JPH06173166A - Glass woven fabric substrate and laminated plate using the same - Google Patents

Abstract

(57) [Abstract] [Purpose] The purpose is to obtain a laminated board with good heat resistance that can withstand the harsh thermal conditions that occur during automatic insertion of ICs, etc. The object is to obtain a glass woven fabric substrate. [Structure] A glass woven fabric substrate having a compound having a molecular structure in which a hydroxyl group, a sulfone group, and a carboxyl group are present in a benzene ring individually or in a mixture, and a silane coupling agent attached to the surface, Laminated board with cloth base material as reinforcement.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass woven cloth base material suitable as a reinforcing material for a laminated board which is particularly required to have high heat resistance, and a laminated board using the glass woven cloth base material as a reinforcing material.

[0002]

2. Description of the Related Art Glass fibers are widely used in the electronics field because of their excellent heat resistance, dimensional stability, electrical characteristics, etc. Due to its excellent dimensional stability, it is in great demand as a material for laminated boards used in printed wiring boards and the like. In recent years, a mounting method for automatically inserting an IC or the like into a printed wiring board is increasing. This automatic insertion involves drying of the solder resist, heating such as fusing, and the like, and the printed wiring board is exposed to severe conditions. However, due to these steps, the printed wiring board is liable to cause delamination and whitening at intersections, and in order to prevent such a phenomenon from occurring, improvement in heat resistance of the board is desired.

Since the conventional treatment with an organic silane coupling agent is not sufficient, a new silane coupling agent has been developed. (See JP-A-62-100462) Also, low-temperature plasma treatment of a glass woven fabric substrate before or after treatment with an organic silane coupling agent (JP-A-62-93992, 62-111493). Or treating a glass woven fabric substrate with an organic silane coupling agent and an epoxy resin (JP-A-62-13).
However, the heat resistance is still insufficient, and further improvement is required.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a glass woven fabric substrate for providing a printed wiring board having excellent heat resistance,
And it aims at providing the laminated board which uses this glass woven fabric base material as a reinforcing material. That is, a glass woven fabric base material for providing a printed wiring board in which delamination and cross-point whitening are suppressed even when the solder resist is placed in a high temperature environment during a process such as drying or fusing, and this glass fabric. It is an object of the present invention to provide a laminate having a fabric substrate as a reinforcement.

[0005]

The present invention has been made to achieve the above object, and the glass woven fabric substrate of the present invention has a hydroxyl group, a sulfone group, a carboxyl group, or It is a glass woven fabric substrate for a laminated plate, characterized in that a compound having a molecular structure existing in a benzene ring mixedly and a silane coupling agent are attached to the surface. The laminated plate of the present invention is characterized by using the above-mentioned glass woven fabric substrate as a reinforcing material.

As the glass fibers used in the glass woven fabric substrate of the present invention, glass fibers such as E glass, S glass and D glass which have been conventionally used as a reinforcing material for glass fiber reinforced resin laminated plates are used. You can The glass woven fabric substrate of the present invention is used after being deoiled to remove the sizing agent. A degreased glass woven base material having a silane coupling agent and a hydroxyl group, a sulfone group, or a carboxyl group, or a substance having a molecular structure present in a benzene ring mixed with them attached to the surface thereof. Is.

Examples of the substance having a molecular structure in which a hydroxyl group, a sulfone group, a carboxyl group, or a mixture thereof are present in a benzene ring used in the present invention include phenol, catechol, resorcin, hydroquinone, and other benzene rings. A compound having one or more hydroxyl groups in the benzene ring, such as benzenesulfonic acid and benzenedisulfonic acid, a compound having one or more sulfone groups in the benzene ring, such as benzoic acid, phthalic acid, and terephthalic acid. A compound having one or a plurality of carboxyl groups on the benzene ring, and a compound having a mixture of a hydroxyl group and a carboxyl group on the benzene ring such as salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, and hydroxybenzene sulfone. A compound that has a hydroxyl group and a sulfone group on the benzene ring like an acid And the like. These compounds are used in the state of an aqueous solution or an alcohol solution, or in the state of a water-alcohol mixed solution. The concentration of the solution is 0.05 to 3%, preferably 0.1 to 1.5%. The adhesion rate of these compounds to the glass woven fabric substrate is 0.01 to 0.2%, preferably 0.05 to
0.1% is desirable. If the adhesion rate is less than this range, the effect of the invention will be insufficient, and if it is more than this range, it will be unfavorable because it will affect the water absorption characteristics and the like after molding the laminate.

