JPH03287869A - Glass fiber base material and glass fiber-reinforced resin laminate using the same - Google Patents

Abstract

PURPOSE:To provide the title base material excellent in heat resistance and dimensional stability, with delamination, etc., suppressed even if subjected to high-temperature soldering treatment, composed of glass fibers with both silane coupling agent and silicone oil stuck to their surfaces. CONSTITUTION:The objective base material composed of glass fibers with pref. 0.01-0.2wt.% of a silane coupling agent [e.g. vinyltrichlorosilane, vinyltris(2- methoxy)silane] and pref. 0.01-0.3wt.% of a silicone oil (e.g. dimethylpolysiloxane) stuck to their surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a glass fiber base material suitable as a reinforcing material for glass fiber reinforced resin laminates that require particularly heat resistance, and a method for using this glass fiber base material as a reinforcing material. The present invention relates to a glass fiber reinforced resin laminate.

[Prior Art] Glass fiber reinforced resin laminates such as glass fiber reinforced epoxy resin laminates used for manufacturing printed wiring boards, etc.
Generally, after impregnating a glass fiber base material with a thermosetting resin such as an epoxy resin, the resulting resin-impregnated glass fiber base material (
It is manufactured by press-molding a laminate formed by laminating a plurality of prepregs (hereinafter referred to as prepreg) into a desired shape.

At this time, the surface of the glass fiber base material is previously treated with a silane coupling agent in order to improve the bond strength between the glass fiber base material and the resin.

This is because the silane coupling agent has a molecular structure that allows it to bond to both the glass substrate and the resin.

By the way, in recent years, with rapid technological progress in the electronics industry, various demands have been made on related materials, and improvements in reliability and heat resistance are strongly desired in the field of printed wiring boards as well. For example, in the process of manufacturing printed wiring boards, wave solder, solder coater, etc.
Since high-temperature treatments such as soldering at 240 to 260°C using reflow solder are performed, it is known that such high-temperature treatments tend to cause delamination inside the laminate and cracks in the through-hole plating. It is being

[Problems to be Solved by the Invention] However, in conventional glass fiber reinforced resin laminates using glass fiber base materials surface-treated with a silane coupling agent, the above-mentioned delamination and through-hole plating cracks occur. has not yet been sufficiently suppressed.

In other words, although surface treatment with a silane coupling agent strengthens the bonding force between the glass fiber and the resin, the strength in the thickness direction of the glass fiber base material caused by the thermal stress applied during high-temperature treatment as described above Due to expansion,
The above-mentioned delamination and cracks in through-hole plating will occur.

Therefore, in order to prevent defects caused by heat as described above, it is strongly desired to improve the heat resistance and linear expansion coefficient of glass fiber reinforced resin laminates.

Therefore, a first object of the present invention is to provide a glass fiber base material that has excellent heat resistance and an improved coefficient of linear expansion.

A second object of the present invention is to provide a glass fiber reinforced resin laminate that uses the glass fiber base material as a reinforcing material and has excellent heat resistance and suppresses delamination and the like.

[Means for Solving the Problems] The present invention has been made in order to achieve the above object, and the glass fiber base material of the present invention has a silane coupling agent and a silicone oil attached to the surface thereof. It is characterized by being made of glass fiber.

Furthermore, the glass fiber reinforced resin laminate of the present invention is characterized in that the above-mentioned glass fiber base material is used as a reinforcing material.

As the glass fibers used in the glass fiber base material of the present invention, glass fibers such as E glass, S glass, and D glass, which are conventionally used as reinforcing materials for glass fiber reinforced resin laminates, can be used. The glass fibers may be long glass fibers or short glass fibers. Further, the shape of the glass fiber base material of the present invention is preferably a sheet-like material such as a glass fiber woven fabric, a glass fiber nonwoven fabric, or paper.

The glass fiber base material of the present invention is made by adhering a silane coupling agent and silicone oil to the surface of the glass fiber as described above. For example, After processing, process the glass fibers into a desired base shape, such as a sheet, by a conventional method. After processing the glass fibers as described above into a desired base shape, such as a sheet, by a conventional method, Obtained by treatment with a silane coupling agent and silicone oil, etc.

As the silane coupling agent used in the present invention, conventionally known ones can be used as appropriate. Typical examples include vinyltrichlorosilane, vinyltris(2
-methoxy)silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-(2-aminoethyl)aminopropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-
γ-aminopropyltrimethoxysilane hydrochloride, N-
Phenyl-γ-aminopropyltrimethoxysilane, γ
Examples include -chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, and β-(3°4-epoxycyclohexyl)ethyltrimethoxysilane.

