JP6295663B2 - LAMINATE, LAMINATE, MULTILAYER LAMINATE, PRINTED WIRING BOARD AND METHOD FOR PRODUCING LAMINATE - Google Patents

Description

  The present invention relates to a laminated body and a laminated board suitable for semiconductor packages and printed wiring boards, a printed wiring board using the laminated board, a multilayer laminated board, and a method for producing the laminated board.

In recent years, demands for thinner and lighter electronic devices have become stronger, and semiconductor packages and printed wiring boards are becoming thinner and higher in density. In order to stably mount electronic components corresponding to these reductions in thickness and density, it is important to suppress warpage that occurs during mounting.
One of the main causes of warpage occurring in the semiconductor package during mounting is a difference in thermal expansion coefficient between the laminated plate used in the semiconductor package and the silicon chip mounted on the surface of the laminated plate. For this reason, efforts are being made to bring the coefficient of thermal expansion close to the coefficient of thermal expansion of the silicon chip, that is, to lower the coefficient of thermal expansion, in the laminate for semiconductor packages. Further, since the low elastic modulus of the laminated plate also causes warpage, it is also effective to increase the elasticity of the laminated plate in order to reduce warpage. Thus, in order to reduce the warpage of the laminate, it is effective to reduce the expansion coefficient and increase the elasticity of the laminate.

Various methods for lowering the thermal expansion coefficient and increasing the elasticity of the laminated board are conceivable. Among them, it is known to lower the thermal expansion coefficient of the resin for the laminated board and to increase the inorganic filler in the resin. In particular, the high filling of the inorganic filler is a technique that can be expected to improve the heat resistance and flame retardancy as well as the low thermal expansion coefficient (Patent Document 1). However, increasing the filling amount of the inorganic filler in this way is known to cause a decrease in insulation reliability, insufficient adhesion between the resin and the wiring layer formed on the surface, and press molding failure during the production of the laminate. Therefore, there is a limit to high filling.
In addition, attempts have been made 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 wiring boards and increasing the Tg to reduce the coefficient of thermal expansion is generally used (Patent Documents 2 and 3). However, increasing the crosslinking density shortens the molecular chain between the functional groups, but shortening the molecular chain beyond a certain level has a limit in terms of reaction and causes a problem of causing a decrease in resin strength. . For this reason, there is a limit to the reduction in the coefficient of thermal expansion by the method of increasing the crosslinking density.
As described above, in the conventional laminated plate, a low thermal expansion coefficient and a high elasticity have been achieved by high filling with an inorganic filler and adoption of a low thermal expansion coefficient resin, but the limit has been 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 the electronic component (silicon chip), and the resin and the glass film are pressed and laminated. Attempts have been made to reduce the shock stress (Patent Document 4), but since the elastic modulus of the resin layer is low and the thermal expansion coefficient is high, it is insufficient to realize a low warpage of the substrate.

JP 2004-182851 A JP 2000-243864 A JP 2000-114727 A Japanese Patent No. 4657554

As described above, since the substrate obtained by the manufacturing method of Patent Document 4 still has a low elastic modulus and a high coefficient of thermal expansion, it is insufficient for realizing a low warpage of the substrate.
The present invention has been made in view of such circumstances, and has a low thermal expansion coefficient and a high elastic modulus, can suppress warpage, and is less prone to cracking, and can be used to manufacture 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 the laminate and the multilayer laminate, and a method for producing the laminate.

Patent Document 4 has no description of containing an inorganic filler in a resin in a substrate formed by laminating a glass film and a resin. From the description of Patent Document 4, it is considered that the resin should contain an inorganic filler.
That is, in patent document 4, it is set as the essential structure that the thermal expansion effect | action of the whole board | 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. To that end, it is necessary to keep the elastic modulus of the resin low (if the resin has a high elastic modulus, this high elasticity The thermal expansion effect of the entire substrate is greatly affected by the resin of the rate). On the other hand, if the resin contains an inorganic filler, the resin has a high elastic modulus. Therefore, from the description in Patent Document 4, it should be avoided that the resin contains an inorganic filler.
Moreover, when an inorganic filler is contained in the resin of Patent Document 4, it can be considered that the glass substrate is easily cracked starting from the inorganic filler. Also from this point, in patent document 4, it is estimated that it contains avoiding containing an inorganic filler in resin.
At present, there is no example of a laminate in which an inorganic filler is contained in a resin layer in a laminate of a glass substrate layer and a resin layer as in Patent Document 4.

  Surprisingly, however, the present inventors have conducted extensive research to solve the above problems, and as a result, in the laminate including the resin cured product layer and the glass substrate layer, the resin cured product layer contains an inorganic filler. It was found that a laminate having a low thermal expansion coefficient and a high elastic modulus, suppressing warpage, and hardly causing cracks can be obtained.

This invention is completed based on the said knowledge, Comprising: The following [1]-[12] make it a summary.
[1] A laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a resin composition comprising a thermosetting resin and an inorganic filler. A laminate in which the glass substrate layer is 10 to 95% by volume with respect to the entire laminate.
[2] The laminate according to [1], wherein the glass substrate layer has a thickness of 30 μm to 200 μm.
[3] The thermosetting resin is an epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, The laminate according to [1] or [2], which is one or more selected from silicone resins, triazine resins, and melamine resins.
[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. ] To [3].
[5] A laminate comprising one or more cured resin layers and one or more glass substrate layers, wherein the cured resin layer includes a thermosetting resin and an inorganic filler. The laminated board which consists of 10 to 95 volume% with respect to the said laminated board whole.
[6] The laminate according to [5], wherein a dynamic storage elastic modulus at 40 ° C. is 10 GPa to 70 GPa.
[7] The laminated plate according to [5] or [6] obtained by heating and pressurizing the laminated body according to any one of [1] to [4].
[8] A multilayer laminate including a plurality of laminates, wherein at least one laminate is the laminate 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 comprising 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 board according to any one of [5] to [7], including a resin cured product layer forming step of forming a resin cured product layer on the surface of the glass substrate.
[12] The method for producing a laminated board according to [11], wherein the resin cured material layer forming step is a step of drying and curing after the resin composition is applied on the glass substrate.
[13] The laminate 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 board according to [11], wherein the resin cured product layer forming step is a step of pressing and curing after disposing a film made of the resin composition on the glass substrate.