As the silane coupling agent used in the present invention, conventionally known ones can be appropriately used. Typical examples of conventionally known silane coupling agents include, for example, γ-glycidoxypropyltrimethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, N-β-
(N-Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane-hydrochloride, N-phenyl-γ-
Examples thereof include aminopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane. The silane coupling agent is usually 0.01 to 5% by weight as an aqueous solution or a solution of an organic solvent such as alcohols, ketones, glycols, ethers and dimethylformamide, or a solution of a mixed solvent of water and these organic solvents. Used at a concentration of%. The amount of the silane coupling agent attached to the surface of the glass woven fabric substrate (based on solid content) is 0.0
The range of 01 to 0.5% by weight is preferable, and the range of 0.01 to 0.2% by weight is more preferable.

As a method for attaching these to the glass woven fabric substrate, various known methods such as a dipping method and a spray method can be applied. In a commonly used dipping method, for example, a glass woven fabric substrate is dipped in a solution containing a silane coupling agent and the compound for a few seconds at a temperature close to room temperature, and then squeezed with a mangle to obtain a 30% by weight pickup. Then, dry curing is performed at 100 to 180 ° C. for several seconds. In this case, the treatment with the compound solution and the treatment with the silane coupling agent solution may be performed separately. Next, the laminated plate of the present invention will be described. The laminated plate of the present invention uses the glass woven fabric substrate of the present invention described above as a reinforcing material. The laminated plate of the present invention is obtained, for example, by the following method. First, the glass woven fabric base material of the present invention described above is impregnated with an epoxy resin, which is often used as a matrix resin for a printed wiring board, by a conventional method such as a dipping method or a spray method, and then semi-dried and solidified to form a prepreg. obtain. After that, stack the desired number of prepregs,
The laminated plate of the present invention can be obtained by molding by a conventional method such as a pressing method. The glass fiber reinforced epoxy resin laminated board, which is often used in the production of printed wiring boards and the like, can be obtained by, for example, impregnating the glass woven fabric base material of the present invention with an epoxy resin varnish and then using the method described above.

Examples of the epoxy resin used at this time include diglycidyl ether of bisphenol A,
Examples thereof include diglycidyl ether of bisphenol F, brominated epoxy resin, and polyglycidyl ether of novolac resin. Usually, a curing agent (accelerator) is used in combination with these epoxy resins, and these curing agents (accelerators) include amine-based, acid anhydride-based, epoxy-based curing agents (accelerators) shown below. Can be mentioned. Examples of the amine-based curing agent include diethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, aliphatic polyethertriamine, dicyandiamide, 4,4′-methylenedianiline (MD
A), m-phenylenediamine (MPDA), 4,4 '
-Diaminodiphenyl sulfone, 2,6-diaminopyridine (DAP), 33.3% MPDA-33.3% M
DA-33.3% Isopropyl MPDA, 40% MDA
-60% Diethyl MDA, 40% MPDA-60% MD
A, aminopolyamide, 2-ethyl-4-methylimidazole, 2,4,6-tris (dimethylaminoethyl)
Examples include phenol. Further, as an acid anhydride-based curing agent, phthalic anhydride, hexahydrophthalic anhydride, nadic methyl hydride, dodecyl succinic anhydride, chlorendican hydride, trimellitic anhydride, maleic anhydride, Succinic anhydride, methyltetrahydrophthalic anhydride, 3,3 ', 4,4'-
Examples thereof include benzophenone-tetracarboxylic dianhydride. Further, as an epoxy-based curing agent, butyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, acrylic glycidyl ether,
Pt-butyl phenyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, etc. are mentioned.

