JP2009215488A - Resin composition and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition of low dielectric loss, and a prepreg, a resin-bearing metallic foil, an adhesive film, a metallic-foil-clad laminated board, and a printed wiring board, each using the same. <P>SOLUTION: The resin composition containing a silicone resin is provided. A prepreg, a resin-bearing metallic foil, an adhesive film, a metallic-foil-clad laminated board, and a printed wiring board, each using the same, are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition, a prepreg using the same, a metal foil with resin, an adhesive film, a metal foil-clad laminate, and a printed wiring board.

With the progress of miniaturization and higher functionality of electric / electronic devices, demands for high-speed computation, high-speed transmission, etc. are increasing, and transmission loss at the time of signal transmission attracts attention. In order to cope with high-speed transmission and low transmission loss, it is an effective technique to use a material having a low dielectric loss characteristic as the material of the insulator portion of the printed wiring board. However, generally used resin for glass epoxy has a high dielectric loss, and it is necessary to develop a new product having a low dielectric loss.
JP 2002-317085 A

  An object of the present invention is to provide a resin composition having a low dielectric loss, a prepreg using the resin composition, a metal foil with resin, an adhesive film, a metal foil-clad laminate, and a printed wiring board.

The present invention relates to the following.
1. A resin composition comprising a silicone resin.
2. Item 2. The resin composition according to Item 1, wherein the silicone resin is an uncured or semi-cured thermosetting resin or a room temperature (25 ° C.) curable resin.
3. Item 3. The resin composition according to Item 1 or 2, which is an alkylsiloxane or a derivative thereof.
4). A prepreg obtained by impregnating and drying the resin composition according to any one of Items 1 to 3 on a base material.
5. The resin-coated metal foil obtained by coating and drying the resin composition according to any one of Items 1 to 3 on a metal foil.
6). The adhesive film formed by apply | coating and drying the resin composition in any one of claim | item 1 -3 to a resin film.
7). A metal foil-clad laminate obtained by laminating and integrating a metal foil on both sides or one side of a predetermined number of prepregs according to item 4.
8). A printed wiring board comprising at least one of the prepreg according to Item 4, the metal foil with resin according to Item 5, the adhesive film according to Item 6, and the metal foil-clad laminate according to Item 7.

  According to the present invention, it is possible to provide a resin composition having a low dielectric loss, a prepreg using the resin composition, a metal foil with resin, an adhesive film, a metal foil-clad laminate, and a printed wiring board.

Hereinafter, embodiments of the present invention will be described in detail.
The present invention relates to a resin composition containing a silicone resin, a printed wiring board material using the resin composition, and a printed wiring board. By using a resin composition using a silicone resin as a main component, low dielectric loss insulation is achieved. You can acquire materials. Furthermore, by using these insulating materials, a flexible printed wiring board can be manufactured.
Here, the insulating material means a general material capable of forming an insulating material such as a prepreg, an adhesive sheet, and a resin-coated copper foil, and the required characteristics as an insulating material and a printed wiring board to be manufactured must be remarkably impaired. There is no particular limitation.

  The silicone resin that can be used for the resin composition (insulating material) is not particularly limited, such as a thermosetting silicone resin, a thermoplastic resin, and the like, but it is a thermosetting or room temperature (25 ° C.) curable silicone resin. Is preferably used. Specifically, it is a polyalkylsiloxane or a derivative thereof, preferably the SOTEFA series manufactured by Toray Dow Corning Co., Ltd. and similar silicone resins, among which SOTEFA 70M or SOTEFA 50M is particularly preferable.

The molecular weight, shape, etc. of the silicone resin are not particularly specified, but if it is a thermoplastic resin, it is a single resin, and if it is a thermosetting resin, it is at least a single resin after curing. This is preferable.
In addition, as long as the properties as an insulating material with a high dielectric constant are not impaired, epoxy resin, urea resin, melamine resin, phenol resin, etc. for the purpose of assisting curing reaction, imparting mechanical strength, imparting adhesiveness, etc. Arbitrary resins other than silicone resins such as a resin having a dihydrobenzoxazine ring can also be used in combination at any ratio.

