TWI566930B - Laminate, metal-clad laminate, printed wiring board, and multilayer printed wiring board - Google Patents

Description

Laminated board, metal-clad laminate, printed wiring board, multilayer printed wiring board

The present invention relates to a laminated board and a metal-clad laminated board used for manufacturing a printed wiring board or the like, and a printed wiring board and a multilayer printed wiring board manufactured using the same.

In the past, various types of laminates have been developed to satisfy low thermal expansion properties and the like.

For example, the laminated plate described in Patent Document 1 is B-staged by impregnating and coating a thermosetting resin composition containing a predetermined bismaleimide derivative on a fibrous sheet-like reinforcing substrate. After the prepreg is obtained, the prepreg is used for lamination molding.

Further, the laminated board described in Patent Document 2 is obtained by impregnating or coating a thermosetting resin composition containing a predetermined thermosetting resin and molten vermiculite on a substrate to obtain a prepreg, and then prepreg the prepreg. The material layer is formed by a predetermined number of sheets.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-195476

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2012-52110

However, in particular, for laminates used in packages such as CSP (chip size package), from the viewpoint of productivity and connection reliability, not only the coefficient of thermal expansion (CTE) but also the coefficient of thermal expansion (CTE) is improved. Elastic coefficient. In order to achieve this, it is considered that the blending amount of the inorganic filler in the resin composition is increased. However, in actuality, productivity is lowered due to the viscosity increase of the resin composition, and thus there is a limit in the increment of the inorganic filler.

Further, only the inorganic filler is increased, and the resin and the inorganic filler are separated, and the appearance of the laminate is likely to be poor.

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a laminate, a metal-clad laminate, a printed wiring board, and a multilayer printed wiring board which can reduce the coefficient of thermal expansion, improve the modulus of elasticity, and have a good appearance.

The laminated board of the present invention is a laminated board formed by impregnating a base material and containing a resin composition comprising an inorganic component and an organic component containing an inorganic filler, and heating and pressurizing, and is characterized by a total amount of the laminate , containing the above organic component 5 to 20% by mass, and using the aforementioned inorganic filler The filler is a first filler having an average particle diameter of less than 0.2 μm, a second filler having an average particle diameter of 0.2 μm or more, less than 1.0 μm, and a third filler having an average particle diameter of 1.0 μm or more. At least two or more types are included in the group.

In the above laminated sheet, it is preferred that the inorganic filler contains a Si component.

In the above laminated sheet, it is preferred that the laminated sheet has a thermal decomposition temperature (5% weight reduction temperature) of 400 ° C or higher.

In the above laminate, it is preferred that the laminate has a glass transition temperature (Tg) of 250 ° C or higher.

In the above laminated sheet, it is preferred that the organic component contains an ICI viscosity of 0.3 Pa at 150 ° C. The resin below s.

In the above laminate, it is preferred that the substrate has a thickness of 10 to 200 μm.

The metal-clad laminate of the present invention is characterized in that it is formed on the double-sided or single-layer metal foil of the laminate.

The printed wiring board of the present invention is characterized in that a conductor pattern is provided on both sides or one surface of the laminated board or the metal-clad laminate.

The multilayer printed wiring board of the present invention is characterized in that at least three or more layers of the conductor pattern are provided using the printed wiring board.

According to the present invention, it is possible to reduce the coefficient of thermal expansion, increase the modulus of elasticity, and have a good appearance.

1‧‧‧Resin composition

2‧‧‧Substrate

3‧‧‧Laminated boards

4‧‧‧Prepreg

5‧‧‧metal foil

1 is a cross-sectional view showing a laminated board of the present invention, (a) is a sectional view of a double-sided metal-clad laminate, (b) is a sectional view of a single-sided metal-clad laminate, and (c) is a metal foil which is not laminated. A sectional view of the laminate.

Embodiments of the present invention will be described below.

The laminated board of the present invention is formed by laminating one or a plurality of prepregs 4 and heating and pressurizing the prepreg. Further, the metal-clad laminate of the present invention is formed on the double-sided or single-layer metal foil 5 of the laminate 3 described above. In other words, the metal foil 5 is superimposed on one surface of one prepreg 4 or a plurality of prepregs 4, and this is heated and pressurized to form a double-sided cover as shown in Fig. 1(a). Metal laminate. Further, the metal foil 5 is superposed on one surface of one prepreg 4 or a plurality of prepregs 4, and this is heated and pressurized to form a single-sided metal as shown in Fig. 1(b). Laminated board. For the metal foil 5 described above, for example, a copper foil, an aluminum foil, a stainless steel foil or the like can be used. Among them, the laminate shown in Fig. 1(c) is a laminate in which the metal foil 5 is not laminated.

