JP6801632B2 - Manufacturing method of laminate, laminate, multilayer laminate, printed wiring board and laminate - Google Patents

Description

The present invention relates to a laminate and a laminate suitable for a semiconductor package and a printed wiring board, a printed wiring board using the laminate, a multilayer laminate, and a method for manufacturing the laminate.

In recent years, there has been an increasing demand for thinner and lighter electronic devices, and semiconductor packages and printed wiring boards are becoming thinner and denser. In order to stably mount electronic components in response to these thinning and high density, it is important to suppress the warp that occurs during mounting.
One of the main causes of warpage in a semiconductor package at the time of mounting is the difference in coefficient of thermal expansion between the laminated plate used in the semiconductor package and the silicon chip mounted on the surface of the laminated plate. Therefore, in the laminated plate for semiconductor packages, efforts are being made to bring the coefficient of thermal expansion closer to the coefficient of thermal expansion of the silicon chip, that is, to reduce the coefficient of thermal expansion. Further, since the low elastic modulus of the laminated plate also causes warpage, it is effective to increase the elastic modulus of the laminated plate in order to reduce the warp. As described above, in order to reduce the warp of the laminated plate, it is effective to reduce the expansion coefficient and increase the elasticity of the laminated plate.

Various methods for lowering the coefficient of thermal expansion and increasing the elasticity of the laminated board can be considered. Among them, it is known to lower the coefficient of thermal expansion of the resin for the laminated board and to increase the filling of the inorganic filler in the resin. In particular, increasing the filling of the inorganic filler is a method that can be expected to improve heat resistance and flame retardancy as well as lower the coefficient of thermal expansion (Patent Document 1). However, it is known that increasing the filling amount of the inorganic filler in this way causes a decrease in insulation reliability, insufficient adhesion between the resin and the wiring layer formed on the surface thereof, and poor press molding during the production of laminated plates. There is a limit to high filling.
Further, it has been attempted to achieve a low coefficient of thermal expansion by selecting or improving the resin. For example, a method of increasing the crosslink density of the resin for a wiring board and increasing the Tg to reduce the coefficient of thermal expansion is common (Patent Documents 2 and 3). However, although increasing the crosslink density is to shorten the molecular chain between functional groups, shortening the molecular chain beyond a certain level has a limit in terms of reaction, and there is also a problem that the resin strength is lowered. .. For this reason, there is a limit to reducing the coefficient of thermal expansion by the method of increasing the crosslink density.
As described above, in the conventional laminated board, low thermal expansion rate and high elasticity have been achieved by high filling of the inorganic filler and adoption of the low thermal expansion coefficient resin, but the limit is being reached.

Further, as a method different from the above, a glass film is used as a layer having a coefficient of thermal expansion substantially matching the coefficient of thermal expansion of an electronic component (silicon chip), and the resin and the glass film are pressed and laminated to generate heat. Although attempts have been made to reduce shock stress (Patent Document 4), the resin layer has a low coefficient of elasticity and a high coefficient of thermal expansion, so that it is insufficient to realize a low warp of the substrate.

Japanese Unexamined Patent Publication No. 2004-182851 Japanese Unexamined Patent Publication No. 2000-243864 Japanese Unexamined Patent Publication No. 2000-114727 Patent No. 46575554

As described above, the substrate obtained by the production method of Patent Document 4 still has a low elastic modulus and a high coefficient of thermal expansion, and thus is insufficient to realize a low warp of the substrate.
The present invention has been made in view of such circumstances, and is used for manufacturing a laminated board and a multilayer laminated board having a low coefficient of thermal expansion and a high elastic modulus, suppressing warpage, and hardly causing cracks, and a laminated board and a multilayer laminated board. It is an object of the present invention to provide a suitable laminate, a printed wiring board using these laminates and a multilayer laminate, and a method for manufacturing the laminate.

Patent Document 4 does not describe that the resin contains an inorganic filler in the substrate formed by laminating a glass film and a resin. From the description of Patent Document 4, it is considered that the inclusion of an inorganic filler in the resin should be avoided.
That is, in Patent Document 4, it is an essential configuration that the thermal expansion action of the entire substrate is substantially determined by the glass film (Claim 1 of Patent Document 4). In view of this, it is necessary to minimize the influence of the resin on the thermal expansion action of the substrate, and for that purpose, it is necessary to keep the elastic modulus of the resin low (if the resin has a high elastic modulus, this high elastic modulus is required). The coefficient of thermal expansion greatly affects the thermal expansion effect of the entire substrate). On the other hand, when the resin contains an inorganic filler, the resin has a high elastic modulus. Therefore, from the description of Patent Document 4, it should be avoided that the resin contains an inorganic filler.
Further, when the resin of Patent Document 4 contains an inorganic filler, it is conceivable that the glass substrate is easily cracked starting from the inorganic filler. From this point as well, it is presumed that Patent Document 4 avoids containing an inorganic filler in the resin.
At present, there is no example of a laminated plate in which an inorganic filler is contained in the resin layer in a laminated plate of a glass substrate layer and a resin layer as in Patent Document 4.

Surprisingly, however, the present inventors have conducted diligent research to solve the above problems, and as a result, the resin cured product layer contains an inorganic filler in the laminated plate including the resin cured product layer and the glass substrate layer. It has been found that a laminated board having a low thermal expansion coefficient and a high elastic modulus, suppressing warpage, and being less prone to cracking can be obtained.

The present invention has been completed based on the above findings, and has the following gist of [1] to [12].
[1] A laminate containing one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a thermosetting resin and a resin composition containing an inorganic filler. A laminated body in which the glass substrate layer is 10 to 95% by volume based on the entire laminated body.
[2] The laminate according to the above [1], wherein the thickness of the glass substrate layer is 30 μm to 200 μm.
[3] The thermosetting resin is an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, or a dicyclopentadiene resin. The laminate according to the above [1] or [2], which is one kind or two or more kinds selected from a silicone resin, a triazine resin and a melamine resin.
[4] The inorganic filler is one or more selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate and borosilicate glass [1]. ] To [3].
[5] A laminated plate containing one or more cured resin layers and one or more glass substrate layers, wherein the cured resin layer is a cured product of a resin composition containing a thermosetting resin and an inorganic filler. A laminated plate made of, wherein the glass substrate layer is 10 to 95% by volume with respect to the entire laminated plate.
[6] The laminated board according to the above [5], wherein the dynamic storage elastic modulus at 40 ° C. is 10 GPa to 70 GPa.
[7] The laminate according to the above [5] or [6], which is obtained by heating and pressurizing the laminate according to any one of [1] to [4].
[8] A multilayer laminated board including a plurality of laminated boards, wherein at least one laminated board is the laminated board according to any one of [5] to [7].
[9] A printed wiring board having the laminated board according to any one of [5] to [7] and wiring provided on the surface of the laminated board.
[10] A printed wiring board having the multilayer laminated board according to [8] and wiring provided on the surface of the multilayer laminated board.
[11] The method for producing a laminated plate according to any one of [5] to [7], which comprises a step of forming a cured resin layer on the surface of a glass substrate.
[12] The method for producing a laminated plate according to [11], wherein the resin cured product layer forming step is a step of applying the resin composition on the glass substrate, and then drying and curing the resin composition.
[13] The laminated plate according to [11], wherein the resin cured product layer forming step is a step of laminating a film made of the resin composition on the glass substrate using a vacuum laminator or a roll laminator and curing the film. Manufacturing method.
[14] The method for producing a laminated plate according to [11], wherein the resin cured product layer forming step is a step of arranging a film made of the resin composition on the glass substrate, pressing the film, and curing the film.

