JP2854591B2 - Processing method of fiber base material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for treating a glass fiber base material suitable for a printed wiring board and the like.

(Conventional technology and its problems) In general, fiber-filled composite materials include an impregnated mat of a fiber base material, a prepreg laminated material composed of a fiber base material and a resin, a material obtained by a filament winding method, and an injection molded product in which short fibers are dispersed. Etc. All of these have been made with the expectation of effects such as improvement in tensile strength, impact strength, Young's modulus, etc., improvement in step stability, improvement in heat resistance, and the like, and actual effects have been exhibited. However, the properties are affected by the properties of the resin, the structure, shape, and texture of the filler, but the effect of the interface between the filled fiber substrate and the matrix resin is particularly large. Is customary. An important one of the fiber base materials used for the fiber-filled composite material is an inorganic fiber glass fiber, which has been subjected to the above treatment to improve the adhesiveness between the two. In particular, the above-mentioned fiber base material has excellent electrical properties, excellent heat resistance, and a low thermal expansion coefficient to form a fiber-filled composite material in combination with an appropriate matrix resin,
Further, they have been widely used for industrial equipment as printed wiring boards which are laminated and cured.

However, in recent years, with the high performance and miniaturization of electronic devices, the characteristics required for printed wiring boards have become even more advanced, and there is some difficulty in bonding the fiber base material to the matrix resin. However, there is a problem in that the characteristics at high temperatures are insufficient, and in particular, the dimensional stability is lacking, and it is difficult to manufacture a high-precision circuit.

The object of the present invention is to improve these drawbacks, and to improve the heat resistance of the fiber base material and the matrix resin sufficiently utilizing the heat resistance of the matrix resin, and to improve the adhesion between the two in producing a composite material having excellent dimensional stability. Another object of the present invention is to provide a method for treating a fiber base material in advance.

(Means for Solving the Problems) The above-described object is to provide a fiber base made of a woven or knitted material containing at least a part of glass fiber with water before or after the coupling agent treatment or after the coupling agent treatment. Alternatively, it is achieved by a method for treating a fibrous base material, wherein the treatment is performed with the fluid pressure of an aqueous solution.

The fiber substrate used in the method of the present invention includes glass fibers alone, or woven fabrics and knitted fabrics obtained by blending or interweaving them with other inorganic fibers or organic fibers,
Usually, woven fabrics are preferred because of their high mechanical strength.

The organic fibers for blending and weaving are not particularly limited as long as they are rigid polymer-based ones, but usually aromatic polyamide fibers or aromatic polyester fibers are used.
More specifically, the aromatic polyamide fibers are preferably poly-p-phenylene terephthalamide, poly-m
-Phenylene terephthalamide, and the aromatic polyester fiber preferably includes polyalkylene terephthalate, polyalkylene isophthalate and polyalkylene naphthalate, and particularly preferably,
Examples include polymers and copolymers obtained from terephthalic acid, isophthalic acid, or an ester-forming derivative thereof, and ethylene glycol, 1,4-butanediol, or an ester-forming derivative thereof.

Usually, when producing glass fiber-filled composite materials,
Before the impregnation of the matrix resin, the glass fiber substrate is treated with a coupling agent or the like.However, in the method of the present invention, before the glass fiber substrate is subjected to the coupling agent treatment, the glass fiber substrate is treated with water or an aqueous solution. In treating with a fluid pressure of a glass fiber substrate, or when performing a coupling agent treatment on a glass fiber substrate, treating the glass fiber substrate with a fluid pressure in the presence of a coupling agent, or treating the glass fiber substrate with a coupling agent Then, the glass fiber substrate is treated with the fluid pressure of water or an aqueous solution.

In the method of the present invention, a device for applying the action of fluid pressure is not particularly limited, but usually a vibro washer proposed in Japanese Patent Publication No. 36-15747 is effectively used. Briefly describing this vibro washer, a rotating cylinder in which a perforated cylinder (casing) is arranged in a tank, and a vane (runner) that rotates with its outer surface in contact with the inner surface inside the tank is formed in an equilibrium state. And a supporter (basket rotor) for rotating the fabric under tension while freely approaching the outer periphery of the perforated cylinder. Fluid pressure is generated when the water compressed by the runner is discharged from the casing, and the fiber base is opened by the fluid pressure. As a condition of the vibration applied to the fluid, a vibration frequency of 4000 to 7000 times / minute is preferable. If the speed is less than 4000 times / minute, the glass fiber substrate may not be opened, and 7000
If the rate is more than times / minute, the opening of the glass fiber base material proceeds too much, and the appearance may deteriorate.