The prepreg 4 can be produced by impregnating the resin composition 1 with the substrate 2 and heating and drying it to a semi-hardened state (B-stage state).

The base material 2 can be formed, for example, of an inorganic fiber such as glass cloth, cellophane, or a glass mat, or an organic fiber such as a guanamine cloth. The thickness of the substrate 2 is preferably from 10 to 200 μm. As shown above, Since the thickness of the substrate 2 is 10 μm or more, the elastic modulus of the laminated plate 3 can be further improved. Further, the thickness of the substrate 2 is 200 μm or less, whereby the thickness of the package can be reduced.

The resin composition 1 is composed of an inorganic component and an organic component.

The above inorganic component contains an inorganic filler. In the inorganic filler, at least two types of the first filler, the second filler, and the third filler are included in the group. The first filler material has an average particle diameter of less than 0.2 μm (the lower limit is about 0.01 μm), the second filler has an average particle diameter of 0.2 μm or more and less than 1.0 μm, and the third filler has an average particle diameter of 1.0 μm. Above (the upper limit is about 5.0 μm). As described above, when inorganic fillers having different average particle diameters are used in combination, an inorganic filler having a small particle diameter is filled in a gap between inorganic fillers having a large particle diameter. Thereby, the content of the inorganic filler in the resin composition 1 can be increased, the thermal expansion coefficient of the laminated plate 3 can be lowered, the elastic modulus can be improved, and a good appearance can be obtained.

As the material of the inorganic filler, for example, vermiculite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, talc, alumina, or the like can be used. In particular, the inorganic filler is preferably a Si component as in the case of vermiculite. Thereby, the coefficient of thermal expansion of the laminated board 3 can be further reduced.

The organic component includes, for example, a thermosetting resin, a curing agent, a curing accelerator, and the like. The organic component as described above is contained in an amount of 5 to 20% by mass based on the total amount of the laminate. When the content of the organic component is less than 5% by mass, the inorganic component is relatively excessive, and the resin composition 1 is thickened and is difficult to be impregnated into the substrate 2, and the productivity of the laminated sheet 3 is lowered. If the content of organic ingredients exceeds 20% by mass, the inorganic component is relatively too small, the thermal expansion coefficient of the laminated sheet 3 becomes high, and the elastic modulus becomes low. However, the mass of the base material 2 is included in the total amount of the laminated plate 3, but the quality of the metal foil 5 is not included.

As the thermosetting resin, for example, an epoxy resin, a phenol resin, a cyanate resin, a melamine resin, a quinone imide resin, or the like can be used. In particular, in the case of an epoxy resin, for example, a polyfunctional epoxy resin, a bisphenol epoxy resin, a novolac epoxy resin, a biphenyl epoxy resin, or the like can be used.

In particular, the organic component preferably has an ICI viscosity of 0.3 Pa at 150 ° C. The resin below s. The lower the ICI viscosity, the lower the limit is not particularly limited. If the combined ICI viscosity is 0.3Pa. The resin below s, and the ICI viscosity is more than 0.3Pa. When the resin is s, the ICI viscosity is 0.3Pa. The resin of s or less is preferably contained in an amount of 5 to 70% by mass based on the total amount of the organic component. As described above, since the organic component contains a resin having a low viscosity, the impregnation property of the resin composition 1 with respect to the substrate 2 can be improved. Therefore, even if a small gap remains between the inorganic fillers, the organic component can be filled in the gap, and the appearance of the laminate 3 can be improved. Further, it is also possible to suppress the decrease in productivity of the laminated board 3. Among them, the ICI viscosity can be measured using, for example, an ICI viscometer manufactured by Research Equipment (London) Limited.

As the hardener, for example, a phenolic hardener, a dicyandiamine hardener, or the like can be used.

As the hardening accelerator, for example, an imidazole, a phenol compound, an amine, an organic phosphine or the like can be used.

Then, it can be prepared by blending the above inorganic component and organic component The resin composition 1 is further diluted with a solvent to prepare a varnish of the resin composition 1. As the solvent, for example, methyl ethyl ketone, toluene, styrene, methoxypropanol or the like can be used.

Next, the prepreg 4 is obtained by impregnating the resin composition 1 with the base material 2, heating it, and drying it until it is semi-hardened.