According to the present invention, a laminated board and a multilayer laminated board having a low coefficient of thermal expansion and a high elastic modulus, capable of suppressing warpage, and less likely to cause cracks, and a laminated body suitable for manufacturing these laminated boards and the multilayer laminated board. And a printed wiring board using these laminated boards and a multilayer laminated board, and a method for manufacturing the laminated board can be provided.

It is a schematic cross-sectional view explaining the manufacturing method of Examples 1 to 2 and 4. It is a schematic cross-sectional view explaining the manufacturing method of Example 5.

Hereinafter, the laminate, the laminate, the multilayer laminate, the printed wiring board, and the method for manufacturing the laminate of the present invention will be described in detail.
In the present invention, the laminated body means that the thermosetting resin which is a component thereof is uncured or semi-cured, and the laminated board means that the thermosetting resin which is a component thereof is cured. Means what you are doing.

[Laminate]
The laminate of the present invention is a laminate containing one or more resin composition layers and one or more glass substrate layers, and the resin composition layer is a resin composition containing a thermosetting resin and an inorganic filler. It is made of a material, and the glass substrate layer is 10 to 95% by volume based on the entire laminate.
The size of the laminate of the present invention may be selected in the range of width 10 mm to 1000 mm and length 10 mm to 3000 mm (when used in a roll, the length is appropriately applied) from the viewpoint of handleability. preferable. In particular, the width is preferably in the range of 25 mm to 550 mm and the length is preferably in the range of 25 mm to 550 mm.
The thickness of the laminate of the present invention is preferably selected in the range of 35 μm to 20 mm depending on the application. The thickness of the laminate is more preferably 50 to 1000 μm, further preferably 100 to 500 μm, and even more preferably 120 to 300 μm.
The laminated plate obtained by curing the resin composition layer of the laminate of the present invention to form a cured resin layer has a glass substrate layer having a coefficient of thermal expansion and a high elastic modulus comparable to that of a silicon chip. It has a low coefficient of thermal expansion and a high elastic modulus, warpage is suppressed, and cracks are unlikely to occur. In particular, since this laminated board has a glass substrate layer having high heat resistance, it has remarkably low thermal expansion in a temperature range from 100 ° C. to less than Tg of the cured resin product. Further, since the cured resin layer contains an inorganic filler, the cured resin layer has a low thermosetting rate and a high elastic modulus, and the laminated board containing the cured resin layer has a lower expansion rate and a higher elastic modulus. It has a high elastic modulus.

<Resin composition>
The resin composition of the present invention contains a thermosetting resin and an inorganic filler.
≪Thermosetting resin≫
The thermosetting resin is not particularly limited, and for example, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, and dicyclo Examples thereof include pentadiene resin, silicone resin, triazine resin, and melamine resin. Among these, epoxy resins and cyanate resins are preferable because they are excellent in moldability and electrical insulation.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol F novolac type epoxy resin. , Stilben type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene Examples thereof include type epoxy resins, alicyclic epoxy resins, polyfunctional phenols, and polycyclic aromatic diglycidyl ether compounds such as anthracene. Further, a phosphorus-containing epoxy resin in which a phosphorus compound is introduced into these epoxy resins can be mentioned. Among these, a biphenyl aralkyl type epoxy resin and a naphthalene type epoxy resin are preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in admixture of two or more.
Examples of the cyanate resin include bisphenol type cyanate resins such as novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and tetramethylbisphenol F type cyanate resin, and prepolymers in which these are partially triazined. .. Of these, the novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in admixture of two or more.
The content of the thermosetting resin contained in the resin composition is preferably in the range of 20 to 80% by mass, preferably 40 to 80% by mass, based on the total amount of the resin composition minus the content of the inorganic filler. 80% by mass is more preferable, 50 to 80% by mass is further preferable, and 60 to 75% by mass is further preferable.

≪Inorganic filler≫
Examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass.
Among these, silica is preferable from the viewpoint of low thermal expansion, and spherical amorphous silica having a very small coefficient of thermal expansion of about 0.6 ppm / K and a small decrease in fluidity when highly filled in resin is used. More preferred.
The spherical amorphous silica preferably has a cumulative 50% particle diameter of 0.01 to 10 μm, preferably 0.03 to 5 μm.
Here, the cumulative 50% particle size is the particle size of a point corresponding to exactly 50% of the volume when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the powder as 100%. It can be measured with a particle size distribution measuring device or the like using.
The content of the inorganic filler in the resin composition is preferably 5 to 75% by volume, more preferably 15 to 70% by volume, and further preferably 30 to 70% by volume of the total amount of the resin composition. preferable. When the content of the inorganic filler is 5 to 75% by volume of the resin composition, the effect of reducing the coefficient of thermal expansion is sufficient, the fluidity is appropriate, and the moldability is excellent. That is, when the content of the inorganic filler is 5% by volume or more, the effect of reducing the coefficient of thermal expansion is sufficient, and when it is 75% by volume or less, the fluidity is increased and the moldability is improved.
When expressed in mass%, for example, when the inorganic filler is silica, the content of silica in the resin composition is preferably 8 to 85% by mass, preferably 24 to 82% by mass. More preferably, it is more preferably 44 to 82% by mass.
Further, by using silica (nanosilica) having an average primary particle size of 1 μm or less as the inorganic filler, fine wiring can be formed on the resin cured product layer of the laminated plate. The nanosilica preferably has a specific surface area of 20 m ² / g or more. Further, from the viewpoint of reducing the surface shape after the roughening treatment in the plating process, the average primary particle size is preferably 100 nm or less. This specific surface area can be measured by the BET method.
The "mean primary particle size" here does not mean the average diameter of agglomerated particles, that is, the secondary particle size, but the average particle size of a single non-aggregated particle. The average primary particle size can be determined by measuring with, for example, a laser diffraction type particle size distribution meter. Humed silica is preferable as such an inorganic filler.
Further, the inorganic filler is preferably treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance, and is preferably hydrophobized in order to improve dispersibility.
When the fine wiring is formed on the cured resin layer of the laminated plate, the content of the inorganic filler is preferably 20% by mass or less in the resin composition. When the blending amount is 20% by mass or less, a good surface shape after the roughening treatment can be maintained, and deterioration of plating characteristics and insulation reliability between layers can be prevented. On the other hand, since the resin composition can be expected to have low thermal expansion and high elasticity by containing the inorganic filler, the content of the inorganic filler is high when low thermal expansion and high elasticity are emphasized as well as fine wiring formation. It is preferably 3 to 20% by mass, and more preferably 5 to 20% by mass.

≪Other ingredients≫
In addition to the above components, this resin composition includes a curing agent, a curing accelerator, a thermoplastic resin, an elastomer, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, etc. Can be added.
Examples of the curing agent include, when an epoxy resin is used, a polyfunctional phenol compound such as phenol novolac and cresol novolac; an amine compound such as dicyandiamide, diaminodiphenylmethane and diaminodiphenyl sulphon; phthalic anhydride and pyromellitic anhydride. , Maleic anhydride, maleic anhydride copolymer and other acid anhydrides; polyimide can be used. Several types of these curing agents can be used in combination.
Examples of the curing accelerator include, for example, imidazoles and derivatives thereof; organophosphorus compounds; secondary amines, tertiary amines, and quaternary ammonium salts as curing accelerators for epoxy resins.
Examples of UV absorbers include benzotriazole-based UV absorbers.
Examples of the antioxidant include hindered phenolic and styrenated phenolic antioxidants.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
Examples of fluorescent whitening agents include fluorescent whitening agents such as stilbene derivatives.
Examples of the adhesion improver include urea compounds such as ureasilane and adhesion improvers for silane coupling agents.

