JPS63125532A - Bonding of polyimide molding - Google Patents

Abstract

PURPOSE:To obtain a laminated article of a polyimide molding of excellent bonding force, by laying a polyimide sheet adhesive on the treated surface of a polyimide molding subjected to specified treatments, laying an adhered on the assemblage and heating the final assemblage under a pressure. CONSTITUTION:A polyimide molding such as a film, a flexible printed wiring board or a laminate is treated with a solution of 0.1-50wt% basic compound (e.g., KOH) in water and/or an alcohol at room temperature to 80 deg.C for 0.1 min-1hr, optionally treated with an acid solution, treated with a solution (e.g., acetone) in which 0.01-30wt% silane coupling agent (e.g., gamma- aminopropyltriethoxysilane) for 0.5-10min and further heat-treated at 80 deg.C or above for 1-60min to obtain a treated polyimide molding (A). A polyamide sheet adhesive (B) of a softening point <=400 deg.C is laid on the treated surface component A, a desired adhered (C) (e.g., copper foil) is laid on the adhesive, and the assemblage is heated to a temperature above the softening point of component B at a pressure of 0.1-100kg/cm<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for adhering polyimide molded products, and more particularly to a method for adhering polyimide molded products that provides a laminate with an adhesive strength of 4&n.

[Conventional technology]

Polyimide molded products, especially polyimide films, are electrically P2
It is widely used as a border material. For example, flexible wiring boards are manufactured by bonding polyimide film to gold W4 foil such as copper foil.
Acrylic adhesives have been used as shown in Japanese Patent No. 34640. However, acrylic adhesives have low heat resistance and do not take full advantage of the inherent heat resistance of polyimide films. Therefore, in order to take advantage of the heat resistance of polyimide film, polyimide adhesives were developed (see, for example, Japanese Patent Laid-Open No. 60755/1983). However, since polyimide adhesives generate water during ring closure, they have drawbacks such as requiring complex and long drying times and low peel strength due to their high elastic modulus. In order to improve the adhesion, attempts have been made to mechanically roughen the surface of the polyimide film by sandblasting, etc., or to perform plasma treatment.
-21878). However, mechanical roughening is not sufficient for adhesion, plasma treatment is somewhat effective but requires expensive equipment, and the treatment effect deteriorates in a short period of time. - 10,000, special public service Sho 52-3677
As shown in Publication No. 8, there is a method in which a polyimide film is treated with an alkali and then treated again with a metal salt that has a smaller ionization tendency than an alkali metal, but this method requires the use of heavy metals and Although it is effective for certain polyimide adhesives, it has drawbacks such as insufficient effectiveness for many other polyimide adhesives.

[Problem that the invention seeks to solve]

It is an object of the present invention to overcome the drawbacks of the prior art as described above and to provide a bonded polyimide molded product that can obtain sufficient adhesive strength.

[Means for solving problems]

The bonded polyimide molded product of the present invention can be thermally melted onto the treated surface of the polyimide molded product whose surface has been treated with FJ liquid containing a basic additive, treated with a silane coupling agent, and then heat treated. A sheet of polyimide adhesive is layered, and an arbitrary adherend is layered on top of the YM adhesive, which has a temperature higher than the softening point of the Wi agent.
Pressure and heat at 100%.

In addition to films, the polyimide molded product used in the method of the present invention may be one in which the polyimide resin is exposed on the surface, such as a flexible paulownia wiring board or a laminate. Further, the polyimide may be one having the same imide structure, such as polyamideimide, polyetherimide, polyesterimide, etc.

The basification adducts used in the method of the present invention include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and tetramethylammonium hydroxide, tetraethelammonium hydroxide, and hydroxide. Quaternary anthonium hydroxides such as tetrabutylammonium are preferred, and potassium hydroxide, hydroxide, and sodium chloride are particularly preferred.

As the solvent for dissolving the above-mentioned basification adduct, C is preferably water, alcohol such as methanol, ethanol, propatool, isopropanol, or a mixed solvent of water and alcohol.

The concentration of the basifying additive in the solution containing the basifying additive, the degree of treatment, and the time for treating the polyimide molded article are determined by the desired degree of treatment, and there are no particular limitations on the degree of treatment (although there is no Q at 111 degrees, 1 to 50% by weight, temperature from room temperature to 80 degrees Celsius, and time rc from 0 degrees to 1 minute to 1 hour.Surface treatment of polyimide molded articles with a bath solution containing this basic additive is effective, for example. Any known method may be used, such as immersing the molded article in the liquid or casting the molded article using an applicator, doctor knife, or the like.

