JPH09132652A - Laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated sheet markedly improved in electrolytic corrosion resistance and being useful as a laminated sheet for reinforcing a printed wiring board by chemically bonding an ion exchanger to the surface of a glass fiber as a base material. SOLUTION: This laminated sheet is prepared by using at least one glass fiber cloth made of a glass fiber to the surface of which an ion exchanger is chemically bonded as a base material. Examples of the methods for forming the ion exchanger on the surface of glass include one comprising applying e.g. a colloidal ion exchanger dispersed in a hydrophilic solvent especially water or an alcohol to a glass fiber cloth and one comprising applying starting materials, for example, a metal salt, acid, etc., for an ion exchanger to a glass fiber cloth and forming an ion exchanger by a chemical reaction (e.g. hydrolysis). The ion exchanger used is desirably an inorganic ion exchanger. The amount of the ion exchanger formed on the surface of the glass fiber cloth is usually 0.1mol/m<2> glass cloth or below.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a printed wiring board reinforcing laminate used in the electronic and electrical fields. More specifically, according to the present invention, by chemically bonding an ion exchanger to the surface of a glass fiber as a base material, metal ions, which are the cause of electrolytic corrosion, are adsorbed to significantly improve the electrolytic corrosion resistance of a laminate. The present invention relates to an improved laminated base material.

[0002]

2. Description of the Related Art In recent years, in printed wiring boards, the density of wiring patterns has increased, and a phenomenon called electrolytic corrosion has often occurred. Electrolytic corrosion is a phenomenon in which copper and silver, which are the constituent elements of the wiring pattern, are ionized by the voltage applied between the circuits, move in the matrix resin of the substrate, and deposit on the opposing circuit side. Will short circuit and cause malfunction of the equipment. In order to prevent such a phenomenon, attempts have been made to add a substance that traps metal ions, a substance that prevents metal ionization, etc. into the matrix resin, but no satisfactory effect has been obtained.

[0003]

It has been confirmed that the phenomenon of electrolytic corrosion proceeds on the surface of the glass fiber which is the base material of the laminated substrate, and it has been desired to modify the glass surface. That is, the present invention aims to improve the electrolytic corrosion resistance of the laminate by modifying the surface of the glass fiber as the base material and chemically forming an ion adsorption capacity for capturing the metal ions on the glass surface. To do.

[0004]

As a result of various studies on the above-mentioned problems, the present inventor has found that by chemically bonding an ion-exchanger to the surface of glass fiber which is a base material of a laminated board constituting a printed wiring board. The inventors have found that the electrolytic corrosion resistance of the laminated plate can be remarkably improved, and have completed the present invention. That is, the present invention provides: a laminate using at least one glass fiber cloth formed by chemically bonding an ion exchanger to the glass fiber surface as a reinforcing substrate. Another feature is that the ion exchanger is an inorganic ion exchanger.

The present invention also includes the following embodiments. 1) It is also characterized in that the ion exchanger described is a hydrous oxide composed of a single metal or a plurality of metals. It is also characterized in that the ion exchanger described in 2) is a phosphate or a mixture of a phosphate and a hydrous oxide composed of a single metal or a plurality of metals. It is also characterized in that the phosphate described in 3) and 2) is zirconium phosphate. It is also characterized in that the ion exchanger described in 4) is an aluminosilicate.

The term "ion exchanger" as used herein is a general term for substances that exhibit a generally-known ion exchange phenomenon. For example, a conductive metal element, copper, silver, or the like that constitutes the wiring pattern of the printed wiring board according to the present invention. It refers to a substance capable of adsorbing and capturing cations such as metal ions or anions that promote ionization of these metals, such as chloride ions, bromine ions, sulfate ions and sulfonate ions, by an ion exchange phenomenon. The chemical bond between the glass fiber surface and the ion exchanger is mainly a bond due to a condensation reaction with a hydroxyl group or the like on the glass surface, and indicates a bonding state including other general chemical bonds, which is easily removed by washing with water. It is in the state of being fixed to the glass surface without being attached.

As a method for forming the ion exchanger on the glass surface, for example, the colloidal ion exchanger dispersed in various solvents, particularly hydrophilic solvents such as water and alcohol, is made into glass fiber cloth, particularly glass. A method in which a fiber fabric is applied, dried, and optionally heat-treated, or the like; or a raw material for the ion exchanger, such as a metal salt or an acid, is separately added to the glass fiber such as a glass fiber fabric. Examples include a method of applying the composition to a cloth, forming the ion exchanger by a chemical reaction such as hydrolysis on a glass fiber cloth, drying it, and optionally heat treating it to form it.

