,4-dimethyl-1,2,3-triazole, 4-ethyl-1-methyl-1,2,3-triazole, 4, , 5-dimethyl-1,2,3-triazole, 4,5-diethyl-1,2,3-triazole, 4-ethyl-5-propyl-1,2,3-triazole, 1-amino-1,2 , 3-Triazo 1-amino-5-methyl-1,2,3-triazole, 1-amino-5-ethyl-1,2,3-triazole, 1-amino-5-propyl-1,2,3-triazole, 1-amino-5-isopropyl-1,2,3-triazole, 1-amino-4,5-dimethyl-1,2,3-triazole, 4-amino-1,2,3-triazole, 4-amino- 5-methyl-1,2,3-triazole, 4-amino-1-methyl-1,2,3-triazole, 4-amino-1-ethyl-1,2,3-triazole, 4-amino-1- Propyl-1,2,3-triazole, 4-amino-1-isopropyl-1,2,3-triazole, 4-mercapto-1,2,3-triazole, 5-mercapto-4-methyl-1,2, 3-triazole, 4- Methylthio) -1,2,3-triazole, 4- (ethylthio) -1,2,3-triazole, 4- (propylthio) -1,2,3-triazole, 4- (isopropylthio) -1,2, Examples include 3-triazole, 4- (ethylthio) -5-methyl-1,2,3-triazole, 4-amino-5-mercapto-1,2,3-triazole and the like.
Among these, 1,2,3-triazole, 4-
Mercapto-1,2,3-triazole is preferably used.

<Azole compound (1H-tetrazole compound) represented by chemical formula (VIII)>
Examples of the title 1H-tetrazole compound include 1H-tetrazole, 1-methyltetrazole, 1-ethyltetrazole, 1-propyltetrazole, 1-isopropyltetrazole, 5-methyltetrazole, 5-ethyltetrazole, 5-propyltetrazole, 5-isopropyltetrazole, 1,5-dimethyltetrazole, 5-ethyl-1-methyltetrazole, 5-propyl-1-methyltetrazole, 5-isopropyl-1-methyltetrazole, 1,5-diethyltetrazole, 1-aminotetrazole 1-amino-5-methyltetrazole, 1-amino-5-ethyltetrazole, 1-amino-5-propyltetrazole, 1-amino-5-isopropyltetrazole, 5-aminotetrazole, 5-amino-1 Methyltetrazole, 5-amino-1-ethyltetrazole, 5-amino-1-propyltetrazole, 5-amino-1-isopropyltetrazole, 5-mercaptotetrazole, 5-mercapto-1-methyltetrazole, 1-ethyl-5 Mercaptotetrazole, 5-mercapto-1-propyltetrazole, 1-isopropyl-5-mercaptotetrazole, 5- (methylthio) tetrazole, 5- (ethylthio) tetrazole, 5- (propylthio) tetrazole, 5- (isopropylthio) tetrazole, 1-methyl-5- (methylthio) tetrazole, 1-methyl-5- (ethylthio) tetrazole, 1-amino-5-mercaptotetrazole, 2H-tetrazole, 2-methyltetrazole, 2-ethyltetrazole, - isopropyl tetrazole, 5-amino-2-methyl tetrazole, 5-amino-2-ethyl tetrazole, 5-mercapto-2-methyl-tetrazole, and the like.
Among these, it is preferable to use 1H-tetrazole and 5-aminotetrazole from the viewpoint of the haloing suppression effect.

<Azole compound represented by chemical formula (IX) (indole compound)>
Examples of the indole compound include indole, 1-methylindole, 1-ethylindole, 1-propylindole, 1-isopropylindole, 2-methylindole, 3-methylindole, 4-methylindole, and 5-methylindole. 6-methylindole, 1,2-dimethylindole, 2,5-dimethylindole, 1-aminoindole, 2-aminoindole, 3-aminoindole, 4-aminoindole, 6-aminoindole, 5-amino-2 -Methylindole, 2-mercaptoindole, 2- (methylthio) indole, 2- (ethylthio) indole, 2- (propylthio) indole, 3-mercaptoindole, 3- (methylthio) indole, 3- (ethylthio) indole, 4 − Mercaptoethyloleates indole, 4- (methylthio) indole, 4- (ethylthio) indole, and the like.
Of these, indole, 2-mercaptoindole, 3-mercaptoindole, 2-aminoindole, 3-aminoindole, 4-aminoindole, 1-aminoindole, 6-aminoindole, 5 It is preferred to use -amino-2-methylindole.

<Azole compound represented by chemical formula (X) (isoindole compound)>
Examples of the title isoindole compound include isoindole, 2-methylisoindole, 2-ethylisoindole, 2-propylisoindole, 1,3-dimethylisoindole, 1-aminoisoindole, and 2-aminoisoindole. 1- (ethylthio) -2-methylisoindole and the like.
Among these, it is preferable to use isoindole, 1-aminoisoindole, and 2-aminoisoindole from the viewpoint of the haloing suppression effect.

