WO2013042752A1

WO2013042752A1 - Laminated body, laminated board, multi-layer laminated board, printed wiring board, and production method for laminated board

Info

Publication number: WO2013042752A1
Application number: PCT/JP2012/074120
Authority: WO
Inventors: 真裕青嶌; 佳弘高橋; 由香山崎; 上方　康雄; 村井　曜
Original assignee: 日立化成株式会社
Priority date: 2011-09-22
Filing date: 2012-09-20
Publication date: 2013-03-28
Also published as: CN203351575U; CN103009720A; TW201343010A; JPWO2013042752A1

Abstract

A laminated body including at least one resin composition layer and at least two glass substrate layers, wherein: at least one of the at least one resin composition layers is a fiber-containing resin composition layer comprising a fiber-containing resin composition including a heat-curable resin and a fiber base material; and at least one resin composition layer exists between any two glass substrate layers. A laminated board including at least one cured resin layer and at least two glass substrate layers, wherein: at least one of the at least one cured resin layers is a fiber-containing cured resin layer comprising a fiber-containing cured resin product including a heat-curable resin and a fiber base material; and at least one cured resin layer exists between any two glass substrate layers. A printed wiring board having the laminated board, and wiring provided on the surface of the laminated board. A production method for the laminated board, including a cured resin layer-forming step in which the cured resin layer is formed on the surface of the glass substrate.

Description

LAMINATE, LAMINATE, MULTILAYER LAMINATE, PRINTED WIRING BOARD AND METHOD FOR PRODUCING LAMINATE

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

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 laminated sheet 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 the production of these laminated boards and multilayer laminated boards. It is an object of the present invention to provide a laminate suitable for the above, a printed wiring board using the laminate and the multilayer laminate, and a method for producing the laminate.

In Patent Document 4, there is no description that a fiber base material is contained 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 a fiber base material.
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, when the fiber base material is contained in the resin, the resin has a high elastic modulus. Therefore, from the description of Patent Document 4, it should be avoided that the resin contains a fiber base material.
Moreover, when a fiber base material is contained in the resin of Patent Document 4, it is considered that the glass substrate easily breaks starting from the fiber base material. Also from this point, in patent document 4, it is estimated that it contains avoiding containing a fiber base material in resin.
At present, there is no example of a laminate in which a fiber base material 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 a fiber base material. It has been found that a laminated board having a low thermal expansion coefficient and a high elastic modulus, suppressing warpage, and hardly causing cracks can be obtained.

The present invention has been completed based on the above findings, and has the following [1] to [18].
[1] A laminate including one or more resin composition layers and two or more glass substrate layers, wherein at least one of the one or more resin composition layers includes a thermosetting resin and a fiber. It is a fiber containing resin composition layer which consists of a fiber containing resin composition containing a base material, and the laminated body in which the said resin composition layer exists one or more layers between two arbitrary glass substrate layers.
[2] The laminate according to [1], wherein the glass substrate layer has a thickness of 30 to 200 μm.
[3] Of the two or more glass substrate layers, the glass substrate layer on the outermost surface side and the glass substrate layer on the outermost surface side are respectively present on the front surface side and the back surface side of all the resin composition layers. The laminate according to [1] or [2].
[4] The one or more resin composition layers are provided on the back surface of the first resin composition layer that is in contact with the surface of the outermost glass substrate layer and the outermost glass substrate layer. A second resin composition layer that is in contact with the first resin composition layer, and the first resin composition layer and the second resin composition layer include a thermosetting resin and a fiber substrate. The laminate according to any one of [1] to [3], which is a non-fiber-containing organic composition layer comprising a non-fiber-containing organic composition.
[5] The laminate according to [4], wherein the first resin composition layer and the second resin composition layer have a thickness of 3 to 40 μm.
[6] The laminate according to any one of [1] to [5], wherein the fiber-containing resin composition layer includes an inorganic filler.
[7] The inorganic filler is one or more selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. [6] The laminated body as described in.
[8] The laminate according to any one of [1] to [7], wherein the fiber base material is at least one selected from glass fiber, polyimide fiber, polyester fiber, and polytetrafluoroethylene fiber.
[9] 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 any one of [1] to [8], which is one or more selected from silicone resins, triazine resins, and melamine resins.
[10] A laminate including one or more resin cured product layers and two or more glass substrate layers, wherein at least one of the one or more resin cured product layers includes a thermosetting resin and a fiber. A laminate comprising a fiber-containing resin cured product layer comprising a fiber-containing resin cured product including a base material, and one or more resin cured material layers are present between any two glass substrate layers.
[11] The laminated board according to [10], wherein the storage elastic modulus at 40 ° C. is 10 GPa to 70 GPa.
[12] The laminated plate according to [10] or [11], which is obtained by heating the laminated body according to any one of [1] to [9].
[13] A multilayer laminate including a plurality of laminates, wherein at least one laminate is the laminate according to any one of [10] to [12].
[14] A printed wiring board comprising the laminated board according to any one of [10] to [12] and wiring provided on a surface of the laminated board.
[15] A printed wiring board having the multilayer laminated board according to [13] and wiring provided on the surface of the multilayer laminated board.
[16] The method for producing a laminated board according to any one of [10] to [12], including a resin cured product layer forming step of forming a resin cured product layer on the surface of the glass substrate.
[17] The laminate according to [16], wherein the cured resin 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. Manufacturing method.
[18] The method for producing a laminated board according to [16], wherein the resin cured product layer forming step is a step of pressing and curing the 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.