Next, the laminated board 3 of the present invention is produced by laminating one or a plurality of prepregs 4, and if necessary, by additionally laminating the metal foil 5 and subjecting it to heat and pressure molding. The prepreg 4 is hardened to form an insulating layer. The heat and pressure forming system at this time can be carried out using, for example, multi-stage vacuum pressing, double belt pressing, a line press roll, a vacuum lamination apparatus, or the like. The molding conditions are, for example, a temperature of 140 to 350 ° C, a pressure of 0.5 to 6.0 MPa, and a time of 1 to 240 minutes.

The thermal decomposition temperature (5% weight reduction temperature) of the laminated plate 3 obtained as described above is preferably 400 ° C or higher (the upper limit is about 600 ° C). When the content of the total amount of the organic component in the laminated plate 3 is 20% by mass or less, as described above, the thermal decomposition temperature of the laminated plate 3 is likely to be 400 ° C or higher. As described above, since the thermal decomposition temperature is high, the heat resistance of the laminated plate 3 can be improved, and the low molecular component which is generated by the decomposition of the organic component can be reduced. In the above, the thermal decomposition temperature is a temperature of 5% when the laminated plate 3 is heated at a temperature increase rate of 10 ° C /min using a thermogravimetric analysis (TGA) apparatus.

Further, the glass transition temperature (Tg) of the laminated sheet 3 is preferably 250 ° C or more (the upper limit is about 400 ° C). When the content of the entire organic component of the laminated board 3 is 20% by mass or less, as described above, the laminated board 3 The glass transition temperature (Tg) tends to be above 250 °C. As described above, since the glass transition temperature (Tg) is high, the heat resistance of the laminated plate 3 can be further improved, and the amount of change in physical properties such as the thermal expansion coefficient or the elastic modulus can be reduced. Among them, the glass transition temperature (Tg) can be determined by the DMA method.

Next, although the printed wiring board of the present invention is not shown, a conductor pattern is formed on both sides or one surface of the laminated board 3 or the metal-clad laminate. For example, a conductor pattern can be formed on the surface of the above-mentioned laminated board 3 by an additive method or the like, thereby manufacturing a printed wiring board. Further, a printed wiring board can be manufactured by forming a conductor pattern on the surface of the above-mentioned metal-clad laminate by a subtractive method or the like. The printed wiring board manufactured as described above also has a low thermal expansion coefficient and a high modulus of elasticity.

Further, in the multilayer printed wiring board of the present invention, the printed wiring board is used, and at least three or more layers of the conductor pattern are formed. In the printed wiring board, the layer of the conductor pattern is usually two or less layers. However, as described below, the layer in which the conductor pattern can be produced is a multilayer printed wiring board of three or more layers.

In other words, the multilayer printed wiring board of the present invention can laminate the metal foil 5 through the prepreg 4 on both sides or one side of the printed wiring board, thereby removing unnecessary portions of the metal foil. It is formed by providing a layer of a conductor pattern. At this time, it is preferable to use the above-mentioned prepreg 4, but other prepregs can also be used. Further, in the case of the metal foil 5, the same as described above can be used. The build-up molding and molding conditions are the same as those in the production of the above laminated sheet 3. The formation of the conductor pattern can be performed in the same manner as in the case of manufacturing a printed wiring board. That is, if the metal foil 5 is present, the layer of the conductor pattern can be formed by a subtractive method. If the metal foil 5 is not present, the lead can be formed by an additive method. The layer of the body pattern. The multilayer printed wiring board manufactured as described above also has a low coefficient of thermal expansion and a high modulus of elasticity. However, the number of layers of the conductor pattern is not particularly limited.

Thereafter, a semiconductor element is packaged on the printed wiring board or the multilayer printed wiring board to be packaged, whereby a package such as a CSP (chip size package) can be manufactured.

[Examples]

The invention will be specifically described below by way of examples.

[inorganic component]

For the inorganic component constituting the resin composition 1, the first filler, the second filler, and the third filler shown below are used.

(first filler)

. "YA010C-MFF" manufactured by Admatechs Co., Ltd. (meteorite, average particle diameter 0.01 μm)

. "YC100C-MLE" manufactured by Admatechs Co., Ltd. (meteorite, average particle diameter 0.1 μm)

(second filler)

. "S0-25R" made of Admatechs Co., Ltd. (meteorite, average particle diameter 0.5μm)

. "MGZ-5" (magnesium hydroxide, average particle diameter 0.8 μm) manufactured by Suga Chemical Industry Co., Ltd.