  According to the present invention, laminates and multilayer laminates that have a low thermal expansion coefficient and a high elastic modulus, can suppress warpage, and are less likely to crack, and laminates suitable for manufacturing these laminates and multilayer laminates And the printed wiring board using these laminated boards and multilayer laminated boards, and the manufacturing method of this laminated board can be provided.

It is typical sectional drawing explaining the manufacturing method of Examples 1-2, 4. 10 is a schematic cross-sectional view illustrating the manufacturing method of Example 5. FIG.

Hereinafter, the laminate, the laminate, the multilayer laminate, the printed wiring board, and the method for producing the laminate of the present invention will be described in detail.
In the present invention, the laminate means that the thermosetting resin that is a constituent component is uncured or semi-cured, and the laminate means that the thermosetting resin that is a constituent component is cured. Means what

[Laminate]
The laminate of the present invention is a laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a thermosetting resin and an inorganic filler. It consists of a thing and the said glass substrate layer is 10-95 volume% with respect to the said laminated body whole.
The size of the laminate of the present invention is selected in the range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll) from the viewpoint of handleability. preferable. In particular, the width is preferably 25 mm to 550 mm and the length is 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, still more preferably 100 to 500 μm, and still more preferably 120 to 300 μm.
Since the laminate 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 low thermal expansion coefficient and a high elastic modulus as much as a silicon chip, It becomes a thing with a low coefficient of thermal expansion and a high elastic modulus, warping is suppressed, and cracks are less likely to occur. In particular, since this laminate has a glass substrate layer with high heat resistance, it has a low thermal expansion in a temperature range from 100 ° C. to less than Tg of the cured resin. Further, since the cured resin layer contains an inorganic filler, the cured resin layer has a low thermal expansion coefficient and a high elastic modulus, and the laminate including the cured resin layer has a lower expansion coefficient and 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 examples thereof include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclohexanes. Examples include pentadiene resin, silicone resin, triazine resin, and melamine resin. Among these, an epoxy resin and a cyanate resin 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 novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene 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 -Type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl ether compounds of polycyclic aromatics such as anthracene And the like. Moreover, the phosphorus containing epoxy resin which introduce | transduced the phosphorus compound into these epoxy resins is mentioned. Among these, biphenylaralkyl type epoxy resins and naphthalene type epoxy resins are preferred from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.
Examples of the cyanate resin include bisphenol type cyanate resins such as novolak 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 triazine. . Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination 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 with respect to the mass obtained by subtracting the content of the inorganic filler from the total amount of the resin composition. 80 mass% is more preferable, 50-80 mass% is still more preferable, and 60-75 mass% is still more preferable.

≪Inorganic filler≫
Examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass.
Of these, silica is preferable from the viewpoint of low thermal expansion, and further, the thermal expansion coefficient is as small as about 0.6 ppm / K, and spherical amorphous silica with little decrease in fluidity when highly filled in a resin is used. More preferred.
The spherical amorphous silica preferably has a cumulative 50% particle size of 0.01 to 10 μm, preferably 0.03 to 5 μm.
Here, the cumulative 50% particle diameter is the particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the powder as 100%. It can be measured with a particle size distribution measuring apparatus using
The content of the inorganic filler in the resin composition is preferably 5 to 75% by volume of the total amount of the resin composition, more preferably 15 to 70% by volume, and further preferably 30 to 70% by volume. 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, and the moldability is excellent with appropriate fluidity. 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 by mass%, for example, when the inorganic filler is silica, the content of silica in the resin composition is preferably 8 to 85 mass% of the resin composition, and is 24 to 82 mass%. It is more preferable, and it is still more preferable that it is 44-82 mass%.
Moreover, a fine wiring can be formed on the cured resin layer of the laminate by using silica (nanosilica) having an average primary particle size of 1 μm or less as the inorganic filler. The nano silica 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 “average primary particle size” here refers to the average particle size of aggregated particles, that is, not the secondary particle size, but the average particle size of single particles that are not aggregated. The average primary particle size can be determined by measuring with, for example, a laser diffraction particle size distribution meter. As such an inorganic filler, fumed silica is preferable.
Furthermore, 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 to improve dispersibility.
When forming fine wiring on the cured resin layer of the laminate, 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 interlayer insulation reliability can be prevented. On the other hand, since the low thermal expansion and high elasticity of the resin composition can be expected by containing the inorganic filler, the content of the inorganic filler is as follows when emphasizing low thermal expansion and high elasticity as well as fine wiring formation: It is preferable to set it as 3-20 mass%, and it is more preferable to set it as 5-20 mass.

≪Other ingredients≫
In addition to the above components, the 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, and the like. Can be added.
Examples of curing agents include, for example, when epoxy resin is used, polyfunctional phenolic compounds such as phenol novolac and cresol novolac; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride Acid anhydrides such as maleic anhydride and maleic anhydride copolymers; polyimides can be used. Several kinds of these curing agents can be used in combination.
Examples of curing accelerators include, for example, epoxy resin curing accelerators such as imidazoles and derivatives thereof; organophosphorus compounds; secondary amines, tertiary amines, and quaternary ammonium salts.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.
Antioxidants include hindered phenols and styrenated phenol antioxidants.
Examples of the photopolymerization initiator include photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones.
Examples of fluorescent whitening agents include fluorescent whitening agents such as stilbene derivatives.
Examples of the adhesion improver include urea compounds such as urea silane 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 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll). In particular, the width of 25 mm to 550 mm and the length of 25 mm to 550 mm are preferable from the viewpoint of handleability.
The thickness per layer of the resin composition layer of the present invention is preferably selected in the range of 3 μm to 200 μm. From the viewpoint of lowering the thermal expansion and increasing the elastic modulus of the laminate and the laminate, the thickness per layer of the resin composition is preferably 3 to 150 μm, more preferably 3 to 100 μm, It is still more preferable that it is 50 micrometers, and it is still more preferable that it is 5-30 micrometers.