<Azole Compound (Indazole Compound) Represented by Chemical Formula (XI) and Chemical Formula (XII)>
Examples of the title indazole compound include indazole, 1-methylindazole, 1-ethylindazole, 1-propylindazole, 1-isopropylindazole, 2-methylindazole, 2-ethylindazole, 2-propylindazole, and 2-isopropylindazole. 4-methylindazole, 5-methylindazole, 7-methylindazole, 1-aminoindazole, 3-aminoindazole, 5-aminoindazole, 6-aminoindazole, 4-amino-1-methylindazole, 5-amino-6 -Methylindazole, 7-amino-4-methylindazole, 3-mercaptoindazole, 5-mercaptoindazole, 3- (methylthio) indazole, 5-amino-6-mercaptoindazole 5-Amino-6- (ethylthio) indazole, and the like.
Among these, indazole, 1-aminoindazole, 3-aminoindazole, 5-aminoindazole, 6-aminoindazole, 4-amino-1-methylindazole, 5-amino-6-methyl from the viewpoint of haloing suppression effect Indazole, 7-amino-4-methylindazole, 3-mercaptoindazole, and 5-mercaptoindazole are preferably used.

<Azole compound represented by chemical formula (XIII) (benzimidazole compound)>
Examples of the title benzimidazole compound include benzimidazole, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-propylbenzimidazole, 1-isopropylbenzimidazole, 2-methylbenzimidazole, 2-ethylbenzimidazole, 2 -Propylbenzimidazole, 2-isopropylbenzimidazole, 1,2-dimethylbenzimidazole, 5,6-dimethylbenzimidazole, 1-aminobenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, 2-mercaptobenzimidazole 2-mercapto-5-methylbenzimidazole, 2- (methylthio) benzimidazole, 2- (ethylthio) benzimidazole, 2- (propylthio) benzen Imidazole, 2- (isopropylthio) benzimidazole, 5-amino-2-mercaptobenzimidazole and the like.
Among these, from the viewpoint of the haloing suppression effect, benzimidazole, 1-aminobenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 5 It is preferable to use -amino-2-mercaptobenzimidazole.

<Azole compound represented by chemical formula (XIV) (benzotriazole compound)>
Examples of the title benzotriazole compound include benzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1-propylbenzotriazole, 1-isopropylbenzotriazole, 2-methylbenzotriazole, 2-ethylbenzotriazole, 2 -Propylbenzotriazole, 2-isopropylbenzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, 5,6-dimethylbenzotriazole, 1-aminobenzotriazole, 2-aminobenzotriazole, 4-aminobenzotriazole, 5 -Aminobenzotriazole, 5-mercaptobenzotriazole, 5- (methylthio) benzotriazole, 5- (propylthio) benzotriazole and the like.
Among these, it is preferable to use benzotriazole, 1-aminobenzotriazole, 2-aminobenzotriazole, 4-aminobenzotriazole, 5-aminobenzotriazole, and 5-mercaptobenzotriazole from the viewpoint of the haloing suppression effect.

The azole compound represented by the chemical formula (II) can be synthesized, for example, according to the method described in Science of Synthesis, Vol. 9, page 441 (2000).
The azole compound represented by the chemical formula (III) can be synthesized, for example, according to the method described in Science of Synthesis, Vol. 12, page 15 (2002).
The azole compound represented by the chemical formula (IV) can be synthesized in accordance with, for example, the method described in Science of Synthesis, Vol. 12, 325 (2002).
The azole compound represented by the chemical formula (V) can be synthesized, for example, according to the method described in International Publication No. 92/02853.
The azole compound represented by the chemical formula (VI) can be synthesized, for example, according to the method described in Molecules, Vol. 9, page 204 (2004).
The azole compound represented by the chemical formula (VII) can be synthesized, for example, according to the method described in US Pat. No. 7,550,601.
The azole compound represented by the chemical formula (VIII) can be synthesized, for example, according to the method described in Journal of the Chemical Society, Dalton Transactions, page 3373 (2001).
The azole compound represented by the chemical formula (IX) can be synthesized in accordance with, for example, the method described in Science of Synthesis, Vol. 10, page 361 (2000).
The azole compound represented by the chemical formula (X) can be synthesized, for example, according to the method described in Science of Synthesis, Vol. 10, page 653 (2000).
The azole compounds represented by the chemical formulas (XI) and (XII) can be synthesized in accordance with, for example, the method described in Science of Synthesis, Vol. 12, 227 (2002).
The azole compound represented by the chemical formula (XIII) can be synthesized, for example, according to the method described in Science of Synthesis, Vol. 12, 529 (2002).
The azole compound represented by the chemical formula (XIV) can be synthesized in accordance with, for example, the method described in Science of Synthesis, Vol. 13, 540 (2003).
Moreover, a commercially available thing can also be used, for example, a reagent made from Wako Pure Chemical Industries, Ltd. as 3-amino-1,2,4-triazole contained in chemical formula (V), 4 contained in chemical formula (VI). -Amino-1,2,4-triazole as a reagent manufactured by Tokyo Chemical Industry Co., Ltd., as a 1,2,3-triazole contained as a reagent manufactured by Tokyo Chemical Industry Co., Ltd., 1H included in Chemical Formula (VIII) -Reagents manufactured by Tokyo Chemical Industry Co., Ltd. may be mentioned as tetrazole.

