JPH06279462A - Novel azole silane compound and its production and metal surface-treating agent using the same - Google Patents

Abstract

PURPOSE:To obtain the subject novel compound excellent in a corrosion-resistant action and useful as a metal surface-treating agent, especially a surface-treating agent for copper foils. CONSTITUTION:A compound of formula I (R1, R2 are each 1-3C alkyl; (n) is 0-3). For example, a compound of formula II. The compound of formula I is obtained by dropwisely reacting 3-amino-1,2,4-triazole of formula III heated to 80-200 deg.C with 0.1-10 times moles of a 3-glycidoxypropylsilane compound of formula IV, e.g. a 3-glycidoxypropyltrialkoxysilane. Since the reaction is easily damaged with water, the reaction is preferably performed in a dry atmosphere such as dry nitrogen or argon gas.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel surface treatment agent for improving rust prevention of a metal surface, and particularly useful as a surface treatment agent for copper foil used for copper clad laminates for printed circuits. Azole-based silane compound, a method for producing the same, and uses thereof.

[0002]

A copper clad laminate for a printed circuit is formed by laminating a copper foil on a paper-phenol resin-impregnated base material or glass-epoxy resin-impregnated base material by heating and pressurizing it. A board for electronic equipment is made by forming a circuit network and mounting an element such as a semiconductor device on the circuit network.
In these processes, adhesion with a base material, heating, immersion in an acid or alkaline solution, application of resist ink, soldering, etc. are performed, so that various performances are required for the copper foil. For example, the side that is usually called the M surface (roughened surface, the same applies below) is mainly required to have adhesiveness with the base material, chemical resistance, etc. Usually S side (glossy surface,
The same shall apply hereinafter) is mainly required to have heat resistance and moisture resistance. It is also required that the copper foils on both sides of the copper foil do not undergo oxidative discoloration during storage. In order to satisfy these requirements, a brass layer forming treatment (Japanese Patent Publication No. 51-57711, 54-6701) on the M side of the copper foil, chromate treatment, zinc or oxidation on both sides of M and S. A coating treatment of a zinc-chromium group mixture consisting of zinc and chromium oxide (Japanese Patent Publication No. 58-7077) has been carried out.

[0003]

However, since the printed circuit has been densified recently as described above, the characteristics required for the copper foil for the printed circuit used have become more and more severe. The present invention provides a novel silane compound that can meet such demands, that is, has a high anticorrosive action on a metal surface, a method for producing the same, and a novel metal surface treating agent using the same, especially a surface treating agent for copper foil. That is the purpose.

[0004]

As a result of intensive studies, the present inventor has found that a silane compound having a specific azole ring has an excellent rust preventive action on a metal surface. The present invention has been made based on such findings, and the gist thereof is (1) a novel azole-based silane compound represented by the following general formula (1).

[0005]

[Chemical 3]

(However, in the general formula (1), R ¹ ,
R ² is an alkyl group having 1 to 3 carbon atoms, n is 0 to 3) (2) 3-amino-1, represented by the following general formula (2),
2,4-triazole and 3 represented by the following general formula (3)
-Glycidoxypropyl silane compound,
A method for producing an azole-based silane compound according to (1) above, which comprises reacting at 0 ° C.

[0007]

[Chemical 4]

(However, in the general formula (3), R ¹ ,
R ² is an alkyl group having 1 to 3 carbon atoms, n is 0 to 3) (3) At least one azole-based silane compound represented by the general formula (1) described in (1) above is used as an active ingredient. A metal surface treatment agent, and (4) a surface treatment agent for copper foil containing as an active ingredient at least one azole-based silane compound represented by the general formula (1) described in (1) above.

The present invention will be described in more detail below. R ¹ or R ² in the above general formula (1) is an alkyl group having 1 to 3 carbon atoms, and a methyl group and an ethyl group are particularly preferable from the viewpoint of easy synthesis. Further, n is 0 to 3.

The above-mentioned azole silane compound (1) of the present invention comprises 3-amino-1, represented by the general formula (2):
2,4-triazole and a 3-glycidoxypropylsilane compound represented by the general formula (3) were mixed at 80 to 200 ° C.
It can be produced by reacting with. The reaction is expressed by the following equation.

[0011]

[Chemical 5]

(Wherein R ¹ and R ² are alkyl groups having 1 to 3 carbon atoms, and n is 0 to 3) The 3-glycidoxypropylsilane compound represented by the general formula (3) is , 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyldialkoxyalkylsilane, 3-glycidoxypropylalkoxydialkylsilane, 3-glycidoxypropyltrialkylsilane, and particularly preferred of these. Examples of 3-glycidoxypropyltrialkoxysilane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
Further, 3-glycidoxypropyldialkoxyalkylsilane is 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylalkoxydialkylsilane is 3-glycidoxypropylethoxydimethylsilane, 3-glycid Examples of the xypropyltrialkylsilane include 3-glycidoxypropyltriethylsilane and the like.

The reaction of the above 3-amino-1,2,4-triazole with the 3-glycidoxypropylsilane compound is carried out by heating 3-amino-1,2, which is heated to a temperature of 80 to 200 ° C.
It is advisable to carry out the reaction while dropwise adding 0.1 to 10 mole times the amount of the 3-glycidoxypropylsilane compound to 2,4-triazole, and a reaction time of about 5 minutes to 2 hours is sufficient. This reaction does not require a solvent in particular, but an organic solvent such as chloroform, dioxane, methanol or ethanol may be used as a reaction solvent. In addition, since this reaction does not like water, dry nitrogen,
It is preferable to carry out under an atmosphere of a gas containing no water such as argon.

