JPH02157143A - Glass fiber base material for producing printed circuit substrate - Google Patents

Abstract

PURPOSE:To obtain a glass fiber base material for producing a printed circuit substrate which is excellent in heat resistance and heat shock resistance by sticking both a silane coupling agent and an olefin polymer or an olefin copolymer on the surface of glass fiber. CONSTITUTION:A glass fiber base material for producing a printed circuit substrate is formed by sticking both a silane coupling agent and an olefin polymer and/or an olefin copolymer on the surface of glass fiber. A glass fiber reinforced plastic plate excellent in heat resistance and heat shock resistance can be formed of the glass fiber base material. As the above-mentioned coupling agent, e.g. vinyltrichlorosilane, etc., are utilized and its build-up amount is regulated to about 0.001 - 0.5wt.% for glass fiber. Further the mol. wt. of the olefin polymer or copolymer is properly about 500 - 1,000,000 and its build-up amount is regulated to about 0.001 - 0.5%. These are applied as a soln. or emulsion respectively and thereafter preferably dried and cured at about 100 - 180 deg.C for several seconds.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a glass fiber base material for manufacturing printed wiring boards, and more specifically, a glass fiber base material used for manufacturing glass fiber reinforced plastic boards for printed wiring boards. It is related to.

[Prior Art] When manufacturing a printed wiring board made of a glass fiber base material and a thermoplastic or thermosetting resin, the glass fiber base material is coated with organic silane in advance in order to improve the bonding strength between the glass base material and the resin. This is because the organic silane coupling agent, for which a method of surface treatment with a coupling agent is adopted, has a molecular structure that allows it to bond to the glass substrate and further chemically bond to the resin.

In recent years, with the rapid technological progress in the electronics industry, the demand for related materials has been increasing, and there is also a strong desire for improved heat resistance in the field of printed wiring boards. In other words, in the process of processing printed wiring boards, soldering at 240 to 260°C using wave solder, solder coater, reflow solder, etc.
Treatment at high temperatures such as hot air treatment at 00 to 400°C can cause peeling at the intersection of the warp and weft of the glass cloth near the surface of the printed wiring board (measling), and peeling between the eyebrows inside the board (delamination). In order to prevent such phenomena from occurring, it is desired to improve the heat resistance and heat shock resistance of the substrate.

Since treatment with conventional organosilane coupling agents is not sufficient, new coupling agents are being developed (
(See Japanese Patent Application Laid-Open No. 100462/1982). Furthermore, the glass substrate may be subjected to low-temperature plasma treatment before or after treatment with an organic silane coupling agent (Japanese Patent Laid-Open No. 62-93992
(see Japanese Patent Laid-open No. 62111493) and treating a glass substrate with an organic silane coupling agent and an epoxy resin (Japanese Unexamined Patent Publication No. 135534/1982), but the heat resistance and heat shock resistance have not been improved. is still not sufficient, and further improvements are required.

[Problems to be Solved by the Invention] It is an object of the present invention to solve the problems of the prior art described above, and to provide a glass fiber base material that can manufacture printed wiring boards with excellent heat resistance and heat shock resistance. It's about doing.

[Means for Solving the Problem] As a result of intensive studies to solve this problem, the present inventors found that a silane coupling agent and an olefin polymer and/or olefin copolymer can be used as a base material for manufacturing printed wiring boards. By using glass fiber with and attached to its surface,
The present inventors have discovered that the present invention is effective in improving the heat resistance, heat shock resistance, etc. of printed wiring boards, and have completed the present invention.

That is, the present invention resides in a glass fiber base material for manufacturing printed wiring boards, characterized in that it consists of glass fibers having a silane coupling agent and an olefin polymer and/or olefin copolymer attached to the surface thereof.

The present invention will be explained in detail below.

As the glass fiber constituting the glass fiber base material for manufacturing a printed wiring board of the present invention, sheet-like materials such as woven fabric, nonwoven fabric, and paper made of glass fiber can be used as appropriate.

In the present invention, the glass fiber has a silane coupling agent and an olefin polymer and/or olefin copolymer attached to its surface.

As the silane coupling agent, 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 vinylbenzylamino ethyl)-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Examples include aminopropyltriethoxysilane, vinyltriethoxysilane, and β-(34-epoxycyclohexyl)ethyltrimethoxysilane.

The silane coupling agent is usually 0.01 to 5% by weight as an aqueous solution, a solution in an organic solvent such as alcohols, ketones, glycol ethers, dimethylformacide, or a mixed solvent of water and these organic solvents. used at a concentration of The amount of the silane coupling agent attached to the glass fiber substrate (based on solid content) is preferably in the range of 0.001 to 0.5% by weight, preferably 0.01 to 0.2% by weight.