<Glass substrate layer>
The thickness per layer of the glass substrate layer is preferably 30 to 200 μm from the viewpoint of thinning the laminate and workability, and the thickness is 50 to 150 μm considering practicality such as ease of handling. Is more preferable, and 80-120 micrometers is still more preferable.
The thickness of a glass substrate layer here refers to the average thickness of a glass substrate layer. The average thickness of the glass substrate layer can be measured using a known thickness measuring instrument such as a micrometer or a film thickness measuring instrument. For example, in the case of a rectangular or square glass substrate layer, the thickness of 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 for the glass substrate layer, glass such as alkali silicate glass, non-alkali glass and quartz glass can be used, but borosilicate glass is preferred 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 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll). 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.
As the thermal expansion coefficient of the glass substrate layer is closer to the thermal expansion coefficient (about 3 ppm / ° C.) of the silicon chip, warpage of the laminated plate or the laminated plate obtained from the laminated body may be suppressed, but preferably 8 ppm / ° C. It is below, More preferably, it is 6 ppm / degrees C or less, More preferably, it is 4 ppm / degrees C or less.
The larger the storage elastic modulus of this glass substrate layer at 40 ° C., the better, but it is preferably 20 GPa or more, more preferably 25 GPa or more, and further preferably 30 GPa or more.
This glass substrate layer is preferably 10 to 95% by volume, more preferably 15 to 90% by volume, and still more preferably 20 to 85% by volume with respect to the entire laminate. When the content of the glass substrate is 10% by volume or more, it is advantageous for obtaining a laminate having low thermal expansion and high elasticity, and conversely, when the content of the glass substrate is 95% by volume or less, workability and This is advantageous in terms of handling properties (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 adhesion to a conductor layer described later.
That is, as described later, when a printed wiring board is manufactured using the laminate of the present invention, a conductor layer may be formed by plating or the like on the surface of the laminate obtained by curing the laminate. Moreover, it may be set as the laminated body and laminated board with metal foil which have metal foil (conductor layer) on the surface. In these cases, a conductor layer may be formed on the resin composition layer or the cured resin layer obtained by curing the resin composition layer, but the interlayer insulating composition is further formed on the resin composition layer or the cured resin layer. A conductor layer may be formed on a physical layer or an interlayer insulating layer obtained by curing the physical layer. In this case, by using a layer having a high adhesiveness to the conductor layer as the interlayer insulating composition layer, the adhesiveness between the laminate and the conductor layer is improved.
In addition, as will be described later, a desmear process may be performed after forming a via hole in the laminated board. In this case, the surface of the laminate (that is, the interlayer insulating layer formed by curing the interlayer insulating composition layer) is excessively uneven by providing an interlayer insulating composition layer having excellent desmear resistance. It becomes possible to prevent the size from becoming large and to form a fine wiring pattern on the surface.

As a structure when the laminate has a composition layer for interlayer insulation in this way, for example,
It may have a three-layer structure such as glass substrate layer / resin composition layer / interlayer insulation composition layer,
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 may be used. The expression “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.
In addition to the above examples, any configuration can be used as long as the composition for interlayer insulation can be disposed between the conductor layer and the laminate of the present invention, and the present invention is not particularly limited to the above examples.

  The material for the interlayer insulating composition layer is not particularly limited. 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 to the conductor layer. Moreover, the composition layer for interlayer insulation may contain the inorganic filler, and does not need to contain it.

<Adhesive layer>
Further, the laminate of the present invention has a resin composition layer containing a thermosetting resin and an inorganic filler, but has an adhesive layer containing a thermosetting resin and no inorganic filler. It doesn't matter. For example, the adhesive layer is disposed between the glass substrate layer and the resin composition layer, and can be used for the purpose of improving the adhesion between the two layers.

<Ratio of each layer in the laminate>
From the viewpoint of obtaining a laminate having a low thermal expansion coefficient and a high elastic modulus, the resin composition layer of the present invention is preferably 5 to 60% by volume, and preferably 5 to 55% by volume with respect to the entire laminate. It is more preferable that it is 10-50 volume%, and it is still more preferable that it is 20-40 volume%.
The glass substrate layer of the present invention is preferably 20 to 90% by volume, and preferably 30 to 85% by volume with respect to the entire laminate, from the viewpoint of obtaining a laminate having a low coefficient of thermal expansion and a high elastic modulus. More preferably, it is more preferably 35 to 80% by volume, and still more preferably 40 to 75% by volume.
In the case where 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 with respect to the entire laminate. More preferably, it is 10 volume%.
In the case where the laminate has an adhesive layer, the adhesive layer is preferably 1 to 20% by volume, more preferably 2 to 15% by volume, with respect to the entire laminate. More preferably, it is volume%.

<Support film and protective film>
Said laminated body may have a support body film and a protective film on the surface. About these support body films and protective films, it demonstrates in detail in description of the manufacturing method of the following laminated body.

