JPH05271543A - Liquid for surface-treatment of glass fiber and glass fiber product - Google Patents

Abstract

PURPOSE:To provide a glass fiber product capable of giving a laminated board having excellent heat-resistance and to provide a glass fiber treating liquid for the production of the glass fiber product. CONSTITUTION:A glass fiber is treated with a treating liquid containing a silane coupling agent and a surfactant having double bond. A laminated board produced from the glass fiber product treated with the silane coupling agent is resistant to measling and has high heat-resistance such as soldering resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment liquid such as a glass fiber product and a glass fiber product treated with the surface treatment liquid. Specifically, it treats inorganic substances such as glass fiber products or mica products used as reinforcing materials for composite materials,
The present invention relates to a surface treatment liquid for glass fiber products and mica products, which is used to improve adhesion with matrix organic resins such as unsaturated polyester resins, and glass fiber products and mica products treated with the same treatment liquid. is there. This glass fiber product or the like is used as a reinforcing material for a composite material such as a printed substrate.

[0002]

2. Description of the Related Art Printed circuit boards have been widely used in various fields, but in recent years, their importance has been increasing in relation to computers and communication devices. Among printed circuit boards, those using glass fibers as a reinforcing material are becoming mainstream from the viewpoint of their performance, and among them, those using glass fiber woven fabric as a reinforcing material are becoming the mainstream. The printed board manufactured in this way becomes a printed wiring board on which a copper foil circuit is formed, and chip parts such as IC and LSI are mounted on the printed wiring board for use in computers, communication devices and the like.

In the case of mounting a chip component on a printed circuit board, conventionally, the legs of the chip are inserted into the through holes, and the chips are dipped in molten solder, and the chips are fixed by soldering. However, when the surface mounting technology comes to be performed with the high integration of chips, the method of fixing the chips is changing from the method of dipping to the molten solder to the method of spotting with solder paste. In the case of the solder paste method, since it is necessary to instantaneously melt the solder paste to bond and fix the chip, heating at a higher temperature is performed by far infrared irradiation than the method of dipping in the molten solder. It has been confirmed that this heating causes a thermal shock to the printed circuit board itself, and as a result, a small peeling phenomenon called a measling may occur at the intersection of the warp and the weft of the base fabric. If such a peeling phenomenon occurs, the plating solution will penetrate into this peeled portion during through-hole plating,
As a result, circuit continuity occurs in unnecessary parts. It also affects the roughness of the inner wall of the through hole.

Among these printed circuit boards, a laminated board for a printed circuit board, which uses an unsaturated polyester resin as a matrix resin, has recently been remarkably expanded, and this laminated board for a printed circuit board is also immersed in molten solder during a wiring process. Strong heat resistance is required. In order to improve heat resistance, it has been attempted to prepare a composite material with a matrix resin by pretreating a reinforcing material with γ-methacryloxy bromopyrtrimethoxysilane, but the heat resistance of the silane compound itself is poor. Therefore, the heat resistance of the composite material was not sufficient.

Further, it has been attempted to pretreat the reinforcing material with a hydrochloride of N (vinylbenzyl) -β-aminoethyl-γ-aminopropyltrimethoxysilane, but this silane compound has poor water solubility. Not enough effect has been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a composite material containing a glass fiber product or a mica product as a reinforcing material and an unsaturated polyester resin or the like as a matrix resin. Composite material that secures a strong bond and has a high degree of heat resistance,
In particular, it provides a glass fiber product and a mica product suitable for producing a laminate for a printed circuit board which is excellent in maze ring characteristics and solder heat resistance, and a surface treatment solution suitable for producing such a glass fiber product and a mica product. The purpose is to do.

[0007]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have made extensive studies. As a result, they have found that the objective of the present invention can be achieved by incorporating a glass fiber containing a surfactant having a double bond into a treatment liquid containing a silane coupling agent. That is, the gist of the present invention is a treatment liquid for glass fiber surface treatment containing a silane coupling agent and a surfactant having a double bond. The present invention also provides a glass fiber product treated with such a treatment liquid. The present invention will be described in detail below.

The treatment liquid of the present invention contains at least a silane coupling agent, a surfactant having a double bond, and a solvent. The silane coupling agent is not particularly limited, but the present invention is effective in the case of a silane coupling agent having insufficient water solubility. The concentration of the silane coupling agent in the treatment liquid is 0.1 to 5.0% by weight, preferably 0.2 to 1.0% by weight.

The surfactant having a double bond used in the present invention refers to a substance having a double bond and having a surface activity, and at least one double bond is present in the surface activity exhibiting portion as a matrix. Has a structure in which The double bond is an ethylenic double bond, and examples thereof include a vinyl group, a propen-2-yl group, an allyl group and a methallyl group. These groups are bonded to the base through an ester bond, an ether bond, an alkylene group, a phenylene group, or the like. The matrix portion is not particularly limited as long as it can exhibit the surface activity and any of ionic, nonionic, anionic and cationic can be used. The concentration of the double bond-containing surfactant in the treatment liquid is 0.005 to 1.0% by weight, preferably 0.01 to 0.3% by weight.

As the solvent, water or a mixed solvent of water and a water-soluble organic solvent, for example, 0.5 to 5.0% by weight aqueous acetic acid solution, 5 to 99% hydrous alcohol solution, or hydrous alcohol containing acetic acid is used. A solution etc. can be mentioned.
If necessary, dyes, pigments, antistatic agents, lubricants, etc. may be added to the treatment liquid.