The amount of silane coupling agent attached to the surface of glass fiber (based on solid content) is 0.001 to 0.5% by weight.
The range is preferably 0.01 to 0.2, more preferably 0.01 to 0.2.
% by weight.

The adhesion of the silane coupling agent to the glass fiber surface is 1
An aqueous solution containing one or more types of silane coupling agents, a solution of an organic solvent such as alcohols, ketones, glycol ethers, dimethylformamide, etc., or a solution of a mixed solvent of water and these organic solvents is applied to the glass. This can be done by adhering it to the fibers and then drying it. The concentration of the silane coupling agent in this solution is
It is preferably about 0.01 to 5% by weight.

Moreover, various known methods such as a dipping method and a spray method can be applied as a method for attaching the solution of the silane coupling agent to the glass fibers.

The treatment of glass fiber substrates by the dipping method is, for example, immersing a sheet-like workpiece in a solution of a silane coupling agent for several seconds at a temperature close to room temperature, squeezing the liquid with a mangle to a pick-up of 30% by weight, and then This can be carried out by dry curing for several seconds at 100 to 180°C.

In addition, the silicone oil used in the present invention includes:
Conventionally known silicone oils can be used as appropriate, and examples include silicone oils made of dimethylpolysiloxane, methylhydrodienepolysiloxane, methylphenylpolysiloxane, etc. It is also possible to use various modified silicone oils. As a modified silicone oil,
Alkyl modified type, amino modified type, epoxy modified type, epoxy polyether modified type, carboxyl modified type, mercapto modified type, chloroalkyl modified type, alkyl higher alcohol ester modified type, alcohol modified type, polyether modified type, alkyl aralkyl - Examples include polyether modified type and fluorine modified type.

The silicone oil can be attached to the surface of the glass fiber by a dipping method, a spray method, or the like, similar to the treatment of the glass fiber with the silane coupling agent described above. Moreover, the amount of silicone oil attached to the glass fiber is 0.
The range is preferably from 0.001 to 0.5% by weight, and more preferably from 0.01 to 0.3% by weight.

The treatment of glass fibers with the above-mentioned silane coupling agent and silicone oil can be carried out by performing treatment with silicone oil after treatment with the silane coupling agent, or by preparing a solution containing the silane coupling agent and silicone oil, This solution may be applied to glass fibers and then dried.

Next, the glass fiber reinforced resin laminate of the present invention will be explained. The glass fiber reinforced resin laminate of the present invention uses the glass fiber base material of the present invention described above as a reinforcing material.

The glass fiber reinforced resin laminate of the present invention can be obtained, for example, by the method shown below.

First, the aforementioned glass fiber base material of the present invention is impregnated with a resin such as an epoxy resin, a polyester resin, or a polyimide resin by a conventional method such as a dipping method or a spray method, and then semi-dry and solidified to obtain a prepreg. Thereafter, a desired number of sheets of this prepreg are laminated and molded into a desired shape by a conventional method such as a pressing method or a compression molding method, thereby obtaining the glass fiber reinforced resin laminate of the present invention.

Glass fiber-reinforced epoxy resin laminates, which are often used in the production of printed wiring boards and the like, can be obtained, for example, by the method described above after impregnating the glass fiber base material of the present invention with an epoxy resin varnish.

Examples of the epoxy resin used in this case include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, brominated epoxy resin, and polyglycidyl ether of novolac resin.

These epoxy resins are usually combined with a curing agent (accelerator), and these curing agents (accelerators) include the following amine-based, acid anhydride-based, and epoxy-based curing agents (accelerators). can be mentioned.

Examples of amine-based curing agents include diethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, aliphatic polyethertriamine, dicyandiamide, 4,4'-methylene dianiline (MDA), and m-phinylene diamine. (MPDA)
, 44'-diaminodiphenylsulfone, 2,6
- Diamitubiridine (DAP), 33.3% MPDA
-33°3% MDA -33.3% isopropyl MPDA
.

40% MDA-60% diethyl MDA, 40% MPDA
-60% MDA, aminopolyamide, 2-ethyl-4-
Examples include methylimidazole, 2,4.6-tris(dimethylaminoethyl)phenol, and the like. Examples of acid anhydride curing agents include phthalic anhydride, hexahydrophthalic anhydride, nadic methyl anhydride, dodecyl succinic anhydride, chlorendic anhydride, trimellidic anhydride, maleic anhydride, Succinic anhydride, methyltetrahydrophthalic anhydride, 3.3'
, 4,4'-benzophenone-tetracarboxylic dianhydride, and the like. Furthermore, examples of the epoxy curing agent include butyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, allyl glycidyl ether, p-1-butylphenyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, and the like.

