JP2002194226A - Thermosetting resin composition, prepreg, laminated sheet, and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having black appearance, no decrease in insulation and reliability as a printed circuit board, and capable of appearance inspection by fluorescent light inspection type appearance inspector and suitable for manufacturing a laminated sheet, prepreg, laminated sheet, and printed circuit board. SOLUTION: This thermosetting resin composition contains a pyrazoline fluorescent dye as a fluorescent dye and an azo or disazo compound as a black dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition, a prepreg, a laminate, and a printed wiring board.

[0002]

2. Description of the Related Art A printed wiring board is formed by laminating one or a required number of prepregs obtained by impregnating and drying a varnish of a thermosetting resin composition on a fiber base material, and forming a laminate by heating and pressing. Then, a circuit is formed on the surface of the laminated board as a substrate to manufacture the laminated board. Usually, when manufacturing a laminate, metal foil such as copper foil is simultaneously laminated to form a metal-clad laminate, and the metal foil is etched to form a circuit. Therefore, in the present invention, the laminate is meant to include a metal-clad laminate.

In recent years, printed wiring boards used for applications such as 'package for mounting semiconductors' are mainly based on black since it is easy to determine the quality of connection such as wire bonding. As a method for making the substrate black, there is a method of using a black fiber base material for a prepreg for manufacturing a laminate, or a method of blending a carbon-based pigment such as carbon black or spirit black with a thermosetting resin composition. Are known.

[Problems to be solved by the invention]

[0004] However, in the method of using a black fiber base material to make the substrate black, the fiber base material may not have a sufficient blackness, and there is a problem in appearance. In addition, in the method of blending a carbon-based pigment such as carbon black or spirit black into the thermosetting resin composition, the carbon itself has conductivity, so that the insulation of the substrate is reduced, and the insulation between circuits due to electrolytic corrosion is reduced. It was easy to happen. For this reason, there has been a problem that the reliability as a printed wiring board (hereinafter simply referred to as reliability) is reduced.

On the other hand, the method of blending a black chromium complex azo dye or a disazo black dye is an organic dye, and has no problem of lowering the reliability of a printed writing board because it has no conductivity. Was. On the other hand, the optical appearance inspection device for printed wiring boards has fluorescence (460n) from the substrate.
m or more) is used to detect defects such as wire breakage, and the other is to detect defects using a method that detects reflected light from copper foil. In the detection method, since the azo-based and disazo-based dyes are black and have high light absorbing ability and do not emit fluorescence, a printed wiring board made of a thermosetting resin composition containing the black dye is incompatible. There was no other way than to perform an appearance inspection by a method of detecting reflected light.

According to the present invention, there is provided a heat-insulating board suitable for producing a laminated board which has a black appearance, does not deteriorate insulation and reliability as a printed wiring board, and can be inspected by a method of detecting fluorescence. An object of the present invention is to provide a curable resin composition, a prepreg, a laminate, and a printed wiring board.

[0007]

SUMMARY OF THE INVENTION The present inventors have found that when an azo-based and / or disazo-based compound is blended as a pyrazoline-based fluorescent dye and a black dye, there is no decrease in insulation and reliability and fluorescence can be reduced. The present inventors have found that a black laminated plate that can be inspected for appearance by a detection method can be obtained, and have reached the present invention.

The present invention relates to each of the following items (1) to (4). (1) A thermosetting resin composition containing a fluorescent dye and a black dye, comprising a pyrazoline fluorescent dye as a fluorescent dye and an azo or disazo compound as a black dye. Resin composition. (2) A prepreg obtained by impregnating a varnish of the black thermosetting resin composition according to (1) into a fiber base material. (3) A laminate obtained by heating and pressing a prepreg construct including at least one prepreg according to (2). (4) A printed wiring board obtained by forming a circuit on the surface of the laminate according to (3).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, by including a pyrazoline-based fluorescent dye as a fluorescent dye in a resin composition, a fluorescence detection type appearance inspection can be performed without sacrificing reliability or other characteristics. Neopyrazolin-based fluorescent dyes include Neo.
Super HR-50 (manufactured by Chuo Gosei Chemical Co., Ltd.
Are commercially available and can be used. Solvent Black 2 as azo black dye
NeoSuper Black known as 7
C-832 (manufactured by Chuo Gosei Kagaku Co., Ltd., trade name) and the like. Also, as the disazo black dye, Chuo known as Solvent Black 3 is used.
Sudan Black 141 (manufactured by Chuo Gosei Kagaku Co., Ltd., trade name) and the like.