[Manufacturing method of laminate]
There is no restriction | limiting in particular in the manufacturing method of the said laminated body, It can manufacture by the lamination to the glass substrate of the film which consists of a resin composition, the application | coating to the glass substrate of a resin composition, etc. Among these, the method using lamination is preferable from the viewpoint of easy production.
Next, each manufacturing method will be described in detail.
<Manufacturing method of laminate by lamination>
Said laminated body can be suitably manufactured by laminating | stacking the adhesive film using the said resin composition, and a glass substrate by pressure lamination like vacuum lamination and roll lamination. This adhesive film will be described later. Moreover, vacuum lamination and roll lamination can be performed using a commercially available vacuum laminator and roll laminator.
In addition, as a thermosetting resin in said resin composition and said composition for interlayer insulation, what fuse | melts below the temperature at the time of lamination is used suitably. For example, when laminating using a vacuum laminator or a roll laminator, since it is generally performed at 140 ° C. or less, the thermosetting resin in the resin composition and the composition for interlayer insulation are melted at 140 ° C. or less. Those that do are preferred.
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 pressure laminator, the above resin composition is generally prepared as an adhesive film.
As an adhesive film used for this invention, what has the following laminated structure is used suitably.
(1) Support film / resin composition layer (2) Support film / interlayer insulation composition layer / resin composition layer In the laminated structure of (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 the adhesion and scratches of foreign matters.
In addition, what remove | excluded the support body film and the protective film from these adhesive films may be called an adhesive film main body.

The adhesive film having the laminated structure (1) to (4) can be produced according to a method known to those skilled in the art.
As an example for producing the adhesive film of the above (1), 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 the varnish using the support film as a support and drying the organic solvent by heating, hot air blowing, or the like.
As an example for producing the adhesive film of (2), a composition layer for interlayer insulation is dissolved in an organic solvent to prepare a varnish. Subsequently, a varnish is apply | coated to a support body film and the organic solvent is dried by heating, hot air spraying, etc., and the composition layer for interlayer insulation is formed. Thereafter, a resin composition layer may be formed on the surface of the interlayer insulating composition layer in the same manner as in the above (1).
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 disposed on the varnish, and the organic solvent of the varnish is dried by heating, hot air blowing, or the like. Thus, a resin composition layer may be formed.
As an example for 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 support film, and heating, hot air blowing, etc. By drying the organic solvent, an interlayer insulation composition layer is formed. Subsequently, the surface of the laminate on the side of the interlayer insulating composition and the surface of the laminate prepared in advance as described in (1) above are brought into contact with each other, and a vacuum laminator or a roll laminator described later is provided. What is necessary is just to laminate using the pressurization laminator like. As another example, an interlayer insulating layer is formed on a support film using a varnish, and then a varnish for a resin composition is applied thereon and a protective film is disposed thereon, by heating, hot air blowing, etc. What is necessary is just to form a resin composition layer by drying the organic solvent of this varnish.

As a coating apparatus for the interlayer insulation composition layer and the resin composition layer, a coating apparatus 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 support film serves as a support when producing an adhesive film, and is usually peeled off or removed when used in producing 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 thereof include metal foil such as foil and aluminum foil. When copper foil is used for the support film, the copper foil can be used as a conductor layer as it is 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 using a thin copper foil, a copper foil with a carrier may be used in order to improve workability.
The support film may be subjected to a release treatment in addition to the mat treatment and the 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, handling becomes difficult. On the other hand, as described above, since the support film is usually finally peeled or removed, a thickness exceeding 150 μm is not preferable from the viewpoint of energy saving.
The protective film is peeled off before lamination or hot pressing. In addition, as a protective film, the same material as a support body film may be used, and 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.

≪Lamination method using the above adhesive film≫
Next, an example of a 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. The lamination is preferably performed by preheating the adhesive film and the glass substrate as necessary, and laminating at a pressure bonding temperature (laminating temperature) of preferably 60 ° C. to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm ² . Moreover, when using a vacuum laminator, it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll.
As described above, after the adhesive film is laminated on the glass substrate, it is cooled to around room temperature. The support film is peeled off as necessary.

<Method for producing laminate by coating>
There is no restriction | limiting in particular in the manufacturing method of the laminated body by application | 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 the varnish to a glass substrate and drying the organic solvent by heating or blowing hot air. This resin composition layer may be further semi-cured. Thus, a laminated body can be manufactured.

[Laminated board]
The laminate of the present invention is a laminate comprising one or more cured resin layers and one or more glass substrate layers, wherein the cured resin layer includes a thermosetting resin and an inorganic filler. It consists of hardened | cured material of a thing, and the said glass substrate layer is 10-95 volume% with respect to the said laminated board whole.
It is preferable that this laminated board has a structure in which the resin composition layer of the above-described laminated body is a resin cured product layer.
The size of the laminate of the present invention is preferably selected in the range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll). 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 laminate of the present invention is preferably selected in the range of 36 μm to 20 mm depending on the application. The thickness of the laminate is more preferably 50 to 1000 μm, still more preferably 100 to 500 μm, and still more preferably 120 to 300 μm.
The details of the glass substrate layer and the resin composition are as described in the description regarding the laminate.

<Resin cured product layer>
The thickness of the resin cured product layer is preferably 3 to 200 μm. If it is 3 μm or more, cracking of the laminate is suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate is relatively increased, so that the thermal expansion coefficient and the high elastic modulus of the laminated plate can be reduced. From this viewpoint, the thickness of the cured resin layer is more preferably 3 to 150 μm, further preferably 3 to 100 μm, still more preferably 5 to 50 μm, and still more preferably 5 to 30 μm. . However, since the appropriate range of the thickness of the cured resin layer varies depending on the thickness and number of layers of the glass substrate layer, and the type and number of layers of the cured resin layer, it can be appropriately adjusted.
The storage elastic modulus at 40 ° C. of the cured resin layer is preferably 1 to 80 GPa. A glass substrate layer is protected as it is 1 GPa or more, and the crack of a laminated board is suppressed. When it is 80 GPa or less, stress due to the difference in coefficient of thermal expansion between the glass substrate layer and the cured resin layer is suppressed, and warpage and cracking of the laminate are suppressed. From this viewpoint, 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, and still more preferably 20 to 50 GPa. is there.
You may have metal foil, such as copper, aluminum, and nickel, on the single side | surface or both surfaces of a laminated board. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.