6 is a schematic cross-sectional view illustrating a method for manufacturing a laminated board according to Example 4. 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 two or more glass substrate layers, and at least one of the one or more resin composition layers is thermoset. A fiber-containing resin composition layer comprising a fiber-containing resin composition containing a functional resin and a fiber base material, and one or more resin composition layers are present between any two glass substrate layers It is.
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 (in the case of use in a roll, the length is appropriately applied) 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 80 to 600 μm, still more preferably 100 to 500 μm, and still more preferably 110 to 400 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. Moreover, since the fiber-containing organic cured product layer contains a fiber base material, the fiber-containing organic cured product layer has a low thermal expansion coefficient and a high elastic modulus as compared with a resin cured product that does not contain a fiber base material, and includes the fiber-containing resin cured product layer. The plate has a low expansion coefficient and a high elastic modulus. Further, the laminate of the present invention has two or more glass substrate layers, and one or more resin composition layers are interposed between any two glass substrate layers. Compared to a laminate having a single glass substrate layer having the same thickness as the total thickness, the laminate has a lower thermal expansion coefficient and a higher elastic modulus when formed into a laminate as described above.

<Laminated structure of laminated body>
In the laminate structure of the laminate, one or more resin composition layers are present between any two glass substrate layers, and at least one of the one or more resin composition layers is heated. If it is a fiber containing resin composition layer which consists of a fiber containing resin composition containing curable resin and a fiber base material, there will be no restriction | limiting in particular.
≪First laminated structure≫
For example, the structure in which the glass substrate layer on the outermost surface side and the glass substrate layer on the outermost surface side in the laminate are present on the front surface side and the back surface side than all of the resin composition layers may be used. Examples of such a structure include the following.
“(Glass substrate layer / resin composition layer) _m / glass substrate layer” (m is an integer of 1 or more)
Here, “glass substrate layer / resin composition layer” means that a glass substrate layer and a resin composition layer are laminated. That is, “/” means that two layers described on the left and right sides of “/” are laminated.
For example, the structures when m is 1 and 2 are as follows.
"Glass substrate layer / resin composition layer / glass substrate layer"
"Glass substrate layer / resin composition layer / glass substrate layer / resin composition layer / glass substrate layer"
At least one of these resin composition layers needs to be a fiber-containing resin composition layer made of a fiber-containing resin composition containing a thermosetting resin and a fiber base material. Thus, the laminated board obtained from the laminated body containing a resin base material becomes a low expansion coefficient and a high elasticity modulus.
Further, all of the resin composition layer may be composed of the above-mentioned fiber-containing resin composition, but a part thereof is composed of a non-fiber-containing organic composition containing a thermosetting resin and no fiber substrate. It may be.

