JPH02264072A - Treatment of fiber or structure thereof with coupling agent - Google Patents

Abstract

PURPOSE:To provide a fiber-reinforced resin composite material having heat resistance and dimensional stability by applying a coupling agent to fibers or fiber structure under a reduced pressure to improve the interfacial adhesion thereof to a matrix resin. CONSTITUTION:A coupling agent such as a silane, e.g. gamma-aminopropyl triethoxy silane is homogeneously adhered under a reduced pressure to a woven fabric comprising inorganic fibers such as glass fibers or carbon fibers, especially aromatic polyamide fiber or a mixture thereof. The treating agent-adhered fiber basic materials are impregnated with a matrix resin (e.g. epoxy resin) to provide a composite material suitable for printed circuit boards having excellent heat resistance and small dimensional change after etching and heating treatments.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for treating a fiber base material with a coupling agent, which is particularly suitable for use in printed wiring boards and the like.

(Prior art) In general, υ rod reinforced tree B A compound containing material II7! ; j, 5 Prepreg laminate material 3 made of a weft base material and resin, one made by the filament winding method, n, 17i A fret molded product with dispersed females, etc. What about tensile strength, impact strength, Young's modulus, etc.? 6! This was done in hopes of improving the product's productivity, dimensional stability, heat resistance, and properties. Significant effects have also been achieved. However, the effect is due to the properties of m-fat, which strengthens it! ! ! It is influenced by the structure, shape, ia, etc. of the sharpness, and among them, the total base material and ma!・The external image adhesion of RIX resin has a large influence, and it is customary to treat the C 1-M absolute base material *100 with a -Jyγ butting agent. 17. Conventional methods for treating such six purifying agents and 17ti,
A method is used in which a fiber base material is impregnated with an aqueous solution containing a hydrolyzed coupling agent, applied as an Ill solution, and then dried.

&l&L&l&L-bond base material used in the $8-fatty compound additive is, for example, glass fiber. Charcoal! There are organic fibers such as aromatic boria IDO&3A and aromatic M polyester W11, but the adhesion with the matrix IIJBJt is usually improved by applying the above treatment. I'm tired of it. 1. ” - The organization basics committee I mentioned is wt.
By taking advantage of the characteristics of heat resistance and low coefficient of thermal expansion, it is possible to create an appropriate matrix 1/Iv with fat.
By intervening & 51 bond strengthening tree squeezed material, furthermore this is 811! It has been hardened to make printed wiring boards, which are widely used in industrial equipment.

However, in recent years, as electronic devices have become more sophisticated and more compact, the characteristics required of printed wiring boards have become even more sophisticated. However, there was a problem that the heat resistance, especially the solder heat resistance after moisture absorption (electrostatic swell resistance) was poor.

(Problems to be Solved by the Invention) The purpose of the present invention is to improve the interfacial adhesion between the fiber base material and the matrix 1.1m in producing a fiber-reinforced resin composite material with excellent heat resistance and dimensional stability. The present invention provides a method for treating fibers and am structures with a coupling agent.

(Means for Solving the Problems) The above object is to apply a coupling agent treatment to fibers or fiber structures at 300 mmHf.
This is achieved by the following method for treating a fiber or fiber structure with a coupling agent, which is characterized by applying the coupling agent under reduced pressure.

The inorganic fibers used in the method of the present invention are not particularly limited, but are usually glass alu! Or carbon fiber is used. 1! The organic fiber is not particularly limited as long as it is a rigid polymer type, but aromatic polyester fiber or aromatic polyester m#1 is usually used. Among these, aromatic boria fibers are particularly preferred. More specifically, aromatic polyamide fibers include poly-p-phenylene terephthalamide, poly-m-phenylene isophthalamide, etc., and aromatic polyester fibers include aromatic dicarboxylic acids such as terephthalic acid, aromatic polyamides such as hydroquinone, etc. Examples include diols of the ξ group and derivatives thereof.

In the method of the present invention, the fiber or m-fiber structure refers to the above-mentioned inorganic thread or the above-mentioned organic thin fiber alone, or a yarn or cord network made by blending or interweaving them.

means woven and knitted fabrics. Woven fabrics are usually preferred because of their high mechanical strength.

Normally, when manufacturing G fiber reinforced resin composite materials, the fiber base material is treated with a coupling agent or the like before being impregnated with matrix IJBII, but in the method of the present invention,
The coupling agent is applied under reduced pressure of 0 mmof or less. Such an application method is preferably carried out by charging a solution of the coupling agent into a treatment tank equipped with a vacuum pump or the like, and immersing the m-fiber base material in the solution.

As a coupling agent, silane-based ones can be used, such as r-aminopropyltrimethoxysilane, r-aminopropyltrimethoxysilane, imidacillinsilane, N-adenoether amino Aminosilanes such as propyltrimethoxysilane, N-phenyl-r-aminopropyltrimethoxysilane, N-β-(N-vinylpensylaminoethyl)-r-aminopropyltrimethoxysilane hydrochloride; Epoxysilanes such as sidoxypropyltrimethoxysilane,
Examples include chlorosilanes such as r-chloropropyltrimethoxysilane, methacrylsilanes such as r-methacryloxypropyltrimethoxysilane, and vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane. The amount of coupling agent attached to the fiber base material is also -
0, 01~ used for settlement! % by weight, preferably from 0.1 to t% by weight.