<Resin composition layer>
The resin composition layer is made of the above resin composition. The resin composition layer includes a semi-cured product as well as an uncured product of the resin composition.
The size of the resin composition layer of the present invention is preferably selected in the range of width 10 mm to 1000 mm and length 10 mm to 3000 mm (when used in a roll, the length is appropriately applied). In particular, a width of 25 mm to 550 mm and a length of 25 mm to 550 mm are preferable from the viewpoint of handleability.
The thickness of the resin composition layer of the present invention per layer is preferably selected in the range of 3 μm to 200 μm. From the viewpoint of low thermal expansion and high elastic modulus of the laminated body and the laminated plate, the thickness per layer of the resin composition is preferably 3 to 150 μm, more preferably 3 to 100 μm, and 5 to 5 It is more preferably 50 μm, and even more preferably 5 to 30 μm.

<Glass substrate layer>
The thickness of the glass substrate layer per layer is preferably 30 to 200 μm from the viewpoint of thinning the laminate and workability, and the thickness is 50 to 150 μm in consideration of practicality such as ease of handling. Is more preferable, and 80 to 120 μm is further preferable.
The thickness of the glass substrate layer referred to here refers to the average thickness of the glass substrate layer. The average thickness of the glass substrate layer can be measured using a known thickness measuring device such as a micrometer or a film thickness measuring device. For example, in the case of a rectangular or square glass substrate layer, the thicknesses at the four corners and the center can be measured using a micrometer, and the average value can be obtained as the average thickness of the glass substrate layer. Further, as the material of the glass substrate layer, glass such as alkaline silicate glass, non-alkali glass, and quartz glass can be used, but borosilicate glass is preferable from the viewpoint of low thermal expansion.
The size of the glass substrate layer of the present invention is preferably selected in the range of width 10 mm to 1000 mm and length 10 mm to 3000 mm (when used in a roll, the length is appropriately applied). In particular, a width of 25 mm to 550 mm and a length of 25 mm to 550 mm are more preferable from the viewpoint of handleability.
The closer the coefficient of thermal expansion of the glass substrate layer is to the coefficient of thermal expansion of the silicon chip (about 3 ppm / ° C.), the more the warpage of the laminate or the laminate obtained from the laminate may be suppressed, but it is preferably 8 ppm / ° C. It is less than or equal to, more preferably 6 ppm / ° C. or less, still more preferably 4 ppm / ° C. or less.
The storage elastic modulus of this glass substrate layer at 40 ° C. is better, but is preferably 20 GPa or more, more preferably 25 GPa or more, and further preferably 30 GPa or more.
The glass substrate layer is preferably 10 to 95% by volume, more preferably 15 to 90% by volume, still more preferably 20 to 85% by volume, based on the entire laminate. When the content of the glass substrate is 10% by volume or more, it is advantageous to obtain a laminate having low thermal expansion and high elasticity. On the contrary, when the content of the glass substrate is 95% by volume or less, the processability and workability are improved. It is advantageous in terms of handleability (ease of handling).

<Composition layer for interlayer insulation>
The laminate of the present invention may have a composition layer for interlayer insulation in order to improve the adhesion to the conductor layer described later.
That is, as will be described later, when a printed wiring board is manufactured using the laminate of the present invention, a conductor layer may be formed on the surface of the laminate formed by curing the laminate by plating or the like. Further, it may be a laminate or a laminate with a metal foil having a metal foil (conductor layer) on the surface. In these cases, the conductor layer may be formed on the above-mentioned resin composition layer or the cured resin layer obtained by curing the resin composition layer, but the composition for interlayer insulation is further formed on the resin composition layer or the cured resin layer. A material layer or an interlayer insulating layer obtained by curing the material layer may be provided, and a conductor layer may be formed on the material layer. In this case, by using a composition layer for interlayer insulation having high adhesion to the conductor layer, the adhesion between the laminated plate and the conductor layer becomes good.
Further, as will be described later, a desmear treatment may be performed after forming a via hole in the laminated plate. In this case, by providing a composition layer for interlayer insulation having excellent desmear resistance, the surface of the laminated board (that is, the interlayer insulating layer obtained by curing the composition layer for interlayer insulation) is excessively uneven. It is possible to prevent the size from becoming large and to form a fine wiring pattern on the surface thereof.

As a structure when the laminate has a composition layer for interlayer insulation as described above, for example,
It may have a three-layer structure such as a glass substrate layer / resin composition layer / composition layer for interlayer insulation.
It may have a five-layer structure such as a composition layer for interlayer insulation / a resin composition layer / a glass substrate layer / a resin composition layer / a composition layer for interlayer insulation. The notation "glass substrate layer / resin composition layer / interlayer insulation composition layer" means that the glass substrate layer, the resin composition layer, and the interlayer insulation composition layer are laminated in this order. To do. The same applies to the notation regarding the five-layer structure.
Other than the above example, the structure is not particularly limited to the above example as long as the composition for interlayer insulation can be arranged between the conductor layer and the laminate of the present invention.

The material of the interlayer insulating composition layer is not particularly limited, and for example, the resin composition described above may be used, but it is desirable to select a resin from the viewpoint of improving the adhesion with the conductor layer. Further, the interlayer insulating composition layer may or may not contain an inorganic filler.

<Adhesive layer>
Further, the laminate of the present invention has a resin composition layer containing a thermosetting resin and an inorganic filler, but also has an adhesive layer containing a thermosetting resin and not containing an inorganic filler. It doesn't matter. The adhesive layer can be arranged, for example, between the glass substrate layer and the resin composition layer, and can be used for the purpose of enhancing the adhesiveness of both layers.

<Ratio of each layer in the laminate>
The resin composition layer of the present invention is preferably 5 to 60% by volume, preferably 5 to 55% by volume, based on the entire laminated body, from the viewpoint of obtaining a laminated board having a low coefficient of thermal expansion and a high elastic modulus. It is more preferably 10 to 50% by volume, further preferably 20 to 40% by volume.
The glass substrate layer of the present invention is preferably 20 to 90% by volume, preferably 30 to 85% by volume, based on the entire laminate from the viewpoint of obtaining a laminated plate having a low coefficient of thermal expansion and a high elastic modulus. It is more preferably 35 to 80% by volume, and even more preferably 40 to 75% by volume.
When the laminate has an interlayer insulating layer, the interlayer insulating layer is preferably 1 to 20% by volume, more preferably 2 to 15% by volume, based on the entire laminate. It is more preferably from 10% by volume.
When the laminated body has an adhesive layer, the adhesive layer is preferably 1 to 20% by volume, more preferably 2 to 15% by volume, and 3 to 10% by volume with respect to the entire laminated body. It is more preferably by volume.

<Support film and protective film>
The above-mentioned laminate may have a support film or a protective film on its surface. These support films and protective films will be described in detail in the following description of the method for producing the laminate.