After treatment with a solution containing a salt M-containing adduct, treatment with an acid solution such as hydrochloric acid, sulfuric acid, or acetic acid may be performed before treatment with a silane coupling agent.

Examples of the silane coupling agent used in the method of the present invention include vinyl 7-lanes such as vinyltrimethoxysilane, epoxysilanes such as r-glycidoxibu p-virtrimethoxy 7-silane, and mercapto-7 silanes such as γ-mercapdobu-pyltrimethoxy 7-silane. Ran, γ-aminoglovirtri to xy7
Ran, N-722-γ-aminopropyltrimethoxysilane, N-β(aminoethane γ-aminogapyltrimethoxy7ran, N-β(aminoether)γ-aminopropylmethyldimethoxysilane, γ- Ureidoglobil triethoxy 7rane, N-benzyl-γ-aminepropyltrimethoxysilane, aminoethelaminometherphenethertrimethoxysilane, p-aminophenyltrimethoxysilane, trimethoxycyclylpropyldietherenetriamine, 1-trimethoxysilane A-1-minosilane such as 2-(aminomethyl)phenylethane should be used.
Among them, mercaptosilane and aminosilane are preferable, and T-mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane are particularly preferable.

The treatment with a silane coupling agent is carried out after treatment with a solution containing a basic additive.The treatment method includes, for example, immersing a polyimide molded article in a silane coupling agent solution, or using an applicator or a doctor. It is possible to use a known method such as casting using a knife or the like.

The solvent for dissolving the silane coupling agent may be water, alcohol, acetone, ethyl acetate, toluene, etc., as long as it dissolves the silane coupling agent.
Among them, water, alcohol, and acetone are preferable. The concentration of the silane coupling agent in the silane coupling agent solution is not particularly limited, but α01 to 3031% by weight.
It is particularly preferable that it is <, (Ll ~ 5] [11%. The effect of the silane coupling agent treatment is poor at a concentration of less than α01Xit%, and the effect is weak even at a concentration exceeding 30% by weight. There are no particular restrictions on the temperature or time, but generally it is soaked at room temperature for 15 to 10 minutes, or after the cloth is soaked,
It is sufficient to leave it for 5 to 10 minutes at room temperature.

After treatment with a silane coupling agent, heat treatment is performed.
The temperature and time of the heat treatment must be at least conditions that can dry the solvent of the silane coupling agent solution, and generally 8
It is preferable to carry out the reaction at a temperature of 0° C. or higher for 60 minutes. It is preferably carried out at a temperature of 150 to 250°C for 5 to 20 minutes.

Next, a polyimide sheet-like adhesive that can be melted in a heat bath is applied to the treated surface of the polyimide molded product treated as described above, and the adherend ′jr,j@ is heated under pressure to form a strong bond. becomes.

As a sheet-like adhesive of thermoplastic polyimide that can be used in the present invention, a film of chili resin alone may be used.
You can also use one that has been soaked in fat. Examples of polyimides include those containing an imide structure such as polyamideimide, polyesterimide, and polyetherimide (with a softening point of 40
Preferably, the temperature is 0°C or lower.

Adherent and mouth polyimide extruded product, @ foil, metal foil such as aluminum foil, steel plate, iron plate, aluminum plate, stainless steel plate, 421
It may be anything, such as a metal plate such as a 0i plate.

Adhesion conditions vary depending on the physical properties of the sheet adhesive used, but in general, the temperature should be above the softening point of the adhesive. Specifically, it is above the softening point of the adhesive and below the thermal decomposition start temperature, and the pressure is l 1 kg/- to 100 kg/aII+. This bonding method rc is not particularly limited, but can be carried out, for example, by stacking an arbitrary adherend on the adhesive layer and heating and pressurizing it in a roll lamination, press, or autoclave.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
The scope of the present invention is not limited in any way by these examples.1 Example 1 Kapton 200H (manufactured by DuPont, 50 am polyimide film) was added to a 30% potassium hydroxide aqueous solution at room temperature for 1 hour.
Soak for 0 minutes fj! After that, wash it with water. Next, add γ-amitube abitriethoxy772 to a 1% acetone solution at room temperature.
After immersion for 0 seconds, it was dried at 200° C. for 10 minutes.