≪Second laminated structure≫
Also, for example, a first resin composition layer that is in contact with the surface of the glass substrate layer on the outermost surface side, and a second surface that is in contact with the rear surface of the glass substrate layer on the outermost surface side. And a resin composition layer. Examples of such a structure include the following.
“First resin composition layer / (glass substrate layer / resin composition layer) _n / glass substrate layer / second resin composition layer” (n is an integer of 1 or more)
For example, the structures when n is 1 and 2 are as follows.
"First resin composition layer / glass substrate layer / resin composition layer / glass substrate layer / second resin composition layer"
"First resin composition layer / glass substrate layer / resin composition layer / glass substrate layer / resin composition layer / glass substrate layer / second resin composition layer"
At least one of these resin composition layers needs to be a fiber-containing resin composition layer made of a fiber-containing resin composition containing a thermosetting resin and a fiber base material. Thus, the laminated board obtained from the laminated body containing a resin base material becomes a low expansion coefficient and a high elasticity modulus.
Further, by having the first resin composition layer and the second resin composition layer, it is avoided that the glass substrate layer is exposed and directly contacted with an object outside the laminate, and the glass substrate layer is cracked. It is possible to improve prevention and handling (ease of handling). The first resin composition layer and the second resin composition layer are non-fiber-containing organic composition layers made of a non-fiber-containing organic composition that contains a thermosetting resin and does not contain a fiber base material. preferable. Thereby, it is possible to further improve the prevention of cracking of the glass substrate layer and the handling property (ease of handling). Moreover, by not including a fiber base material in the first resin composition layer and the second resin composition layer, the thickness of the resin composition layer can be reduced, and the laminate can be made more elastic. Can do.

<Fiber-containing resin composition>
Said fiber-containing resin composition contains a thermosetting resin and a fiber base material.
≪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 novolac 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, triphenol phenol 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 fiber-containing resin composition is in the range of 20 to 80% by mass with respect to the mass of the non-fiber substrate component excluding the fiber substrate from the total amount of the fiber-containing resin composition. It is preferably 25 to 60% by mass, more preferably 25 to 50% by mass, still more preferably 25 to 40% by mass.

≪Fiber base material≫
There is no restriction | limiting in particular as a fiber base material, Organic fiber, such as E glass, D glass, S glass, and Q glass, Organic fibers, such as a polyimide, polyester, and polytetrafluoroethylene, those mixtures, etc. are mentioned. These fiber base materials have shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary. , Alone or in combination of two or more materials and shapes.
The thickness of the base material is not particularly limited, and can be, for example, about 0.03 to 0.5 mm, and is surface-treated with a silane coupling agent or the like or mechanically subjected to fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.
The total content of the fiber base material is preferably in the range of 10 to 80% by volume, more preferably 15 to 75% by weight, still more preferably 20 to 70% by weight, based on the total amount of the fiber-containing resin composition. 30 to 60% by mass is even more preferable, and 30 to 55% by mass is even more preferable.

≪Inorganic filler≫
The fiber-containing resin composition may further contain an inorganic filler.
When the fiber-containing resin composition contains an inorganic filler, the content of the inorganic filler is in the range of 5 to 75% by volume with respect to the non-fiber base component excluding the fiber base from the fiber-containing resin composition. It is preferable that Further, the content of the inorganic filler is more preferably 15 to 70% by mass, and still more preferably 30 to 70% by mass with respect to the non-fiber base component obtained by removing the fiber base from the fiber-containing resin composition.
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
Moreover, a fine wiring can be formed on the fiber-containing resin cured product 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 fiber-containing resin cured product layer of the laminate, the content of the inorganic filler is 20% by mass or less in the non-fiber component excluding the fiber substrate from the fiber-containing resin composition. It is preferable. 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 fiber-containing resin composition can be expected to have low thermal expansion and high elasticity by containing an inorganic filler, the inclusion of an inorganic filler is important when low thermal expansion and high elasticity are also considered as well as fine wiring formation. The amount is preferably 3 to 20% by mass.

≪Other ingredients≫
In addition to the above components, this fiber-containing 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, and improved adhesion. An agent or 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.
Examples of ultraviolet absorbers 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, adhesion improvers for silane coupling agents, and the like.