  Among the above-mentioned specific azole compounds used in the practice of the present invention, compounds represented by the chemical formulas (IV) to (VIII), (XIII), and (XIV) are preferable, and specifically, imidazole, 2-mercaptoimidazole, 2-aminoimidazole, 2-amino-4-methylimidazole, 1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5-dimercapto-1,2,4- Triazole, 3-mercapto-1,2,4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1,2,3-triazole, 4- Mercapto-1,2,3-triazole, 1H-tetrazole, 5-aminotetrazole, benzimidazole, 2-aminobenzimidazole Lumpur, 2-mercaptobenzimidazole, benzotriazole, 5-amino benzotriazole, 5-mercaptobenzothiazole is more preferred.

  The content of the specific azole compound in the surface treatment liquid of the present invention is preferably 0.0001 to 5% by mass. When the content of the specific azole compound is 0.0001% by mass or more, the surface treatment liquid of the present invention is treated on the metal surface, thereby providing excellent rust prevention (preventing oxidation of the metal surface) and halo. Ing can be suppressed. Moreover, even if it contains more than 5% by mass, the effect of rust prevention is saturated, the effect commensurate with the content cannot be expected, and if the content is too much, the specific azole compound may not be completely dissolved Therefore, the upper limit is preferably 5% by mass. The content of the specific azole compound is more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and more preferably 3% by mass or less in the surface treatment liquid. A mass% or less is more preferable.

The surface treatment liquid of the present invention is prepared by mixing the specific azole silane compound, the specific azole compound, and water.
Examples of the water used for the preparation of the surface treatment liquid include tap water, ion exchange water, distilled water, purified water, and the like, and it is preferable to use pure water such as ion exchange water or distilled water.

  By the way, the azole silane compounds (I-2) to (I-4) having a hydroxysilyl group generated in the surface treatment liquid gradually react with each other to undergo dehydration condensation, and the hydroxysilyl group has a siloxane bond (Si— O-Si) (see the above-mentioned scheme (A)) and converted into a silane oligomer (an azole silane compound having a group represented by the chemical formula (e) in the scheme (A)) that is hardly soluble in water.

  When the amount of silane oligomer produced in the surface treatment liquid increases, the insoluble matter precipitates (the surface treatment liquid becomes cloudy) and is immersed in the treatment tank, piping connected to the treatment tank, or the surface treatment liquid. There is a risk that the surface treatment may be hindered due to adhesion to sensors for detecting the temperature and level of the treatment liquid.

  In order to avoid this, it is preferable that an organic solvent is contained in the surface treatment liquid as a solubilizer for the silane oligomer that is hardly soluble in water. In preparation of the surface treatment liquid, it is preferable to contain an acid or an alkali in order to promote dissolution of the specific azole silane compound or the specific azole compound. In addition, since the said organic solvent also has the function to improve the solubility of a specific azole silane compound and a specific azole compound, the surface treatment liquid of the present invention includes an acid, an alkali, and an organic solvent as a solubilizer. It is preferable to contain at least one selected from the group consisting of:

  Examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malonic acid, succinic acid, levulinic acid and benzoic acid. And organic acids such as oxalic acid, tartaric acid, malic acid and amino acids. These acids may be used alone or in combination of two or more.

  Examples of the alkali include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, and ethylenediamine. , Diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 1-amino-2-propanol, 3 -Amino-1-propanol, 2-amino-1-propanol, N, N-dimethylethanolamine, cycl Hexylamine, aniline, pyrrolidine, piperidine, piperazine, amines such as pyridine and the like. These alkalis may be used alone or in combination of two or more.

  Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, butanol, tert-butyl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-butoxy-2- Propanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether Ter, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, Examples include formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone and the like. These organic solvents may be used alone or in combination of two or more.

  The content of the solubilizer is preferably 0.1 to 50% by mass in the surface treatment liquid. When the content of the solubilizer is 0.1% by mass or more, the effect of increasing the solubility of the specific azole silane compound and the specific azole compound in the surface treatment liquid is remarkable. Moreover, since it is not economical when it exceeds 50 mass%, it is preferable to make 50 mass% into an upper limit. The content of the solubilizer is more preferably 0.5% by mass or more in the surface treatment solution, further preferably 1% by mass or more, and more preferably 30% by mass or less, and 15% by mass. The following is more preferable.

  In preparation of the surface treatment liquid, a solubilizer may be added after mixing the specific azole silane compound, the specific azole compound and water, or water and a solubilizer may be added to the specific azole silane compound and the specific azole compound. A mixed solution may be added, or water may be added after mixing the specific azole silane compound, the specific azole compound and the solubilizer.

  In addition, in order to improve the stability of the surface treatment solution and the uniformity of the formed chemical film, halogen ions such as chlorine ions, bromine ions and iodine ions, and metal ions such as copper ions, iron ions and zinc ions are generated. A substance may be included.

  In addition, a known coupling agent may be included in the surface treatment liquid as long as the effects of the present invention are not impaired. Known coupling agents include silane coupling agents having a thiol group (mercapto group), vinyl group, epoxy group, (meth) acryl group, amino group, chloropropyl group, and the like.