The resin used with the above silane coupling agent is
They are olefin polymers and/or olefin copolymers (hereinafter these may be referred to as olefin resins).

Among olefin resins, the olefin polymer means an olefin homopolymer or a copolymer of two or more olefins, and examples thereof include olefin homopolymers such as ethylene, propylene, butene, isobutyne, isoprene, butadiene, etc. Alternatively, copolymers consisting of two or more of the above olefins, petroleum resins, etc. may be mentioned. Moreover, the olefin copolymer means a copolymer of the above-mentioned olefin and a comonomer other than olefin, and includes, for example, a copolymer of ethylene and a comonomer such as acrylic acid, methacrylic acid, or vinyl acetate.

The molecular weight of these olefin polymers or olefin copolymers is preferably in the range of 500 to 1,000,000.

These olefin resins are used in the form of solutions or aqueous emulsions.

The amount of olefin resin adhered to the glass fiber substrate (based on solid content) is 0.001 to 0.5% by weight, preferably 0.001 to 0.5% by weight.
The content is preferably in the range of 0.01 to 0.3% by weight.

When attaching a silane coupling agent and an olefin resin to a glass fiber base material, the glass fiber base material is simultaneously treated with a mixture of the silane coupling agent and olefin resin, or the glass fiber base material is treated with a silane coupling agent. It is then treated with an olefin resin. As a method for attaching these to glass fibers, known methods such as a dipping method and a spray method can be applied. In the commonly used immersion method, for example, a glass fiber substrate is immersed in a solution containing a silane coupling agent and/or olefin resin for several seconds at a temperature close to room temperature, and then squeezed with a mangle to obtain a 30% pick-up. , followed by dry curing for several seconds at 100-180°C.

[Example] The present invention will be further explained below with reference to Examples. Note that % and parts mean % by weight and parts by weight, respectively, unless otherwise specified.

Example 1 γ-Aminopropyltriethoxysilane Unicar, Aminosilane A-1100>0.

Polyethylene emulsion (Toho Chemical Industry ■, HYTECE-4B, solid content concentration 40%) was added to an aqueous solution containing 5% acetic acid and 0.1% acetic acid so that the solid content concentration was 0.1%, mixed, and treated. I got the liquid.

After immersing a heat-treated and degreased glass fiber fabric (Nitto Boseki (I group WEA-18W)) in this treatment solution, the liquid was squeezed using a mangle to a pick-up concentration of 30%, heated and dried at 110°C, and silane coupling was performed. A glass fiber base material to which the agent and polyethylene were attached was obtained.

Example 2 In Example 1, polypropylene emulsion (Toho Chemical Industry ■, HYTE) was used instead of polyethylene emulsion.
A glass fiber base material to which a silane coupling agent and polypropylene were attached was obtained by processing in the same manner as in Example 1, except that CE-433N (solid content concentration: 30%) was used.

Example 3 The glass fiber fabric used in Example 1 was used in Example 1,
After immersing in an aqueous solution containing 0.5% silane coupling agent and 0.1% acetic acid, the liquid was squeezed using a mangle to a pick-up concentration of 30%, and then dried by heating at 110°C. Next, this fabric was immersed in an aqueous dispersion in which the polyethylene emulsion used in Example 1 was diluted to 0.1%, and the liquid was squeezed to a pick-up of 30%.
It was heated and dried at ℃ to obtain a glass fiber base material to which the silane coupling agent and polyethylene were attached.

Comparative Example 1 A glass fiber fabric was treated in the same manner as in Example 1 except that only a silane coupling agent was used without using a polyethylene emulsion, to obtain a glass fiber substrate to which only a silane coupling agent was attached.

Comparative Example 2 A glass fiber fabric was treated in the same manner as in Example 1 except that a bisphenol A type epoxy resin was used instead of the polyethylene emulsion to obtain a glass fiber base material to which a silane coupling agent and an epoxy resin were attached.

Test Example 1 The performance of the glass fiber base materials obtained in Examples 1 to 3 and Comparative Examples 1 to 2 was evaluated by the following method.

Epoxy resin varnish (G-
10 formulation) was impregnated and pre-dried to obtain a prepreg.

Epoxy resin varnish (G-10 formulation) Epicoat 1001 (manufactured by Yuka Shell Epoxy ■) 80
Part Epicote 154 (manufactured by Yuka Shell Epoxy ■) 20 parts Dicyandiamide 4 parts Benzyldimethylamine 0.2 parts Dimethylformamide
30 copies Next, eight sheets of this prepreg were laminated with copper foil on both surfaces, and heated and molded by a conventional method to obtain a copper-clad laminate having a resin content of 40%.

Next, these copper-clad laminates were subjected to a solder heat resistance test and a heat shock resistance test. The test method is as follows.

