JP2005238497A - Copper clad laminated sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new copper clad laminated sheet capable of being reduced in its thickness to suppress the occurrence of warpage to result in the more reduction of thickness and reduced in the coefficient of linear expansion in its thickness direction and plane direction to be enhanced in reliability and density, and its manufacturing method. <P>SOLUTION: In the copper clad laminated sheet constituted by integrating an impregnated article, which is obtained by impregnating a glass base material with varnish containing a radical polymerization type thermosetting resin, and the copper foil arranged at least on one side thereof, the varnish has 4-6 wt.% of a methylsilicone powder and 20-40 wt.% of a filter dispersed therein. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The invention of this application relates to a copper clad laminate useful as a material for a printed wiring board or the like as a part of an electronic device or the like, and a manufacturing method thereof.

  Conventionally, as a material for printed wiring boards, etc., an impregnated product impregnated in glass equipment with a varnish containing a thermosetting resin and a copper foil disposed on at least one surface of the impregnated product are integrally molded. A copper-clad laminate is known, and it is also known to disperse a filler in the varnish in order to reduce the linear expansion coefficient (Patent Documents 1-3).

  On the other hand, in recent years, a copper-clad laminate as a material for printed wiring boards has been strongly demanded to have a thinner thickness, higher reliability, and higher density.

However, when the thickness is reduced, there is a problem that warpage becomes large particularly in the case of a single-sided copper-clad laminate or a copper foil with a large residual copper ratio. Further, in order to increase the reliability and increase the density, it is necessary to further reduce the linear expansion coefficient in the thickness direction and in the plane direction.
JP-A-8-48001 JP-A-2001-339130 JP-A-2000-71385

  Therefore, the invention of this application can reduce the occurrence of warpage by reducing the thickness from the background as described above, thereby enabling the thickness to be further reduced, and the thickness direction and the surface direction. It is an object of the present invention to provide a new copper-clad laminate and a method for manufacturing the same, which can improve the reliability and increase the density by reducing the linear expansion coefficient.

  The invention of this application is to solve the above-mentioned problems. First, an impregnated product in which a glass substrate is impregnated with a varnish containing a radical polymerization type thermosetting resin, and copper disposed on at least one surface thereof. A copper-clad laminate obtained by integrating foil, wherein the varnish is a varnish in which 4 to 6% by weight of methyl silicone powder and 20 to 40% by weight of filler are dispersed. I will provide a.

  Secondly, the present invention provides a copper clad laminate, wherein the varnish further contains 0.4 to 0.6% by weight of 3-methacryloxypropyldimethoxysilane. Thirdly, the copper-clad laminate according to any one of the above is provided, wherein the copper foil is a double-side roughened copper foil.

  According to a fourth aspect of the present invention, there is provided a copper clad laminate, wherein the copper clad laminate is a method for producing any one of the above copper clad laminates, wherein the copper foil is continuously laminated on the impregnated product and thermoformed. A method for manufacturing a copper clad laminate is provided. Fifth, a method for manufacturing a copper clad laminate is provided, in which a release foil is continuously laminated on an impregnated product and heat-molded.

  According to the first invention of this application, even if the thickness is reduced, the occurrence of warpage can be suppressed, whereby the thickness can be further reduced, and the linear expansion in the thickness direction and in the surface direction is achieved. There is provided a new copper clad laminate that can improve the reliability and the density by reducing the coefficient.

  Further, the thin single-sided copper clad laminate of the invention of this application having a small warpage and a small linear expansion coefficient in the thickness direction and the plane direction can be used as a material for a multi-layer.

  According to the second invention, the peel strength of the copper foil is improved by blending a predetermined amount of 3-methacryloxypropyldimethoxysilane with the effect of the first invention. A more reliable copper clad laminate is provided.

  According to the third invention, the use of the double-side roughened copper foil improves the peel strength in addition to the effects as described above. It can be omitted and the efficiency of the process can be improved.