In the present invention, the pressure when applying the coupling agent is
s o mm Hy or less, preferably 200 m
m1N or less, more preferably 100 mmHf or less. When the pressure during treatment is 300 mmHf or less, there are fewer bubbles on the fiber or IIm# structure, and the coupling agent adheres uniformly to the fiber surface.The larger the reduced pressure, the greater the treatment effect ( However, due to problems with the equipment, it is generally practical to reduce the pressure to about i0 mm HI.

Coupling agent treated! The step of impregnating the G-fiber base material with a matrix resin to prepare a fiber-reinforced S resin composite material can be carried out according to a conventional method. These matrices m
1iI! The material may be a common material, such as an epoxy resin, an unsaturated polyester resin, or a polyelectrode resin.

(Effect of the invention) The coupling agent is uniformly adhered to the υ fiber or kA fiber structure obtained by the method of the present invention, and the adhesiveness with the matrix resin is good, so both fibers are reinforced @ resin composite. The printed wiring board made of 82 layers of material has excellent heat resistance and has little dimensional change after etching and heat treatment, so it can be used for circuits of high-performance, miniaturized electronic devices. It is something that can be done.

The present invention will be explained in detail with reference to Examples below.

(Example) Example 1 Warp and weft both BOG 115 1 / Os twist number 1
Uses Z glass cord yarn, density warp 44/! 8 m
Glass fiber plain woven fabric was woven at m% 14 ga/2 S mm.

Next, the fabric was heat cleaned at sTO°C to remove the Harahiro binder and warp sizing agent.

In a treatment tank whose pressure was reduced to sommnI by a vacuum pump, the fabric after the heat cleaning was impregnated with 1% by weight of Nixisilane (manufactured by Toshi Silicone Co., Ltd. 8H@040) in a treatment solution adjusted to pH 3 to 4 with an acetic acid aqueous solution,
After processing for about 20 seconds and squeezing the liquid so that the impregnation rate was about 25% by weight, it was heated at 120°C for 2. After drying for S minutes, a glass fiber fabric treated with a coupling agent was obtained.

On the other hand, 100 parts by weight of bisphenol-type engineered poxy resin (manufactured by Ciba Geigy, GZ110117B), 6 parts by weight of dicyandiamide, 0.2 parts by weight of penzyldimethylamine, 18 parts by weight of acetone, methyl cellosolve! ON quantity part,
An epoxy resin solution was prepared using 10 parts by weight of dimethylformamide.

The glass fiber fabric treated with the coupling agent was impregnated with the epoxy resin solution and dried at 1150° C. for 4 minutes to obtain a prepreg to which 60% by weight of epoxy resin was added. 8 sheets of this prepreg were stacked, silver foil with a thickness of 18μ was placed on both outermost surfaces, and this was placed under a pressure of 50 kg/cm''.
C. for 2 hours to obtain a printed wiring board having a thickness of 1 fJ mm using the fiber base material of the example of the present invention.

Example! Using the same glass fiber plain weave as in Example 1, 3OOmm
Example 1 except that the coupling agent treatment was performed under reduced pressure of
The glass and textile fabrics treated with the coupling agent of Examples were obtained in the same manner as above. Subsequently, print layout lJ! was carried out in the same manner as in Example 1. , a substrate was obtained.

Comparative Example 1 The same glass section plain weave fabric as in Example 1 was used, and the coupling agent was treated in the same manner as in Example 1, except that the coupling agent was treated at atmospheric pressure instead of under reduced pressure. A treated glass fiber fabric was obtained. Subsequently, a printed wiring board was obtained in the same manner as in Example 1.

Next, the results of comparing the heat resistance and dimensional stability of printed wiring boards obtained according to examples of the present invention with those of comparative examples will be described.

Regarding heat resistance, see Example 1. Example! Using the printed wiring board obtained in Comparative Example 1, the boiling retention time, that is, the time until the interface of the printed wiring board started peeling in a 280° C. solder bath was measured. The measurement results are shown in Table 1.

Regarding the dimensional changes in Table 1, see Example 1. Example 2 and comparative example 1
Using the printed wiring board obtained in the above, dimensional changes were measured by the JI8 (3-8488 method) between the etched one and the one treated in a constant temperature bath at 170° C. for 30 minutes.

The measurement results are shown in Table 2.

No.! As is clear from Tables 1 and 2, the heat resistance and dimensional stability of the printed wiring boards obtained in the examples were significantly improved compared to the comparative examples of conventional products. Furthermore, poly-p-phenylene terephthalamide fiber cloth (DuPont Kevlar 49. Plain weave, thread: (warp/weft) 1!l!5
D/1118D, density: 154 S4 trees (per 26mm), thickness: Q, 1mm.

When the same treatment as in Example 1 was performed using a material having a basis weight of 8297 m, the same effect was obtained.

Procedural amendment (voluntary) 1. Indication of the case 1999 Patent Application No. 85079 2. Name of the invention Method for treating fibers or fiber structures with a coupling agent 3. Person making the amendment Relationship to the case Patent applicant address Tokyo 5-17-4 Sumida 5-chome, Sumida-ku, Tokyo 534 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka City Patent Department 5, Kanebo Co., Ltd. Column 6 of "Detailed Description of the Invention" of the specification to be amended, Amendment Contents (1) On page 2, line 12 of the specification, the text "r glass fiber, carbon fiber, etc." will be corrected to "r glass fiber, etc."

(2) Delete r or carbon fiber j in the first line of page 4 of the specification.

that's all

Claims (1)

[Claims] A method for treating fibers or fibrous structures with a coupling agent, which comprises applying the coupling agent to the fibers or fibrous structures under a reduced pressure of 300 mmHg or less.