JP2016017221A - Surface preparation agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface preparation agent of a metal, used for a process for integrating a copper foil with a printed wiring board, capable of heightening heat resistance and humidity resistance of a metal surface, and improving adhesiveness between the metal and a resin.SOLUTION: A surface preparation agent of a metal contains an imidazole silane compound shown by formula (I) as a component: (formula 1) (R-Rare each H, C1-20 alkyl group or phenyl group; Rand Rare each H or C1-3 alkyl group; m is an integer of 1-3; and n is an integer of 0-5;).SELECTED DRAWING: None

Description

  The present invention relates to a metal surface treatment agent.

In recent years, printed wiring boards have been multi-layered to cope with the downsizing and thinning of electronic devices and electronic components. So-called multilayer printed wiring boards are provided with a circuit made of copper foil or the like on one or both sides. In addition, an outer layer circuit board or a copper foil is laminated on an inner layer circuit board via a prepreg, and these are integrated.
In these processes, adhesion to the base material, heating, immersion in acid or alkaline liquid, application of resist ink, etc. are performed, so copper foil has heat resistance and moisture resistance, as well as adhesion to resin, Chemical resistance is required.

  Patent Document 1 discloses that a specific silane compound having an imidazole ring exhibits an excellent rust preventive action on the metal surface and improves the adhesion between the metal and the resin substrate. However, satisfactory adhesiveness has not yet been obtained.

JP-A-5-186479

  An object of the present invention is to provide a metal surface treatment agent that can improve the heat resistance and moisture resistance of a metal surface and improve the adhesion between the metal and the resin.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventor has provided a certain kind of imidazole silane compound with excellent heat resistance and moisture resistance on the metal surface and adhesion between the metal and the resin. The present inventors have found that the property is improved and have completed the present invention.

  That is, the first invention is a metal surface treatment agent comprising an imidazolesilane compound represented by the chemical formula (I) as a component.

（式中、Ｒ^１〜Ｒ^５は水素原子、炭素数１〜炭素数２０のアルキル基またはフェニル基を表し、Ｒ^６およびＲ^７は水素原子または炭素数１〜炭素数３のアルキル基を表し、ｍは１〜３の整数を表し、ｎは０〜５の整数を表す。）

Wherein R ^{1 to} R ⁵ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁶ and R ⁷ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents an integer of 1 to 3, and n represents an integer of 0 to 5.)

  ADVANTAGE OF THE INVENTION According to this invention, the heat resistance of a metal surface and moisture resistance can be improved, and the adhesiveness of a metal and resin can be improved.

Hereinafter, the present invention will be described in detail.
The metal surface treatment agent of the present invention comprises an imidazole silane compound represented by the above chemical formula (I) as a component.

  The steps for synthesizing the imidazole silane compound are shown in Reaction Scheme (A) and Reaction Scheme (B), respectively.

（式中、Ｒ^１〜Ｒ^７、ｍおよびｎは、前記と同様である。Ｒ^８は炭素数１〜炭素数２０のアルキル基またはフェニル基を表す。）

(In the formula, R ^{1 to} R ⁷ , m and n are the same as described above. R ⁸ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group.)

  Reaction scheme (A): The imidazole silane compound of the present invention represented by the chemical formula (I) by reacting the imidazole carbamate compound represented by the chemical formula (IIa) with the 3-aminopropylsilane compound represented by the chemical formula (IIIa). Produces.

The reaction temperature between the imidazole carbamate compound and the 3-aminopropylsilane compound is preferably 50 to 250 ° C., and the reaction time is appropriately determined according to the set reaction temperature, but 30 minutes to A range of 48 hours is preferred.
This reaction proceeds stoichiometrically, but depending on the conditions such as reaction temperature, reaction time, type and amount of reaction solvent used, reaction scale, etc., the amount of imidazole carbamate compound used (amount charged) was changed to 3-amino It can be set as the appropriate ratio in the range of 0.1-10 times mole with respect to a propylsilane compound.

  In this reaction, as a reaction solvent, methanol, ethanol, propanol, tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexa An appropriate amount of an appropriate solvent selected from methylphosphoric triamide and the like may be used. In addition, the solvent used as a reaction solvent may be used individually by 1 type, and may use it combining a solvent from which a kind differs as needed.

（式中、Ｒ^１〜Ｒ^４、Ｒ^６、Ｒ^７、ｍおよびｎは、前記と同様である。）

(Wherein R ^{1 to} R ⁴ , R ⁶ , R ⁷ , m and n are the same as described above.)