The thermosetting resin used as the base of the thermosetting resin composition can be a thermosetting resin widely used in the production of laminates, and is not particularly limited. For example, an epoxy resin, a pismaleimide resin, a polyimide resin, a phenol resin, an unsaturated polyester resin, and the like can be given. Among them, an epoxy resin is preferably used.

The epoxy resin may be any compound having two or more epoxy groups in the molecule. Examples thereof include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a resole type epoxy resin, and a bisphenol type epoxy resin. Epoxy resin (phenolic epoxy resin) which is a glycidyl ether of phenol, alicyclic epoxy resin, epoxidized polybutadiene, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, isocyanurate type epoxy resin, flexible epoxy resin, etc. Is mentioned. These polyfunctional epoxy resins may be used alone or in combination of two or more. When an epoxy resin is used as the thermosetting epoxy resin, a curing agent and a curing accelerator are blended to cure the epoxy resin.

Examples of the curing agent include novolak type phenol resins, dicyandiamide, acid anhydrides and amines, and examples of the curing accelerator include imidazoles. These may be used alone or in combination of two or more. Further, the curing agent and the curing accelerator are blended in a necessary range according to the amount of the polyfunctional epoxy resin used.

[0013] In addition to the thermosetting resin and the curing agent to be blended if necessary, an inorganic filler can be blended from the viewpoint of improving the mechanical properties and reducing the cost by increasing the amount. Examples of such an inorganic filler include alumina, finely divided silica, aluminum hydroxide, zirconium silicate, and talc.

The amount of the black dye is preferably in the range of 0.01 to 2% by weight in the thermosetting resin composition.
Even if it is added in a large amount exceeding 2% by weight, the effect does not change.
The amount of the pyrazoline-based fluorescent dye is preferably in the range of 0.2 to 2% by weight. Even if it is added in a large amount exceeding 2% by weight, the effect does not change.

The thermosetting resin composition according to the present invention is impregnated into a fiber base as a varnish and dried to form a prepreg.
As the solvent used when forming the varnish, a conventionally known solvent that can dissolve the thermosetting resin to be used can be used, and there is no particular limitation. When a liquid thermosetting resin is used, it may be solventless. As the solvent, for example, water, methanol, ethanol, propyl alcohol, butyl alcohol, acetone, methyl ethyl ketone, toluene, xylene, dioxane, N, N dimethylformamide, ethylene glycol monomethyl ether,
Examples thereof include ethylene glycol monomethyl ether, and these solvents may be used alone or in combination as needed.

The fiber base material used in the present invention can be a fiber base material commonly used in the production of laminates, and is not particularly limited. Among them, a glass woven fabric or a glass nonwoven fabric is preferably used in view of characteristics such as heat resistance.

The method and production conditions for impregnating and drying the fiber base material with the thermosetting resin composition varnish to produce a prepreg can be determined according to conventionally known methods and conditions for the base thermosetting resin. There is no particular limitation. The same applies to the method and conditions for manufacturing a laminated board, and the method and conditions for manufacturing a printed wiring board by performing circuit processing on a metal-clad laminate.

There is no particular limitation on the position where the prepreg of the present invention is disposed in the material constitution when manufacturing the laminated board. However, from the viewpoint of easy identification of wire bonding quality and appearance, it is preferable that the prepreg according to the present invention be configured as the outermost layer.

[0019]

EXAMPLES Example 1 A brominated epoxy resin having an epoxy equivalent of 480 (using YDB-400 (trade name) manufactured by Toto Kasei Co., Ltd.) 100
Parts (parts by weight, hereinafter the same) 3 parts of dicyandiamide, 0.17 part of 2-ethyl-4-methylimidazole and as a disazo dye (manufactured by Chuo Gosei Kagaku Co., Ltd., trade name: Ch)
uo Sudan Black 141) O. 5 parts, 0.5 parts of pyrazoline-based fluorescent dye (manufactured by Chuo Synthetic Chemical Co., Ltd., trade name: Neo Super HR-50),
25 parts of ethylene glycol monomethyl ether, N, N
-An epoxy resin composition varnish was prepared by dissolving in a solvent consisting of 25 parts of dimethylformamide. Prepared epoxy resin composition varnish thickness 0.1 mm, the glass woven fabric weighing 104 g / m ² (produced by Nitto Boseki, G
A-7010S136 (trade name)) was impregnated and dried so that the adhesion amount after the impregnation and drying became 50% by weight to prepare a prepreg. Two prepared prepregs were stacked, and copper foil having a thickness of 18 μm was placed on both surfaces thereof, and the pressure was set to 10 kPa.
Under a reduced pressure atmosphere of 175 ° C. and a pressure of 3 MPa for 60 minutes to produce a double-sided copper-clad laminate. A circuit was formed by etching the produced double-sided copper-clad laminate to form a double-sided printed wiring board. The produced double-sided printed wiring board was based on a black appearance of the substrate, and it was easy to identify the quality of wire bonding.