As the ion exchanger used in the present invention, a substance having a polymeric acid to which an acidic group such as an acidic hydroxyl group, a carboxyl group or a sulfo group is bonded; a basic group such as an amino group or an imino group A substance having a polymeric base to which is bound; a hydrous oxide of a metal called an inorganic ion exchanger,
For example, Si, Ti, Nb, Sn, Zr, Al, Sb,
Hydrous oxides such as Fe; Phosphates such as Zr, Sn, Ti
Phosphates with tetravalent metals such as; or synthetic zeolites such as aluminosilicates and mixtures thereof. The latter inorganic ion exchanger is used for the laminate of the present invention in view of its suitability for the bonding to the glass surface and the heating process that is generally performed in the process of processing glass fiber cloth, in particular, woven cloth, particularly woven cloth. Is more preferable for.

Further, from the viewpoint of easy production of cloth, particularly woven fabric, a hydrous oxide composed of a single metal or a plurality of metals is preferable, and zirconium phosphate or zirconium phosphate is preferable from the viewpoint of the capacity of ion exchange. And a hydrous oxide composed of a single metal or a plurality of metals are preferable. The amount of the ion exchanger formed on the surface of the glass fiber is not particularly limited, but the heat resistance of the laminated plate is affected, so
mol / glass cloth 1 m ² or less, preferably 0.0
It is the amount of formation of 25 to 0.001 mol / glass cloth 1 m ² . The shape of the glass fiber cloth serving as the base material may be either a non-woven fabric or a woven fabric, but a woven fabric is particularly preferable in terms of the ease of the step of forming an ion exchanger and the high tensile strength of the base material.

The glass fiber woven fabric is basically a plain weave structure, but may be a woven fabric having a structure such as a satin weave, a satin weave, and a twill weave. Although glass called E glass (non-alkali glass) is usually used as a base material of a laminated board used for a printed wiring board, in addition to E glass, D glass,
It is also possible to use glass fibers such as S glass, quartz, and high dielectric constant glass. Further, the specification of the glass fiber woven fabric is not particularly limited, and for example, the driving density of the glass fiber woven fabric as the base material of the present invention is 10 to 100 fibers / 25.
mm, preferably 30 to 80 fibers / 25 mm, and / or a fabric weight (area weight) of 20 to 400 g / m ² , preferably 30 to 300 g / m ² of inorganic fiber woven fabric is suitably used.

The glass fiber cloth used in the present invention, especially the woven cloth, is usually subjected to a high-temperature desizing treatment and then treated with a surface treatment agent such as a silane coupling agent, but is not limited thereto. Not a thing. The ion exchanger of the present invention may be formed on the glass surface either before or after the surface treatment with a silane coupling agent or the like, but the matrix resin (impregnating agent) and the glass fiber (base material) for forming the laminated plate may be used. In order to maintain the adhesiveness with (1), it is preferable to form the ion exchanger on the glass surface and then perform surface treatment with a silane coupling agent or the like. Further, before the high-temperature desizing treatment, or after the surface treatment with a silane coupling agent or the like, the opening process and the like may be carried out in the same manner as the process of ordinary glass fiber woven fabric.

The laminated plate of the present invention may be prepared by a conventional method. For example, a normal glass fiber woven fabric is impregnated with a matrix resin such as an epoxy resin to prepare a resin-impregnated prepreg (prepreg A). A prepreg prepared by impregnating the glass fiber woven fabric in which the ion exchanger of the present invention is formed on the glass surface in a plurality of prepregs, with a similar matrix resin or, if necessary, with another matrix resin (prepreg B) It is obtained by putting at least one of the above, laminating, and heat-pressing. It is more effective to arrange the prepreg B in the layer in which the wiring pattern is formed in the laminated board. Further, it goes without saying that the laminated plate made of only the prepreg B is more effective due to the electrolytic corrosion resistance. Further, as the base material of the prepreg A, it is possible to use a woven fabric and a non-woven fabric together.