On the other hand, 3. 3', 4. 64.4 g of 4'-benzo2enonetetracarboxylic dianhydride, 12.2 g of m) lylene diamine, 480 g of bis(4-(3-1minophenoki7)phenyl)sulfone 4i2gtN-methylpyrrolidone dissolved at 180°C After heating for 6 hours,
N,N'-di2enylmethane bismaleimide 11.
A polyimide molded article was obtained by dissolution in a 3 g'Th bath. The concentration of polyimide in the varnish was 20%. The obtained varnish was cast onto a glass plate, dried at 80°C for 10 minutes, peeled off from the glass plate, fixed on an iron frame, and dried at 200°C for 1 hour to obtain a polyimide adhesive tape/LA. A polyimide adhesive film and 35 μm single-sided granulated copper were sequentially layered on the surface of the Kapton surface treated above and heated at 275°C for 5 minutes.
A steel-clad substrate was obtained by pressing at 0 kg/at for 30 minutes. The 90° peel strength between Kapton and the polyimide adhesive of this @-clad board was 0.83 kg/am.

Comparative Example 1 γ-aminopropyltriethoxy7silane t? A steel-clad substrate was obtained in the same manner as in Example 1 except that /fl was not used. The 90° peel strength between the Kapton adhesive and the polyimide adhesive of this copper-clad board was 104 kg/cm, which was very weak.

Comparative Example 2 An @-clad substrate was obtained in the same manner as in Example 1, except that untreated Kapton was used. The 90° peel strength between Kapton and polyimide adhesive of this steel-clad substrate is 0.05/
am, which was very weak.

Example 2 After immersing in Kapton 200Ht-30% sodium hydroxide water bath solution at room temperature for 30 minutes, it was washed with water. Next, add 30% of γ-mercapdobutyltrimethoxysilane to a 1% acetone solution.
After being immersed for a second, it was dried at 250°C for 10 minutes. A polyimide adhesive film was sandwiched between the surface-treated Kapton layers, and a laminate was obtained in the same manner as in Example 1. The 90° peel strength between the Kapton polyimide adhesives of this laminate was 0.80 kg/cm.

Example 3 γ-1 instead of γ-1minopropyltriethoxy7rane
A steel-clad substrate was obtained in the same manner as in Example 1 except that a 5% acetone solution of mercaptoglobiltrimethoxysilane was used. The 90° peel strength between the Kapton and polyimide adhesive film of the stiff copper-clad substrate was cL94 kg/cm.

Comparative Example 3 A laminate was obtained in the same manner as in Example 2 except that it was not immersed in the potassium hydroxide solution. The 900 peel strength between the Kapton and polyimide adhesive films of this laminate is (10
It was very weak at 4 kg and 7 cm.

Example 4 Kapton 200 H'i was immersed in a 10% aqueous solution of sodium hydroxide at 40°C for 20 minutes, then washed with water once.

Next, it was immersed in a 1% acetone solution of γ-amitube Ω piltrietquine 7 run at room temperature for 1 minute, and then dried at 200° C. for 10 minutes. Polyimide prepreg l-67 or l-68 (
Himata Kasei Kogyo ■Product name)'t-Hasamiso nzon170℃
60■/aIF1.5 hours, 200℃40kg/aIi
A laminate was obtained by pressing under conditions of 12 hours. The 90° peeling strength between Kapton and prepreg of this laminate is: n-f:n 0.98 kg/cm, 0.65 kg
/co+ is ly.

Example 5 3. 3', 4. Example 1 except that a polyimide adhesive film prepared using 4'-benzophenone tetracarboxylic dianhydride and 3,3'-diaminodiphenyl ketone was pressed at 350°C, 30 kg/a+f, and 20 minutes. A laminate was obtained in the same manner. The 90° peel strength between the adhesive films of this laminate was α75 kg/Cf1l.

〔Effect of the invention〕

As described in detail above, it is possible to obtain a laminated product of polyimide molded products having a strong adhesive strength depending on the bonding depth of the present invention, and its characteristic value is large.

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Claims (1)

[Claims] 1. After the surface is treated with a solution containing a basic compound, it is treated with a silane coupling agent, and then a heat-meltable polyimide sheet adhesive is layered on the treated surface of the heat-treated polyimide molded product, and an optional adhesive is applied on top of the treated surface of the polyimide molded product. A method for bonding polyimide molded products, which involves stacking adherends and applying pressure and heating at a temperature above the softening point of the adhesive.