<Interlayer insulation layer>
The laminate may have an interlayer insulating layer. This interlayer insulating layer is obtained, for example, by curing the interlayer insulating composition layer in the laminate.
As a structure when the laminated plate has an interlayer insulating layer as described above, for example,
A three-layer structure such as glass substrate layer / resin cured product layer / interlayer insulating layer may be used,
A five-layer structure such as an interlayer insulating layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer may be used. In addition to the above examples, any configuration can be used as long as the composition for interlayer insulation can be disposed between the conductor layer and the laminate of the present invention, and the present invention is not particularly limited to the above examples.

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

<Ratio of each layer in the laminate>


From the viewpoint of obtaining a laminated board having a low thermal expansion coefficient and a high elastic modulus, the cured resin layer of the present invention is preferably 5 to 60% by volume, and preferably 5 to 55% by volume with respect to the entire laminated board. It is more preferable that it is 10-50 volume%, and it is still more preferable that it is 20-40 volume%.
The glass substrate layer of the present invention is preferably 20 to 90% by volume, and preferably 30 to 85% by volume with respect to the entire laminate from the viewpoint of obtaining a laminate having a low coefficient of thermal expansion and a high elastic modulus. More preferably, it is more preferably 35 to 80% by volume, and still 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 with respect to the entire laminated board. More preferably, it is 10 volume%.
In the case where the laminate has an adhesive layer, the adhesive layer is preferably 1 to 20% by volume, more preferably 2 to 15% by volume, with respect to the entire laminate. More preferably, it is volume%.

[Manufacturing method of laminate]
There is no restriction | limiting in particular in the manufacturing method of said laminated board. Next, a specific example of a method for manufacturing a laminated board will be described.
<Example of production by heat curing of laminate>
In the laminate obtained by the above-mentioned lamination, a laminate can be produced by peeling the support film as necessary and then heat-curing the resin composition layer.
The conditions for heat curing are selected in the range of 20 to 80 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C. When a support film subjected to a release treatment is used, the support film may be peeled off after being cured by heating.
According to this method, since it is not necessary to pressurize at the time of manufacture of a laminated board, it is controlled that a crack arises at the time of manufacture.

<Example of production by the press method>
Moreover, the laminated board which concerns on this invention can be manufactured by the press method.
For example, a laminate can be produced by curing the laminate obtained by the above-mentioned laminate by heating and pressurizing by a pressing method.
In addition, the adhesive film and / or the adhesive film main body formed by removing the support film and the protective film from the adhesive film, and the glass substrate are overlaid, and heated and pressed by a press method to be cured and laminated. A plate can also be manufactured.
Furthermore, a laminated board can also be manufactured by applying and drying a resin composition on a glass substrate and superimposing them in a B-stage state, followed by heating and pressing by a pressing method and curing.

[Multi-layer laminate and its manufacturing method]
The multilayer laminate of the present invention is a multilayer laminate including a plurality of laminates, and at least one laminate is the aforementioned laminate of the present invention.
There is no restriction | limiting in particular in the manufacturing method of this multilayer laminated board.
For example, a plurality of the above-described laminated plates may be laminated by way of an adhesive film body obtained by removing the support film and the protective film from the above-mentioned adhesive film.
Or a multilayer laminated board can also be manufactured by laminating | stacking the said laminated body several sheets (for example, 2-20 sheets), and carrying out lamination | stacking shaping | molding. Specifically, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., 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 manufacturing method thereof]
The printed wiring board of this invention has said laminated board or multilayer laminated board, and the wiring provided in the surface of the laminated board or multilayer laminated board.
Next, a method for manufacturing this printed wiring board will be described.

<Formation of via holes>
The above laminated plate is drilled by a method such as drilling, laser, plasma, or a combination thereof as necessary to form a via hole or a through hole. As the laser, a carbon dioxide laser, a YAG laser, a UV laser, an excimer laser, or the like is generally used. After forming the via hole or the like, desmear treatment may be performed using an oxidizing agent. Suitable oxidants include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid (ie, a mixture of hydrogen peroxide and sulfuric acid), and nitric acid. A sodium hydroxide aqueous solution (alkaline permanganate aqueous solution) 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 laminate by dry plating or wet plating.
As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used.
In the case of wet plating, first of all, the surface of the cured resin layer of the laminate is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, Roughening treatment is performed with an oxidizing agent such as nitric acid to form uneven anchors. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. This roughening treatment may also serve as the desmear treatment. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
In addition, when using what has the support body film which consists of metal foil on the surface as a laminated body, the formation process of this conductor layer can be skipped.

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

[Multilayer printed wiring board and manufacturing method thereof]
As one form of the printed wiring board described above, a multilayer printed wiring board may be formed by laminating a plurality of laminated boards on which wiring patterns are formed as described above.
In order to manufacture this multilayer printed wiring board, a multilayer is formed by laminating a plurality of laminated boards on which the above wiring patterns are formed via the above-mentioned adhesive film. Thereafter, 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 plate and multilayer laminated plate with metal foil, and methods for producing them]
The laminate and multilayer laminate may be a laminate with a metal foil and a multilayer laminate having a metal foil such as copper, aluminum or nickel on one or both sides.
There is no restriction | limiting in particular in the manufacturing method of this laminated sheet with metal foil. For example, as described above, a laminate with a metal foil can be produced by using a metal foil as the support film. In addition, by laminating one or a plurality (for example, 2 to 20) of laminates obtained by the above-described lamination or coating, and laminating and forming the metal foil on one or both sides, a metal foil is attached. Laminates can also be manufactured.
The molding conditions can be applied to a laminate for an electrical insulating material or a multilayer board, for example, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250 ° C., a pressure of 2 Molding can be performed in a range of about 100 MPa and a heating time of about 0.1 to 5 hours.
<Evaluation method of thermal expansion coefficient>
The thermal expansion coefficient of the laminated plate can be measured by using a thermomechanical analyzer (TMA: Thermal Mechanical Analysis), a temperature-dependent three-dimensional displacement measuring device (DIC: Digital Image Correlation), a laser interferometry, or the like.
<Evaluation method of elastic modulus>
The elastic modulus of the laminated plate can be measured as a bending elastic modulus as a static elastic modulus, including measurement of storage elastic modulus using a wide area viscoelasticity measuring device. The bending elastic modulus can be obtained by performing a three-point bending test.