Example 2 Neo Super Black C-83 which is a chromium complex azo dye instead of a disazo dye as a black dye
An epoxy resin composition varnish was prepared, a prepreg was prepared, and a double-sided printed wiring board was prepared in the same manner as in Example 1 except that 2 (manufactured by Chuo Synthetic Chemical Co., Ltd., trade name) was used. The substrate of the produced double-sided printed wiring board was based on black in appearance, and the quality of wire bonding was easily identified.

Comparative Example 1 As a pyrazoline fluorescent dye (manufactured by Chuo Gosei Kagaku Co., Ltd., trade name: Neo Super HR-50) 0.5
An epoxy resin composition varnish was prepared, a prepreg was prepared, and a double-sided printed wiring board was prepared in the same manner as in Example 1 except that no parts were blended. The substrate of the produced double-sided printed wiring board was based on black in appearance, and the quality of wire bonding was easily identified.

Comparative Example 2 As a pyrazoline fluorescent dye (manufactured by Chuo Gosei Kagaku Co., Ltd., trade name: Neo Super HR-50) 0.5
An epoxy resin composition varnish was prepared, a prepreg was prepared, and a double-sided printed wiring board was prepared in the same manner as in Example 2 except that no part was blended. The substrate of the produced double-sided printed wiring board was based on black in appearance, and the quality of wire bonding was easily identified.

Comparative Example 3 An epoxy resin composition varnish was prepared, a prepreg was prepared, and a double-sided printed wiring board was prepared in the same manner as in Example 1 except that carbon black was used as a black dye. The substrate of the produced double-sided printed wiring board was based on black in appearance, and the quality of wire bonding was easily identified. Using the double-sided copper-clad laminate obtained above,
Circuit processing was performed on the copper foil surface. These were inspected for appearance with a fluorescence inspection type appearance inspection machine. Also,
300μm or 200μ distance between holes in double-sided copper-clad laminate
m, a circuit pattern 2 circuit is formed by electrically connecting the front and back circuits with 100 holes of electroplating having a hole diameter of Φ0.5.
A voltage of 100 V DC was applied between these two circuits for 1000 hours in a constant temperature / humidity phase at 5 ° C. and a relative humidity of 85%. Thereafter, the electrical resistance to corrosion was examined by measuring the insulation resistance between the two circuits. The results are shown in Table 1.

[0024]

[Table 1] Conditions: temperature 85 ° C, relative humidity 85%, applied voltage 100
V, processing time 1000 hours

From Table 1, it can be seen that Examples 1 and 2 in which an azo-type, disazo-type black dye and a pyrazoline-type fluorescent dye are blended have good reliability because there is no insulation deterioration due to electrolytic corrosion of the printed wiring board. This indicates that there is no false alarm at the time of inspection in the appearance inspection by the method of detecting fluorescence. On the other hand, in Comparative Examples 1 and 2 in which the structural formula does not contain a pyrazoline-based fluorescent dye, there is no insulation deterioration due to electrolytic corrosion, but the reliability is good, but a false report occurs at the time of inspection. In Comparative Example 3 in which carbon black was used as the black dye, the reliability was not good because insulation loss due to electrolytic corrosion was large.

[0026]

According to the present invention, a prepreg according to the second aspect of the present invention is produced using the thermosetting resin composition according to the first aspect of the present invention, and a laminate based on black is produced by using the prepreg. Boards can be manufactured. This laminate has excellent reliability because there is no insulation deterioration due to electrolytic corrosion, and does not generate false alarms even when an appearance inspection is performed by an appearance inspection machine of a type that detects fluorescence.

Continued on the front page F-term (reference) 4F072 AB09 AB28 AB29 AD13 AD26 AD27 AD28 AD38 AD45 AG03 AH21 AJ04 AL09 4J002 AA021 BH021 CC031 CD021 CD041 CD051 CD061 CD131 CD141 CD181 CF211 CM041 EQ016 EQ036 EU126 FD096

Claims (4)

[Claims] 1. A thermosetting resin composition comprising a fluorescent dye and a black dye, wherein the thermosetting resin composition comprises a pyrazoline fluorescent dye as a fluorescent dye and an azo or disazo compound as a black dye. Thermosetting resin composition. 2. A prepreg obtained by impregnating a varnish of the black thermosetting resin composition according to claim 1 into a fiber base material. 3. A laminate obtained by heating and pressing a prepreg construct containing at least one prepreg according to claim 2. 4. A printed wiring board comprising a circuit formed on the surface of the laminate according to claim 3.