Reaction scheme (B): A reaction represented by the chemical formula (I ′) by reacting the 1-aminoalkylimidazole compound represented by the chemical formula (IIb) with the 3-isocyanatopropylsilane compound represented by the chemical formula (IIIb). The imidazole silane compound of the invention is formed.
The chemical formula (I ′) is equivalent to the chemical formula (I) in which R ⁵ is specified as a hydrogen atom.

The reaction temperature between the 1-aminoalkylimidazole compound and the 3-isocyanatopropylsilane compound is preferably -20 to 80 ° C., and the reaction time is appropriately determined according to the set reaction temperature. However, the range of 15 minutes to 12 hours is preferable.
This reaction also proceeds stoichiometrically in the same manner as the reaction shown in Reaction Scheme (A). However, for the same reason as described above, the amount of 1-aminoalkylimidazole compound used (charge amount) was changed to 3-isocyanate. It can be set as the appropriate ratio in the range of 0.1-10 times mole with respect to a natopropylsilane compound.

  In addition, this reaction may be performed without a solvent, or may be performed using the same solvent as the reaction solvent shown in the reaction scheme (A) as a reaction solvent.

In the chemical formulas appearing in the claims and specification of the present application, the alkyl group having 1 to 20 carbon atoms that can be adopted by R ^{1 to} R ⁵ and R ⁸ is
Represents a saturated hydrocarbon group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl.

Further, the alkyl group of ^{R 6} and ^{R 7} carbon number 1 to 3 carbon atoms which may be employed,
Represents a saturated hydrocarbon group such as methyl, ethyl, propyl and the like.

As an imidazole carbamate compound represented by the chemical formula (IIa),
1-methoxycarbonylaminomethylimidazole,
1- (2-methoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-ethoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-propoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-butoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-phenoxycarbonylaminoethyl) -2-methylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-ethoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-propoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-butoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-phenoxycarbonylaminopropyl) -2-methylimidazole,
1- (2-methoxycarbonylaminoethyl) -2-phenylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-phenylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-ethyl-4-methylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-phenyl-4-methylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-undecylimidazole and the like can be mentioned.

As the 3-aminopropylsilane compound represented by the chemical formula (IIIa),
3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane,
3-aminopropyltripropoxysilane,
N-methyl-3-aminopropyltrimethoxysilane,
N-phenyl-3-aminopropyltrimethoxysilane,
3-aminopropyldimethoxymethylsilane,
Examples include 3-aminopropylmethoxydimethylsilane.

As the 1-aminoalkylimidazole compound represented by the chemical formula (IIb),
1- (2-aminoethyl) imidazole,
1- (3-aminopropyl) imidazole,
1- (2-aminoethyl) -2-methylimidazole,
1- (3-aminopropyl) -2-methylimidazole,
1- (2-aminoethyl) -2-phenylimidazole,
1- (3-aminopropyl) -2-phenylimidazole,
1- (3-aminopropyl) -2-undecylimidazole,
1- (3-aminopropyl) -2-ethyl-4-methylimidazole,
Examples include 1- [2- (methylamino) ethyl] -2-phenylimidazole.

As the 3-isocyanatopropylsilane compound represented by the chemical formula (IIIb),
3-isocyanatopropyltrimethoxysilane,
3-isocyanatopropyltriethoxysilane,
3-isocyanatopropyl tripropoxysilane,
3-isocyanatopropyldimethoxymethylsilane,
3-isocyanatopropylmethoxydimethylsilane etc. are mentioned.

As the imidazolesilane compound represented by the chemical formula (I) of the present invention,
1- [3- (imidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (triethoxysilyl) propyl] urea,
1- [3- (2-methylimidazol-1-yl) propyl] -3- [3- (triethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (dimethoxymethylsilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -1-methyl-3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3-phenyl-3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-ethyl-4-methylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-ethyl-4-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-undecylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-undecylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-phenylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-phenylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
Examples include 1- [2- (2-phenylimidazol-1-yl) ethyl] -1-methyl-3- [3- (trimethoxysilyl) propyl] urea.

The metal surface treatment agent of the present invention is prepared by mixing the above-mentioned imidazolesilane compound and water, but may be mixed with a mixed solution of water and an organic solvent.
Moreover, after mixing the said imidazolesilane compound with water, water may be distilled off and it may mix with an organic solvent and may prepare a surface treating agent.
The said imidazole silane compound can be used 1 type or in combination of 2 or more types.