Next, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to these descriptions.
In the examples and comparative examples, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.
Moreover, FIG. 1 is typical sectional drawing explaining the manufacturing method of Examples 1-2, 4. As shown in FIG. FIG. 2 is a schematic cross-sectional view illustrating the manufacturing method of the fifth embodiment.

[Example 1]
<Manufacture of Resin Film (Laminate of Interlayer Insulating Composition Layer 2 and Support Film 1) 3>
Nippon Kayaku Co., Ltd. as a thermosetting resin with respect to 135.4 parts of a polyamide resin “BPAM-155” (product name) manufactured by Nippon Kayaku Co., Ltd. dissolved in a dimethylacetamide solvent to a concentration of 10%. 62.0 parts of epoxy resin “NC3000-H” (trade name, concentration 100%) manufactured by DIC Corporation, and triazine-containing phenolic novolac resin “LA-1356-60P” (trade name, concentration 60) as a curing agent. %) 23.5 parts, Shikoku Kasei Kogyo Co., Ltd. 2-phenylimidazole "2PZ" (trade name, concentration 100%) as a curing accelerator 0.6 parts, inorganic filler made by Nippon Aerosil Co., Ltd. Fumed silica “AEROSIL R972” (trade name, concentration 100%, average particle diameter of primary particles: 16 nm, specific surface area by BET method: 110 ± 0 m ² / g) 8.8 parts, other components as BYK Chemie Japan polyester modified K.K. polydimethylsiloxane "BYK-310" (trade name, after a concentration of 25%) was added 3.6 parts of Further, 314.3 parts of dimethylacetamide solvent was added, and dissolution, mixing, and bead mill dispersion treatment were performed to prepare a varnish.
A 38 μm-thick polyethylene terephthalate film (PET film) was used as the support film 1, and this varnish was applied and dried with a comma coater. The coating thickness is set to 5 μm, the drying temperature is set to 140 ° C., and the drying time is set to 3 minutes, whereby the interlayer insulating composition layer 2 is formed on the support film 1. A resin film 3 having a width of 270 mm was obtained (FIG. 1A).

<Manufacture of varnish for resin composition layer>
31.8 parts of an epoxy resin “NC3000-H” (trade name, concentration 100%) manufactured by Nippon Kayaku Co., Ltd. as a thermosetting resin, and a triazine-containing cresol novolak “LA-3018-” manufactured by DIC Corporation as a curing agent. "50P" (trade name, concentration: 50%) 7.2 parts, phosphorus-containing phenolic resin "HCA-HQ" (trade name, concentration 100%) 5.1 parts, DIC 4.4 parts of phenol novolak “TD2131” (concentration 100%) manufactured by Co., Ltd., 1-cyanoethyl-2-phenylimidazolium trimellitate “2PZCNS-PW” (product) manufactured by Shikoku Kasei Kogyo Co., Ltd. as a curing accelerator Name, concentration 100%) is 0.1 part, and the aminosilane coupling in the methyl isobutyl ketone solvent so that the solid content is 70% as an inorganic filler. Adma subjected to grayed agent treatment Fine-Techno Co., Ltd. silica filler "SO-C2" (trade name, density of 100% and an average particle diameter of primary particles: 500 nm, specific surface area by BET method: 6.8m ² / g) After adding 78.6 parts of each, 42.7 parts of methyl ethyl ketone was further added as an additional solvent, followed by dissolution, mixing, and bead mill dispersion treatment to prepare a varnish for the resin composition layer.

<Production of Adhesive Film (Support Film 1 / Interlayer Insulation Composition Layer 2 / Resin Composition Layer 4) 5a>
By forming the resin composition layer 4 on the resin film 3, the adhesive film 5a was manufactured.
As a method, the 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. Set the coating thickness to 20 μm (interlayer insulation composition layer 2; 5 μm, resin composition layer 4; 15 μm setting), and set the drying temperature to 105 ° C. and the drying time to 1.2 minutes. By using the resin composition layer 4, an adhesive film 5a having a width of 270 mm was obtained (FIG. 1B).

<Manufacture of laminate (interlayer insulating layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer)>
As the glass substrate layer 6, an ultrathin glass film “OA-10G” (trade name, thickness 100 μm, 250 × 250 mm) manufactured by Nippon Electric Glass was used. The adhesive film 5a is disposed on both surfaces of the glass substrate layer 6 so that the resin composition layer 4 is in contact with the glass substrate layer 6, and a batch type vacuum pressure laminator "MVLP-500" (Trade name, manufactured by Co., Ltd.) was used for lamination (FIGS. 1C and 1D). The degree of vacuum at this time 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 atmosphere 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 cured resin layer 4a, respectively. In this way, a laminated board (interlayer insulating layer / resin cured layer / glass substrate layer / resin cured layer / interlayer insulating layer) 7a having a five-layer structure was obtained (FIG. 1 (e)).

[Example 2]
<Manufacture of adhesive film (support film / interlayer insulation composition layer / resin composition layer) 5b>
Similar to the adhesive film 5a of Example 1, except that the coating thickness of the varnish was set to 40 μm (interlayer insulating composition layer 2; 5 μm, resin composition layer 4; 35 μm setting) instead of 20 μm. Thus, an adhesive film 5b of 250 mm × 250 mm was obtained.
<Manufacture of laminate (interlayer insulating layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer)>
The same operation as in Example 1 was performed except that the above-described adhesive film 5b was used instead of the adhesive film 5a, and a laminate having a five-layer structure (interlayer insulating layer / resin cured material layer / glass substrate layer / resin cured material) Layer / interlayer insulating layer).

