JPS5921774B2 - Manufacturing method of cyanate resin laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a cyanate resin laminate, in which cyanate resin is mixed into an epoxy resin in an amount of 20 to 40% by weight based on the total amount, and the resin adhesion rate is 5.
A method for manufacturing a cyanate resin laminate, which comprises: impregnating a glass base material to a concentration of ~15%, then further impregnating it with cyanate resin to produce a prepreg, and then laminating the prepregs and hot pressing. The purpose of this invention is to provide a method for producing a cyanate resin laminate having good measling resistance.

In general, cyanate resins are known as aromatic cyan ester resins obtained by reacting bisphenol A and chlorocyan, for example, in German Patent No. 1195764, German Patent No. 1201839, German Patent No. 1220132, German Patent No. 1220133, etc. Because it has excellent heat resistance and dimensional stability, it is used as a laminate by impregnating it into a glass substrate.

However, this cyanate resin has a weak bond with glass, so when it is impregnated into a glass substrate to obtain a laminate, the measling phenomenon tends to occur, and the bond between the cyanate resin and glass is easily caused by chemical treatment such as alkali or boiling treatment. The drawback was that peeling easily occurred at the bonding interface. That is, the disadvantages such as deterioration in solder heat resistance and alkali resistance after boiling, and deterioration in insulation resistance after boiling were more significant than in epoxy resin laminates. Therefore, an attempt was made to obtain a laminate by mixing an epoxy resin with a high bonding force with glass with a cyanate resin, impregnating a glass base material with a varnish of this mixed resin and drying it to form a prepreg, and then laminating and molding the prepreg. ing. However, if an epoxy resin is simply mixed with a cyanate resin like this, the properties originally possessed by the cyanate resin will be impaired by the epoxy resin, and the expected properties in terms of heat resistance and dimensional stability will not be achieved. It was something that could not be obtained. The present invention aims to overcome these conventional drawbacks and will be described in detail below.

First, a cyanate resin such as an aromatic cyan ester resin obtained by reacting bisphenol A and chlorocyan is mixed into an epoxy resin in an amount of 20 to 40% by weight based on the total amount. The surface of the glass fiber base material is impregnated with the epoxy resin varnish so that the resin content is 5 to 15%. Here, if the cyanate resin is less than 20% by weight based on the total amount, the effect of the cyanate resin on heat resistance will be small as in Comparative Example 2 described below, and if the cyanate resin exceeds 40% by weight based on the total amount, as will be described later. As in Comparative Example 3, the measling phenomenon tends to occur more easily. Furthermore, if the resin content (resin adhesion rate) is less than 5%, Comparative Example 5 described below
Measling phenomenon tends to occur as shown in 15%
If it exceeds this, it becomes difficult to impregnate the next cyanate resin varnish as in Comparative Example 4 described below, and the adhesion of this cyanate resin to the glass substrate may peel off, making stable production difficult. There is a risk that this is not practical.
The resin adhesion rate is calculated as a percentage of the weight of the solid content of the impregnated resin divided by the sum of the weight of the solid content and the weight of the glass substrate. Next, after drying the impregnated material, cyanate resin varnish is further added to the glass fiber base material.
The prepreg is soaked and dried to obtain a prepreg in a dry or semi-dry state. Thereafter, a suitable number of prepreg sheets are superimposed and hot-press molded to obtain a laminate. In the present invention, as described above, the glass substrate is pretreated with the cyanate resin-containing epoxy resin, and then the glass substrate is impregnated with the cyanate resin. Therefore, the glass substrate is first impregnated with the cyanate resin-containing epoxy resin. By doing this, the bonding of the cyanate resin to the glass substrate is strengthened by the strong bonding property of the epoxy resin to the glass substrate, and the cyanate resin is allowed to penetrate into the glass substrate, and then further impregnated with cyanate resin. The surface side of the impregnated resin layer can be made rich in cyanate resin, and therefore cyanate resin is present throughout the entire layer in the resin layer impregnated into the glass substrate. The surface side of the prepreg is rich in cyanate resin, and the heat resistance, which is the inherent property of cyanate resin, is fully exhibited. A cyanate resin laminate with good measling resistance can be obtained without impairing good properties such as heat resistance and dimensional stability.

The present invention will be specifically described below based on examples.

[Example 1] Cyanate resin (KU6573, Bayer prototype)
100 parts octect zinc
A cyanate resin varnish was obtained using 0.1 part of the above formulation.

A pretreatment varnish was obtained by mixing 70 parts of an epoxy resin (Epicron 827, Dainippon Ink) with 30 parts of this cyanate resin varnish. Using this varnish, glass cloth (Nittobo,
WE-18G) and dried at 155 to 160°C for 30 minutes to obtain a pretreated glass cloth with a resin adhesion rate of 5 to 10%. The glass cloth thus obtained was impregnated with the same cyanate resin varnish as above and dried in the same manner to obtain a prepreg with a resin adhesion rate of 37 to 40%. Nine prepreg sheets obtained in this way and copper foil with a thickness of 35 μm were stacked and sandwiched between mold plates at 180±3°C and 20°C.
ni f/0! A copper-clad cyanate resin laminate (thickness 1.6±0.131i1) was prepared by heating and pressing for 60±5 minutes under the conditions of
t) was obtained. In addition, the resin adhesion rate is 5 to 10% as mentioned above.
It will be shown with a range of 37 to 40%,
In this method, the glass cloth is impregnated with resin varnish by passing a long glass cloth through an impregnation bath filled with resin varnish, and the amount of resin varnish impregnated into the glass cloth is adjusted at each length in the longitudinal direction. This is because they differ depending on the location.

