JP2018029204A - Laminated body, laminate, multilayer board, printed-wiring board, multilayer printed-wiring board, and laminate manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which includes a resin hardener layer and a glass substrate layer and is less likely to be broken because the same can solve a problem of being damaged with a broken glass substrate during lamination or cutting due to excessively large thermal expansion force applied to the glass substrate when a thickness of the resin composite layer is large.SOLUTION: A laminated body includes one or more resin composition layer and one or more glass substrate layer. The resin composition layer is made of a resin composition which includes thermosetting resin and either inorganic filler or a fiber substrate. In the laminated body, a product d×σ of an average thickness d of the hardened resin composition layer and an average σ of a thermal expansion coefficient thereof in a temperature range from 30 to 100°C is not more than 1000 μm ppm °C. A laminate can be obtained through hot forming of the laminated body and a printed-wiring board can be obtained by forming a circuit on the laminate.SELECTED DRAWING: None

Description

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

There is an increasing demand for thinner and lighter electronic devices, 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 a semiconductor package during mounting is a difference in thermal expansion coefficient between a laminated board used in the semiconductor package and a silicon chip mounted on the surface of the laminated board. For this reason, efforts are being made to bring the coefficient of thermal expansion close to that of a silicon chip, that is, to a low coefficient of thermal expansion, in the laminate for semiconductor packages. Further, since the elastic modulus of the laminated plate also becomes a factor of warping, it is also effective to make the laminated plate highly elastic 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 plate are conceivable, and among them, the lower thermal expansion coefficient of the resin for the laminated plate and the higher filling of the inorganic filler in the resin are known. In particular, the high filling of the inorganic filler is a technique that can be expected to improve heat resistance and flame retardancy as well as a low thermal expansion coefficient (Patent Document 1). However, increasing the filling amount of the inorganic filler in this manner causes 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. There is a limit to the 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 a resin for wiring boards and increasing the Tg to reduce the thermal expansion coefficient is common (Patent Documents 2 to 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. It was.

As a method different from the above, a heat shock stress is obtained by using a glass film as a layer having a thermal expansion coefficient substantially matching the thermal expansion coefficient of an electronic component (silicon chip) and pressing and laminating the resin and the glass film. Attempts have been made to reduce (Patent Document 4). However, since the elastic modulus is low and the thermal expansion coefficient is high, it is insufficient to realize low warpage of the substrate.
Furthermore, Patent Document 4 does not define the thickness of the resin layer and the type of the glass substrate.

  The glass substrate is excellent in strength, transparency, surface smoothness, gas barrier property, heat resistance, and chemical resistance, but has low impact resistance and is limited in size and application. For example, there is a drawback that it is easily broken during handling. Further, even with a thin glass substrate (hereinafter also referred to as a glass film) having a changed thickness, the above characteristics are basically the same, and the handling is difficult because the strength is lowered. Further, since the glass film is mounted at a desired location, there are problems such as secondary processing into a predetermined size and damage when applying an adhesive to the glass film.

  When a laminated board is manufactured using such a glass substrate, a resin layer is provided on the surface. However, in order to prevent damage to the glass substrate during pressing or laminate molding, it is necessary to increase the thickness of the resin layer. However, since the thermal expansion coefficient differs greatly between the resin layer and the glass substrate, if the resin layer is thick, the glass substrate cannot be held up by the thermal expansion force, and may be broken during or after lamination. Moreover, when cut | disconnecting in a manufacturing process, a small crack may enter into a cut surface. The difference in thermal expansion coefficient between the resin composition layer and the glass substrate layer as described above promotes this crack and may damage the laminate.

JP 2004-182851 A JP 2000-243864 A JP 2000-114727 A Japanese translation of PCT publication No. 2004-512667

  As described above, the laminated board using the glass substrate obtained by the above-described manufacturing method still has a low elastic modulus and a high thermal expansion coefficient, and thus is insufficient for realizing a low warpage of the substrate. On the other hand, if the resin composition layer is thick, the glass substrate cannot be held by its thermal expansion force, and cracks at the time of lamination or cutting.