As the coupling agent, a silane-based coupling agent can be generally used, such as, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, imidazoline silane, N-aminoethylaminopropyltrimethoxysilane, Aminosilanes such as N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, and γ-glycidoxypropyltrimethoxysilane; Epoxy silanes,
Examples include chlorosilanes such as γ-chloropropyltrimethoxysilane, methacrylsilanes such as γ-methacryloxypropyltrimethoxysilane, and vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane. The amount of the coupling agent adhering to the glass fiber substrate is generally 0.01 to 2% by weight, and preferably 0.1 to 1% by weight.

The process of preparing a fiber-filled composite material by impregnating a matrix resin into a glass fiber base material that has been subjected to the coupling agent treatment and the fiber opening treatment can be performed according to a conventional method. These matrix resins may be conventional ones, for example, epoxy resins, unsaturated polyester resins, polyimide resins and the like.

(Action) When the glass fiber substrate is treated with the fluid pressure of water or a coupling agent, the fluid pressure causes the warps and wefts constituting the glass fiber substrate to be loosened and opened, and impregnated with a matrix resin. In this case, the matrix resin adheres uniformly. Therefore, the heat resistance and dimensional stability of the obtained composite material are improved.

(Example) Example 1 A glass fiber plain fabric was woven at a density of 44 yarns / 25 mm and a weft of 33 yarns / 25 mm using glass fiber yarns of ECG751 / 0 and a twist number of 1Z for both warp and weft.

Next, the woven fabric was heat-cleaned at 370 ° C. to remove the raw fiber binder and the warp paste.

1% by weight of epoxy silane (SH6040 manufactured by Toray Silicone Co., Ltd.) is added to the fabric after heat cleaning using an aqueous acetic acid solution.
Impregnated with a treatment solution adjusted to pH 3 to 4, and treated for about 20 seconds with a vibrating washer (manufactured by Daiwa Machinery Co., Ltd.) while applying a fluid pressure of 5,000 times / min. After the solution was squeezed so as to be dried at 120 ° C. for 2.5 minutes.

On the other hand, 100 parts by weight of a bisphenol A type epoxy resin (manufactured by Ciba Geigy, GZ601A75), 3 parts by weight of dicyandiamide, 0.2 parts by weight of benzyldimethylamine, 15 parts of acetone
An epoxy resin solution was prepared with parts by weight, 20 parts by weight of methyl cellosolve, and 10 parts by weight of dimethylformamide.

The silane-treated glass fiber fabric is impregnated with the above-mentioned epoxy resin solution and dried at 150 ° C. for 4 minutes.
A prepreg provided with 0% by weight was obtained. Eight sheets of this prepreg are stacked, copper foil having a thickness of 18 μm is placed on both outermost surfaces, and heated at 170 ° C. under pressure of 50 kg / cm ² for 2 hours to print a 1.6 mm thick print of the method of the present invention. A wiring board was obtained.

Comparative Example 1 Using the same glass fiber plain fabric as in Example 1, Example 1
The printed wiring board of the comparative example was obtained in the same manner as in Example 1 except for the portion subjected to the fluid pressure treatment of. Next, the heat resistance and the dimensional stability of the printed wiring board obtained according to the example of the present invention will be described as a result of comparison with a comparative example.

With respect to heat resistance, the printed wiring boards obtained in Example 1 and Comparative Example 1 were used to measure the boiling retention time, that is, the time until the peeling of the interface of the printed wiring board started in a 260 ° C. solder bath. . Table 1 shows the measurement results.

Regarding the dimensional change, etching was performed using the printed wiring boards obtained in Example 1 and Comparative Example 1;
Dimensional change from that treated in a thermostat at 0 ° C for 30 minutes
It was measured by the -6486 method. Table 2 shows the measurement results.

As is clear from Tables 1 and 2, the heat resistance and the dimensional stability of the printed wiring board obtained in the example are greatly improved as compared with the comparative example of the conventional product.

Furthermore, poly-p-phenylene terephthalamide fiber cloth (Dupont Kevlar 49, plain weave, yarn: (warp / weft) 195D / 19)
5D, density: 34/34 (per 25mm), thickness: 0.1mm, basis weight: 62
g / m ² ), and the same treatment as in Example 1 and Comparative Example 1 was performed, and the same effect was obtained.

(Effects of the Invention) As described in detail above, the glass fiber substrate obtained by the method of the present invention has a good adhesion to the matrix resin since the coupling agent is attached and the fiber is opened, so that both of them are used. The fiber-filled composite material is then used to laminate and cure the printed wiring board, which has excellent heat resistance,
The dimensional change after the heat treatment is small, so that it can be used for a circuit of an electronic device with high performance and miniaturization.

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Claims (1)

(57) [Claims] 1. A method for treating a fiber base made of a woven or knitted fabric containing at least a part of glass fiber with a fluid pressure of water or an aqueous solution before, during, or after the coupling agent treatment. A method for treating a fiber base material.