<Fiber-containing resin composition layer>
A fiber containing resin composition layer consists of said fiber containing resin composition. The fiber-containing resin composition layer includes a semi-cured product in addition to an uncured product of the fiber-containing resin composition.
The size of the fiber-containing 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 fiber-containing 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 laminate, the thickness of the resin composition per layer is preferably 3 to 150 μm, more preferably 10 to 120 μm, and more preferably 20 to It is further preferably 120 μm, and further preferably 25 to 110 μm.
The fiber-containing resin composition layer of the present invention is preferably contained in a proportion of 4 to 90% by volume, more preferably 10 to 80% by volume, still more preferably 20 to 70% by volume, more based on the entire laminate. More preferably, it is contained in a proportion of 25 to 60% by volume.
Moreover, although the laminated body and laminated board of this invention have the resin composition layer in which at least 1 layer of fiber base material is contained, you may have the resin composition layer which does not contain a fiber base material in addition to that. Absent. The resin composition layer not containing the fiber base material can be used for the purpose of, for example, arranging between the glass layer and the resin composition layer containing the fiber base material to improve the adhesion between the two layers.
The resin content after drying of the fiber-containing resin composition layer is preferably 20 to 90% by mass, more preferably 25 to 85% by mass or more, further preferably 30 to 80% by mass or more, and 40 to 70% by mass. Even more preferred is 45 to 70% by weight. When it is 20% by mass or more, processability and handling properties (ease of handling) are improved. When the content is 90% by mass or less, the content of the fiber base material increases, and a laminate obtained by curing the fiber-containing resin composition layer of the laminate has a low coefficient of thermal expansion and high elasticity. In addition, resin content means the amount of components other than the fiber base material in the total amount of a fiber containing resin composition.
Further, when the fiber-containing resin composition contains an inorganic filler, the total amount of the thermosetting resin and the inorganic filler is preferably 5 to 75% by volume, more preferably 15 to 70% by volume. 30 to 70% by volume is more preferable. When the content of the inorganic filler is 5 to 75% by volume of the total amount of the thermosetting resin and the inorganic filler, the effect of reducing the coefficient of thermal expansion is sufficient, and the moldability is appropriate with appropriate fluidity. 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.

<Non-fiber-containing resin composition layer>
The non-fiber-containing resin composition layer is composed of a non-fiber-containing organic composition containing a thermosetting resin and no fiber substrate. This non-fiber-containing resin composition contains a thermosetting resin, and may further contain an inorganic filler and other components. Details of these thermosetting resins, inorganic fillers, and other components are as described for the fiber-containing resin composition.
When this non-fiber-containing resin composition layer is used as the first and second resin composition layers, 3 μm from the viewpoint of preventing cracking of the glass substrate layer and improving handling properties (ease of handling). The above is preferable. On the other hand, 40 μm or less is preferable from the viewpoint of ensuring a low thermal expansion coefficient and a high elastic modulus of a laminate obtained by curing the resin composition layer. From these viewpoints, the thickness of the first and second resin composition layers is preferably 3 to 40 μm, more preferably 10 to 30 μm, and further preferably 15 to 25 μm. Moreover, it is preferable that these 1st and 2nd resin composition layers do not contain an inorganic filler.
When the non-fiber-containing resin composition layer of the present invention is used, the non-fiber-containing resin composition layer is preferably contained in a proportion of 1 to 40% by volume, more preferably 1 to It is contained in a proportion of 30% by volume, more preferably 1 to 25% by volume.

<Glass substrate layer>
As the glass substrate constituting the glass substrate layer, a thin glass film having a thickness of 30 to 200 μm is preferable for the purpose of reducing the thickness of the laminate and from the viewpoint of workability, In consideration of practicality such as ease of handling, the thickness is more preferably 50 to 150 μm, and further preferably 80 to 120 μm. 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. 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 70% by volume, more preferably 15 to 70% by volume, still more preferably 20 to 70% by volume, still more preferably 30 to 70% by volume, and more preferably 40 to 70% by volume is even more preferable. When the content of the glass substrate layer is 10% by volume or more, it is advantageous to obtain a laminate having low thermal expansion and high elasticity, and conversely, when the content of the glass substrate layer is 70% by volume or less, processing is performed. It is advantageous in terms of the properties and handling properties (ease of handling).
From the same viewpoint, the total amount of the resin composition layer, that is, the fiber-containing resin composition layer and the non-fiber-containing resin composition layer is preferably 30 to 90% by volume, and 30 to 85% by volume with respect to the entire laminate. More preferably, it is 30 to 80% by volume, still more preferably 30 to 70% by volume, still more preferably 30 to 60% by volume.