As a result of advancing research to solve the above problems, the inventors of the present invention have obtained a cured resin composition layer, that is, a thickness d of the cured resin layer, in a laminate including a cured resin layer and a glass substrate layer, It has been found that by carrying out a lamination molding under a specific condition obtained from the product of the coefficient of thermal expansion σ, a laminated board that is less prone to cracking can be obtained.
Furthermore, by including an inorganic filler and a fiber base material in the cured resin layer, the elastic modulus, which has been a problem in Patent Document 4, is improved, and a highly elastic and low thermal expansion base material effective for low warping of the substrate. Can be provided. That is, the present invention is as follows.

[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 a product d · σ of an average thickness d of the cured resin composition layer and an average value σ of a thermal expansion coefficient at 30 to 100 ° C is 1000 µm · ppm · ° C ^-1 or less.
[2] A laminate comprising one or more resin composition layers and one or more glass substrate layers,
The resin composition layer is made of a resin composition including a thermosetting resin and a fiber base material, and an average thickness d of the cured resin composition layer and an average value σ of a thermal expansion coefficient at 30 to 100 ° C. The product d · σ is 1000 μm · ppm · ° C. ⁻¹ or less.
[3] The laminate according to [2], wherein the fiber base material is one or more selected from glass fiber, polyimide fiber, polyester fiber, polytetrafluoroethylene fiber, and aramid resin.
[4] The laminate according to [2] or [3], wherein the resin composition layer further includes an inorganic filler.
[5] The inorganic filler is one or more selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. [1] Or the laminated body as described in [4].
[6] The laminate according to any one of [1] to [5], wherein the glass substrate layer has a thickness of 30 to 200 μm.
[7] 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 [6], which is one or more selected from silicone resins, triazine resins, and melamine resins.
[8] A laminate obtained by heating and pressing the laminate according to any one of [1] to [7].
[9] A multilayer laminate comprising one or more laminates according to [8].
[10] A printed wiring board in which a circuit is provided on the laminated board according to [8].
[11] A multilayer printed wiring board in which a circuit is provided on the multilayer laminate according to [9].
[12] A method for producing a laminate comprising one or more cured resin layers made of a cured product of the resin composition and one or more glass substrate layers, the cured resin product on the surface of the glass substrate layer The manufacturing method of the laminated board which has the resin hardened | cured material layer formation process which forms a layer.
[13] The method for producing a laminated board according to [12], wherein the resin cured product layer forming step is heating and pressing of an adhesive film made of the resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated board and multilayer laminated board which a glass substrate layer cannot break easily, and has high elasticity and low thermal expansibility, the laminated body suitable for manufacture of these laminated boards and multilayer laminated boards, these laminated boards, and multilayers A printed wiring board using a laminate and a method for producing the laminate can be provided.

Hereinafter, the laminate, the laminate, the multilayer laminate, the printed wiring board, the multilayer 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, which is a component in the resin composition layer constituting the laminate, is uncured or semi-cured, and the laminate refers to the laminate. It means that the thermosetting resin which is a component in the resin composition layer to be formed is cured, or 90% or more of the thermosetting resin is cured to form a cured resin layer. The degree of cure of the thermosetting resin can be determined from the reaction rate measured from a differential scanning calorimeter.

<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. Or a resin composition containing a thermosetting resin and a fiber substrate, and further containing an inorganic filler as necessary.
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 that is as low in thermal expansion and high elasticity as a silicon chip. Swelling and high elasticity are obtained, warpage 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. In addition, since the resin cured product layer contains an inorganic filler and a fiber base material, it has low thermal expansion and high elasticity, and the laminate including the resin cured product layer has lower expansion and high elasticity. It becomes.
In addition, the resin composition containing a thermosetting resin and a fiber base material is called a fiber containing resin composition. The following is blended in the resin composition or the fiber-containing resin composition to constitute a resin composition layer or a fiber-containing resin composition layer.