In this reaction, the azole silane compound represented by the above general formula (1) is obtained in the form of a mixture, and these compounds are known by a method utilizing a difference in solubility, preparative liquid chromatography and the like. Can be purified and isolated by means of. When used as a metal surface treatment agent, these azole-based silane compounds do not necessarily have to be isolated, and it is preferable to use the mixture as it is because it is simple.

When the above-mentioned azole type silane compound is used as a metal surface treating agent, the target metal is not particularly limited. For example, it is useful as a surface treatment agent for copper, zinc and alloys thereof. However, it is suitable to be used as a surface treatment agent for copper, and particularly when used as a surface treatment agent for a copper foil used for a copper clad laminate for printed circuits, the effects of the present invention can be sufficiently exhibited. The copper foil includes a copper foil whose surface has been roughened, a copper foil which has been subjected to a brass layer formation treatment, a chromate treatment, a zinc-chromium group mixture coating treatment, and the like.

At least one of the above-mentioned azole type silane compounds may be directly applied to the metal surface as it is, but alcohols such as methanol and ethanol, or a mixed solution thereof with water, and further acetone and ethyl acetate. It is convenient and preferable to dilute the solution with a solvent such as toluene to a concentration of 0.001 to 20% by weight and immerse the metal in this solution. The azole-based silane compound may be used alone, or may be mixed with another rust preventive agent and used.

[0017]

Example Synthesis of azole-based silane compound ( reaction of 3-amino-1,2,4-triazole with 3-glycidoxypropyltrimethoxysilane) Example 1 3-amino-1,2,4-triazole 4.2 g (0.
(05 mol) was heated at 130 ° C., and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise over 30 minutes while stirring under an argon atmosphere. After the dropping was completed, the reaction was further performed at a temperature of 130 ° C. for 1 hour. The reaction product was obtained as a clear yellow viscous liquid.

The product was a clear yellow viscous liquid and was stable without gelation for several weeks or longer. It was also soluble in alcohol, tetrahydrofuran and the like. The product was purified by gel permeation chromatography (hereinafter referred to as compound 1) and analyzed by ¹ H-NMR. As a result, the> NH peak disappeared completely, and IR also confirmed a stretching vibration peak of the OH group. Then, it was found that the above-mentioned reaction proceeded from now on (Figs. 1 and 2).

From these results, it was found that the compound 1 has a structure of the following formula (1-1) in which R ¹ is methyl and n is 3 in the general formula (1).

[0020]

[Chemical 6]

Next, the azole silane compound 1 thus produced was evaluated as a surface treatment agent for copper foil. The evaluation method is as follows.

Moisture resistance test Electrolytic copper foil (thickness 75 μm, 4.5 × 4.5 cm) was degreased with acetone and washed with a 3% aqueous sulfuric acid solution. On the shiny side of this copper foil, the azole silane compound of Compound 1 obtained above was dissolved in methanol to a concentration of 6% by weight, and this solution was applied by a spin coater to give a thickness of 0.3 μm.
A thin film of the azole-based silane compound was prepared and used as a test piece.

This test piece was placed in a thermo-hygrostat having a temperature of 80 ° C. and a humidity of 95% for 24 hours, and the moisture resistance was evaluated by the degree of discoloration. For comparison, 3-glycidoxypropyltrimethoxysilane (hereinafter simply referred to as “epoxysilane”) and 3-amino-1,2,2,3, which are commercially available as silane coupling agents, instead of the azole-based silane compound. 4-
The same test was performed on a copper foil on which a methanol solution of triazole was similarly applied in a thickness of 0.3 μm and a copper foil on which nothing was applied (hereinafter referred to as “blank”). The results are shown in Table 1.

[0024]

[Table 1]

(Note) Moisture resistance test; 5: No discoloration, 4: Slight discoloration, 3: Slight discoloration, 2: Orange or yellow discoloration,
1: Discoloration to blackish brown It can be seen from the above results that the compound of the present invention is excellent as a metal surface treating agent in moisture resistance (anticorrosion effect) and the like.

[0026]

INDUSTRIAL APPLICABILITY The novel azole-based silane compound of the present invention is useful as a metal surface treating agent, especially as a surface treating agent for copper foil, and has an effect of excellent rust prevention.

[Brief description of drawings]

FIG. 1 ¹ H-NMR spectrum of Compound 1

FIG. 2 Same IR spectrum

Front Page Continuation (72) Inventor Yukio Ogino 3-17-35, Shinzonan, Toda City, Saitama Prefecture Nikko Kyoishi Co., Ltd.

Claims (4)

[Claims] 1. A novel azole silane compound represented by the following general formula (1). [Chemical 1] (However, in the general formula (1), R ¹ and R ² are alkyl groups having 1 to 3 carbon atoms, and n is 0 to 3) 2. A compound comprising 3-amino-1,2,4-triazole represented by the following general formula (2) and a 3-glycidoxypropylsilane compound represented by the following general formula (3):
The method for producing an azole-based silane compound according to claim 1, wherein the reaction is performed at about 200 ° C. [Chemical 2] (However, in the general formula (3), R ¹ and R ² are alkyl groups having 1 to 3 carbon atoms, and n is 0 to 3) 3. A metal surface treating agent comprising at least one azole-based silane compound represented by the general formula (1) as an active ingredient. 4. A surface treatment agent for a copper foil, which contains at least one azole-based silane compound represented by the general formula (1) as an active ingredient.