[Manufacturing method of laminate]
The method for producing the above-mentioned laminate is not particularly limited, and the laminate can be produced by laminating a film made of a resin composition on a glass substrate, applying the resin composition to a glass substrate, or the like. Of these, the laminating method is preferable because it is easy to produce.
Next, each manufacturing method will be described in detail.
<Manufacturing method of laminated body by laminating>
The above-mentioned laminate can be suitably produced by laminating an adhesive film using the resin composition and a glass substrate by pressure laminating such as vacuum laminating or roll laminating. This adhesive film will be described later. Further, vacuum laminating and roll laminating can be performed using a commercially available vacuum laminator or roll laminator.
As the thermosetting resin in the resin composition and the interlayer insulating composition, those that melt at a temperature lower than the temperature at the time of laminating are preferably used. For example, when laminating using a vacuum laminator or a roll laminator, it is generally performed at 140 ° C. or lower, so that the thermosetting resin in the resin composition and the interlayer insulating composition are melted at 140 ° C. or lower. It is preferable to do.
First, the adhesive film will be described, and then a laminating method using the adhesive film will be described.

≪Adhesive film≫
When a laminate is produced using a vacuum laminator or a pressurized laminator, the above resin composition is generally prepared as an adhesive film.
As the adhesive film used in the present invention, one having the following laminated structure is preferably used.
(1) Support film / resin composition layer (2) Support film / interlayer insulation composition layer / resin composition layer Further, in the laminated structure of the above (1) and (2), a protective film was further laminated. Those having the following laminated structure are also preferably used.
(3) Support film / resin composition layer / protective film (4) Support film / composition layer for interlayer insulation / resin composition layer / protective film The protective film is a support for the resin composition layer of the present invention. It is formed on the opposite side of the film and is used for the purpose of preventing foreign matter from adhering and scratching.
The adhesive film obtained by removing the support film and the protective film from these adhesive films may be referred to as an adhesive film main body.

The adhesive film having the laminated structure of (1) to (4) above can be produced according to a method known to those skilled in the art.
As an example of producing the adhesive film of (1) above, the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed. Next, the resin composition layer may be formed by applying this varnish using the support film as a support and drying the organic solvent by heating, blowing hot air, or the like.
As an example of producing the adhesive film of (2), a composition layer for interlayer insulation is dissolved in an organic solvent to prepare a varnish. Next, a varnish is applied to the support film, and the organic solvent is dried by heating, hot air blowing, or the like to form an interlayer insulating composition layer. After that, the resin composition layer may be formed on the surface of the interlayer insulating composition layer in the same manner as in (1) above.
As an example of producing the adhesive film of (3), the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed. Next, the varnish is applied to one of the support film and the protective film, the other of the support film and the protective film is placed on the varnish, and the organic solvent of the varnish is dried by heating, hot air blowing, or the like. As a result, the resin composition layer may be formed.
As an example of producing the adhesive film of (4) above, a varnish is prepared by dissolving the above-mentioned interlayer insulation composition in an organic solvent, and this varnish is applied to the above-mentioned support film, and heating, hot air blowing, etc. The composition layer for interlayer insulation is formed by drying the organic solvent. Next, the surface of the laminate on the side of the interlayer insulation composition is brought into contact with the surface of the laminate produced in advance as described in (1) on the side of the resin composition layer, and a vacuum laminator or roll laminator described later is provided. It may be laminated using a pressurized laminator such as. As another example, an interlayer insulating layer is formed on the support film using a varnish, then a varnish for a resin composition is applied onto the support film, and a protective film is placed on the varnish, which is then heated or blown with hot air. The resin composition layer may be formed by drying the organic solvent of this varnish.

As the coating device for the interlayer insulation composition layer and the resin composition layer, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used. , It is preferable to select appropriately depending on the film thickness to be produced.
In the above adhesive film, the interlayer insulating composition layer and the resin composition layer may be semi-cured.
The above-mentioned support film serves as a support when manufacturing an adhesive film, and is peeled off or removed when it is usually used in manufacturing a multilayer printed wiring board.

Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and release paper and copper. Examples include metal foils such as foils and aluminum foils. When a copper foil is used for the support film, the copper foil can be used as it is as a conductor layer to form a circuit. In this case, examples of the copper foil include rolled copper and electrolytic copper foil, and those having a thickness of 2 μm to 36 μm are generally used. When a copper foil having a thin thickness is used, a copper foil with a carrier may be used in order to improve workability.
The support film may be subjected to a mold release treatment in addition to a matte treatment and a corona treatment.

The thickness of the support film is usually 10 μm to 150 μm, preferably 25 to 50 μm. If it is thinner than 10 μm, it becomes difficult to handle. On the other hand, as described above, the support film is usually finally peeled off or removed. Therefore, if the thickness exceeds 150 μm, it is not preferable from the viewpoint of energy saving.
The protective film is peeled off before laminating or hot pressing. As the protective film, the same material as the support film may be used, or a different material may be used. The thickness of the protective film is not particularly limited and may be the same as that of the support film, but more preferably in the range of 1 to 40 μm.

≪Laminating method using the above adhesive film≫
Next, an example of the laminating method using the above adhesive film will be described.
When the adhesive film has a protective film, after removing the protective film, the adhesive film is pressure-bonded to the glass substrate while being pressurized and heated. As for the laminating conditions, it is preferable that the adhesive film and the glass substrate are preheated as necessary, and the crimping temperature (lamination temperature) is preferably 60 ° C. to 140 ° C., and the crimping pressure is preferably 1 to 11 kgf / cm ² . When a vacuum laminator is used, it is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the laminating method may be a batch method or a continuous method using a roll.
As described above, the adhesive film is laminated on the glass substrate and then cooled to around room temperature. The support film is peeled off as needed.

<Manufacturing method of laminate by coating>
There is no particular limitation on the method for producing the laminate by coating. For example, the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed. The resin composition layer is formed by applying this varnish to a glass substrate and drying the organic solvent by heating, blowing hot air, or the like. This resin composition layer may be further semi-cured. In this way, the laminate can be manufactured.

[Laminate board]
The laminated board of the present invention is a laminated board including one or more resin cured product layers and one or more glass substrate layers, and the resin cured product layer has a resin composition containing a thermosetting resin and an inorganic filler. It is made of a cured product of a material, and the glass substrate layer is 10 to 95% by volume based on the entire laminated plate.
It is preferable that this laminated board has a structure in which the resin composition layer of the above-mentioned laminated body is a cured resin layer.
The size of the laminated board of the present invention is preferably selected in the range of width 10 mm to 1000 mm and length 10 mm to 3000 mm (when used in a roll, the length is appropriately applied). In particular, a width of 25 mm to 550 mm and a length of 25 mm to 550 mm are more preferable from the viewpoint of handleability.
The thickness of the laminated board of the present invention is preferably selected in the range of 36 μm to 20 mm depending on the application. The thickness of the laminated board is more preferably 50 to 1000 μm, further preferably 100 to 500 μm, and even more preferably 120 to 300 μm.
The details of the glass substrate layer and the resin composition are as described in the above description of the laminate.

<Resin cured product layer>
The thickness of the cured resin layer is preferably 3 to 200 μm. When it is 3 μm or more, cracking of the laminated plate is suppressed. When it is 200 μm or less, the thickness of the glass substrate becomes relatively large, and the laminated plate can have a low coefficient of thermal expansion and a high elastic modulus. From this point of view, the thickness of the cured resin layer is more preferably 3 to 150 μm, further preferably 3 to 100 μm, even more preferably 5 to 50 μm, and even more preferably 5 to 30 μm. .. However, since the appropriate range of the thickness of the cured resin layer differs depending on the thickness of the glass substrate layer, the number of layers, the type of the cured resin layer, and the number of layers, it is possible to adjust the thickness as appropriate.
The storage elastic modulus of this cured resin layer at 40 ° C. is preferably 1 to 80 GPa. When it is 1 GPa or more, the glass substrate layer is protected and cracking of the laminated plate is suppressed. When it is 80 GPa or less, the stress due to the difference in the coefficient of thermal expansion between the glass substrate layer and the cured resin layer is suppressed, and warpage and cracking of the laminated plate are suppressed. From this point of view, the storage elastic modulus of the cured resin layer is more preferably 3 to 70 GPa, further preferably 5 to 60 GPa, still more preferably 10 to 50 GPa, still more preferably 20 to 50 GPa. is there.
A metal foil such as copper, aluminum or nickel may be provided on one side or both sides of the laminated plate. The metal foil is not particularly limited as long as it is used for electrical insulating material.