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

[Manufacturing method of laminate]
The manufacturing method of the said laminated body includes the resin cured material layer formation process of forming the said resin cured material layer on the surface of the said glass substrate. This resin cured product layer forming step is not particularly limited, but for example, a step of laminating a film made of a resin composition on a glass substrate by pressure lamination using a vacuum laminator or a roll laminator and curing the film. Is preferred. Vacuum lamination and roll lamination can be performed using a commercially available vacuum laminator or roll laminator.
In addition, as a thermosetting resin in said resin composition layer, what melt | dissolves 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 lower, the thermosetting resin is preferably melted at 140 ° C. or lower.
Next, a production example of a fiber-containing resin composition layer (prepreg), a production example of a non-fiber-containing resin composition layer, and a production example of a laminate by pressure lamination will be described.

<Production example of fiber-containing resin composition layer (prepreg)>
The prepreg is impregnated or coated on a fiber base material with the thermosetting resin and, if necessary, the resin composition containing the inorganic filler, and then dried by heating to be B-staged (semi-cured). Is preferably obtained. This B-stage can be usually performed by heating and drying at a temperature of 100 to 200 ° C. for about 1 to 30 minutes.

As a coating device for this 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.

This prepreg may be formed on a support film, and a protective film for protecting the surface may be provided on the surface of the prepreg opposite to the support film forming surface.
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.
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.

<Example of production of non-fiber-containing resin composition layer>
As an example of the method for producing the non-fiber-containing resin composition layer, the non-fiber-containing resin composition is dissolved in an organic solvent to prepare a varnish. Next, the non-fiber-containing 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. Moreover, you may provide the said protective film with respect to the surface in which the support body film is not formed among this non-fiber-containing resin composition layer before drying, during drying, or after drying.

<Example of production of laminate by pressure lamination>
The pressure laminate uses a pressure laminator such as a vacuum laminator or a roll laminator, a prepreg laminated body in which one prepreg or a plurality of (for example, 2 to 20) prepregs are stacked, a glass substrate, As needed, it can carry out by laminating | stacking said non-fiber containing resin composition layer. Vacuum lamination and roll lamination can be performed using a commercially available vacuum laminator or roll laminator.
In addition, when using the thing to which the support body film and the protective film adhered as these prepregs and non-fiber containing resin composition layers, pressure lamination is performed after removing these support body films and the protective film. However, the prepreg constituting the outermost surface of the laminate and the support film of the non-fiber-containing resin composition layer may be subjected to pressure lamination without being removed.

The laminating conditions are as follows: a prepreg, a glass substrate, and, if necessary, a non-fiber-containing composition layer are preheated as necessary, and a pressure bonding temperature (laminating temperature) is preferably 60 ° C. to 140 ° C., and a pressure bonding pressure is preferably 1 to It is preferable to laminate at 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.
After laminating as above, cool to near room temperature. Thus, a laminated body can be manufactured.
In addition, as a thermosetting resin in said resin composition, what melt | dissolves 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 lower, the thermosetting resin in the resin composition is preferably one that melts at 140 ° C. or lower.

[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 at least one of the one or more cured resin layers is a heat It is a fiber-containing resin cured product layer made of a fiber-containing resin cured product including a curable resin and a fiber base material, and at least one resin cured material layer is present between any two glass substrate layers. Is.
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 its application. The thickness of the laminate is more preferably 50 to 1000 μm, still more preferably 80 to 600 μm, still more preferably 100 to 500 μm, and still more preferably 110 to 400 μm.
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. In this case, the details of the glass substrate layer and the resin composition are as described in the description regarding the laminate. The thickness of the cured resin layer is preferably equal to the thickness of the resin composition layer described above, and the ratio of the resin cured product and the glass substrate layer in the laminate is the same as the resin composition in the laminate described above. And it is preferable that it is equivalent to the ratio of a glass substrate layer.

<Fiber-containing cured resin layer>
The thickness of the fiber-containing 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 fiber-containing cured resin layer is more preferably 3 to 150 μm, still more preferably 10 to 120 μm, still more preferably 20 to 120 μm, and still more preferably 40 to 110 μm. It is. However, the appropriate range of the thickness of the fiber-containing resin cured product layer varies depending on the thickness of the glass substrate layer, the number of layers, and the type and number of layers of the fiber-containing resin cured product layer, and thus is not limited to the above range.
The storage elastic modulus at 40 ° C. of this fiber-containing resin cured product layer is preferably 10 to 80 GPa. A glass substrate layer is protected as it is 10 GPa or more, and the crack of a laminated board is suppressed. When it is 80 GPa or less, the stress due to the difference in thermal expansion coefficient between the glass substrate layer and the fiber-containing resin cured product layer is suppressed, and warpage and cracking of the laminate are suppressed. From this viewpoint, the storage elastic modulus of the fiber-containing cured resin layer is more preferably 12 to 75 GPa, and further preferably 15 to 70 GPa.
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.