[Example 3]
<Manufacture of laminate (interlayer insulating layer / resin cured layer / interlayer insulating layer / resin cured layer / glass substrate layer / resin cured layer / interlayer insulating layer / resin cured layer / interlayer insulating layer)>
As the glass substrate, an ultrathin glass film “OA-10G” (trade name, thickness 100 μm, 250 × 250 mm) manufactured by Nippon Electric Glass was used. The adhesive film 5b is disposed on both surfaces of the glass substrate so that the cured resin layer is in contact with the glass substrate, and a batch-type vacuum pressure laminator “MVLP-500” (manufactured by Meiki Co., Ltd., product) Name). The degree of vacuum at this time 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 composition layer for interlayer insulation exposed by peeling of the support film so that the cured resin layer is in contact with it, and a batch type vacuum pressure laminator “MVLP-500” ( The product was manufactured by laminating using a product manufactured by Meiki Co., Ltd. The degree of vacuum at this time was 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 atmosphere set at 180 ° C. for 60 minutes to obtain a laminate of 9 layers (interlayer insulating layer / cured resin layer / interlayer insulating layer / cured resin) Layer / glass substrate layer / cured resin layer / interlayer insulating layer / cured resin layer / interlayer insulating layer).
[Example 4]
<Manufacture of adhesive film (support film / interlayer insulation composition layer / resin composition layer) 5c>
Similar to the adhesive film 5a of Example 1, except that the coating thickness of the varnish was set to 30 μm (interlayer insulating composition layer 2; 5 μm, resin composition layer 4; 25 μm setting) instead of 20 μm. Thus, an adhesive film 5c having a width of 270 mm was obtained.
<Manufacture of laminate (interlayer insulating layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer)>
The same operation as in Example 1 was performed except that the above-described adhesive film 5c was used instead of the adhesive film 5a, and that a thickness of 150 μm was used as the glass substrate 6 instead of a thickness of 100 μm. A plate (interlayer insulation layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulation layer) was obtained.
[Example 5]
<Manufacture of varnish for resin composition layer>
Nippon Kayaku Co., Ltd. as a thermosetting resin with respect to 135.4 parts of a polyamide resin “BPAM-155” (product name) manufactured by Nippon Kayaku Co., Ltd. dissolved in a dimethylacetamide solvent to a concentration of 10%. 62.0 parts of epoxy resin “NC3000-H” (trade name, concentration 100%) manufactured by DIC Corporation, and triazine-containing phenolic novolac resin “LA-1356-60P” (trade name, concentration 60) as a curing agent. %) 23.5 parts, Shikoku Kasei Kogyo Co., Ltd. 2-phenylimidazole "2PZ" (trade name, concentration 100%) as a curing accelerator 0.6 parts, inorganic filler made by Nippon Aerosil Co., Ltd. Fumed silica “AEROSIL R972” (trade name, concentration 100%, average particle diameter of primary particles: 16 nm, specific surface area by BET method: 110 ± 0 m ² / g) 4.8 parts, other components as BYK Chemie Japan polyester modified K.K. polydimethylsiloxane "BYK-310" (trade name, after a concentration of 25%) was added 1.7 parts of Further, 66.3 parts of dimethylacetamide solvent was added. Thereafter, a uniform resin varnish was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).
<Manufacture of adhesive film (support film 1 / resin composition layer 4) 5d>
An adhesive film 5d was produced by forming a resin composition layer 4 on the support film 1 (FIG. 2 (a)).
As a method, the thickness after drying is 20 μm on the release-treated surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Co., Ltd.) which is a support varnish. The film was applied using a comma coater and dried at 140 ° C. for 5 minutes to form a 270 mm wide adhesive film 5 d composed of the resin composition layer 4 and the support film 1.
<Manufacture of laminated board (resin cured product layer / glass substrate layer / resin cured product layer)>
As the glass substrate layer 6, an ultrathin glass film “OA-10G” (trade name, thickness 150 μm, 250 × 250 mm) manufactured by Nippon Electric Glass was used. The adhesive film 5d is placed on both surfaces of the glass substrate layer 6 so that the resin composition layer 4 is in contact with the glass substrate layer 6, and a batch type vacuum pressure laminator “MVLP-500” 2 (b) and (c)) laminated by lamination using a product name, manufactured by Co., Ltd. The degree of vacuum at this time was 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 atmosphere set at 180 ° C. for 60 minutes. By this curing, the resin composition layer 4 became the cured resin 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. 2D).

[Comparative Example 1]
<Manufacture of resin film>
A resin film was produced in the same manner as in the resin film 3 of Example 2 except that the inorganic filler (fumed silica) was not added.
<Manufacture of varnish>
A varnish was produced in the same manner as in the varnish for the resin composition layer of Example 2 except that the inorganic filler (silica filler) was not added.
<Manufacture 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 an adhesive film (for support film / interlayer insulation) Composition layer / resin composition layer).
<Manufacture of laminate (interlayer insulating layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer)>
The same operation as in Example 2 was carried out except that the above adhesive film was used in place of the adhesive film 5a of Example 2, and a laminate having a five-layer structure (interlayer insulating layer / cured resin layer / glass substrate layer / resin) A cured product layer / interlayer insulating layer) was obtained.

[Reference Example 1]
Next, a laminated board laminate using prepreg, which is generally used as a laminated board for semiconductor packages and printed wiring boards, is manufactured as follows.
<Manufacture of Solution of Resin Composition Having Unsaturated Maleimide Group>
In a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 4,4′-bis (4-aminophenoxy) biphenyl: 69.10 g, bis (4 -Maleimidophenyl) sulfone: 429.90 g, p-aminophenol: 41.00 g, and propylene glycol monomethyl ether: 360.00 g were 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.