<Interlayer insulation layer>
The laminated board may have an interlayer insulating layer. This interlayer insulating layer is obtained, for example, by curing the interlayer insulating composition layer in the above-mentioned laminate.
As a structure when the laminated board has an interlayer insulating layer in this way, for example,
It may have a three-layer structure such as a glass substrate layer / a cured resin layer / an interlayer insulating layer.
It may have a five-layer structure such as an interlayer insulating layer / a cured resin layer / a glass substrate layer / a cured resin layer / an interlayer insulating layer. Other than the above example, the structure is not particularly limited to the above example as long as the composition for interlayer insulation can be arranged between the conductor layer and the laminate of the present invention.

<Characteristics of laminated board>
The storage elastic modulus of the laminated plate at 40 ° C. is preferably 10 to 70 GPa, more preferably 20 to 60 GPa, still more preferably 25 to 50 GPa, and more, from the viewpoint of suppressing warpage and cracking of the laminated plate. More preferably, it is 25 to 45 GPa.
The average coefficient of thermal expansion of the laminated board in the range of 50 to 120 ° C. is preferably 1 to 10 ppm / ° C., more preferably 2 to 8 ppm / ° C. from the viewpoint of suppressing warpage and cracking of the laminated board. It is even more preferably 2 to 6 ppm / ° C, even more preferably 2 to 5 ppm / ° C.
The average coefficient of thermal expansion of the laminated board in the range of 120 to 190 ° C. is preferably 1 to 15 ppm / ° C., more preferably 2 to 10 ppm / ° C. from the viewpoint of suppressing warpage and cracking of the laminated board. It is more preferably 2 to 8 ppm / ° C, still more preferably 2 to 6 ppm / ° C.

<Ratio of each layer in the laminated board>
The cured resin layer of the present invention is preferably 5 to 60% by volume, preferably 5 to 55% by volume, based on the entire laminated plate, from the viewpoint of obtaining a laminated plate having a low coefficient of thermal expansion and a high elastic modulus. It is more preferably 10 to 50% by volume, further preferably 20 to 40% by volume.
The glass substrate layer of the present invention is preferably 20 to 90% by volume, preferably 30 to 85% by volume, based on the entire laminated plate, from the viewpoint of obtaining a laminated plate having a low coefficient of thermal expansion and a high elastic modulus. It is more preferably 35 to 80% by volume, and even more preferably 40 to 75% by volume.
When the laminated board has an interlayer insulating layer, the interlayer insulating layer is preferably 1 to 20% by volume, more preferably 2 to 15% by volume, based on the entire laminated board. It is more preferably 10% by volume.
When the laminated board has an adhesive layer, the adhesive layer is preferably 1 to 20% by volume, more preferably 2 to 15% by volume, and 3 to 10% by volume with respect to the entire laminated board. It is more preferably by volume.

[Manufacturing method of laminated board]
There is no particular limitation on the method for manufacturing the above-mentioned laminated board. Next, a specific example of the method for manufacturing the laminated board will be described.
<Production example by heat curing of laminated body>
In the laminate obtained by the above-mentioned lamination, a laminate can be produced by peeling off the support film, if necessary, and then heat-curing the resin composition layer.
The conditions for heat curing are selected in the range of 20 minutes to 80 minutes at 150 ° C. to 220 ° C., and more preferably 30 minutes to 120 minutes at 160 ° C. to 200 ° C. When a support film that has undergone a mold release treatment is used, the support film may be peeled off after being heat-cured.
According to this method, it is not necessary to pressurize during the production of the laminated board, so that cracks are suppressed during the production.

<Manufacturing example by press method>
Further, the laminated board according to the present invention can be manufactured by a pressing method.
For example, a laminated board can be manufactured by heating, pressurizing, and curing the laminated body obtained by the above-mentioned lamination by a pressing method.
Further, the adhesive film main body obtained by removing the support film and the protective film from the adhesive film and / or the adhesive film and the glass substrate are superposed, and are laminated by heating, pressurizing and curing by a pressing method. It is also possible to manufacture a board.
Further, a laminated plate can also be manufactured by superimposing a glass substrate coated with a resin composition and drying it in a B stage state, and heating, pressurizing and curing by a pressing method.

[Multi-layer laminate and its manufacturing method]
The multilayer laminated board of the present invention is a multilayer laminated board including a plurality of laminated boards, and at least one laminated board is the laminated board of the present invention described above.
There is no particular limitation on the manufacturing method of this multilayer laminated board.
For example, a plurality of the above-mentioned laminated plates may be laminated via an adhesive film main body obtained by removing the support film and the protective film from the above-mentioned adhesive film to form a multilayer.
Alternatively, a multi-layer laminated board can be manufactured by laminating a plurality of (for example, 2 to 20) laminated bodies and molding them. Specifically, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. are used, and the temperature is about 100 to 250 ° C., the pressure is about 2 to 100 MPa, and the heating time is about 0.1 to 5 hours. Can be molded.

[Printed wiring board and its manufacturing method]
The printed wiring board of the present invention has the above-mentioned laminated board or multi-layer laminated board and wiring provided on the surface of the laminated board or multi-layer laminated board.
Next, a method of manufacturing this printed wiring board will be described.

<Formation of beer halls, etc.>
If necessary, the above laminated plate is drilled by a method such as drilling, laser, plasma, or a combination thereof to form via holes and through holes. As the laser, a carbon dioxide gas laser, a YAG laser, a UV laser, an excimer laser and the like are generally used. After the formation of via holes and the like, desmear treatment may be performed using an oxidizing agent. Preferable oxidants are permanganate (potassium permanganate, sodium permanganate, etc.), permanganate, ozone, hydrogen peroxide / sulfuric acid (ie, a mixture of hydrogen peroxide and sulfuric acid), and nitrate. Therefore, an aqueous solution of sodium hydroxide (an aqueous solution of alkaline permanganate) such as potassium permanganate and sodium permanganate is more preferable.

<Formation of conductor layer>
Next, a conductor layer is formed on the cured resin layer on the surface of the laminated plate by dry plating or wet plating.
As the dry plating, known methods such as thin film deposition, sputtering, and ion plating can be used.
In the case of wet plating, first, the surface of the cured tree resin layer of the laminated board is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, etc. Roughening is performed with an oxidizing agent such as nitric acid to form an uneven anchor. As the oxidizing agent, an aqueous solution of sodium hydroxide (aqueous solution of alkaline permanganate) such as potassium permanganate and sodium permanganate is particularly preferably used. This roughening treatment may also serve as the above-mentioned desmear treatment. Next, the conductor layer is formed by a method that combines electroless plating and electrolytic plating. It is also possible to form a plating resist having a pattern opposite to that of the conductor layer, and to form the conductor layer only by electroless plating.
When a laminate having a support film made of a metal foil on the surface is used, the step of forming the conductor layer can be omitted.