(third filler)

. MGChemical Industries Co., Ltd. "MGZ-6" (Hydroxide Magnesium, average particle diameter 1.6μm)

. "S0-C6" manufactured by Admatechs Co., Ltd. (meteorite, average particle diameter 2.0 μm)

. Sumitomo Chemical Co., Ltd. "CL-303" (aluminum hydroxide, average particle diameter 4.0 μm)

[organic ingredients]

As the organic component constituting the resin composition 1, a thermosetting resin, a curing agent, and a curing accelerator as described below are used.

(thermosetting resin)

. "830S" manufactured by DIC Co., Ltd. (epoxy resin, ICI viscosity at 150 ° C <0.01Pa.s (below the detection limit))

. "HP9500" manufactured by DIC Co., Ltd. (epoxy resin, ICI viscosity at 150 ° C 2.6 Pa.s)

. "N540" made of DIC Co., Ltd. (epoxy resin, ICI viscosity at 150 ° C 0.04Pa.s)

. "EPPN502H" manufactured by Nippon Kayaku Co., Ltd. (epoxy resin, ICI viscosity at 150 ° C 0.2 Pa.s)

. "BADCy" manufactured by LONZA Co., Ltd. (cyanate resin, ICI viscosity at 150 ° C <0.01Pa.s (below the detection limit))

. "BANI-M" manufactured by Maruzen Petrochemical Co., Ltd. (Imine amide resin, ICI viscosity at 150 ° C 0.7 Pa.s)

. "BMI2300" manufactured by Daiwa Kasei Co., Ltd. (醯Imine resin, ICI viscosity at 150 ° C 0.08 Pa.s)

(hardener)

. TD Corporation's "TD2090" (phenolic hardener)

. DIC Co., Ltd. "HPC9500" (phenolic hardener)

. "MEH7600" (phenolic hardener) manufactured by Minghe Chemical Co., Ltd.

(hardening accelerator)

. "2E4MZ" (imidazole) manufactured by Shikoku Chemical Industry Co., Ltd.

[substrate]

The substrate 2 as shown below was used.

. Nitto Spinning Co., Ltd. "1037" (glass cloth, thickness 27μm)

. Nitto Spinning Co., Ltd. "1036" (glass cloth, thickness 28μm)

. Nippon Spinning Co., Ltd. "2116" (glass cloth, thickness 94μm)

. Nitto Spinning Co., Ltd. "1017" (glass cloth, thickness 15μm)

[prepreg]

The inorganic component and the organic component were blended in a blending amount (parts by mass) shown in Tables 1 to 3, and diluted with a solvent (methyl ethyl ketone) to prepare a varnish of the resin composition 1.

Then, the resin composition 1 is impregnated into the substrate 2, and is dried in a drying oven at 100 to 200 ° C for 1 to 5 minutes until it is in a semi-hardened state, thereby producing a prepreg 4 . .

[Laminated board]

Two sheets of the prepreg 4 were stacked, and the double-sided copper foil ("3EC-VLP" manufactured by Mitsui Mining Co., Ltd., thickness: 12 μm) was used as the metal foil 5 to perform heat-pressure molding to produce copper-clad. A laminate (CCL) is used as the laminate 3 (Examples 1 to 10, 12 to 14). The above-described heating and press forming is performed using multi-stage vacuum pressing. The molding conditions were a temperature of 230 ° C, a pressure of 4 MPa, and a time of 120 minutes.

[Printed wiring board]

A copper-clad laminate (CCL) was produced as the laminate 3 (Example 11) except that the number of the prepreg 4 was one. Next, a conductor pattern is formed on both sides of the laminated board 3 by a subtractive method, thereby manufacturing a printed wiring board.

[Multilayer printed wiring board]

One prepreg 4 is placed on one surface of the printed wiring board, and one copper foil ("3EC-VLP" manufactured by Mitsui Mining Co., Ltd., thickness: 12 μm) is placed as a metal foil 5 to perform heat and pressure molding. Thereby, a multilayer printed wiring board (Example 15) was produced. The above-described heating and press forming is performed using multi-stage vacuum pressing. The molding conditions were a temperature of 220 ° C, a pressure of 6.0 MPa, and a time of 160 minutes.

(CCL appearance)

The metal foil 5 of the laminated board 3 was removed by etching, and the removed surface was visually observed, whereby the appearance was judged as follows.

"○": No holes, stains, or resin separators were found

"△": Although no holes or stains were found, the resin separator was found.