Note that the glass fiber reinforced resin laminate of the present invention may have a conductive metal layer made of copper, gold, silver, etc. on at least one of the main surfaces. Such a conductive metal layer can be formed by a conventional method such as a pressing method. Further, the glass fiber reinforced resin laminate of the present invention may be provided with an inner layer circuit.

Glass fiber reinforced resin laminates having these conductive metal layers are suitable as materials for printed wiring boards and the like.

[Function] Since the glass fiber base material of the present invention consists of glass fibers with a silane coupling agent and silicone oil attached to the surface, a state in which silicone oil is dispersed around the glass fibers is obtained, and this silicone oil acts as a low stress agent.

Therefore, in the glass fiber-reinforced resin laminate of the present invention using the glass fiber base material as a reinforcing material, the thermal shock applied during high-temperature processing such as soldering is alleviated by the silicone oil, so there is no possibility of delamination or through-holes. Cracks in plating are suppressed.

[Examples] Examples of the present invention will be described below. Note that % and parts in the following text mean % by weight and parts by weight, respectively, unless otherwise specified.

Example 1 (1) Production of glass fiber base material N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (trade name: 5Z-6032, Toshishi) was used as a silane coupling agent.・After obtaining an aqueous solution containing 0.5% (solid content) of this silane coupling agent and 3.0% acetic acid using Dow Corning Silicone Co., Ltd., a small amount of methanol was added to this aqueous solution to form a silane cup. A processing solution containing a ring agent was prepared.

Next, as a material for the glass fiber base material, a heat-treated and degreased glass fiber fabric (product name: WEA-18W, manufactured by Nitto Boseki ■) was immersed in the above treatment solution, and squeezed using a mangle so that the pick-up ratio was 30%. After liquidizing, the mixture was heated and dried at 110° C. to obtain glass cloth A1 made of glass fibers with a silane coupling agent adhered to the surface.

On the other hand, as a silicone oil, epoxy/polyether modified silicone oil (product name: 5F8421, Toshi
After obtaining an aqueous solution containing 1% of this silicone oil using Dow Corning Silicone Co., Ltd., a small amount of methanol was added to this aqueous solution to prepare a processing liquid containing silicone oil.

Then, after immersing the glass cloth A1 in the treatment solution containing the silicone oil, it was squeezed using a mancle so that the pick-up ratio was 30%, and then heated and dried at 110°C to remove the silane coupling agent and the silicone oil. A glass fiber base material A2 was obtained, which was made of glass fibers and had the surface thereof adhered to the glass fibers.

The amount of the silane coupling agent deposited on this glass fiber base material A2 after drying (based on solid content) was 0.1%.

In addition, the amount of silicone oil adhered after drying is 0.1%.
Met.

(2) Production of glass fiber reinforced resin laminate The above glass fiber base material A2 is used as a reinforcing material, and this glass fiber base material A2 is immersed in an epoxy resin varnish (G-10 formulation) having the following composition,
It was pre-dried to form a prepreg.

[Epoxy resin varnish set rfj, l ・Epicoat 1001 (product name, Yuka Shell Epoxy stock system) 80 parts ・Epicoat 154 (product name, Yuka Shell Epoxy stock system) ・
・・・・・・・・・ 20 parts ◆Dicyandiamide ・
・・・・・・・・・ 4 parts・Benzyldimethylamine ・・・ 0.2 parts・Dimethylformamide ・・・・
... 30 copies Next, 8 sheets of this prepreg were laminated,
Copper foil was laminated on the upper and lower surfaces of the obtained laminate and heat-molded by a conventional method to obtain a glass fiber reinforced epoxy resin laminate A3 having a resin content of 40%.

Example 2 (1) Production of glass fiber base material γ-glycidoxypropyltrimethoxysilane (trade name: A-187, Nippon Unicar Co., Ltd.) was used as a silane coupling agent. .5%
(solid content), an aqueous solution containing 0.5% acetic acid was prepared. Then, a glass cloth B1 made of glass fibers having a silane coupling agent adhered to the surface was obtained in the same manner as in Example 1 except for using the treatment liquid containing this silane coupling agent.

In addition, using epoxy-modified silicone oil (product name: KF103, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone oil, an aqueous solution containing 1% of this silicone oil was obtained, and then a small amount of methanol was added to this aqueous solution to obtain a silicone oil. A treatment solution containing the following was prepared.