Examples of such silane coupling agents include:
3-mercaptopropyltrimethoxysilane,
Mercaptosilane compounds such as 3-mercaptopropylmethyldimethoxysilane,
Vinyltrichlorosilane,
Vinyltrimethoxysilane,
Vinylsilane compounds such as vinyltriethoxysilane,
styrylsilane compounds such as p-styryltrimethoxysilane,
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldiethoxysilane,
Epoxy silane compounds such as 3-glycidoxypropyltriethoxysilane,
Acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane,
Methacryloxypropylmethyldimethoxysilane,
Methacryloxypropyltrimethoxysilane,
Methacryloxypropylmethyldiethoxysilane,
Methacryloxysilane compounds such as methacryloxypropyltriethoxysilane,
N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane,
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane,
N-2- (aminoethyl) -3-aminopropyltriethoxysilane,
3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane,
3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine,
N-phenyl-3-aminopropyltrimethoxysilane,
Aminosilane compounds such as N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane;
Ureidosilane compounds such as 3-ureidopropyltriethoxysilane,
Chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane,
Examples thereof include sulfide silane compounds such as bis (triethoxysilylpropyl) tetrasulfide and isocyanatosilane compounds such as 3-isocyanatopropyltriethoxysilane.
In addition, an aluminum coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like can also be exemplified. These coupling agents may be used alone or in combination of two or more.

(Processing method)
The method for treating metal using the surface treatment liquid of the present invention is not particularly limited as long as the surface treatment liquid and the metal surface can be brought into contact with each other. As a method for bringing the surface treatment liquid into contact with the metal surface, for example, means such as spraying, dipping or coating can be employed.

  The time (treatment time) for bringing the surface treatment liquid of the present invention into contact with the metal surface is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. If the treatment time is 1 second or longer, a specific azole silane compound and a chemical conversion film derived from the specific azole compound can be sufficiently formed on the metal surface, and a desired rust preventive effect can be obtained, and the metal and the insulation can be obtained. Adhesive strength when the resin layer is bonded can also be sufficiently obtained. Further, even if the treatment time is longer than 10 minutes, there is no great difference in the film thickness of the chemical conversion film, so that an increase in adhesive force cannot be expected. From the viewpoint of productivity, the treatment is preferably carried out in 10 minutes or less.

  The temperature of the surface treatment liquid when adhering the surface treatment liquid to the metal surface is preferably 5 to 50 ° C., but may be set as appropriate in relation to the treatment time.

After bringing the surface treatment liquid into contact with the metal surface, it is preferable to wash with water if necessary, and then dry the metal surface.
The drying is preferably performed at a temperature of room temperature to 150 ° C., preferably 60 to 120 ° C. for 1 second to 10 minutes, and preferably about 10 seconds to 3 minutes.
The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but the washing method and time are not particularly limited, and may be an appropriate time by means such as spraying or dipping.

  In the present invention, the surface of the chemical conversion film may be modified by performing treatments such as plasma, laser, ion beam, ozone, heating, and humidification on the chemical conversion film after drying. Alternatively, cleaning for the purpose of removing the resin / ion residue on the metal surface may be performed by using a mechanical polishing method such as plasma, laser, ion beam, permis brush, or a drilling method.

  In addition, when a metal is copper or a copper alloy, before making a surface treatment liquid contact the surface of copper or a copper alloy, you may make the aqueous solution containing a copper ion contact the surface of the said copper or copper alloy. The copper ion source of the aqueous solution containing copper ions is not particularly limited as long as it is a copper salt that dissolves in water, and examples thereof include copper salts such as copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. In order to solubilize the copper salt in water, ammonia or hydrochloric acid may be added.

  After the surface treatment liquid is brought into contact with the surface of copper or a copper alloy, an acidic or alkaline aqueous solution may be brought into contact with the surface of the copper or copper alloy. The acidic aqueous solution and the alkaline aqueous solution are not particularly limited. Examples of the acidic aqueous solution include an aqueous solution containing a mineral acid such as sulfuric acid, nitric acid, and hydrochloric acid, and an aqueous solution containing an organic acid such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acid. Is mentioned. Examples of the alkaline aqueous solution include aqueous solutions containing hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine and monopropanolamine.

  By performing the treatment as described above, a specific azole silane compound in the surface treatment liquid and a chemical conversion film derived from the specific azole compound can be formed on the surface of the metal, the specific azole compound acts on the metal surface, While being able to suppress oxidation, the specific azole silane compound can enhance the adhesion between the metal surface and the resin material. Therefore, in a printed wiring board provided with a metal wiring layer and an insulating resin layer, etc., while improving the adhesion between the metal wiring layer (metal circuit) and the insulating resin layer (resin material) without particularly roughening treatment, The formation of metal oxides can be reduced to suppress haloing.