<Thermosetting resin>
There is no restriction | limiting in particular as a thermosetting resin, An epoxy resin, a phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin , Silicone resin, triazine resin, melamine resin and the like. 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, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene type epoxy resin, Alicyclic epoxy Examples thereof include diglycidyl ether compounds of polycyclic aromatics such as resins, polyfunctional phenols and anthracene. 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 novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, bisphenol-type cyanate resin such as tetramethylbisphenol F-type cyanate resin, and prepolymers in which these are partially triazine. It is done. 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.

<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, more 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 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.

<Fiber base>
There is no restriction | limiting in particular as a fiber base material, Organic fiber, such as glass fibers, such as E glass, D glass, S glass, and Q glass, polyimide, polyester, polytetrafluoroethylene, aramid, and mixtures thereof Etc. 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 fiber substrate is not particularly limited. For example, a fiber substrate having a thickness of about 0.01 to 0.5 mm can be used, and the fiber surface treated with a silane coupling agent or the like or mechanically opened. What was given is suitable from the surface of heat resistance, moisture resistance, and workability.

<Other ingredients>
In addition to the above components, the resin composition or 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, and a fluorescent whitening agent. An adhesion improver 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 salts.

Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers.
Examples of the antioxidant include antioxidants such as hindered phenols and styrenated phenols.

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 a urea compound such as urea silane and an adhesion improver such as a silane coupling agent.

<Resin composition layer>
A resin composition layer is comprised from the resin composition containing said thermosetting resin and an inorganic filler. The resin composition layer includes a semi-cured product as well as an uncured product of the resin composition.
As content of an inorganic filler, 5-75 volume% of the total amount of a thermosetting resin and an inorganic filler is preferable, It is more preferable that it is 15-70 volume%, It is that it is 30-70 volume%. Further preferred. 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 thermal expansion coefficient 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 thermal expansion coefficient 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 8 to 85 mass% of the total amount of the thermosetting resin and silica resin composition. It is preferably 24 to 82% by mass, more preferably 44 to 82% by mass.

<Fiber-containing resin composition layer>
The fiber-containing resin composition layer is composed of a fiber-containing resin composition containing the thermosetting resin and the fiber base material and, if necessary, an inorganic filler. The fiber-containing resin composition layer includes a semi-cured product in addition to an uncured product of the fiber-containing resin composition.
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, and still more preferably 30 to 80% by mass. 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 this laminate has low 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.
When the fiber-containing resin composition contains an inorganic filler, the content of the inorganic filler is preferably 5 to 75% by volume of the total amount of the thermosetting resin and the inorganic filler, and is 15 to 70. It is more preferable that it is volume%, and it is still more preferable that it is 30-70 volume%. 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 thermal expansion coefficient 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 thermal expansion coefficient is sufficient, and when it is 75% by volume or less, the fluidity is increased and the moldability is improved.

<Glass substrate layer>
As the thickness of the glass substrate layer, a thin glass film having a thickness of 30 to 200 μm is preferable from the viewpoint of thinning the laminate and workability, and the thickness is 50 considering practicality such as ease of handling. -150 micrometers is more preferable. Further, as a material for the glass substrate, 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.
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 board or the multilayer laminated board obtained from this laminated body may be suppressed, but preferably 8 ppm / Or less, more preferably 6 ppm / ° C. or less, and even more preferably 4 ppm / ° 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.
The glass substrate layer preferably occupies 10 to 70% by volume, more preferably 15 to 70% by volume, and still more preferably 20 to 70% by volume with respect to the entire laminate. When the exclusive amount of the glass substrate is 10% by volume or more, it is advantageous for obtaining a laminate having low thermal expansion and high elasticity. Conversely, when the exclusive amount of the glass substrate is 70% by volume or less, workability and This is advantageous in terms of handling properties (ease of handling).
In particular, glass molded by the fusion method (overflow method) has very high surface flatness, but melted glass enters the molded part from the pipe, and from the upper part of the molded part to the free surface on both sides. Since the glass on both sides that overflowed and overflowed below the forming part is combined to form the glass, there is a possibility of breakage at the combined part. By using the structure of the present invention, this destruction can be prevented.