<Characteristics of laminated board>
The storage elastic modulus of the laminate at 40 ° C. is preferably 10 to 70 GPa, more preferably 20 to 60 GPa, and further preferably 25 to 50 GPa, from the viewpoint of suppressing warpage and cracking of the laminate. More preferably, it is 25 to 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 to 6 ppm / ° C, and still more preferably 2 to 5.5 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 to 8 ppm / ° C, and still more preferably 2 to 6 ppm / ° C.

[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 a laminate obtained by laminating>
In the laminate obtained by the above-described lamination, a laminate can be produced by heating and curing the resin composition layer.
The heat curing conditions are selected in the range of 150 ° C. to 220 ° C. for 20 minutes to 80 minutes, more preferably 160 ° C. to 200 ° C. for 30 minutes to 120 minutes. 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, a prepreg superposed body obtained by superimposing one prepreg or a plurality of prepregs (for example, 2 to 20 sheets), a glass substrate, and a non-fiber-containing composition layer as necessary are overlaid by a pressing method. A laminated board can also be manufactured by heating and pressurizing and curing. At this time, a laminate may be produced by attaching a support film to the surface of the outermost prepreg and then curing by heating and pressurizing by a pressing method.
This pressing method is preferable from the viewpoint of uniform molding, but the lamination conditions may be limited because the glass substrate is easily broken during lamination. On the other hand, as described above, the production method by heat curing (laminating method) of the laminate obtained by laminating is preferable from the viewpoint that the glass substrate is hard to break and easy in production, but the fiber-containing resin composition and Molding may be difficult depending on the properties and content of the fiber substrate. Therefore, it is preferable to use the pressing method and the laminating method properly as necessary.

[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 multilayer laminate can be produced by stacking and laminating a plurality of the above laminates (for example, 2 to 20). Specifically, 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 about 2 to 100 MPa, and a heating time of 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.

<Formation of conductor layer>
Next, a conductor layer is formed on 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, the surface of the laminate is permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid (ie, hydrogen peroxide and (Rough mixture with sulfuric acid) and an oxidizing agent such as nitric acid to form rough 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. 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. Further, by laminating one or a plurality of (for example, 2 to 20) laminates obtained by the above-mentioned laminate and arranging metal foil on one or both sides thereof, a laminate with metal foil is obtained. It can also be manufactured.
The molding conditions can be applied to laminates for electrical insulating materials and multilayer boards. For example, a multistage press, a multistage 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 2 to 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.

[Production of a resin composition solution having an unsaturated maleimide group]
In a reaction vessel with a volume of 2 liters that can be 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, 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.

[Production of varnish containing thermosetting resin composition]
(1) As a curing agent (A), a solution of a resin composition having the unsaturated maleimide group,
(2) Bifunctional naphthalene type epoxy resin (trade name, HP-4032D, manufactured by Dainippon Ink & Chemicals, Inc.) as the thermosetting resin (B),
(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 70%, average primary particle diameter: 500 nm, specific surface area by BET method: 6.8 m ² / G],
(5) As a phosphorus-containing compound (E) that imparts flame retardancy, a phosphorus-containing phenol resin [manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ, phosphorus content 9.6% by mass],
(6) As a 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 and a solvent of 35% by mass.

[Manufacture of prepreg]
The above-mentioned 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 250 mm × 250 mm prepregs. As the type of E glass cloth, three types of IPC standards 1027, 1078, and 2116 of Asahi Kasei E-materials were used. The resin contents of the prepregs prepared using these three types of glass cloth (sometimes referred to as PP # 1027, PP # 1078, and PP # 2116, respectively) were 66, 54, and 50% by mass, respectively. It was. Moreover, E glass cloth content of these prepregs was 34, 46, and 50 mass%, respectively.