In the present invention, examples of the metal to be treated include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.
As a specific example of the alloy, a copper alloy is not particularly limited as long as it is an alloy containing copper. For example, Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, and Cu-Si Cu-Mn, Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al Alloy of Cu type, Cu-Zn type, Cu-Co type and the like.
Other alloys include aluminum alloy (Al—Si alloy), nickel alloy (Ni—Cr alloy), iron alloy (Fe—Ni alloy, stainless steel) and the like.
Of these metals, copper and copper alloys are preferred.

Examples of the resin material include acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, polyetherimide resin, and polyether. Examples include ether ketone resins, liquid crystal resins, and the like, which may be mixed or modified with each other.
Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferable.

(Adhesion method)
The method for bonding the metal and the resin material is not particularly limited, and can be performed by a known method. In contacting the surface of the metal with the surface treatment liquid of the present invention to form a chemical conversion film on the surface of the metal, and then bonding a base material made of a resin material to the metal surface through the chemical conversion film, For example, a part or the whole of the formed chemical conversion film can be bonded by a means such as applying, pressing, and mixing a resin material, using an adhesive, an adhesive sheet (film), or a combination of these means. .

(Printed wiring board)
Moreover, this invention also provides the manufacturing method of the printed wiring board using the said adhesion | attachment method. That is, the manufacturing method of the printed wiring board of this invention includes the process of making the surface treatment liquid of this invention contact the surface of a metal, and forming a chemical conversion film.

  By using the surface treatment liquid of the present invention to form a chemical conversion film derived from the specific azole silane compound and the specific azole compound on the surface of the metal, the adhesion with the resin material can be improved, so that the metal and the resin material are It can be suitably used for an electronic device provided with various composite electric / electronic parts, printed wiring boards, and the like.

  In the present invention, the surface treatment liquid of the present invention can be suitably used particularly for a substrate formed of copper or a copper alloy. For example, it is suitable for surface treatment of copper or copper alloy for the purpose of enhancing the adhesion (adhesion) between the copper circuit (copper wiring layer) and the prepreg or solder resist (insulating resin layer) In a printed wiring board having an insulating resin layer in contact with the wiring layer, the adhesion between the copper wiring layer and the insulating resin layer can be enhanced.

Specifically, the printed wiring board is obtained by bringing the surface treatment liquid of the present invention into contact with the surface of the copper wiring layer, and then washing with water if necessary, followed by drying, and then an insulating resin layer on the surface of the copper wiring layer. Can be formed. About this contact method, it is as above-mentioned, and immersion of the copper wiring layer in a surface treatment liquid or the spraying to a copper wiring layer by this processing liquid is simple and reliable, and is preferable.
Moreover, there is no restriction | limiting in particular also about the method of the said water washing, but the immersion to the copper wiring layer in washing | cleaning water or the spray to the copper wiring layer surface by washing water is simple and reliable, and preferable.
For the formation of the insulating resin layer, a known method such as a method of attaching a semi-cured resin material or a means of applying a liquid resin material containing a solvent can be employed. Next, a via hole is formed to connect the upper and lower wirings. By repeating this process, a multilayer printed wiring board can be produced.

  The copper wiring layer may be formed by any method such as electroless plating, electrolytic plating, vapor deposition, sputtering, damascene, and includes inner via holes, through holes, connection terminals, and the like. It may be a thing.

  In addition, “copper” according to the present invention is a foil (electrolytic copper foil, rolled copper foil), plating film (electroless copper plating film) used for electronic devices such as printed wiring boards and lead frames, ornaments, and building materials. , Electrolytic copper plating film), wire, rod, tube, plate and the like. In the case of a copper wiring layer through which a high-frequency electric signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less.

(Combination with rust prevention liquid)
In this invention, it can also process with a rust prevention liquid before or after processing a metal with the surface treatment liquid of this invention.
By contacting the surface of the metal before treating with the surface treatment liquid of the present invention or after treating with the surface treatment liquid of the present invention, without damaging the adhesion between the metal and the resin material, Since the oxidation of the treated metal is further suppressed and the chemical resistance is improved, the occurrence of haloing in the plating process can be further suppressed.

  The preferable rust prevention liquid is an active ingredient having at least one azole compound selected from the group consisting of azole compounds represented by the following chemical formulas (V) to (VIII) (hereinafter referred to as “azole compound (V) ˜). (VIII) ").

(In formulas (V) to (VIII), X ^{14 to} X ²⁴ each independently represents a hydrogen atom, an amino group, a mercapto group, an alkyl group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms. Represents.)

  Examples of the azole compound (1,2,4-triazole compound) represented by the chemical formula (V) or the chemical formula (VI) include the compounds exemplified above. From the viewpoint of the haloing suppression effect, 1,2,4- Triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5-dimercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-1, It is preferable to use 2,4-triazole and 3,5-diamino-1,2,4-triazole.

  Examples of the azole compound (1,2,3-triazole compound) represented by the chemical formula (VII) include the compounds exemplified above, and 1,2,3-triazole, 4-mercapto from the viewpoint of the haloing suppression effect. It is preferable to use -1,2,3-triazole.

  Examples of the azole compound (1H-tetrazole compound) represented by the chemical formula (VIII) include the compounds exemplified above, and 1H-tetrazole and 5-aminotetrazole are preferably used from the viewpoint of the haloing suppression effect.