<Support film>
Said laminated body may have a support body film on the surface. The support film will be described in detail in the description of the laminate manufacturing method described below.

<Method for producing laminate>
There is no restriction | limiting in particular in the manufacturing method of the said laminated body, For example, it can manufacture suitably by laminating | stacking the adhesive film which consists of a resin composition, the prepreg which consists of a fiber containing resin composition, and a glass substrate.
As this lamination method, for example, a pressure lamination such as a vacuum lamination or roll lamination described later is suitably applied.

<Manufacturing method of laminate by lamination>
Said laminated body can be 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. Moreover, it is also manufactured by using a prepreg using the fiber-containing resin composition and laminating a single prepreg or a prepreg laminated body in which a plurality of prepregs (for example, 2 to 10 sheets) are stacked and a glass substrate. can do. The adhesive film and prepreg will be described later. In addition, these vacuum lamination and roll lamination can be performed using a commercially available vacuum laminator and roll laminator.
As the thermosetting resin in the resin composition, a resin that melts at a temperature equal to or lower than the temperature at the time of lamination is suitably used. 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.

<Adhesive film>
When a laminate is produced using a pressure laminator such as a vacuum laminator or a roll laminator, the above resin composition is generally prepared as an adhesive film.
As an adhesive film, what has the following laminated structure is used suitably.
(1) Support Film / Resin Composition Layer In the laminated structure of (1), those having the following laminated structure in which a protective film is further laminated are also preferably used.
(2) Support film / resin composition layer / protective film The protective film is formed on the side opposite to the support film with respect to the thermosetting resin composition of the present invention, and is intended to prevent adhesion and scratches of foreign matter. It is used for
The adhesive film having the laminated structure (1) to (2) can be produced according to a known method.
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 of producing the adhesive film of (2), 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 films, and the resin composition layer is formed by drying the organic solvent of the varnish by heating, hot air blowing, or the like. A protective film may be disposed on the side not in contact with the support film.

As a coating apparatus for these resin composition layers, 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.
In the above adhesive film, the resin composition layer may be semi-cured.
The above support film is a support for producing an adhesive film, and the support film is left as it is in a laminate prepared by laminating such an adhesive film with a support film. However, when a printed wiring board or a multilayer printed wiring board is manufactured, these support films are usually finally peeled off or removed.

<Lamination method using 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.

<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 usually be performed by heating and drying at a temperature of 100 to 200 ° C. for about 1 to 30 minutes. In addition, it can also prepare by melt | dissolving said resin composition in an organic solvent, impregnating or coating a fiber base material as a varnish, and drying an organic solvent. When preparing the varnish, the organic solvent used is not particularly limited as long as it can dissolve the resin composition and disperse the inorganic filler. For example, ethanol, propanol, butanol, methyl cellosolve, Alcohol solvents such as butyl cellosolve and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, toluene, xylene , Aromatic solvents such as mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and sulfur atom-containing solvents such as dimethyl sulfoxide. It can be used.

<Support film>
The prepreg used for laminating preferably has a support film disposed on one side.
Examples of the support film include a support film in the case of an adhesive film, for example, polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter may be abbreviated as “PET”) polyester such as polyethylene naphthalate, Examples thereof include polycarbonate, polyimide, and metal foil such as release paper, copper 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.

<Lamination method using prepreg>
The prepreg with the above support film is pressed against a glass substrate while being pressurized and heated. The lamination is preferably performed by preheating a prepreg and a 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 prepreg is laminated on the glass substrate, it is cooled to around room temperature. Thus, a laminated body can be manufactured.