  Moreover, it can also add with a well-known organic material as a flame-retardant component. Specific examples include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide and 10- (2,5-dihydroxy-6-methylphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (1,4-dihydroxy- 2-naphthyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, melamine, melan, melem, and derivatives thereof, but are not limited thereto.

  One or a plurality of known organic / inorganic fillers may be added for the purpose of increasing the rigidity, reducing the thermal expansion, making the flame retardant, and the like. Specific examples include silica, talc, mica, calcium silicate, potassium silicate, calcined clay, titanium oxide, barium sulfate, aluminum oxide, magnesium carbonate, calcium carbonate, barium carbonate, molybdenum oxide, zinc oxide, magnesium silicate, etc. Other metal oxides and metal hydroxides such as aluminum hydroxide can also be used. In addition, compounds such as oxides composed of a plurality of elements such as molybdenum, zinc, calcium, phosphorus, aluminum, and potassium may be used.

Furthermore, the above resin composition contains known pigments, dyes, adhesion assistants, antioxidants, curing accelerators, flame retardants, flame retardant assistants, organic solvents, and the like as long as the characteristics as a printed wiring board are not impaired. Can be added.
Moreover, a prepreg can be prepared by impregnating and drying the resin composition of the present invention on a base material such as a nonwoven fabric or a woven fabric made of glass or an aramid resin. A laminated sheet can be manufactured by stacking a metal foil such as copper foil on this prepreg and stacking and integrating them by heating and pressing.

  Furthermore, by applying the resin composition of the present invention to a metal foil such as copper foil and drying, the resin film with resin is applied to a resin film such as a PET film and dried to produce an adhesive film. Can do. Moreover, a printed wiring board can also be manufactured by etching and removing an unnecessary portion of the metal foil of this laminated board, and if necessary, these printed wiring boards, prepreg, metal foil with resin, or adhesive film A multilayered printed wiring board can also be produced by appropriately laminating and combining metal foils alone or in combination, and heating and pressurizing them. In the production of these prepregs, laminates, resin-coated copper foil, adhesive films, printed wiring boards, etc., ordinary coating, lamination, and circuit processing steps in the industry can be applied.

Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.
In the examples and comparative examples, the following materials were used for the wiring board.
For other organic solvents and the like, raw materials generally used in the chemical industry and the electronics industry were used except those specifically described.
Silicone resin: Silicone resin manufactured by Toray Dow Corning (trade name: SOTEFA 70M)
・ Copper foil: Furukawa Circuit foil copper foil (trade name: GTS-12)
・ Glass cloth: Nittobo (IPC product number 7629 equivalent glass cloth)
-Copper foil with resin: Hitachi Chemical Co., Ltd. (MCF-6000E, copper foil 12 μm, insulation layer thickness 40 μm)
-Copper-clad laminate: Hitachi Chemical Co., Ltd. (MCL-BE-67G (H), t0.2, 12D)

Example 1
The silicone resin was mixed with toluene in a weight ratio of 3: 7 and dissolved. This varnish was applied to a copper foil and dried at 90 ° C. for 3 minutes to prepare a resin-coated copper foil with an insulating layer thickness of 40 μm. Evaluation was made by first laminating two pieces of resin-coated copper foil facing each other on one side of a copper-clad laminate, followed by heating and pressing at a vacuum degree of 40 hPa, a hot plate temperature of 185 ° C., and a product pressure of 3 MPa for 80 minutes. An evaluation substrate was produced. The evaluation substrate was evaluated for dielectric constant characteristics, solder heat resistance, and copper peel strength. At the same time, as a confirmation of the flexibility, the copper foil was etched on the entire surface, and the appearance after the etching and the folding test were performed. The evaluation results are shown in Table 1.