  The content of the azole compounds (V) to (VIII) in the rust prevention treatment liquid is preferably 0.0001 to 5% by mass. When the content of the azole compounds (V) to (VIII) is 0.0001% by mass or more, the metal surface is treated in combination with the surface treatment liquid of the present invention, so that excellent rust prevention property (of the metal surface) Oxidization is prevented, and haloing can be suppressed. Moreover, even if it contains exceeding 5 mass%, the effect of rust prevention is saturated and the effect corresponding to content cannot be expected, and if there is too much content, azole compounds (V)-(VIII) can be dissolved completely. Since there is a fear, it is desirable that the upper limit is 5 mass%. The content of the azole compounds (V) to (VIII) is more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and further 3% by mass or less in the rust prevention treatment liquid. More preferably, it is more preferably 2% by mass or less.

The antirust treatment liquid is prepared by dissolving the azole compounds (V) to (VIII) in water.
Examples of water include tap water, ion exchange water, distilled water, purified water, and the like, and it is preferable to use pure water such as ion exchange water or distilled water.

  The antirust treatment liquid may contain a solubilizer in order to increase the solubility of the azole compounds (V) to (VIII). Examples of the solubilizer include acids, alkalis, organic solvents, and the like. Specific examples that can be used are the same as those that can be contained in the above-described surface treatment liquid of the present invention.

  As content of a solubilizer, it is preferable that it is 0.1-50 mass% in a rust prevention liquid. When the content of the solubilizer is 0.1% by mass or more, the effect of increasing the solubility of the azole compounds (V) to (VIII) in the antirust treatment liquid is remarkable. Moreover, since it is not economical when it exceeds 50 mass%, it is preferable to make 50 mass% into an upper limit. The content of the solubilizer is more preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 30% by mass or less in the rust preventive treatment liquid, and 15% by mass. % Or less is more preferable.

The rust preventive treatment liquid may contain a pH adjuster in order to control the stability and film forming property of the treatment liquid. From the viewpoint of the film forming property of the rust preventive film (chemical conversion film), the pH of the rust preventive treatment liquid is preferably 2 to 11, and a pH adjuster is used to adjust the pH to the above range.
For example, about the rust prevention liquid containing the azole compounds (V) to (VIII) that are easily dissolved in an acid, the solution is dissolved with an acid as a solubilizer to form an aqueous solution, and then an alkaline pH adjuster is used. The film forming property can be adjusted. In addition, in the case of azole compounds (V) to (VIII) that are easily dissolved in an alkali, the solution is dissolved using an alkali as a solubilizing agent to form an aqueous solution, and then the film forming property is adjusted using an acidic pH adjusting agent. can do. Examples of acidic pH adjusters include mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, and organic acids such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acids. Examples of alkaline pH adjusters include Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia and ethanolamine.

  In addition, substances that generate halogen ions such as chlorine ions and bromine ions, and metal ions such as copper ions, iron ions, and zinc ions in order to improve the stability of the anticorrosive treatment liquid and the uniformity of the formed antirust film Can also be included.

  Moreover, in the range which does not impair the effect of this invention, you may make a rust prevention liquid contain a well-known coupling agent. The known coupling agent is the same as the aforementioned known coupling agent.

  The treatment method of the antirust treatment liquid is not particularly limited as long as it can be used in combination with the surface treatment liquid of the present invention and the metal surface can be treated. As a method for treating the surface of the metal, for example, the antirust treatment liquid and the metal may be brought into contact with each other by means such as spraying, dipping or coating.

  The time (treatment time) for contacting the rust preventive treatment liquid and the metal surface is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. When the treatment time is 1 second or longer, a chemical conversion film derived from the azole compounds (V) to (VIII) can be sufficiently formed on the metal surface, and a desired rust prevention effect can be obtained. In addition, even if the treatment time is longer than 10 minutes, there is no great difference in the film thickness of the chemical conversion film, so it is preferable to treat in 10 minutes or less from the viewpoint of productivity.

  The temperature of the antirust treatment liquid when the antirust treatment liquid is adhered to the metal surface is preferably 5 to 50 ° C., but may be set as appropriate in relation to the treatment time.

After bringing the antirust treatment liquid into contact with the metal surface, it is preferable to wash with water if necessary and dry the metal surface.
The drying is preferably performed at a temperature of room temperature to 150 ° C., preferably 60 to 120 ° C. for 1 second to 10 minutes, and preferably about 10 seconds to 3 minutes.
The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but the washing method and time are not particularly limited, and may be an appropriate time by means such as spraying or dipping.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.