  Organic solvents used for the preparation of this surface treatment agent include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene Examples include glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone, tetrahydrofuran, dioxane, acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc. It is possible, it is possible to use one or two or more selected from these.

The concentration of the imidazole silane compound in the surface treatment agent of the present invention is preferably in the range of 0.001 to 20% by weight.
When the concentration of the imidazole silane compound is less than 0.001% by weight, the effect of improving the heat resistance, moisture resistance and adhesion of the metal may not be sufficiently obtained. When the concentration exceeds 20% by weight, The effect of improving heat resistance, moisture resistance and adhesiveness has almost reached its peak, and only the amount of imidazolesilane compound used is increased, which is not economical.

  As long as the effect of the present invention is not impaired, a known rust preventive or coupling agent may be added to the surface treatment agent as necessary.

There is no restriction | limiting in particular as a method of making the said surface treating agent contact the surface of a metal, Means, such as immersion, application | coating, a spray, are employable.
The time (treatment time) for bringing the surface treatment agent into contact with the metal is preferably 1 second to 10 minutes. When the treatment time is less than 1 second, the film thickness of the chemical conversion film formed on the surface of the metal becomes thin, and there is a possibility that the heat resistance and moisture resistance of the metal and the adhesive force between the metal and the resin cannot be obtained sufficiently. is there. On the other hand, when the treatment time exceeds 10 minutes, there is no great difference in the film thickness of the chemical conversion film formed on the surface of the metal, and the effect of improving the heat resistance, moisture resistance and adhesion between the metal and the resin is also achieved. Almost reaches the peak.
Moreover, about the temperature of the surface treating agent at the time of making a surface treating agent contact the metal surface, it is preferable to set it as 5-50 degreeC, However, What is necessary is just to set suitably in relation to the said processing time.

  There are no particular limitations on the metal to be treated with the surface treatment agent, and examples thereof include metals such as copper, zinc, tin, aluminum, titanium, nickel, iron, silver, and gold, and alloys thereof. The treating agent is suitable for surface treatment of copper or copper alloy.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. In addition, the synthesis example of the imidazole silane compound used for the Example is shown in Reference Examples 1-8. The main raw materials used for these syntheses are as follows.
[Main ingredients]
1- (3-aminopropyl) imidazole: manufactured by Tokyo Chemical Industry Co., Ltd. 1- (2-aminoethyl) -2-methylimidazole: conforms to the method described in “Organic Syntheses, Vol 27, 18 (1947)”. And synthesized.
1- (3-aminopropyl) -2-methylimidazole: synthesized according to the method described in “JP 2010-126464 A”.
1- (3-aminopropyl) -2-ethyl-4-methylimidazole: same as above 1- (3-aminopropyl) -2-undecylimidazole: same as above 1- (2-aminoethyl) -2-phenyl Imidazole: Same as above. 1- (3-Aminopropyl) -2-phenylimidazole: Same as above. 1- [2- (Methylamino) ethyl] -2-phenylimidazole: As described in “International Publication No. 2005/123066 pamphlet” Synthesized according to the method.
・ 3-isocyanatopropyltrimethoxysilane: manufactured by Momentive

[Reference Example 1]
<Synthesis of 1- [3- (imidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-1”)>
1.26 g (10.0 mmol) of 1- (3-aminopropyl) imidazole was dissolved in 20 ml of toluene, and 2.06 g (10.0 mmol) of 3-isocyanatopropyltrimethoxysilane was added dropwise while keeping the temperature at 40 ° C. or lower. .
Then, the reaction solution was stirred at room temperature for 1 hour, and then volatile components were distilled off to obtain 3.31 g (10.10 g) of the title imidazolesilane compound represented by the chemical formula (I-1) as a pale yellow viscous liquid. 0 mmol, yield: 100%).

[Reference Example 2]
<Synthesis of 1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-2”)>
The same operation as in Reference Example 1 was performed except that 1.26 g (10.0 mmol) of 1- (2-aminoethyl) -2-methylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 3.31 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (I-2) was obtained.

[Reference Example 3]
<Synthesis of 1- [3- (2-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-3”)>
The same operation as in Reference Example 1 was performed except that 1.40 g (10.0 mmol) of 1- (3-aminopropyl) -2-methylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 3.45 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (I-3) was obtained.

[Reference Example 4]
<Synthesis of 1- [3- (2-ethyl-4-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-4”)>
The same as Reference Example 1 except that 1.68 g (10.0 mmol) of 1- (3-aminopropyl) -2-ethyl-4-methylimidazole was used instead of 1- (3-aminopropyl) imidazole. The operation was performed to obtain 3.73 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (I-4) as a pale yellow viscous liquid.