"X": find holes or stains

(glass transition temperature (Tg))

The glass transition temperature (Tg) of the laminated plate 3 was measured by a DMA method (dynamic mechanical analysis method) in accordance with JIS C 6481. Specifically, first, the metal foil 5 of the laminated plate 3 is removed by etching to prepare a sample. Then, a dynamic viscoelasticity measuring apparatus ("DMS6100" manufactured by SII Nano Technology Co., Ltd.) was used for the sample, and the temperature was raised at 5 ° C /min, and the peak position of tan δ was defined as the glass transition temperature (Tg).

(Thermal expansion coefficient)

The thermal expansion coefficient of the laminated plate 3 was measured by a TMA method (thermal mechanical strength analysis method) in accordance with JIS C 6481.

(elastic coefficient)

The elastic modulus of the laminated plate 3 was measured by a DMA method to form a storage elastic modulus (E ' ) at 25 °C.

(thermal decomposition temperature)

When the laminated plate 3 was heated at a temperature increase rate of 10 ° C /min using a thermogravimetric analysis (TGA) apparatus, the thermal decomposition temperature of the laminated plate 3 was measured at a temperature at which the weight reduction rate was 5%.

In the fifteenth embodiment, even if the outer metal foil 5 is removed, there is a portion having a conductor pattern inside, but when the glass transition temperature (Tg), thermal expansion coefficient, elastic modulus, and thermal decomposition temperature are measured, it is used. A portion where there is no conductor pattern inside.

The above results are shown in Tables 1 to 3.

As is apparent from Tables 1 and 2, in Examples 1 to 15, a laminate having a low coefficient of thermal expansion, a high modulus of elasticity, and a good appearance was obtained. However, as shown in Table 3, in Comparative Examples 1 to 3, a laminate having a good appearance could not be obtained, and in Comparative Example 4, it was difficult to manufacture a laminate, and in Comparative Example 5, thermal expansion of the laminate. The coefficient becomes higher and the modulus of elasticity becomes lower.

1‧‧‧Resin composition

2‧‧‧Substrate

3‧‧‧Laminated boards

4‧‧‧Prepreg

5‧‧‧metal foil

Claims (11)

A laminate which is obtained by impregnating a substrate with a resin composition comprising an inorganic component and an organic component containing an inorganic filler and heating and pressurizing, and is characterized in that the laminate is formed in a total amount relative to the laminate The inorganic filler contains 5 to 20% by mass of the organic component, and the inorganic filler has an average particle diameter of less than 0.2 μm, a second filler having an average particle diameter of 0.2 μm or more and less than 1.0 μm. At least two types of the fillers and the third filler having an average particle diameter of 1.0 μm or more are contained in the group, and the glass transition temperature (Tg) of the laminate is 250° C. or more. The laminate according to the first aspect of the invention, wherein the inorganic filler contains a Si component. The laminate according to claim 1 or 2, wherein the laminate has a thermal decomposition temperature (5% weight reduction temperature) of 400 ° C or higher. The laminate of claim 1 or 2, wherein the substrate has a thickness of 10 to 200 μm. A metal-clad laminate which is formed by a double-sided or single-layer metal foil of a laminate according to any one of claims 1 to 4. A printed wiring board characterized by the double-sided or single-sided design of the laminated board according to any one of the first to fourth aspects of the patent application or the metallized laminated board of claim 5 A conductor pattern is formed. A multilayer printed wiring board comprising: a printed wiring board according to claim 6 of the patent application, wherein at least three or more layers of the conductor pattern are provided. A laminate which is obtained by impregnating a substrate with a resin composition comprising an inorganic component and an organic component containing an inorganic filler and heating and pressurizing, and is characterized in that the laminate is formed in a total amount relative to the laminate The inorganic filler contains 5 to 20% by mass of the organic component, and the inorganic filler has an average particle diameter of less than 0.2 μm, a second filler having an average particle diameter of 0.2 μm or more and less than 1.0 μm. The filler and the third filler having an average particle diameter of 1.0 μm or more contain at least two types or more, and the organic component contains an ICI viscosity of 0.3 Pa at 150 ° C. The resin below s. A metal-clad laminate characterized by being formed on a double-sided or single-layer metal foil of a laminate as set forth in claim 8 of the patent application. A printed wiring board characterized by being formed by providing a conductor pattern on a double-sided or single-sided side of a metal-clad laminate according to claim 8 or a metal-clad laminate according to claim 9. A multilayer printed wiring board characterized by using a printed wiring board as in claim 10 of the patent application, before setting The layer of the conductor pattern is formed by at least three layers or more.