The azole silane compounds or silane compounds and azole compounds used in the following examples and comparative examples are as follows.
<Azole silane compound or silane compound>
Azole silane compound A: 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole (synthesized according to the method described in JP-A-2015-10079)
Azole silane compound B: 3-amino-5- [3- (triethoxysilyl) propylthio] -1,2,4-triazole (same as above)
Azole silane compound C: 3-amino-5- [3- (trimethoxysilyl) hexylthio] -1,2,4-triazole (same as above)
Azole silane compound D: imidazole silane compound (synthesized according to the method described in JP-A-5-186479. A mixture of the following chemical formulas (XV-1) to (XV-3).
Silane compound E: γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-903”)

<Azole compound>
Azole compound a: pyrrole (manufactured by Wako Pure Chemical Industries, Ltd.)
Azole compound b: pyrazole (same as above)
Azole compound c: Imidazole (same as above)
Azole compound d: 3-amino-1,2,4-triazole (same as above)
Azole compound e: 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
Azole compound f: 1,2,3-triazole (same as above)
Azole compound g: 5-aminotetrazole (same as above)
Azole compound h: Indole (Wako Pure Chemical Industries, Ltd.)
Azole compound i: isoindole (synthesized according to the method described in Science of Synthesis, Vol. 10, page 653 (2000))
Azole compound j: 1-methylindazole (manufactured by Wako Pure Chemical Industries, Ltd.)
Azole compound k: 2-methylindazole (same as above)
Azole compound l: benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
Azole compound m: benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)

Example 1
10 g of azole silane compound A and 1 g of azole compound m were measured, 200 g of ethylene glycol monobutyl ether was added, 789 g of water was subsequently added, and the mixture was stirred at room temperature for 2 hours to prepare a surface treatment solution.
About this process liquid, it confirmed that the methoxy silyl group of the azole silane compound was hydrolyzed to the hydroxy silyl group.

(Examples 2-15, Comparative Examples 1-19)
A surface treatment solution was prepared in the same manner as in Example 1 except that the azole silane compound or the silane compound and the azole compound were changed to the combinations shown in Tables 2 and 3.
About these process liquids, it confirmed that the methoxy silyl group and ethoxy silyl group of the said azole silane compound or a silane compound were hydrolyzed to the hydroxy silyl group.

  Using the surface treatment solutions prepared in Examples and Comparative Examples, the following adhesive evaluation tests (a) to (c) and a haloing evaluation test (d) were performed.

<Adhesion evaluation test>
[Adhesion Evaluation Test (a)]
(1) Test piece As a test piece, electrolytic copper foil (thickness: 18 μm) was used.
(2) Treatment of test piece The test piece was treated according to the following steps i to ii. However, in Comparative Example 1, no treatment was performed with the surface treatment liquid.
i. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
ii. Immersion in surface treatment solution / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion between test piece and resin A printed wiring board is prepared by laminating and pressing a glass cloth epoxy resin-impregnated prepreg (FR-4 grade) on the S side (glossy side) of the treated test piece. Was made.
(4) Evaluation of adhesiveness From this printed wiring board, a test piece having a width of 10 mm was prepared according to “JIS C6481 (1996)” and subjected to a pressure cooker treatment (121 ° C./humidity 100% / 100 hours), and then a copper foil. The peel strength (kN / m) was measured.

[Adhesion Evaluation Test (b)]
Instead of “laminate press of glass cloth epoxy resin impregnated prepreg (FR-4 grade)” on the S side (glossy side) of the test piece, “build-up wiring board resin (manufactured by Ajinomoto Fine Techno Co., Ltd., product name“ GX- ”) The adhesiveness between copper and resin was evaluated in the same procedure as in the evaluation test (a) except that “13”) was laminated.

[Adhesion Evaluation Test (c)]
(1) Test piece As a test piece of a printed wiring board, a double-sided copper-clad laminate (base material: FR4, plate thickness: 1.0 mm, copper foil thickness: 18 μm, vertical) subjected to electrolytic copper plating (plating thickness: 20 μm) 120 mm × 110 mm wide) was used.
(2) Treatment of test piece The test piece was treated according to the following steps i to ii. However, in Comparative Example 1, no treatment was performed with the surface treatment liquid.
i. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
ii. Immersion in surface treatment solution / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Formation of insulating resin layer on test piece After applying a solder resist (trade name “PSR-4000AUS308”, manufactured by Taiyo Ink Manufacturing Co., Ltd.) to the treated test piece, drying (80 ° C./30 minutes), post Cure (150 ° C./60 minutes) was performed to form an insulating resin layer (coating film) having a thickness of 13 μm.
(4) Evaluation of adhesiveness According to “JIS K5400-8.5 (1990)”, the coating film formed on the test piece was cross-cut (100 squares) on a 1 mm × 1 mm grid, and pressure cooker treatment (121 ° C. / After a humidity of 100% / 100 hours, a tape peel test was performed to measure the number of squares where the coating film did not peel off. Moreover, the damage condition of the coating film was observed visually.
The criteria for determining adhesiveness are as shown in Table 1.