(Solder heat resistance test) After etching the test piece and removing the copper foil and treating it with a pressure cooker at 133°C, it was immersed in a solder bath at 260°C for 20 seconds, and the damage to the test piece was observed. Judgment was made based on the criteria.

◎No blistering O Slight blistering △ Blistering × Overall blistering (heat shock resistance test) After immersing the copper-clad laminate in liquid nitrogen for 1 minute, immediately hold it at 290°.
The test piece was immersed in a solder bath of C for 30 seconds, and then the copper foil was removed by etching. Damage to the test piece was observed and judged according to the following criteria.

◎No damage ○Slight spot-like defects occur △Many spot defects occur × Overall destruction occurred The results are summarized in Table 1.

Table 1 Example 4 In Example 1, N-β-(N-
vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride (Toshi Silicon ■, 5Z-603
A glass fiber base material to which a silane coupling agent and polyethylene were attached was obtained by processing in the same manner as in Example 1, except that 2> was used.

Example 5 In Example 4, an ethylene/acrylic acid copolymer emulsion (Toho Kagaku Kogyo ■, HYTECE540BB) was used instead of the polyethylene emulsion.

A glass fiber base material to which the silane coupling agent and the ethylene/acrylic acid copolymer were attached was obtained by processing in the same manner as in Example 4, except that a solid content of 30% was used.

Example 6 In Example 4, ethylene/vinyl acetate copolymer (Sumitomo Chemical Co., Ltd., SUM) was used instead of the polyethylene emulsion.
The treatment was carried out in the same manner as in Example 4 except that IKAFLEX 400) was used, and the silane force/sampling agent and ethylene/
A glass fiber base material to which a vinyl acetate copolymer was attached was obtained.

Comparative Example 3 A glass fiber base material to which only the silane coupling agent was attached was obtained by processing in the same manner as in Example 4 except that only the silane coupling agent used in Example 4 was used without using the olefin resin. .

Test Example 2 The performance of the glass fiber base materials obtained in Examples 4 to 6 and Comparative Example 3 was evaluated as follows.

An epoxy resin varnish (FR) with the following composition is applied to a glass fiber base material.
-4 formulation) and pre-dried to obtain a prerig.

Epoxy resin varnish (FR-4 formulation) Epicoat 504B-840 (oiled shell epoxy ■)
100 parts Epicote 154 (oiled shell epoxy ■) 20 parts dicyandiamide 4 parts benzyldimethylamine 0.2 parts methyl ethyl ketone
15 parts dimethylformamide 30
Next, we layered 8 sheets of this prepreg and copper foil on both surfaces,
A copper-clad laminate having a resin content of 40% was obtained by heat molding using a conventional method.

Next, these copper-clad laminates were subjected to a solder heat resistance test and a heat shock resistance test using the method described in Test Example 1. The results are summarized in Table 2.

Table 2 Example 7 In Example 1, γ-methacryloxypropyltrimethoxysilane (union carbide ■) was used instead of aminosilane as the silane coupling agent.

A glass fiber base material to which a silane coupling agent and polyethylene were attached was obtained by processing in the same manner as in Example 1 except that A-174) was used.

Example 8 In Example 7, an ethylene/acrylic acid copolymer emulsion (Toho Chemical Industry ■, HYT) was used instead of polyethylene.
A glass fiber base material to which a silane coupling agent and an ethylene/acrylic acid copolymer were attached was obtained by processing in the same manner as in Example 7 except that ECE540BB (solid content concentration: 30%) was used.

Comparative Example 4 A glass fiber base material to which only the silane coupling agent was adhered was obtained by processing in the same manner as in Example 7 except that only the silane coupling agent was used without using the olefin resin.

Test Example 3 The performance of the glass fiber base materials obtained in Examples 7 to 8 and Comparative Example 4 was evaluated as follows.

A glass fiber base material was impregnated with a polyester resin having the following composition.

Polyester resin Polymer 6304 (Takeda Pharmaceutical ■) 100 parts Methyl ethyl ketone peroxide 1 part Cobalt naphthenate 01 parts Next, 8 glass fiber substrates were stacked using the hand lay-up method, and after defoaming, hot pressure molding was performed using a conventional method. A copper-clad laminate having a resin content of 50% was obtained.

Table 3 shows the results of the solder heat resistance test and heat shock resistance test of the laminate.

Table 3 Defects that tend to occur during high heat treatment steps (measling, delamination, blistering, etc.) can be prevented.

Claims (1)

[Claims] 1. A glass fiber base material for manufacturing printed wiring boards, characterized in that it consists of glass fibers having a silane coupling agent and an olefin polymer and/or olefin copolymer attached to the surface thereof.