The matrix resin used in the present invention is a thermosetting resin such as phenol resin, cresol resin, epoxy resin, unsaturated polyester resin, polyimide resin, polybutadiene resin, polyamide resin, PPO resin, PPE resin or fluororesin. Alone, its variants,
Alternatively, a mixture thereof, a single thermoplastic resin, a modified product thereof, a mixture thereof, a mixture of a thermoplastic resin and a thermosetting resin, or the like can be used. Of course, the matrix resin is appropriately selected depending on the characteristics required for the printed wiring board or the laminated board. The use of epoxy resin is preferable from the viewpoint of economical efficiency and performance.

[0014]

EXAMPLES Hereinafter, the concrete constitution of the present invention will be explained by examples, but they do not limit the scope of the present invention. The laminated plates in the examples were prepared by the following method, and the electrolytic corrosion resistance of the laminated plates was evaluated as follows. The ion exchange capacity of the glass fiber woven fabric which is the basis of the present invention was measured by the following method. Method for producing laminated plate: (i) Epoxy resin (trade name, manufactured by Yuka Shell Epoxy Co., Ltd., “Epicoat 5046B8”, was added to a normal glass fiber woven fabric of the present invention, which was not treated according to Comparative Example 1 below.
0 ") 40 to 50% by weight, and dried at 120 to 130 ° C to obtain a prepreg (comparative prepreg A). (Ii) Similarly, according to the following Examples 1 to 6, a glass fiber woven fabric treated with the ion exchanger of the present invention was applied with an epoxy resin (trade name "Epicoat 50" manufactured by Yuka Shell Epoxy Co., Ltd.).
46B80 ") impregnated with 40 to 50% by weight of 120 to 1
Prepreg dried at 30 ° C. (prepreg B of the present invention)
I got (Iii) A predetermined number of these prepregs A and B are laminated, or only prepreg B is laminated individually,
18μm thick copper foil is laminated on the upper and lower surfaces, 175 ° C, 40K
The laminate was heated and pressed at g / cm ² to obtain a 340 mm square laminated plate.

Method for measuring the electrolytic corrosion resistance of the laminated plate: The laminated plate prepared by the above method was processed into the shape shown in the dimensional diagram of FIG. 1- (a), and 60 V was applied at room temperature of 85 ° C. and constant temperature and humidity of 85%. Continuously measure the change of the resistance value with time (If the ion exchanger is not formed on the surface of the glass fiber, part of the circuit part such as copper is melted between the through holes 2 and metal formation is repeated. A short circuit indicates a large change in resistance, indicating a decrease in electrolytic corrosion resistance).

Measurement of ion exchange capacity of glass fiber woven fabric: About 10 g of glass fiber woven fabric was sampled, and a predetermined amount of a copper ion-containing solution having a constant concentration of pH 4 was added so that the glass fiber woven fabric was completely immersed. The change in the copper ion concentration of the solution thereafter is measured by atomic absorption spectrometry, and the copper ion exchange amount is obtained. (Example 1) Ordinary E glass fiber woven fabric (Style 216 manufactured by Asahi Schebel Co., Ltd.) was mixed with titanium acetylacetonate (hydroxide ion exchanger) 0.01 mol /
L aqueous solution, heat dried at 170 ° C. for 1 minute, and then used as a coupling agent epoxy silane [trade name SH60
40 Toray Dow Corning Silicone Co., Ltd.] 0.0
The surface was treated with 1 mol / l. Furthermore, the fabric is
Using the prepreg B woven fabric obtained by processing according to the method (ii), a 4-ply laminated plate was prepared.

(Example 2) Ordinary E glass fiber woven fabric (Style 216 manufactured by Asahi Schebel Co., Ltd.) was used as zirconium ammonium carbonate (hydroxide ion exchanger).
It was treated with 0.01 mol / L, dried by heating at 170 ° C. for 1 minute, and then surface-treated with 0.01 mol / l of epoxysilane (trade name SH6040) as a coupling agent. Further, a prepreg B woven fabric obtained by treating the woven fabric according to the above-mentioned method (-ii) was used on both surface layers, and an epoxy silane (trade name SH604 as a coupling agent was used as a coupling agent.
0) Surface-treated with 0.01 mol / L,
(i) An ion-exchanger-untreated ordinary glass fiber woven fabric (Style 216 manufactured by Asahi Schwebel Co., Ltd.) prepreg A was used, and two plies were arranged in the inner layer. iii) Thermocompression molding was performed to prepare a 4-ply laminated plate.