<Formation of wiring pattern>
As a method for subsequent pattern formation, for example, a known subtractive method, semi-additive method, or the like can be used.

[Multilayer printed wiring board and its manufacturing method]
As one form of the printed wiring board described above, a plurality of laminated boards having a wiring pattern formed as described above may be laminated to form a multilayer printed wiring board.
In order to manufacture this multilayer printed wiring board, a plurality of laminated boards having the above wiring pattern formed are laminated via the above-mentioned adhesive film to form multiple layers. After that, through holes or blind via holes are formed by drilling or laser processing, and interlayer wiring is formed by plating or conductive paste. In this way, a multilayer printed wiring board can be manufactured.

[Laminated plates with metal foil and multilayer laminated plates, and their manufacturing methods]
The laminated plate and the multilayer laminated plate may be a laminated plate with a metal foil and a multilayer laminated plate having a metal foil such as copper, aluminum, or nickel on one side or both sides.
There is no particular limitation on the method for manufacturing the laminated plate with metal foil. For example, as described above, by using a metal foil as the support film, a laminated board with a metal foil can be manufactured. Further, by laminating one or a plurality of laminated bodies (for example, 2 to 20 sheets) obtained by the above-mentioned laminating or coating, and arranging metal foils on one side or both sides thereof, a metal foil is attached. Laminated plates can also be manufactured.
As the molding conditions, the method of laminated board for electrical insulating material or multi-layer board can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. are used, and the temperature is about 100 to 250 ° C. and the pressure is 2 to 2. It can be molded in the range of about 100 MPa and the heating time of about 0.1 to 5 hours.
<Evaluation method of coefficient of thermal expansion>
The coefficient of thermal expansion of the laminated plate can be measured using a device such as a thermomechanical analyzer (TMA: Thermal Mechanical Analysis), a temperature-dependent three-dimensional displacement measuring device (DIC: Digital Image Correlation), or a laser interferometry method.
<Evaluation method of elastic modulus>
The elastic modulus of the laminated plate can be measured as a static elastic modulus, including the measurement of the storage elastic modulus by a wide-area viscoelasticity measuring device. The flexural modulus can be determined by performing a three-point bending test or the like.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these descriptions.
In addition, in Examples and Comparative Examples, "part" and "%" mean "part by mass" and "% by mass", respectively.
Further, FIG. 1 is a schematic cross-sectional view illustrating the manufacturing methods of Examples 1 to 2 and 4. FIG. 2 is a schematic cross-sectional view illustrating the manufacturing method of Example 5.

[Example 1]
<Manufacturing of resin film (laminate of composition layer 2 for interlayer insulation and support film 1) 3>
Nihon Kayaku Co., Ltd. as a thermosetting resin for 135.4 parts of polyamide resin "BPAM-155" (product name) manufactured by Nippon Kayaku Co., Ltd., which was dissolved in a dimethylacetamide solvent to a concentration of 10%. 62.0 parts of epoxy resin "NC3000-H" (trade name, concentration 100%), and triazine-containing phenolic novolak resin "LA-1356-60P" (trade name, concentration 60) manufactured by DIC Co., Ltd. as a curing agent. %) 23.5 parts, 2-phenylimidazole "2PZ" (trade name, concentration 100%) manufactured by Shikoku Kasei Kogyo Co., Ltd. as a curing accelerator 0.6 parts, manufactured by Nippon Aerosil Co., Ltd. as an inorganic filler. 8.8 parts of fumed silica "AEROSIL R972" (trade name, concentration 100%, average particle size of primary particles: 16 nm, specific surface area by BET method: 110 ± 20 m ² / g), BYK Chemie as other components. After adding 3.6 parts of polyester-modified polydimethylsiloxane "BYK-310" (trade name, concentration 25%) manufactured by Japan Co., Ltd., 314.3 parts of dimethylacetamide solvent was added, and dissolved, mixed, and bead mill dispersed. The treatment was performed to prepare a varnish.
As the support film 1, a polyethylene terephthalate film (PET film) having a thickness of 38 μm was used, and this varnish was applied and dried with a comma coater. The coating thickness is set to 5 μm, and the drying temperature is set to 140 ° C. and the drying time is set to 3 minutes to form the interlayer insulating composition layer 2 on the support film 1. A resin film 3 having a width of 270 mm was obtained (FIG. 1 (a)).

<Manufacturing of varnish for resin composition layer>
31.8 parts of epoxy resin "NC3000-H" (trade name, concentration 100%) manufactured by Nippon Kayaku Co., Ltd. as a thermosetting resin, and triazine-containing cresol novolac "LA-3018-" manufactured by DIC Co., Ltd. as a curing agent. 7.2 parts of "50P" (trade name, concentration; 50%) and 5.1 parts of "HCA-HQ" (trade name, concentration 100%) manufactured by Sanko Co., Ltd., which is a phosphorus-containing phenolic resin, DIC 4.4 parts of phenol novolac "TD2131" (concentration 100%) manufactured by Shikoku Kasei Kogyo Co., Ltd. as a curing accelerator 1-cyanoethyl-2-phenylimidazolium trimerite "2PZCNS-PW" (product) A silica filler "SO" manufactured by Admafine Techno Co., Ltd., which has been treated with an aminosilane coupling agent in a methylisobutylketone solvent so that the solid content is 70% as an inorganic filler with 0.1 part (name, concentration 100%). -C2 "(trade name, concentration 100%, average particle diameter of primary particles: 500 nm, specific surface area by BET method: 6.8 m ² / g) was added in 78.6 parts, and then as an additional solvent. 42.7 parts of methyl ethyl ketone was blended and subjected to dissolution, mixing, and bead mill dispersion treatment to prepare a varnish for the resin composition layer.

<Manufacturing of Adhesive Film (Support Film 1 / Composition Layer 2 for Interlayer Insulation / Resin Composition Layer 4) 5a>
The adhesive film 5a was produced by forming the resin composition layer 4 on the resin film 3.
As a method, the above resin film 3 (support film 1 / interlayer insulation composition layer 2) is used, and a varnish for the resin composition layer is applied and dried on the interlayer insulation composition layer 2 side with a comma coater. did. The coating thickness is set to 20 μm (composition layer 2 for interlayer insulation; 5 μm, resin composition layer 4; 15 μm setting), and the drying temperature is set to 105 ° C. and the drying time is set to 1.2 minutes. By forming the resin composition layer 4, an adhesive film 5a having a width of 270 mm was obtained (FIG. 1 (b)).

<Manufacturing of laminated board (interlayer insulation layer / resin cured product layer / glass substrate layer / resin cured product layer / interlayer insulation layer)>
As the glass substrate layer 6, an ultra-thin glass film "OA-10G" (trade name, thickness 100 μm, 250 × 250 mm) manufactured by Nippon Electric Glass was used. On both surfaces on the glass substrate layer 6, an adhesive film 5 a of the its resin composition layer 4 is disposed so as to contact the glass substrate layer 6, a batch-type vacuum pressure laminator "MVLP-500" (name Laminated by laminating using (trade name) manufactured by Kikai Co., Ltd. (FIGS. 1 (c) and 1 (d)). At this time, the degree of vacuum was 30 mmHg or less, the temperature was set to 90 ° C., and the pressure was set to 0.5 MPa.
After cooling to room temperature, the support film 1 was peeled off and cured in a dry air set at 180 ° C. for 60 minutes. By this curing, the interlayer insulating composition layer 2 and the resin composition layer 4 became the interlayer insulating layer 2a and the resin cured product layer 4a, respectively. In this way, a laminated plate having a five-layer structure (interlayer insulation layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer) 7a was obtained (FIG. 1 (e)).