The laminated plate of the present invention may have a conductive metal layer made of copper, gold, silver or the like 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 laminated board of the present invention may include an inner layer circuit. A laminated board having these conductive metal layers is suitable as a material for a printed wiring board or the like.

[0012]

EXAMPLES Examples of the present invention will be described below. In the following text,% and parts mean% by weight and parts by weight, respectively, unless otherwise specified. <Example> (1) Manufacturing of glass woven fabric substrate <Example 1> γ-glycidoxypropyltrimethoxysilane (Nippon Unicar Co., Ltd.) as a silane coupling agent
(Manufactured by A: 187), an aqueous solution containing 0.5% (solid content) of this silane coupling agent and 0.1% acetic acid was prepared. Further, 0.5% of o-hydroxybenzoic acid (salicylic acid) was added to this treatment liquid. Next, the heat-treated and deoiled glass woven fabric substrate (manufactured by Nitto Boseki Co., Ltd .; WEA 1
8 W) was dipped in the above treatment solution, squeezed with a mangle so that the pickup would be 30%, and then dried by heating at 110 ° C. to attach the silane coupling agent and o-hydroxybenzoic acid to the surface. I got a woven glass cloth. An epoxy resin varnish (G-10 formulation) having the following composition was dipped in the glass woven fabric substrate as a reinforcing material and predried to obtain a prepreg having a resin content of 43%. [Composition of epoxy resin varnish] -Epicoat 1001 ... 80 parts (Okaka Shell Epoxy Co., Ltd.)-Epicoat 154 ... 20 parts (Okaka Shell Epoxy Co., Ltd.)-Dicyandiamide ... 4 parts-Benzyldimethylamine ... 0 .2 parts-Dimethylformamide ... 30 parts

<Example 2> In the same manner as in Example 1 except that phenol was used in place of o-hydroxybenzoic acid,
A prepreg having a resin content of 43% was obtained.

Comparative Example 1 A prepreg having a resin content of 43% was obtained in the same manner as in Example 1 except that o-hydroxybenzoic acid was not used.

(2) Manufacture of glass fiber reinforced resin laminate G-10 1.6 mm plate Next, 8 sheets of each of these prepregs were laminated, and copper foil was superposed on the upper surface and the lower surface of the obtained laminate. By heat molding according to a conventional method, three types of copper clad laminates having a plate thickness of 1.6 mm were obtained. The heat resistance of these three types of copper clad laminates was tested. The results are shown in Table 1. The heat resistance test method is that the copper clad laminate is subjected to etching treatment to remove the copper foil on both sides of the laminate, and the temperature is 133 ° C.
After being treated with the pressure cooker of No. 2, it was immersed in a solder bath at 260 ° C. for 20 seconds, and whether or not delamination and cross-point whitening occurred in the laminated plate after immersion was determined by visual observation.

[0016]

[Table 1] ◎: No delamination and whitening of intersections ○: Very slight delamination and whitening of intersections △: Partial delamination and whitening of intersections

As is clear from Table 1, the laminated plates obtained in Examples 1 and 2 are significantly improved in heat resistance as compared with the laminated plate obtained in Comparative Example 1. It is presumed that this is because the compound attached to the glass woven fabric substrate together with the silane coupling agent reacts with the epoxy resin, and as a result, the glass fiber surface has a good affinity for the epoxy resin.

[0018]

As described above, the glass woven fabric substrate of the present invention is excellent in heat resistance. Therefore, by using the glass woven fabric substrate of the present invention, the solder resist is dried, fusing or the like. It is possible to obtain a printed circuit board in which delamination and whitening at intersections are remarkably reduced even if the printed circuit board is placed in a high temperature environment during the step (1). As a result, it has become possible to manufacture a high quality glass fiber reinforced resin laminate with high productivity.

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Claims (2)

[Claims] 1. A laminate comprising a hydroxyl group, a sulfone group, a carboxyl group, or a mixture thereof and a compound having a molecular structure present in a benzene ring and a silane coupling agent attached to the surface. Glass woven fabric substrate for boards. 2. A laminate comprising the glass woven fabric substrate according to claim 1 as a reinforcing material.