[Example 2] A glass nonwoven fabric (Honshu Paper Industries, GMC-100-05) was prepared in the same manner as in Example 1 using the same pretreatment varnish as in Example 1.
7) and dried to obtain a pretreated glass nonwoven fabric with a resin adhesion rate of 10 to 1501).

This glass nonwoven fabric was impregnated with the same cyanate resin varnish as in Example 1, and dried under the same conditions to give a resin adhesion rate of 72.
A resin paper of ±5% was obtained. Nine sheets of the thus obtained resin paper and 35 μm thick copper foil were stacked and molded in the same manner as in Example 1 to obtain a copper-clad cyanate resin laminate. [Example 3] Glass pine (Nittobo, MC-300D) was impregnated and dried using the same pretreatment varnish as in Example 1 in the same manner as in Example 1 to obtain pretreated glass pine with a resin adhesion rate of 5 to 10%. I got it.

The glass mat thus obtained was impregnated with the same cyanate resin varnish as in Example 1 so that the resin adhesion rate was 50±5q6, and dried at 155 to 160°C for 14 to 16 minutes to obtain a B-stage state. I got something. The three glass mats thus obtained and the copper foil with a thickness of 35μ were stacked and heated and pressed for 60±5 minutes at 180±3°C and 40±5Kt/CTlt to obtain a copper-clad cyanate resin laminate. Ta. [Comparative Example 1] Glass cloth (Nittobo, WE-18G) was impregnated with the cyanate resin varnish obtained in Example 1, and heated at 155 to 160°C for 50 minutes.
A prepreg with a resin adhesion rate of 37 to 40 (fl) was prepared by drying for ~7 minutes, and nine sheets of this prepreg and a 35μ thick copper foil were laminated and molded in the same manner as in Example 1 to form a copper-clad cyanate resin. A laminate was obtained [Comparative Example 2] 10 parts of the cyanate resin varnish obtained in Example 1 was mixed with 90 parts of the above-mentioned epoxy resin varnish for pretreatment to obtain a varnish for pretreatment.

This varnish was impregnated into a glass cloth (Nittobo, WE-18G) and dried at 155 to 160°C for 30 minutes to obtain a pretreated glass cloth with a resin adhesion rate of 4 to 60 t). The glass cloth thus obtained was impregnated with the same cyanate resin varnish as in Example 1 and dried and molded to obtain a copper-clad cyanate resin laminate. [Comparative Example 3] As a pretreatment varnish, a mixture of 50 parts by weight of cyanate resin (same as in Example 1) and 50 parts by weight of epoxy resin (same as in Example 1) was used, and the following was the same as in Example 1. A copper-clad cyanate resin laminate (thickness: 1.6±0.13 mm) was obtained.

[Comparative Example 4] Using the pretreatment varnish obtained in Example 1, a glass cloth (
Nittobo WE-18G) was impregnated to obtain a pretreated glass cloth prepreg with a resin adhesion rate of about 20%, and a copper-clad cyanate resin laminate was obtained in the same manner as in Example 1.

However, in Comparative Example 4, although it was possible to make a prototype in the laboratory in this way, the glass cloth to which 20(f) pretreated resin was attached was industrially required to undergo secondary impregnation with cyanate resin. This is extremely difficult, and the adhered cyanate resin may fall off, making stable production impossible. Another 15%
No improvement in performance was observed even with the above deposition. [
Comparative Example 5] Using the pretreatment varnish obtained in Example 1, a glass cloth (Nittobo WE-18G) was impregnated to obtain a pretreatment glass cloth prepreg with a resin adhesion rate of about 1%, and the following Examples were prepared. A copper-clad cyanate resin laminate was obtained in the same manner as in Example 1.

[Comparative Example 6] 80 parts by weight of the cyanate resin varnish obtained in Example 1 was mixed with 20 parts by weight of an epoxy resin (Epicron 827, Dainippon Ink), and this was applied to a glass cloth (Nittobo, WE-18G).
A prepreg having a resin adhesion rate of 37 to 40% was produced by impregnating the prepreg with water and drying at 155 to 160°C.

Example 1: Nine sheets of this prepreg and a copper foil with a thickness of 35 μm were used.
Lamination molding was carried out in the same manner as above to obtain a copper-clad cyanate resin laminate. [Comparative Example 7] Epoxy resin (Epicron 827,
Dainippon Ink) varnish on glass cloth (Nittobo, WE-1)
A prepreg having a resin adhesion rate of 37 to 40% was produced by impregnating the prepreg with 8G) and drying at 155 to 160°C.

Example 1: Nine sheets of this prepreg and a copper foil with a thickness of 35 μm were used.
Lamination molding was carried out in the same manner as above to obtain a copper-clad epoxy resin laminate. The various properties of the laminates obtained in Examples 1 to 3 and Comparative Examples 1 to 7 were measured as shown in the following table.

Claims (1)

[Claims] 1. Cyanate resin is mixed into epoxy resin in an amount of 20 to 40% by weight based on the total amount, and this is added until the resin adhesion rate is 5.
A method for manufacturing a cyanate resin laminate, which comprises: impregnating a glass base material to a concentration of ~15%, then further impregnating it with cyanate resin to produce a prepreg, and then laminating the prepregs and hot pressing. .