[Example 2]
<Manufacturing of adhesive film (support film / composition layer for interlayer insulation / resin composition layer) 5b>
Same as the adhesive film 5a of Example 1 except that the coating thickness of the varnish was set to 40 μm (setting of composition layer 2 for interlayer insulation; 5 μm, resin composition layer 4; 35 μm) instead of 20 μm. An adhesive film 5b having a size of 250 mm × 250 mm was obtained.
<Manufacturing of laminated board (interlayer insulation layer / resin cured product layer / glass substrate layer / resin cured product layer / interlayer insulation layer)>
The same operation as in Example 1 was performed except that the above-mentioned adhesive film 5b was used instead of the adhesive film 5a, and a five-layer structure laminated plate (interlayer insulation layer / resin cured product layer / glass substrate layer / resin cured product) was performed. Layer / interlayer insulation layer) was obtained.

[Example 3]
<Manufacturing of laminated boards (interlayer insulation layer / resin cured product layer / interlayer insulation layer / resin cured product layer / glass substrate layer / resin cured product layer / interlayer insulating layer / resin cured product layer / interlayer insulating layer)>
As the glass substrate, an ultra-thin glass film "OA-10G" (trade name, thickness 100 μm, 250 × 250 mm) manufactured by Nippon Electric Glass was used. The adhesive film 5b is placed on both sides of the glass substrate so that the cured resin layer is in contact with the glass substrate, and a batch type vacuum pressurizing laminator "MVLP-500" (manufactured by Meiki Co., Ltd.) Name) was used for laminating. At this time, the degree of vacuum was 30 mmHg or less, the temperature was set to 90 ° C., and the pressure was set to 0.5 MPa. After cooling to room temperature, the support film was peeled off.
The adhesive film 5b is placed on the interlayer insulating composition layer exposed by peeling of the support film so that the resin cured product layer is in contact with the adhesive film, and a batch type vacuum pressure laminator "MVLP-500" ( Laminated by laminating using a famous machine Co., Ltd. (trade name). At this time, the degree of vacuum was set to 30 mmHg or less, the temperature was set to 65 ° C, and the pressure was set to 0.5 MPa.
After cooling to room temperature, the support film is peeled off and cured in a dry air set at 180 ° C. for 60 minutes to form a 9-layer laminated board (interlayer insulation layer / resin cured product layer / interlayer insulation layer / resin cured product). A layer / glass substrate layer / cured resin layer / interlayer insulating layer / cured resin layer / interlayer insulating layer) was obtained.
[Example 4]
<Manufacturing of adhesive film (support film / composition layer for interlayer insulation / resin composition layer) 5c>
Same as the adhesive film 5a of Example 1 except that the coating thickness of the varnish was set to 30 μm (setting of composition layer 2 for interlayer insulation; 5 μm, resin composition layer 4; 25 μm) instead of 20 μm. To obtain an adhesive film 5c having a width of 270 mm.
<Manufacturing of laminated board (interlayer insulation layer / resin cured product layer / glass substrate layer / resin cured product layer / interlayer insulation layer)>
The same operation as in Example 1 was performed except that the above-mentioned adhesive film 5c was used instead of the adhesive film 5a and 150 μm in thickness was used instead of 100 μm in thickness as the glass substrate 6, and the five-layer structure was laminated. A plate (interlayer insulation layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer) was obtained.
[Example 5]
<Manufacturing of varnish for resin composition layer>
Nihon Kayaku Co., Ltd. as a thermosetting resin for 135.4 parts of polyamide resin "BPAM-155" (product name) manufactured by Nippon Kayaku Co., Ltd., which was dissolved in a dimethylacetamide solvent to a concentration of 10%. 62.0 parts of epoxy resin "NC3000-H" (trade name, concentration 100%), and triazine-containing phenolic novolak resin "LA-1356-60P" (trade name, concentration 60) manufactured by DIC Co., Ltd. as a curing agent. %) 23.5 parts, 2-phenylimidazole "2PZ" (trade name, concentration 100%) manufactured by Shikoku Kasei Kogyo Co., Ltd. as a curing accelerator 0.6 parts, manufactured by Nippon Aerosil Co., Ltd. as an inorganic filler. 4.8 parts of fumed silica "AEROSIL R972" (trade name, concentration 100%, average particle size of primary particles: 16 nm, specific surface area by BET method: 110 ± 20 m ² / g), BYK Chemie as other components After adding 1.7 parts of polyester-modified polydimethylsiloxane "BYK-310" (trade name, concentration 25%) manufactured by Japan Co., Ltd., 66.3 parts of dimethylacetamide solvent was further added. Then, a uniform resin varnish was obtained using a disperser (nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).
<Manufacturing of adhesive film (support film 1 / resin composition layer 4) 5d>
An adhesive film 5d was produced by forming the resin composition layer 4 on the support film 1 (FIG. 2A).
As a method, a resin varnish is used as a support film on a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Co., Ltd., trade name) so that the thickness after drying is 20 μm. Was coated with a comma coater and dried at 140 ° C. for 5 minutes to form a 270 mm wide adhesive film 5d composed of the resin composition layer 4 and the support film 1.
<Manufacturing of laminated board (resin cured product layer / glass substrate layer / resin cured product layer)>
As the glass substrate layer 6, an ultra-thin glass film "OA-10G" (trade name, thickness 150 μm, 250 × 250 mm) manufactured by Nippon Electric Glass was used. The adhesive film 5d is arranged on both sides of the glass substrate layer 6 so that the resin composition layer 4 abuts on the glass substrate layer 6, and a batch type vacuum pressurizing laminator "MVLP-500" (famous machine). 2 (b), (c)) laminated by laminating using (trade name) manufactured by Co., Ltd. At this time, the degree of vacuum was set to 30 mmHg or less, the temperature was set to 120 ° C., and the pressure was set to 0.5 MPa.
After cooling to room temperature, the support film 1 was peeled off and cured in a dry air set at 180 ° C. for 60 minutes. By this curing, the resin composition layer 4 became the resin cured product layer 4a. In this way, a laminated board (resin cured product layer / glass substrate layer / resin cured product layer) 7b having a three-layer structure was obtained (FIG. 2 (d)).

[Comparative Example 1]
<Manufacturing of resin film>
A resin film was produced by performing the same operation as that of the resin film 3 of Example 2 except that the inorganic filler (fumed silica) was not added.
<Manufacturing of varnish>
A varnish was produced by performing the same operation as the varnish for the resin composition layer of Example 2 except that the inorganic filler (silica filler) was not added.
<Manufacturing of adhesive film C>
The same operation as in Example 2 was performed except that the above resin film and varnish were used in place of the resin film 3 and the varnish for the resin composition layer of Example 2, and the adhesive film (support film / interlayer insulation) was performed. Composition layer / resin composition layer) was produced.
<Manufacturing of laminated board (interlayer insulation layer / resin cured product layer / glass substrate layer / resin cured product layer / interlayer insulation layer)>
The same operation as in Example 2 was performed except that the adhesive film was used in place of the adhesive film 5a in Example 2, and a laminated plate having a five-layer structure (interlayer insulation layer / cured resin layer / glass substrate layer / resin) was performed. A cured product layer / interlayer insulating layer) was obtained.