[Reference Example 5]
<Synthesis of 1- [3- (2-undecylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-5”)>
The same operation as in Reference Example 1 was performed except that 2.80 g (10.0 mmol) of 1- (3-aminopropyl) -2-undecylimidazole was used instead of 1- (3-aminopropyl) imidazole. Thus, 4.85 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (I-5) was obtained as a pale yellow viscous liquid.

[Reference Example 6]
<Synthesis of 1- [2- (2-phenylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-6”)>
The same operation as in Reference Example 1 was performed except that 1.88 g (10.0 mmol) of 1- (2-aminoethyl) -2-phenylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 3.93 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (I-6) was obtained.

[Reference Example 7]
<Synthesis of 1- [3- (2-phenylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-7”)>
The same operation as in Reference Example 1 was performed except that 2.02 g (10.0 mmol) of 1- (3-aminopropyl) -2-phenylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 4.07 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (I-7) was obtained.

[Reference Example 8]
<Synthesis of 1- [2- (2-phenylimidazol-1-yl) ethyl] -1-methyl-3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZS-8”)>
The same operation as in Reference Example 1 except that 2.01 g (10.0 mmol) of 1- [2- (methylamino) ethyl] -2-phenylimidazole was used instead of 1- (3-aminopropyl) imidazole. To obtain 4.07 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (I-8) as a pale yellow viscous liquid.

The silane compounds used in the comparative examples are as follows.
3-glycidoxypropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”, hereinafter abbreviated as “epoxysilane”.
3-Aminopropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-903”, hereinafter abbreviated as “aminosilane”.

  Moreover, the evaluation test methods employed in the examples and comparative examples are as follows.

[Test pieces]
A 45 mm × 45 mm electrolytic copper foil (thickness 75 μm) was degreased with acetone and washed with a 3% sulfuric acid aqueous solution. A metal surface treatment agent was applied to the shiny surface of the copper foil with a spin coater to form a chemical conversion film having a thickness of 0.3 μm, which was used as a test piece for a heat resistance test and a moisture resistance test.

[Heat resistance test]
The test pieces were left in a thermostatic bath at temperatures of 180 ° C., 200 ° C., 220 ° C., and 240 ° C. for 30 minutes, respectively, and the degree of discoloration on the copper surface was visually observed.
The heat resistance of the copper surface was evaluated according to the following evaluation criteria. The lower the degree of discoloration, the better the heat resistance of the chemical conversion film, that is, the heat resistance of the copper surface.
<Evaluation criteria>
5: No discoloration 4: Slightly discolored 3: Discolored slightly 2: Discolored orange or yellow 1: Discolored blackish brown

[Moisture resistance test]
The test piece was left in a constant temperature bath at a temperature of 80 ° C. and a relative humidity of 95% for 24 hours, and then the degree of discoloration on the copper surface was visually observed.
The moisture resistance of the copper surface was evaluated according to the following evaluation criteria. It is determined that the lower the degree of discoloration, the better the moisture resistance of the chemical conversion film, that is, the moisture resistance of the copper surface.
<Evaluation criteria>
5: No discoloration 4: Slightly discolored 3: Discolored slightly 2: Discolored orange or yellow 1: Discolored blackish brown

[Adhesion test (I)]
Brass was plated on a mat surface of a 25 cm × 25 cm electrolytic copper foil (thickness: 33 μm), and then zinc or a mixture of zinc oxide and chromium oxide was plated and used as a test piece. Next, this test piece was immersed in a metal surface treatment agent, taken out, drained, and then dried in a dryer at 100 ° C. for 5 minutes. And the mat | matte surface of this test piece was adhere | attached on the base material which impregnated the epoxy resin to the glass fiber cloth, and the normal peel strength was measured based on "JIS C6481".

[Adhesion test (b)]
(1) Base material of test piece As a base material of the test piece, an electrolytic copper foil (thickness: 18 μm) was used.
(2) Processing of base material It carried out according to the following processes ac.
a. Acid clean / 1 minute (room temperature), water wash b. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
c. Immersion in metal surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion of base material and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the shiny surface of the treated base material, and the base material and the resin were adhered to create a printed wiring board.
(4) Evaluation of adhesiveness From this printed wiring board, a test piece having a width of 10 mm was prepared in accordance with “JIS C6481” and subjected to pressure cooker treatment (121 ° C./humidity 100% / 100 hours). The peel strength was measured.