  According to 4th invention, the copper clad laminated board in which the effect as mentioned above is implement | achieved will be manufactured continuously and efficiently.

  According to 5th invention, manufacture of the material for collective multilayers becomes efficient by continuous pasting of a release foil.

  The invention of this application has the features as described above, and an embodiment thereof will be described below.

  First, the radical polymerization resin used in the copper clad laminate according to the first invention of this application includes radical polymerization resins conventionally used for laminates as materials for printed wiring boards and the like. It may be various things. For example, examples of the radical polymerization resin include vinyl ester resins and unsaturated polyester resins, and the varnish may be a mixture of two or more of these radical polymerization resins. Moreover, you may mix | blend polymerizable monomer components, such as a styrene monomer, with a varnish. The varnish can be prepared by adding a radical polymerization initiator.

  In the first invention of this application, such a varnish is characterized in that 4 to 6 weight percent of methyl silicone powder and 20 to 40 weight percent of filler are dispersed. The methyl silicone powder may be commercially available as a kind of silicone rubber. Various materials having a normal particle diameter known as methyl group-containing silicone may be used. The average particle size is generally preferably 0.05 to 100 μm.

  About such methyl silicone powder, it mix | blends in the range of 4 to 6 weight% with respect to the whole amount of varnish. If it is less than 4% by weight, the effect of suppressing the warp of the copper-clad laminate is hardly obtained, and a contribution effect to reducing the thickness of the laminate cannot be expected. On the other hand, if it exceeds 6% by weight, the warp can be reduced, but the viscosity of the varnish increases and it takes time to defoam the varnish, which is not preferable.

  Along with methylsilicone powder, a filler is dispersed in the varnish, and for this filler, various inorganic materials may be synthetic resin powders. For example, aluminum hydroxide, clay, talc, silica, alumina, magnesium carbonate, calcium carbonate, synthetic resin and the like may be used. The amount of these fillers is in the range of 20% to 40% by weight with respect to the total weight of the varnish. When the amount is less than 20% by weight, it is difficult to suppress the precipitation of the above methylsilicone powder. When the amount exceeds 40% by weight, the linear expansion coefficient (α) decreases, but the peel strength of the copper foil decreases. And thicken.

  For this reason, in the invention of this application, the filler is added to the varnish within a required range of 20 wt% to 40 wt% as described above.

  In preparing the varnish, the above components are mixed and dispersed. And a varnish will be impregnated in the various things for laminated boards for printed wiring boards etc. including the glass base material known until now.

  Examples of the glass substrate include glass cloth, glass mat, and glass paper. A binder, a surface-treated product, or a material containing synthetic fibers can also be used.

  Furthermore, in order to suppress warpage and improve the peel strength of the copper foil, the above varnish is added in a range of 0.4 wt% to 0.6 wt% with respect to the total amount of varnish in order to improve the peel strength of the copper foil. Mixing is also effective. This has a function as a coupling agent. When other coupling agents are blended, the peel strength is improved, but the warpage is increased. The blending in the range of 0.4 wt% to 0.6 wt% is optimal, and if it is out of this range, it is difficult to achieve a good balance between the peel strength improvement and the warpage suppressing effect.

  Of course, in the invention of this application, it goes without saying that required components such as a viscosity modifier may be appropriately blended in the varnish, as long as the object and effect of the invention are not impaired.

  In the invention of this application, a copper foil is integrated on one or both sides of an impregnated product obtained by impregnating a glass substrate with the varnish as described above to obtain a predetermined copper-clad laminate. In addition, the linear expansion coefficient (α) is small. And from such a feature, it can be thinned, and in the case of the single-sided copper-clad laminate, it is extremely useful as a collective multilayer material.

  When considering the use as such a material for a multi-layered multilayer, a copper foil roughening step is omitted in the manufacturing process of the material for a multi-layered multi-layer by using a copper foil that has been roughened in advance. This can improve the efficiency of the process.