[Examples 1 to 3 and Comparative Examples 1 to 3]
As a glass film, a 50 μm thick glass film “trade name OA-10G” (Nippon Electric Glass Co., Ltd., 250 mm × 250 mm) and a 100 μm thick glass film “trade name OA-10G” (Nippon Electric Glass Co., Ltd.) , 250 mm × 250 mm) (which may be referred to as GF50 μm and GF100 μm, respectively).
The glass film and the prepreg are overlaid as shown in Table 2, and an electrolytic copper foil with a thickness of 12 μm is placed up and down, and pressed at a pressure of 3.0 MPa and a temperature of 235 ° C. for 120 minutes to obtain a copper-clad laminate. A plate was made.
[Example 4]
[Production of varnish for non-fiber-containing resin composition layer containing a thermosetting resin composition]
Nippon Kayaku Co., Ltd. as a thermosetting resin for 135.4 parts of 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 an epoxy resin “NC3000-H” (trade name, concentration: 100%) manufactured by DIC, and a triazine-containing phenolic novolak resin “LA-1356-60P” (trade name, concentration: 60) manufactured by DIC Corporation 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, and Nippon Aerosil Co., Ltd. as an inorganic filler. 4.8 parts of fumed silica “AEROSIL R972” (trade name, concentration 100%), other components manufactured by BYK Chemie Japan Co., Ltd. After adding 1.7 parts of polyester-modified polydimethylsiloxane “BYK-310” (trade name, concentration 25%), 66.3 parts of dimethylacetamide solvent was further 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 2) 3>
An adhesive film 3 was produced by forming a resin composition layer 2 on the support film 1. As a method, a varnish for a non-fiber-containing resin composition layer is dried on a release-treated surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Co., Ltd.) as a support film, and then dried to 20 μm It applied so that it might become, and it was made to dry at 140 degreeC for 5 minute (s), and the adhesive film 3 of width 270mm which consists of the resin composition layer 2 and the support body film 1 was formed (FIG. 1 (a)).
<Manufacture of Laminated Plate (Non-Fiber-Containing Resin Cured Material Layer / Glass Substrate Layer / Fiber-Containing Resin Cured Material Layer / Glass Substrate Layer / Non-Fiber-Containing Resin Cured Material Layer)>
As the glass substrate layer 4, an ultrathin glass film “OA-10G” (trade name, thickness 50 μm, 250 mm × 250 mm) manufactured by Nippon Electric Glass was used. The prepreg (PP # 1078) 5 and the glass substrate layer 4 are laminated in the order of glass substrate layer / prepreg (PP # 1078) / glass substrate layer, and a batch type vacuum pressure laminator “MVLP-500” (Product name, manufactured by Meiki Co., Ltd.) was used for lamination (FIG. 1 (b)). The degree of vacuum at this time was 30 mmHg or less, the temperature was set to 140 ° C., and the pressure was set to 0.5 MPa. The laminated body is heated at 235 ° C. for 120 minutes in a nitrogen atmosphere, and the resin in the prepreg is cured to become a fiber-containing resin cured product, whereby a glass substrate layer / fiber-containing cured resin layer / glass substrate layer is obtained. The laminated board 6 which consists of was obtained (FIG.1 (c)). Next, the adhesive film 3 is disposed above and below the laminated plate 6 so that the resin composition layer 2 of the adhesive film 3 is in contact with the glass substrate layer 4 of the laminated plate 6, and a batch type vacuum pressure laminator “MVLP-500” is arranged. "(Trade name, manufactured by Meiki Co., Ltd.) was laminated by lamination (FIG. 1 (d)). 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. Thereby, the resin composition layer 2 became the resin cured material layer 2a. 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 5 layers (non-fiber-containing resin cured layer / glass substrate layer / fiber-containing resin) Cured product layer / glass substrate layer / non-fiber-containing resin cured product layer) 7 was obtained (FIG. 1 (e)).

[Measurement]
About the laminated board obtained by said Example and comparative example, 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 measurement was performed at a rate of 5 ° C./min, 1 st run, measurement range 20 to 200 ° C., 2nd run measurement range −10 to 280 ° C., load 5 g, 10 mm between chucks, and 50 to 120 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 5 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 viscoelasticity measuring device (DVE-V4, manufactured by Rheology), measuring the tensile storage modulus at 40 ° C under the conditions of 20 mm span, 10 Hz frequency, 1 to 3 μm vibration displacement (stop vibration) did. The results are shown in Table 2.