After immersing the glass cloth BY in the treatment liquid containing the silicone oil, the liquid is squeezed using a mangle to a pick-up ratio of 30%, and dried by heating at 110°C to remove the silane coupling agent and the silicone oil. A glass fiber base material B2 was obtained, which was made of glass fibers and had the surface thereof adhered to the glass fibers.

The amount of the silane coupling agent deposited on this glass fiber base material B2 after drying (based on solid content) was 0.1%.

In addition, the amount of silicone oil adhered after drying is 0.1%.
Met.

(2) Production of glass fiber reinforced resin laminate In the same manner as in Example 1 except that the glass fiber base material B2 was used as a reinforcing material,
A glass fiber-reinforced epoxy resin laminate Bq (resin content: 40%) having a copper layer on both surfaces was obtained.

Example 3 (1) Production of glass fiber base material Dimethylpolysiloxane (trade name: BY16-873, Toshi Dow Corning Silicone Corporation) was used as silicone oil, and this silicone oil was dissolved in toluene to form silicone. A processing solution containing 1% oil was prepared.

After immersing the glass cloth C1 produced in the same manner as in Example 2 in the treatment solution containing silicone oil, the liquid was squeezed using a mangle to a pick-up ratio of 30%, and then heated and dried at 110°C. As a result, a glass fiber base material C2 made of glass fibers having a silane coupling agent and silicone oil adhered to the surface was obtained.

The amount of the silane coupling agent deposited on this glass fiber base material C2 after drying (based on solid content) was 0.1%.

In addition, the amount of silicone oil adhered after drying is 0.1%.
Met.

(2) Production of glass fiber reinforced resin laminate In the same manner as in Example 1 except that the glass fiber base material C2 was used as a reinforcing material,
A glass fiber-reinforced epoxy resin laminate C3 (resin content: 40%) having a copper layer on both surfaces was obtained.

Comparative Example 1 A glass fiber-reinforced epoxy resin laminate D3 having a copper layer on the amphoteric surface was produced in the same manner as in Example 1 except that the glass cloth A1 produced in Example 1 was used as a reinforcing material without being treated with silicone oil. ．． (The amount of resin was 40%) was obtained.

Comparative Example 2 A glass fiber-reinforced epoxy resin laminate E3 having a copper layer on the amphoteric surface was produced in the same manner as in Example 1, except that the glass cloth B1 produced in Example 2 was used as a reinforcing material without being treated with silicone oil. (The amount of resin was 40%) was obtained.

Next, the physical properties of the glass fiber reinforced epoxy resin laminates obtained in Examples 1 to 3 and Comparative Example 1.2 were evaluated by the following method.

・Solder heat resistance test The glass fiber-reinforced epoxy resin laminates were etched to remove the copper layer on the ambidextrous surface of each glass fiber-reinforced epoxy resin laminate, and after being treated with a pressure cooker at 133℃, 20°C solder bath
It was immersed for seconds, and it was determined by visual observation whether or not blistering had occurred in each glass fiber reinforced epoxy resin laminate after immersion.

-Measurement of linear expansion coefficient The linear expansion coefficient of the glass fiber reinforced epoxy resin laminate in the thickness direction was measured by thermomechanical analysis (TMA).

These results are shown in Table-1.

(Margin below) Table 1 *: ◎... Indicates that no blistering was observed.

○: Indicates that slight blistering occurred.

△...Indicates that blistering has occurred.

As is clear from Table 1, in each of the glass fiber reinforced epoxy resin laminates obtained in Example 1, Example 2, and Example 3, almost no blistering caused by delamination etc. was observed. , these glass fiber-reinforced epoxy resin laminates are superior to the glass fiber-reinforced epoxy resin laminates of Comparative Examples 1 and 2, which use glass fiber base materials made of glass fibers that have not been treated with silicone oil as reinforcement materials. It can be seen that it has excellent heat resistance. Furthermore, since the coefficient of linear expansion is small, it can be seen that it has excellent stability against high-temperature processing such as soldering.

[Effects of the Invention] As explained above, the glass fiber base material of the present invention has excellent heat resistance and dimensional stability. Even in such cases, it is possible to obtain the glass fiber reinforced resin laminate of the present invention in which defects such as delamination and cracks in through-hole plating are suppressed.

Therefore, by using the glass fiber base material of the present invention, it becomes possible to manufacture a high quality glass fiber reinforced resin laminate with high productivity.

Claims (2)

[Claims] (1) A glass fiber base material comprising glass fibers having a silane coupling agent and silicone oil attached to the surface thereof. (2) A glass fiber reinforced resin laminate, characterized in that the glass fiber base material according to claim (1) is used as a reinforcing material.