JPH06279464A - Novel azole silane, its production and surface treating agent containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a surface-treating agent for copper foil because of its high anticorrosion action on the metal surface by reaction of a specific azole based compound with a glycidoxypropylsilane. CONSTITUTION:The reaction of (A) an azole based compound of formula I (X is NH, S; Y is S, NH) with (B) 3-glycidoxypropylsilane of formula II (R<1>, R<2> are each 1 to 3C alkyl; (n) is 0 to 3) is carried out at 80 to 200 deg.C to give the objective compound of formula III. For example, the component B is 3- glycidoxypropyltrimethylsilane.

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 capable of meeting such demands, that is, having a high anticorrosive action on a metal surface, a method for producing the same, and a novel metal surface treating agent using the same, particularly a surface treating agent for copper foil. The purpose is to do.

[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 silane compound represented by the following general formula (1),

[0006]

[Chemical 3]

(However, in the general formula (1), R ¹ ,
R ² is an alkyl group having 1 to 3 carbon atoms, X is an NH group or sulfur, Y is a sulfur or NH group, and n is 0 to 3) (2) An azole compound represented by the following general formula (2) A method for producing an azole-based silane compound according to (1) above, which comprises reacting a 3-glycidoxypropylsilane compound represented by the following general formula (3) at 80 to 200 ° C.

[0008]

[Chemical 4]

(However, in the general formulas (2) and (3), R ¹ and R ² are alkyl groups having 1 to 3 carbon atoms, and n is 0 to
3, X is an NH group or sulfur, and Y is a sulfur or NH group. (4) Metal surface treatment containing at least one azole silane compound represented by the general formula (1) described in (1) above as an active ingredient. And (5) a surface treatment agent for copper foil, which contains at least one azole-based silane compound represented by the general formula (1) described in (1) above as an active ingredient.

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.

The azole silane compound (1) of the present invention comprises the azole compound represented by the general formula (2) and the 3-glycidoxypropylsilane compound represented by the general formula (3), It can be produced by reacting at ˜200 ° C. The reaction is expressed by the following equation.

[0012]

[Chemical 5]

(Wherein R ¹ and R ² are alkyl groups having 1 to 3 carbon atoms, n is 0 to 3, X is NH group or sulfur, and Y is sulfur or NH group). Preferred as the azole compound represented by) are 2-aminobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and the like. The 3-glycidoxypropylsilane compound represented by the above general formula (3) includes 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyldialkoxyalkylsilane, and 3-glycidoxypropylalkoxydialkyl. Silane and 3-glycidoxypropyltrialkylsilane. Of these, particularly preferable ones are 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycid Xypropyltriethoxysilane, 3-glycidoxypropyldialkoxyalkylsilane is 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylalkoxydialkylsilane is 3-glycidoxypropylethoxydimethyl. Shi Down, as the 3-glycidoxypropyltrimethoxysilane alkyl silane, 3-glycidoxypropyl triethylsilane or the like.

The reaction between the azole compound and the 3-glycidoxypropylsilane compound is carried out by heating the azole compound at a temperature of 80 to 200 ° C. in an amount of 0.1 to 10 mole times the amount of 3-glycidoxypropylsilane. It is advisable to carry out the reaction while dropping the compound, 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. Since this reaction does not like water, it is preferable to carry out the reaction in an atmosphere of a gas containing no water such as dry nitrogen or argon so as not to mix water.

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 benzotriazole silane compound may be used alone, or may be used as a mixture with another rust preventive agent or the like.

[0017]

Example Synthesis of azole silane compound ( reaction of 2-mercaptobenzothiazole with 3-glycidoxypropyltrimethoxysilane) Example 1 8.4 g of 2-mercaptobenzothiazole (0.05 m
ol) was heated at 120 ° 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 120 ° C. for 1 hour.

The reaction product was obtained as a transparent yellow viscous liquid (hereinafter referred to as compound 1). The product was a clear yellow viscous liquid and was stable without gelation for more than several weeks. It was also soluble in alcohol, chloroform, tetrahydrofuran and the like, and was confirmed to be a single component by gel permeation chromatography.

Further, a part of this was taken and analyzed by ¹ H-NMR. As a result, --SH was completely disappeared and the reaction was completely progressed. Further, from IR, a peak of stretching vibration of the OH group was also confirmed, and it was found that the above-mentioned reaction proceeded from this (FIGS. 1 and 2). The results of MS spectrum analysis are shown below.

MS; 403 (M +) From these results, it is found that the above compound 1 has a structure of the following formula (1-1) in which R ¹ is methyl and n is 3 in the above general formula (1). It was

[0021]

[Chemical 6]

Examples 2 and 3 Instead of the 2-mercaptobenzothiazole of Example 1,
Compounds 2 and 3 were synthesized by carrying out the reaction in the same manner as in Example 1 except that the azole compound shown in Table 1 was used and the reaction temperature was changed to the reaction temperature shown in Table 1.

[0023]

[Table 1]

Next, the azole silanes (Compounds 1 to 3) thus produced were 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 compounds of compounds 1 to 3 obtained above were dissolved in methanol to a concentration of 6% by weight, and this solution was applied with 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 humidity resistance was evaluated by the degree of discoloration. For comparison, 3-glycidoxypropyltrimethoxysilane (hereinafter simply referred to as “epoxysilane”) commercially available as a silane coupling agent and 2-aminobenz of the azole compound instead of the above-mentioned azole compound. Similarly, a copper foil coated with a methanol solution of thiazole, 2-mercaptobenzothiazole, and 2-mercaptobenzimidazole in a thickness of 0.3 μm and a copper foil on which nothing was coated (hereinafter referred to as “blank”) were evaluated in the same manner. The results are shown in Table 2.

[0027]

[Table 2]

(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.

[0029]

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 IR spectrum of Compound 1

FIG. 2 Same ¹ H-NMR spectrum

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Ogino 3-17-35, Shinsōnan, 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, X is an NH group or sulfur, Y is a sulfur or NH group, and n is 0 to 3) 2. An azole compound represented by the following general formula (2) and a 3-glycidoxypropylsilane compound represented by the following general formula (3) are reacted at 80 to 200 ° C. The method for producing an azole-based silane compound according to claim 1. [Chemical 2] (However, in the general formulas (2) and (3), R ¹ and R ² are alkyl groups having 1 to 3 carbon atoms, n is 0 to 3, X is NH group or sulfur, and Y is sulfur or NH group.) 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.