As is apparent from Table 2, Examples 1 to 4 of the present invention containing a glass film are excellent in low thermal expansion at 50 to 120 ° C. and high elasticity at 40 ° C. as compared with Comparative Example 1 not containing a glass film. . Also, in the high temperature region of 120 to 190 ° C., the coefficient of thermal expansion is higher in Comparative Example 1 than in the low temperature region (50 to 120 ° C.), whereas in Examples 1 to 4, it is almost the same as the low temperature region. It can be seen that it has a low thermal expansion property. Therefore, Examples 1 to 4 of the present invention maintain low thermal expansion properties not only in the low temperature region but also in the high temperature region.
Further, when Example 2 and Comparative Example 2 in which the glass ratios are both 50% by volume are compared, any of low thermal expansion at 50 to 120 ° C., low thermal expansion at 120 to 190 ° C., and high elasticity at 40 ° C. However, Example 2 having a glass film as the outermost layer is superior.
Similarly, when Example 3 and Comparative Example 3 in which the glass ratio is approximated are compared, any of low thermal expansion at 50 to 120 ° C., low thermal expansion at 120 to 190 ° C., and high elasticity at 40 ° C. In Example 3, Example 3 having a glass film as the outermost layer is superior.

DESCRIPTION OF SYMBOLS 1 Support film 2 Resin composition layer 2a Non-fiber containing resin hardened material layer 3 Resin film 4 Glass substrate layer 5 Prepreg 5a Fiber containing resin hardened material layer 6 Laminate (intermediate body)
7 Laminated board

Claims

A laminate comprising one or more resin composition layers and two or more glass substrate layers,
At least one of the one or more resin composition layers is a fiber-containing resin composition layer comprising a fiber-containing resin composition including a thermosetting resin and a fiber base material,
A laminate in which one or more resin composition layers are present between any two glass substrate layers.
The laminate according to claim 1, wherein the glass substrate layer has a thickness of 30 to 200 µm.
2. The glass substrate layer on the outermost surface side and the glass substrate layer on the outermost surface side among the two or more glass substrate layers are respectively present on the front surface side and the back surface side with respect to all the resin composition layers. Or the laminated body of 2.
The one or more resin composition layers are in contact with the first resin composition layer contacting the surface of the outermost glass substrate layer and the rear surface of the outermost glass substrate layer. A second resin composition layer facing;
The first resin composition layer and the second resin composition layer are non-fiber-containing organic composition layers comprising a non-fiber-containing organic composition containing a thermosetting resin and no fiber substrate. 4. The laminate according to any one of 1 to 3.
The laminate according to claim 4, wherein the first resin composition layer and the second resin composition layer have a thickness of 3 to 40 µm.
The laminate according to any one of claims 1 to 5, wherein the fiber-containing resin composition layer contains an inorganic filler.
The inorganic filler is one or more selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. Laminated body.
The laminate according to any one of claims 1 to 7, wherein the fiber base material is at least one selected from glass fiber, polyimide fiber, polyester fiber, and polytetrafluoroethylene fiber.
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 according to any one of claims 1 to 8, which is one or more selected from triazine resins and melamine resins.
A laminate including one or more cured resin layers and two or more glass substrate layers,
At least one of the one or more resin cured product layers is a fiber-containing resin cured product layer made of a fiber-containing resin cured product including a thermosetting resin and a fiber substrate,
A laminate in which one or more of the cured resin layers are present between any two glass substrate layers.
The laminate according to claim 10, wherein the storage elastic modulus at 40 ° C is 10 GPa to 70 GPa.
The laminate according to claim 10 or 11, which is obtained by heating the laminate according to any one of claims 1 to 9.
A multilayer laminate comprising a plurality of laminates,
A multilayer laminate, wherein the at least one laminate is the laminate according to any one of claims 10 to 12.
A printed wiring board comprising: the laminated board according to any one of claims 10 to 12; and wiring provided on a surface of the laminated board.
A printed wiring board comprising the multilayer laminated board according to claim 13 and wiring provided on a surface of the multilayer laminated board.
The method for producing a laminate according to any one of claims 10 to 12, comprising a resin cured product layer forming step of forming a resin cured product layer on the surface of the glass substrate.
The method for producing a laminate according to claim 16, 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. .
The method for producing a laminated board according to claim 16, wherein the cured resin layer forming step is a step of placing and curing the film made of the resin composition on the glass substrate.