[Laminated board]
The laminate of the present invention is a laminate comprising one or more resin cured product layers or fiber-containing resin cured product layers and one or more glass substrate layers.
This laminate has a structure in which the resin composition layer of the above-mentioned laminate or the fiber-containing resin composition layer containing an inorganic filler as necessary is cured to form a resin cured product layer or a fiber-containing resin cured product layer. Is preferred.
As the structure of the laminate, “glass substrate layer / resin cured product layer”, “resin cured product layer / glass substrate layer / resin” in which the resin cured product layer or the fiber-containing resin cured product layer is laminated on at least one surface of the glass substrate. In addition to the configuration of “cured product layer”, it has a plurality of glass substrate layers, such as “resin cured product layer / glass substrate layer / resin cured product layer / glass substrate layer / resin cured product layer”. There is a laminated board of composition.

<Resin cured product layer or fiber-containing resin cured product layer>
The thickness of the layer when the resin composition layer or the fiber-containing resin composition layer is cured, that is, the thickness of the resin cured product layer or the fiber-containing resin cured product layer is preferably 5 to 200 μm. If the thickness is 5 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, and the thermal expansion coefficient and the elastic modulus of the laminated plate can be reduced. Also, if it is less than 5 μm, the glass may be broken during lamination and pressing processes when creating a laminate, and if it exceeds 200 μm, the glass substrate may not withstand the thermal expansion force of the resin layer and may be broken during lamination or cutting. Yes Processability may be inferior. From these viewpoints, the thickness of the cured resin layer or the fiber-containing cured resin layer is more preferably 10 to 150 μm, and further preferably 10 to 120 μm.
The thickness of such a cured resin layer or fiber-containing cured resin layer can be determined as follows. Hold the cured laminate vertically or horizontally, and add a total thickness of 10 places, 2 places on each side, 6 places above the circumference of the laminate, 2 places on each side and 2 places in the center. Measure with a micrometer to the nearest 0.01 mm. However, measurement at one place is performed twice, and the average value is taken as the thickness of each point. A value obtained by subtracting the total thickness of the “glass substrate layers” included in the laminate from the average thickness thus obtained was defined as an average thickness d. The thickness of the glass substrate layer is measured in advance by the same method.

In addition, the thermal expansion coefficient of such a cured resin layer or fiber-containing cured resin layer is determined by the type of thermosetting resin, the amount of fiber base material or inorganic filler, etc., and is about the same as a glass film. However, it is usually about 3 to 80 ppm / ° C. and preferably about 5 to 60 ppm / ° C. in the temperature range of 30 to 100 ° C.
When the thermal expansion coefficient exceeds 80 ppm / ° C., the difference in thermal expansion coefficient from the glass becomes large, causing warpage and peeling, and it is difficult to obtain those having a thermal expansion coefficient less than 3 ppm / ° C.
Such a thermal expansion coefficient can be measured by TMA (thermomechanical analysis), and an average value in a temperature range of 30 to 100 ° C. is obtained.

  In the present invention, the thickness and thermal expansion coefficient of the cured resin layer or the fiber-containing cured resin layer adjacent to the glass substrate affect the destruction of the glass substrate in the case of laminating or cutting the laminated plate. This has been found, and this effect is defined by the product of the average thickness and the thermal expansion coefficient of the cured resin layer or the fiber-containing cured resin layer, and this is solved.