The dielectric constant is measured by cutting the evaluation substrate into 50 × 50 mm, etching a copper foil on one side into a circle with a diameter of 20 mm, and obtaining a capacitance of 1 MHz with an LCR meter. The dielectric constant was calculated and the dielectric loss was measured.
In the solder heat resistance test, the evaluation board was cut into 25 mm squares, floated on the solder at 260 or 288 ° C., and the case where the time until swelling was 50 seconds or longer was determined as OK.
The copper foil peel strength was measured by using a tensile tester to measure 90 ° peel strength of a test piece prepared by etching the copper foil of the evaluation substrate to a width of 10 mm and attaching it to a reinforcing plate.
Appearance observation confirmed visually that there was no bend, a chip, a hole, etc., after etching a 250 mm square evaluation board | substrate whole surface with a horizontal etching line.
The hull fold test was a bending characteristic test with a radius of 15 mm. An evaluation substrate having a length of 200 mm and a width of 50 mm etched on the entire surface was folded in half with a 30 mm thick spacer, and the upper and lower sides were pressed by a stainless steel plate having a weight of 200 g to form a bent portion having a radius of 15 mm. After 5 minutes, it was returned to its original shape, and it was confirmed that it was not bent and cracked.

Example 2
The varnish produced in Example 1 was impregnated with glass cloth and dried at 90 ° C. for 5 minutes to obtain a prepreg. Copper foil was laid up on both sides of the prepreg and heat-press molded in the same manner as in Example 1 to produce an evaluation substrate. Evaluation was performed in the same manner as in Example 1 using the prepared evaluation substrate. The results are shown in Table 1.

Example 3
Circuit formation (test pattern) was performed on the surface of two copper-clad laminates produced in Example 2 by the subtractive method. Furthermore, the two-sided copper-clad laminate with circuit produced was subjected to an oxidation roughening treatment on the surface of the circuit to improve the adhesion, thereby producing an inner layer substrate. A 6-layer printed wiring board with an inner layer circuit is formed by overlapping the two inner layer substrates with the prepreg produced in Example 2 sandwiched therebetween, and further overlaying the copper foil with resin produced in Example 1 on the outside and heating and pressing. Was made. This printed wiring board was subjected to outer layer circuit processing, through-hole formation, resist ink printing, and component mounting by a standard method, but it was confirmed that it could be manufactured without problems in the normal printed wiring board manufacturing process.

Comparative Example 1
Resin-coated copper foil MCF-6000E was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
The copper clad laminate MCL-BE-67G (H) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  In Examples 1 and 2, the dielectric loss was an order of magnitude lower than that of the comparative example, and there were no particular problems in characteristics such as heat resistance and relative dielectric constant. There was no abnormality in the appearance of the copper foil after the entire etching, and it was also possible to fold, so that the flexibility was confirmed and it was also found that it can be used as a flexible substrate. In Comparative Examples 1 and 2, the dielectric loss was an order of magnitude higher. Based on the above, prepregs using silicone resin compositions, copper foils with resin, adhesive sheets, laminates, and printed wiring boards have lower dielectric loss than conventional insulating materials and are equivalent or more in terms of characteristics. It was confirmed that there was. Therefore, the superiority of the present invention is clear.

Claims (8)

  A resin composition comprising a silicone resin.   The resin composition according to claim 1, wherein the silicone resin is an uncured or semi-cured thermosetting resin or a room temperature (25 ° C.) curable resin.   The resin composition according to claim 1 or 2, wherein the silicone resin is polyalkylsiloxane or a derivative thereof.   A prepreg obtained by impregnating and drying the resin composition according to any one of claims 1 to 3 on a substrate.   A resin-coated metal foil obtained by coating and drying the resin composition according to any one of claims 1 to 3 on a metal foil.   The adhesive film formed by apply | coating and drying the resin composition in any one of Claims 1-3 to a resin film.   A metal foil-clad laminate obtained by laminating a metal foil on both sides or one side of a predetermined number of prepregs according to claim 4, and heating and pressing to laminate and laminate.   The prepreg according to claim 4, the metal foil with resin according to claim 5, the adhesive film according to claim 6, and the metal foil-clad laminate according to claim 7 are used. Printed wiring board.