  The copper-clad laminate of the invention of this application can be produced as a conventional process, for example, by placing a copper foil on one or both sides of the impregnation and heat forming between metal plates. can do. The heating strength at this time can be determined in consideration of the type of varnish-containing resin, the amount of impregnation, the thickness of the glass substrate, and the like.

  In the production of the copper-clad laminate, for example, the impregnated product and the copper foil can be drawn out from the winding roll, and the impregnated product can be continuously bonded to the impregnated product. According to such a method, the production efficiency is good.

  Further, when the copper clad laminate of the invention of this application is used as the collective multilayer material, the continuous lamination of the release foil also improves the productivity. From the viewpoint of reliability, the adhesion with the adhesive layer is important for the surface from which the release foil has been peeled off.

  For this reason, the resin layer on the release surface of the release foil needs to have both the release property and the adhesiveness with the adhesive layer.

It is preferable to apply a release resin containing 5 to 10% by weight of a filler having a particle size of 3 to 4 μm on the contact surface of the release foil with the impregnated product in an amount of 1.5 to 3.0 g / m ^2. .

  At this time, when the filler diameter is less than 3 μm, the releasability is not good, and when it exceeds 4 μm, the adhesion is not sufficient. Also, if the blending amount of the filler is less than 5%, the releasability is not good, and if it exceeds 10%, the releasability is too large and the production becomes difficult. And when there are too few application | coating amounts of mold release resin, mold release property is not favorable, and when too large, manufacture will become difficult.

  Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.

  Varnishes were prepared as the blending ratios exemplified in Table 1. Here, the vinyl ester resin is used as a radical polymerization type resin, and the product number S510 manufactured by Showa High Polymer Co., Ltd. is used. As the methyl silicone powder, product number E-600 manufactured by Toray Dow Coating Silicone Co., Ltd. is used. The filler is a spherical filler of product number SFP10X manufactured by Denki Kagaku Kogyo Co., Ltd. The following formula as a silane coupling agent

The 3-methacryloxypropyldimethoxysilane represented by the formula is the product number Y-9910 manufactured by Nippon Unicar Co., Ltd.

The 3-methacryloxytrimethoxysilane represented by the formula No. KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.

  The polymerization inhibitor is a product number PBQ manufactured by Seiko Chemical Co., Ltd., and the polymerization initiator is CHP: cumene hydroperoxide manufactured by Nippon Oil & Fats Co., Ltd.

  In the preparation of the varnish, each compounding component was collected and mixed with a disper for one hour. This varnish was impregnated into a plain woven glass cloth, and then a copper foil (18 μm thickness) was heated and bonded to one side of the obtained impregnated product at a temperature of 100 ° C. to 180 ° C.

  About the obtained copper clad laminated board, the linear expansion coefficient ((alpha)), curvature, peel strength, and varnish life were evaluated. The results are also shown in Table 1.

  As is clear from the comparison of the examples and comparative examples in Table 1, the excellent effect of the copper-clad laminate of the invention of this application was confirmed.

Claims (5)

  In a copper-clad laminate obtained by integrating an impregnated product obtained by impregnating a glass substrate with a varnish containing a radical polymerization type thermosetting resin and a copper foil disposed on at least one surface thereof, the varnish is 4 to 6 weights A copper-clad laminate, characterized by being a varnish in which 20% by weight of methyl silicone powder and 20 to 40% by weight of filler are dispersed.   The copper-clad laminate according to claim 1, wherein the varnish further comprises 0.4 to 0.6% by weight of 3-methacryloxypropyldimethoxysilane.   The copper clad laminate according to any one of claims 1 to 2, wherein the copper foil is a double-side roughened copper foil.   The method for producing a copper clad laminate according to any one of claims 1 to 4, wherein the copper clad laminate is thermoformed by laminating a copper foil in contact with the impregnated product.   6. The method for producing a copper-clad laminate according to claim 5, wherein the copper-clad laminate is formed by heat-bonding a release foil in contact with the impregnated product.