The glass fiber products treated with the treating agent of the present invention include, for example, conventionally known glass fibers such as alkali glass, non-alkali glass, low dielectric glass and high elasticity glass. Strands (glass yarn) that are bundles of glass filaments spun from E-glass for electrical use, non-woven glass mats, and glass paper. Further, a glass cloth, a glass tape, or the like in which a yarn is woven can be used. The glass fiber product in the present invention is to be understood in a broad sense and includes mica products. As the mica product, for example, a soft laminated mica sheet obtained by making thin sheets, or a baked product thereof can be mentioned.

The treatment of the glass fiber product with the treatment liquid may be carried out by immersing the glass fiber product in the treatment liquid. In some cases, the retention ratio of the treatment liquid in the glass fiber is made constant by using a squeeze roll or the like. Alternatively, the treatment liquid may be applied by spraying. After this process, for example, 60-
The glass fiber product of the present invention is obtained by drying at 150 C to remove the solvent.

[0013]

EXAMPLES In order to explain the present invention more specifically, the following examples are given, but the present invention is not limited to these examples.

Example 1 The following structure was prepared in distilled water containing 1.0% by weight of acetic acid.

[0015]

[Chemical 1]

After dissolving 0.05% by weight of the nonionic surfactant (Adecaria Soap NE-10, manufactured by Asahi Denka Co., Ltd.), N (vinylbenzyl) -β-aminoethyl-γ-aminopropyltrimethoxy Silane hydrochloride (S
Z-6032, Toray Medow Corning Silicone Co., Ltd. 0.7% was dissolved to prepare a treatment liquid. Glass cloth (WEA-18W, Nitto Boseki Co., Ltd.)
Manufactured) was dipped and squeezed with a squeeze roll to a pickup amount of 30%, and this was dried at 110C for 5 minutes. The sum of the amounts of the silane compound and the nonionic surfactant attached to the glass cloth was 0.07% by weight. On the other hand, 100 parts by weight of unsaturated polyester resin, styrene monomer-40
A varnish was prepared by mixing 1 part by weight of cumene hydroperoxide and 1 part by weight of cumene hydroper oxide. Between two glass cloths treated with the silane compound, four glass papers (EPM-
4050, manufactured by Nippon Vilene Co., Ltd. was sandwiched and the above varnish was immersed therein. This is further added with a thickness of 35 μm
The sheet was sandwiched with copper foil, degassed for 2 minutes, and then heated at 150 C for 1 hour to obtain a 1.6 mm laminated plate.

Example 2 In Example 1, the nonionic surfactant of Example 1 (Adecaria Soap NE-10) was added to the following structure.

[0018]

[Chemical 2]

The glass cloth was treated in the same manner as in Example 1 except that the nonionic surfactant (Adecaria Soap NE-20, manufactured by Asahi Denka Kogyo Co., Ltd.) was used. The sum of the amounts of the silane compound and the nonionic surfactant attached to the glass cloth was 0.07% by weight. Next, in the same manner as in Example 1, 1.6 mm laminated plates were produced.

Example 3 In Example 1, the nonionic surfactant of Example 1 (Adecaria Soap NE-10) was added to the following structure.

[0021]

[Chemical 3]

Surfactant (Adeka rear soap NE-
No. 30, manufactured by Asahi Denka Kogyo Co., Ltd., the glass cloth was treated in the same manner as in Example 1. The sum of the amounts of the silane compound and the nonionic surfactant attached to the glass cloth was 0.07% by weight. Next, in the same manner as in Example 1, 1.6 mm laminated plates were produced.

Comparative Example 1 A glass cloth was treated in the same manner as in Example 1 except that the nonionic surfactant was not used. The amount of the silane compound attached to the glass cloth was 0.
It was 067% by weight. Next, in the same manner as in Example 1, 1.6 mm laminated plates were produced.

Solubility Test The solubility of the treatment solutions of Examples 1 to 3 and Comparative Example 1 at room temperature was observed. O: transparent △: slightly cloudy X: cloudy

Performance Tests The solder heat resistance, the results of the measling characteristics test conducted on the laminated plates produced by completely etching the laminated plates produced in Examples 1 to 3 and Comparative Example 1 to remove the copper foil, and the resin The impregnating property is shown in Table 1. The test method is as follows. (1) Solder Heat Resistance Test The laminated plate was boiled in boiling water for 1 hour, 2 hours, and 3 hours, and then immersed in a solder bath at 260 ° C. for 20 seconds, respectively, and checked for blisters. O: No blistering X: Blistering (2) Measling characteristic test A soldering iron with a diameter of 2 mm heated to 250 ° C., 270 ° C., and 300 ° C. was applied to the laminated plate by applying a load of 100 g for 10 seconds. , And the presence or absence of measling was examined. O: Without Measling X: With Measling

(3) Impregnation of Resin (a) During the production of the laminate, the quality of impregnation of the unsaturated polyester resin varnish into the glass cloth was visually observed. ⊚: Very good O: Good Δ: Normal X: Poor (b) The appearance of the laminate was visually observed. . ⊚: Very transparent. O: Almost transparent. Δ: The weft threads of the cloth are slightly whitened. X: The warp and weft threads of the cloth are whitened. The results are summarized in Table 1.

[0027]

[Table 1]

[0028]

The treatment liquid of the present invention is excellent in the solubility of the silane coupling agent, the stability of the treatment liquid is good, and the occasional problematic gelation does not occur at all. Further, the composite material using the glass fiber treated with the treatment liquid of the present invention is excellent in solder heat resistance and measling characteristics. Therefore, it becomes possible to provide a printed circuit board that meets the requirements of the surface mounting technology. Further, the glass fiber product treated with the treatment liquid of the present invention has an excellent resin impregnation property, so that the workability is improved.

Claims (2)

[Claims] 1. A glass fiber surface treatment liquid containing a silane coupling agent and a surfactant having a double bond. 2. A glass fiber product treated with the treatment liquid according to claim 1.