Example 3 Ordinary E glass fiber woven fabric (Style 216 manufactured by Asahi Schebel Co., Ltd.) was added to ammonium zirconium carbonate (hydrated ion exchanger).
A gel-like material prepared by mixing 0.01 mol / L and phosphoric acid 0.01 mol / L is applied and dried by heating at 17 ° C. for 1 minute, and then epoxysilane (trade name SH60
40) Surface treatment was performed with 0.01 mol / L. Using this glass fiber woven fabric, a 4-ply laminate was prepared by the above-mentioned method (-ii).

(Example 4) A conventional E glass fiber woven fabric (Style 216 manufactured by Asahi Schwabel Co., Ltd.) and titanium acetylacetonate (hydroxide ion exchanger) were used.
A gel-like material obtained by mixing 01 mol / L and 0.01 mol / L phosphoric acid is applied and dried by heating at 170 ° C. for 1 minute, and then epoxy silane (trade name SH604 as a coupling agent is used.
0) 0.01 mol / L was surface-treated. Using this glass fiber woven fabric, a 4-ply laminate was prepared by the above-mentioned method (-ii).

Example 5 Ordinary E glass fiber woven fabric (Style 216 manufactured by Asahi Schwabel Co., Ltd.) and tetraethoxysilane (hydrated oxide ion exchanger) 0.01 m
gel / a mixture of ol / L and 0.01 mol / L of aluminum acetate and heat-dried at 170 ° C. for 1 minute, and then epoxysilane (trade name SH6) as a coupling agent.
040) 0.01 mol / L was surface-treated. Using this glass fiber woven fabric, a 4-ply laminate was prepared by the above-mentioned method (-ii).

Example 6 A normal E glass fiber woven fabric (Style 216 manufactured by Asahi Schebel Co., Ltd.) was added with 0.01 m of tetraethoxysilane (hydrous oxide ion exchanger).
sol / L and 0.001 mol / L of aluminum acetate were applied as a gel, dried by heating at 17 ° C for 1 minute, then heated at 400 ° C for 10 hours, and then epoxysilane (trade name SH6040) as a coupling agent. ) 0.01
The surface was treated with mol / L. Using this glass fiber woven fabric, a 4-ply laminate was prepared by the above-mentioned method (-ii).

Comparative Example 1 Ordinary E glass fiber woven fabric (Style 216 manufactured by Asahi Schebel Co., Ltd.) was surface-treated with 0.01 mol / L of epoxysilane as a coupling agent. Using this glass fiber fabric,
A 4-ply laminate was prepared according to the method (i).

[0023]

[Table 1]

[0024]

[Table 2]

(Evaluation of Test Results) As shown in Tables 1 and 2,
By forming an ion exchanger on the surface, a glass fiber woven fabric capable of strongly adsorbing copper ions can be obtained. It was confirmed that the printed wiring board obtained from the glass fiber woven fabric of the present invention did not show copper migration even after 1000 hours and had high reliability as a wiring board. The above is a little different depending on the difference in the components of the ion exchanger, but it is clear that copper migration is prevented by the adsorption of copper by the ion exchanger.

[0026]

As described above, by using the glass fiber woven fabric having the ion exchanger formed on the surface thereof, copper migration is performed under a very severe condition that a high voltage is applied under high temperature and high humidity. It is possible to provide a printed wiring board with high reliability and with less occurrence of heat generation. Therefore, it is effective when applied to a printed wiring board having a narrow circuit interval.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing the shape and structure of a sample used for measuring the electrolytic corrosion resistance of a laminate. FIG. 1- (A) is a dimensional diagram of the sample, and FIG. 1- (B) is a sectional view of the sample.

[Explanation of symbols]

 1 substrate 2 through hole 3 connection terminal 4 land

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[Procedure amendment]

[Submission date] February 1, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a dimensional diagram of a sample used for measuring the electrolytic corrosion resistance of a laminated plate.

FIG. 2 is a cross-sectional view of a sample used for measuring the electrolytic corrosion resistance of a laminated plate.

[Explanation of symbols] 1 substrate 2 through hole 3 connection terminal 4 land

Claims (2)

[Claims] 1. At least one glass fiber cloth formed by chemically bonding an ion exchanger to a glass fiber surface.
A laminated plate characterized by being used as a sheet or a base material. 2. The laminated plate according to claim 1, wherein the ion exchanger is an inorganic ion exchanger.