<Haloing Evaluation Test (d)>
(1) Test piece A copper-clad laminate (copper thickness 35 μm, plate thickness 1.0 mm) was used as a test piece.
(2) Treatment of test piece The test piece was treated according to the following steps i to ii. However, in Comparative Example 1, no treatment was performed with the surface treatment liquid.
i. Acid wash / 1 minute (room temperature), water wash ii. Immersion in surface treatment solution / 1 minute (30 ° C), water washing, drying / 1 minute (100 ° C)
(3) Production of Printed Wiring Board After applying a solder resist (trade name “PSR-4000AUS308”, manufactured by Taiyo Ink Manufacturing Co., Ltd.) to the copper surface of the test piece, the following steps iii to iv are performed to obtain a copper opening ( A printed wiring board was prepared in which a cured product of a solder resist having an opening diameter of 150 μm and 5 holes) and a test piece (copper-clad laminate) were bonded.
iii. Exposure process (420 mJ / cm ² , using HMW-680 manufactured by Oak Seisakusho Co., Ltd.), development process (1% by mass sodium carbonate aqueous solution / 90 seconds (30 ° C.))
iv. Dry (80 ° C / 30 minutes), Post cure (150 ° C / 60 minutes)
(4) Plating treatment For the copper opening of the printed wiring board, a palladium catalyst (made by Okuno Seiyaku Kogyo Co., Ltd., trade name “ICP Nicolon Axela”, nickel plating (made by Okuno Seiyaku Kogyo Co., Ltd., trade name “ICP Nicolon GM”) And gold plating (trade name “Oell II” manufactured by Kojima Chemical Co., Ltd.) was used to perform the following step v to perform gold plating.
v. Soft etching / 1 minute (30 ° C.), water washing, palladium catalyst / 2 minutes (room temperature), nickel plating / 35 minutes (75 ° C.), gold plating / 5 minutes (80 ° C.)
(5) Evaluation of haloing property The width (unit: μm) of the haloing (solder resist peeling) due to the penetration of the chemical solution is measured with the optical microscope SZ for the gold-plated copper opening (opening diameter 150 μm) of the obtained printed wiring board. It measured by -61 (made by OLYMPUS). In addition, the measurement was performed about 5 holes and those average values were computed.

  Tables 2 and 3 show the results of the adhesive evaluation tests (a) to (c) and the haloing evaluation test (d).

  From the results of Tables 2 and 3, in Examples 1 to 15 in which the metal surface was treated with the surface treatment liquid of the present invention, the adhesion between the metal and the resin material was improved, and the width of haloing was Comparative Examples 1 to 1. It was found to be smaller than 19 and exhibit an excellent haloing suppression effect.

Claims (14)

A metal comprising at least one azolesilane compound represented by the following chemical formula (I) and at least one selected from the group consisting of azole compounds represented by chemical formulas (II) to (XIV): Surface treatment liquid.

(In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH _3. Y represents —NH— or —S—. R represents —CH ₃ or —CH _2. CH represents _3. m represents an integer of 1 to 12, and n represents an integer of 0 or 1 to 3).

(In formulas (II) to (XIV), X ^{1 to} X ⁴³ each independently represents a hydrogen atom, an amino group, a mercapto group, an alkyl group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms. Represents.)   The metal surface treatment solution according to claim 1, comprising 0.0001 to 5 mass% of the azolesilane compound.   The metal surface treatment solution according to claim 1 or 2, wherein the azole compound is contained in an amount of 0.0001 to 5 mass%.   Furthermore, at least 1 sort (s) selected from the group which consists of an acid, an alkali, and an organic solvent is contained, The metal surface treatment liquid of any one of Claims 1-3 characterized by the above-mentioned.   The metal surface treatment solution according to any one of claims 1 to 4, wherein the metal is copper or a copper alloy.   A metal surface treatment solution according to any one of claims 1 to 4 is brought into contact with the metal surface.   The metal treatment method according to claim 6, wherein the metal is copper or a copper alloy.   The manufacturing method of the printed wiring board characterized by including the process of making the surface of a metal contact the metal surface treatment liquid of any one of Claims 1-4, and forming a chemical conversion film.   The method for manufacturing a printed wiring board according to claim 8, wherein the metal is copper or a copper alloy.   It is the adhesion method of a metal and a resin material, Comprising: The surface treatment liquid of the metal of any one of Claims 1-4 is made to contact the surface of the said metal, a chemical conversion film is formed, The said metal and the said A method for adhering a metal and a resin material, comprising adhering a resin material via the chemical conversion film.   The method for adhering a metal and a resin material according to claim 10, wherein the metal is copper or a copper alloy. A printed wiring board comprising a metal wiring layer and an insulating resin layer made of a resin material, wherein at least one azolesilane compound represented by the following chemical formula (I) is interposed between the metal wiring layer and the insulating resin layer: A printed wiring board comprising a chemical conversion film derived from at least one selected from the group consisting of a seed and an azole compound represented by the following chemical formulas (II) to (XIV):

(In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH _3. Y represents —NH— or —S—. R represents —CH ₃ or —CH _2. CH represents _3. m represents an integer of 1 to 12, and n represents an integer of 0 or 1 to 3).

(In formulas (II) to (XIV), X ^{1 to} X ⁴³ each independently represents a hydrogen atom, an amino group, a mercapto group, an alkyl group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms. Represents.)   It is a printed wiring board provided with the metal wiring layer and the insulating resin layer which consists of resin materials, Comprising: The metal which comprises the said metal wiring layer, and the said resin material are the metal and resin material of Claim 10 or 11 A printed wiring board, which is bonded by the bonding method. An electronic device comprising the printed wiring board according to claim 12.