[Reference example 1]
Next, a laminated board laminated board using a prepreg, which is generally used as a laminated board for a semiconductor package or a printed wiring board, is manufactured as follows.
<Production of a solution of a resin composition having an unsaturated maleimide group>
4,4'-bis (4-aminophenoxy) biphenyl: 69.10 g, bis (4) in a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, agitator, and a moisture meter with a reflux condenser. -Maleimidephenyl) Sulfone: 429.90 g, p-aminophenol: 41.00 g, and propylene glycol monomethyl ether: 360.00 g are added and reacted at reflux temperature for 2 hours to have an acidic substituent and an unsaturated maleimide group. A solution of the resin composition was obtained.

<Manufacturing of varnish containing thermosetting resin composition>
(1) As the curing agent (A), the above-mentioned solution of the resin composition having an unsaturated maleimide group,
(2) As the thermosetting resin (B), a bifunctional naphthalene type epoxy resin [manufactured by Dainippon Ink and Chemicals Co., Ltd., trade name, HP-4032D],
(3) As the modified imidazole (C), isocyanate mask imidazole [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: G8009L],
(4) As the inorganic filler (D), fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC, concentration 100%, average particle diameter of primary particles: 500 nm, specific surface area by BET method: 6.8 m ² / G],
(5) As the phosphorus-containing compound (E) that imparts flame retardancy, a phosphorus-containing phenol resin [manufactured by Sanko Kagaku Co., Ltd., trade name: HCA-HQ, phosphorus content 9.6% by mass],
(6) As the chemically roughened compound (F), crosslinked acrylonitrile butadiene rubber (NBR) particles [[manufactured by JSR Co., Ltd., trade name: XER-91],
(7) As a diluting solvent, methyl ethyl ketone,
Was mixed at the blending ratio (parts by mass) shown in Table 1 to prepare a uniform varnish (G) having a resin content (total of resin components) of 65% by mass.

<Manufacture of prepreg made of thermosetting resin composition>
The above varnish (G) was impregnated and coated on E glass cloths having different thicknesses, and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg. As the type of E glass cloth, IPC standard 2116 of Asahi Kasei E-Materials was used, and a 250 mm × 250 mm prepreg was prepared. The resin content of the prepared prepreg was 50% by mass. Three of these prepregs were combined, electrolytic copper foils having a thickness of 12 μm were arranged one above the other, and pressed at a pressure of 3.0 MPa and a temperature of 235 ° C. for 120 minutes to prepare a copper-clad laminate.

[Measurement]
The performance of the laminated boards obtained in the above Examples, Comparative Examples and Reference Examples was measured and evaluated by the following methods.
(1) Measurement of coefficient of thermal expansion A 4 mm × 30 mm test piece was cut out from the laminated plate. When a copper-clad laminate was used, the copper foil was removed by immersing it in a copper etching solution, and then the test piece was cut out.
The evaluation was made by observing the thermal expansion characteristics of the test piece to less than Tg using a TMA test apparatus (TMA2940, manufactured by DuPont). Specifically, the temperature rise rate is 5 ° C./min, 1st run, the measurement range is 20 to 200 ° C., the 2nd run measurement range is -10 to 280 ° C., the weight is 5 g, and the chuck distance is 10 mm. The average coefficient of thermal expansion in the range of ° C. and the range of 120 to 190 ° C. was determined, respectively. The results are shown in Table 2.
(2) Measurement of storage elastic modulus A 4 mm × 30 mm test piece was cut out from the laminated plate. When a copper-clad laminate was used, the copper foil was removed by immersing it in a copper etching solution, and then the test piece was cut out.
Using a wide-area viscoelasticity measuring device (DVE-V4 type manufactured by Rheology), the tensile storage elastic modulus at 40 ° C. is measured under the conditions of a span of 20 mm, a frequency of 10 Hz, and a vibration displacement of 1 to 3 μm (stop excitation). did. The results are shown in Table 2.

As is clear from Table 2, Examples 1 to 5 of the present invention are excellent in low thermal expansion at 50 to 120 ° C. and high elasticity at 40 ° C. Further, even in the high temperature region of 120 to 190 ° C., the coefficient of thermal expansion is higher in Reference Example 1 than in the low temperature region (50 to 120 ° C.), whereas in Examples 1 to 5, it is almost the same as in the low temperature region. It can be seen that it has a degree of low thermal expansion. Therefore, Example 1 of the present invention maintains low thermal expansion not only in the low temperature region but also in the high temperature region.

1 Support film 2 Interlayer insulation composition layer 2a Interlayer insulation layer 3 Resin film 4 Resin composition layer 4a Resin cured product layer 5a, 5b, 5c, 5d Adhesive film 6 Glass substrate layer 7a, 7b Laminated plate

Claims (14)

A laminated body for a printed wiring board including one or more resin composition layers and one or more glass substrate layers.
The resin composition layer is composed of a resin composition containing a thermosetting resin and silica .
The content of silica in the resin composition is 24 to 85% by mass.
The glass substrate layer is a layer made of a glass film.
The glass substrate layer is 10 to 95% by volume based on the entire laminated body for the printed wiring board.
The thickness of the glass substrate layer is 80 to 200 μm.
A laminated body for a printed wiring board in which the thickness of the resin composition layer is 40 μm or less. The laminated body for a printed wiring board according to claim 1, wherein the thickness of the glass substrate layer is 80 to 150 μm. The thermosetting resin is an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, and the like. The laminate for a printed wiring board according to claim 1 or 2, which is one kind or two or more kinds selected from a triazine resin and a melamine resin. The laminated body for a printed wiring board according to any one of claims 1 to 3, wherein the content of silica in the resin composition is 44 to 82% by mass . A laminated board for a printed wiring board including one or more cured resin layers and one or more glass substrate layers.
The cured resin layer is composed of a cured product of a resin composition containing a thermosetting resin and silica .
The content of silica in the resin composition is 24 to 85% by mass.
The glass substrate layer is a layer made of a glass film.
The glass substrate layer is 10 to 95% by volume based on the entire laminated board for the printed wiring board.
The thickness of the glass substrate layer is 80 to 200 μm.
A laminated board for a printed wiring board in which the thickness of the cured resin layer is 40 μm or less. The laminated board for a printed wiring board according to claim 5, wherein the storage elastic modulus at 40 ° C. is 10 GPa to 70 GPa. The laminated board for a printed wiring board according to claim 5 or 6, which is obtained by heating the laminated body for a printed wiring board according to any one of claims 1 to 4. A multi-layer laminated board for a printed wiring board including a plurality of laminated boards.
A multilayer laminated board for a printed wiring board, wherein at least one laminated board is a laminated board for a printed wiring board according to any one of claims 5 to 7. A printed wiring board having a laminated board for a printed wiring board according to any one of claims 5 to 7 and wiring provided on the surface of the laminated board for a printed wiring board. A printed wiring board having a multilayer laminated board for a printed wiring board according to claim 8 and wiring provided on the surface of the multilayer laminated board for a printed wiring board. The method for manufacturing a laminated board for a printed wiring board according to any one of claims 5 to 7, further comprising a step of forming a cured resin layer on the surface of a glass substrate. The method for producing a laminated board for a printed wiring board according to claim 11, wherein the resin cured product layer forming step is a step of applying the resin composition on the glass substrate, and then drying and curing the resin composition. The lamination for a printed wiring board according to claim 11, wherein the resin cured product layer forming step is a step of laminating a film made of the resin composition on the glass substrate using a vacuum laminator or a roll laminator and curing the film. How to make a board. The method for producing a laminated board for a printed wiring board according to claim 11, wherein the resin cured product layer forming step is a step of arranging a film made of the resin composition on the glass substrate, pressing the film, and curing the film.