[Adhesion test (C)]
Instead of “laminate press of glass cloth epoxy resin impregnated prepreg (FR-4 grade)” on the shiny surface of the base material, “resin for build-up wiring board (trade name“ GX-13 ”manufactured by Ajinomoto Fine Techno Co., Ltd.) Except for laminating, the peel strength of the copper foil was measured in the same procedure as in the evaluation test (b).

[Adhesion test (d)]
(1) Base material of test piece As a base material of test piece, double-sided copper-clad laminate (substrate: FR4, plate thickness: 1.0 mm, copper foil thickness: 18 μm) subjected to electrolytic copper plating (plating thickness: 20 μm), 120 mm long × 110 mm wide) was used.
(2) Treatment of base material It was performed according to the following steps a to d.
a. Acid clean / 1 minute (room temperature), water wash b. Micro etching with hydrogen peroxide / sulfuric acid / 1 minute (room temperature), water washing c. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
d. Immersion in metal surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Formation of resin layer on substrate After applying a solder resist (trade name “PSR-4000AUS308”, manufactured by Taiyo Ink Manufacturing Co., Ltd.) to the treated substrate, drying (80 ° C./30 minutes), post-cure (150 ° C./60 minutes) was performed to form a 13 μm thick resin layer (coating film), and a printed wiring board test piece was prepared.
(4) Evaluation of adhesiveness According to “JIS K5400-8.5”, the coating film formed on the surface of the test piece was cross-cut (100 squares) on a 1 mm × 1 mm grid, and pressure cooker treatment (121 ° C./humidity) 100% / 100 hours), a tape peel test was performed, and the number of squares where the coating film was not peeled was measured. Moreover, the damage condition of the coating film was observed visually.
The criteria for determining adhesiveness are as shown in Table 1.

[Example 1]
A metal surface treatment agent was prepared by dissolving IMZS-1 in methanol to a concentration of 6% by weight. Next, a heat resistance test and a moisture resistance test were performed using this surface treatment agent. These test results were as shown in Table 2.

[Examples 2 to 8, Comparative Example 1]
In the same manner as in Example 1, metal surface treatment agents having the compositions shown in Table 2 were prepared and subjected to a heat resistance test and a moisture resistance test. These test results were as shown in Table 2.

[Comparative Example 2]
A heat resistance test and a moisture resistance test were performed without subjecting the copper foil to a surface treatment. The test results were as shown in Table 2.

[Examples 9 to 16, Comparative Example 3]
In the same manner as in Example 1, metal surface treatment agents having the compositions shown in Table 3 were prepared. Subsequently, when these surface-treating agents were used to conduct an adhesion test (A), the test results obtained were as shown in Table 3.

[Comparative Example 4]
An adhesion test (I) was performed without subjecting the test piece to surface treatment. The test results were as shown in Table 3.

Example 17
To 10 g of IMZS-1, 200 g of ethylene glycol monobutyl ether (hereinafter abbreviated as “EGBE”) is added, and then 790 g of water is added and stirred at room temperature for 2 hours. Prepared.
When this surface treating agent was used to perform adhesion tests (b) to (d), the test results obtained were as shown in Table 4.

[Examples 18 to 24, Comparative Examples 5 to 6]
In the same manner as in Example 17, a metal surface treatment agent having the composition shown in Table 4 was prepared. Subsequently, when the adhesion tests (b) to (d) were performed using these surface treatment agents, the test results obtained were as shown in Table 4.

[Comparative Example 7]
When the adhesion tests (b) to (d) were performed without subjecting the copper foil to surface treatment, the test results obtained were as shown in Table 4.

According to the test results shown in Table 2, a chemical conversion film having excellent heat resistance and moisture resistance can be formed on the surface of copper by using the metal surface treatment agent of the present invention.
Further, according to the test results shown in Table 3 and Table 4, the adhesion between the metal and the resin can be improved by using the metal surface treatment agent of the present invention.

  The metal surface treatment agent of the present invention can form a chemical conversion film having excellent heat resistance and moisture resistance on the metal surface, and can improve the adhesion between the metal and the resin. It is expected to be used for various parts that require protection from metal surface oxidation and corrosion, and adhesion between metal and resin, such as printed wiring boards, electronic parts, metal foil (copper foil), and electric wires. The

Claims (1)

A metal surface treatment agent comprising an imidazolesilane compound represented by the chemical formula (I) as a component.

Wherein R ^{1 to} R ⁵ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁶ and R ⁷ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents an integer of 1 to 3, and n represents an integer of 0 to 5.)