<Manufacture of varnish containing thermosetting resin composition>
(1) As a curing agent (A), a solution of a resin composition having the unsaturated maleimide group,
(2) As the thermosetting resin (B), a bifunctional naphthalene type epoxy resin [manufactured by Dainippon Ink & Chemicals, trade name, HP-4032D],
(3) As modified imidazole (C), isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L],
(4) As an inorganic filler (D), fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC, concentration: 100%, average particle size of primary particles: 500 nm, specific surface area by BET method: 6.8 m ² / G],
(5) As phosphorus-containing compound (E) that imparts flame retardancy, phosphorus-containing phenol resin [manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ, phosphorus content: 9.6% by mass],
(6) As the compound (F) capable of chemical roughening, crosslinked acrylonitrile butadiene rubber (NBR) particles [manufactured by JSR Corporation, trade name: XER-91],
(7) As a diluent solvent, methyl ethyl ketone,
Were mixed at a 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 a prepreg composed of a thermosetting resin composition>
The varnish (G) was impregnated and coated on E glass cloth 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 prepreg of 250 mm × 250 mm was produced. The resin content of the prepared prepreg was 50% by mass. Three of these prepregs were combined, and an electrolytic copper foil having a thickness of 12 μm was placed up and down, 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]
About the laminated board obtained by said Example, the comparative example, and the reference example, the performance was measured and evaluated with the following method.
(1) Measurement of coefficient of thermal expansion A test piece of 4 mm × 30 mm was cut out from the laminate. When using a copper clad laminated board, after removing copper foil by being immersed in copper etching liquid, the test piece was cut out.
Using a TMA test apparatus (manufactured by DuPont, TMA2940), it was evaluated by observing the thermal expansion characteristics of the test piece below Tg. Specifically, the temperature rise rate is 5 ° C./min, 1st run, measurement range is 20 to 200 ° C., 2nd run measurement range is −10 to 280 ° C., weight is 5 g, and chuck is 10 mm. The average coefficient of thermal expansion in the range of ° C and in the range of 120 to 190 ° C was determined. The results are shown in Table 2.
(2) Measurement of storage elastic modulus A test piece of 4 mm × 30 mm was cut out from the laminate. When using a copper clad laminated board, after removing copper foil by being immersed in copper etching liquid, the test piece was cut out.
Using a wide-area viscoelasticity measurement device (DVE-V4, manufactured by Rheology), measuring the tensile storage modulus at 40 ° C under the conditions of 20 mm span, 10 Hz frequency, and 1-3 μm vibration displacement (stop excitation) did. The results are shown in Table 2.

  As is apparent 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, in the high temperature region of 120 to 190 ° C., the thermal expansion coefficient is increased in Reference Example 1 compared to the low temperature region (50 to 120 ° C.), whereas in Examples 1 to 5, it is almost the same as the low temperature region. It can be seen that it has a low thermal expansion property. 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.

DESCRIPTION OF SYMBOLS 1 Support film 2 Interlayer insulation composition layer 2a Interlayer insulation layer 3 Resin film 4 Resin composition layer 4a Resin hardened material layer 5a, 5b, 5c, 5d Adhesive film 6 Glass substrate layer 7a, 7b Laminate board

Claims (12)

A laminate for a printed wiring board comprising one or more resin composition layers and one or more glass substrate layers,
The resin composition layer is made of a resin composition containing a thermosetting resin and an inorganic filler,
The glass substrate layer is 10 to 95% by volume with respect to the entire laminate,
The glass substrate layer has a thickness of 80 to 200 μm,
The thickness of the resin composition layer, Ri 3~35μm der,
A laminate for a printed wiring board , wherein the inorganic filler is silica having an average primary particle size of 1 µm or less, and the content of the silica in the resin composition is 3 to 20% by mass .   The thermosetting resin is epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, The laminate for a printed wiring board according to claim 1, wherein the laminate is one or more selected from a triazine resin and a melamine resin. A laminate for a printed wiring board comprising one or more resin cured product 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 an inorganic filler,
The glass substrate layer is 10 to 95% by volume with respect to the entire laminate,
The glass substrate layer has a thickness of 80 to 200 μm,
The thickness of the cured resin layer, Ri 3~35μm der,
A laminate for a printed wiring board , wherein the inorganic filler is silica having an average primary particle size of 1 µm or less, and the content of the silica in the resin composition is 3 to 20% by mass . The laminated board for printed wiring boards according to claim 3 whose storage elastic modulus in 40 ° C is 10 GPa-70 GPa. The laminated board for printed wiring boards of Claim 3 or 4 obtained by heating the laminated body for printed wiring boards of Claim 1 or 2 . A multilayer laminate for a printed wiring board including a plurality of laminates,
The multilayer laminated board for printed wiring boards whose at least 1 laminated board is a laminated board for printed wiring boards of any one of Claims 3-5 . The printed wiring board which has a laminated board for printed wiring boards of any one of Claims 3-5 , and the wiring provided in the surface of the said laminated board. The printed wiring board which has the multilayer laminated board for printed wiring boards of Claim 6 , and the wiring provided in the surface of the said multilayer laminated board. The manufacturing method of the laminated board for printed wiring boards of any one of Claims 3-5 including the resin cured material layer formation process of forming a resin cured material layer on the surface of a glass substrate. The method for producing a laminated board for a printed wiring board according to claim 9 , wherein the cured resin layer forming step is a step of drying and curing after applying the resin composition on the glass substrate. 10. The printed wiring board according to claim 9 , wherein the resin cured product layer forming step is a step of laminating and curing a film made of the resin composition on the glass substrate using a vacuum laminator or a roll laminator. A manufacturing method of a laminated board. The method for producing a laminated board for a printed wiring board according to claim 9 , wherein the cured resin layer forming step is a step of pressing and curing the film made of the resin composition on the glass substrate. .