That is, the product d · σ of the thickness d of the cured resin layer or the fiber-containing cured resin layer and the average value σ of the thermal expansion coefficient at 30 to 100 ° C is 1000 µm · ppm · ° C ^-1 or less, Preferably it is 30-1000 micrometers-ppm-degreeC- ¹ . When it is 30 μm · ppm · ° C. ⁻¹ or more, the cured resin layer or the fiber-containing cured resin layer does not become too thin, the glass substrate layer can be protected, and a laminate can be produced. When it exceeds 1000 μm · ppm · ° C.− ¹ , the glass of the glass substrate layer tends not to withstand the thermal expansion force of the cured resin layer or the fiber-containing cured resin layer, so that the workability is inferior. Since the thermal expansion coefficient of the resin cured product layer or the fiber-containing resin cured product layer is determined to some extent by the thermosetting resin used, the fiber base material, the inorganic filler, etc., the thickness d and the thermal expansion coefficient σ are as described above. It is preferable to determine the thickness of the cured resin layer or the fiber-containing cured resin layer, that is, the thickness of the resin composition layer forming the laminate so that the product of
In addition, when the product of the thickness d and the thermal expansion coefficient σ of the resin cured product layer or fiber-containing resin cured product layer adjacent to both surfaces of the glass substrate is different in each resin cured product layer or fiber-containing resin cured product layer In any cured resin layer or fiber-containing cured resin layer, the product of the thickness d and the thermal expansion coefficient σ is preferably 1000 μm · ppm · ° C.− ¹ or less.

On the other hand, as the thermal expansion coefficient of the laminated plate is closer to the thermal expansion coefficient (about 3 ppm / ° C.) of the silicon chip, warpage may be suppressed. It is preferably 8 ppm / ° C. or less, more preferably 6 ppm / ° C. or less, and further preferably 4 ppm / ° C. or less.
Such a thermal expansion coefficient can be measured by TMA (thermal instrument analysis).

  Moreover, the storage elastic modulus at 40 ° C. of this laminate is preferably 10 to 80 GPa. A glass substrate 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, stress due to the difference in thermal expansion coefficient between the glass substrate and the cured resin layer or the fiber-containing cured resin layer is suppressed, and warpage and cracking of the laminate are suppressed. From this viewpoint, the storage elastic modulus of the resin cured product layer or the fiber-containing resin cured product layer is more preferably 12 to 75 GPa, and still more preferably 15 to 70 GPa.

  You may have metal foil, such as copper and aluminum, 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.

<Manufacturing method of laminated board>
The resin cured product layer forming step in the method for producing a laminated board is not particularly limited, although it is performed by heat and pressure molding of an adhesive film made of the resin composition. 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 laminate, the support film is peeled off as necessary, and then the resin composition layer or the fiber-containing resin composition layer is heat-cured to produce a laminate.
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.
Further, a prepreg laminate formed by superimposing one prepreg or a plurality of (for example, 2 to 10) prepregs and a glass substrate are laminated, and heated and pressed by a press method to be cured, thereby being laminated. Can also be manufactured. 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.

<Multilayer 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 10). 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.

<Formation of conductor layer>
Next, a conductor layer is formed on the cured resin layer or the fiber-containing cured resin layer 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, the surface of the cured resin composition layer or fiber-containing resin composition layer is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, Roughening treatment is performed with an oxidizing agent such as hydrogen oxide / sulfuric acid or nitric acid to form an uneven anchor. 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, a multilayer printed wiring board may be formed by laminating a plurality of laminated boards on which a wiring pattern is 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 or aluminum on one side 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. Moreover, the laminated body obtained by the said lamination is laminated | stacked by the structure which laminated | stacked 1 sheet or multiple sheets (for example, 2-10 sheets), and arrange | positioned metal foil on the single side | surface or both surfaces, A laminated board with metal foil is obtained. It 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.

  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 resin solution having unsaturated maleimide groups]
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 resin solution was obtained.

[Production of Varnish (G) Containing Thermosetting Resin Composition]
(1) As a curing agent (A), a solution of a resin having the above 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 inorganic filler (D), fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC],
(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,
Was mixed at the blending ratio (parts by mass) shown in Table 1 to prepare a uniform varnish (G) having a resin content (total of resin components, etc., solid content) of 65% by mass.

[Production of Varnish (H) Containing Thermosetting Resin Composition]
A varnish (H) having a resin content (total of resin components) of 65% by mass was produced in the same manner as in the varnish (G) except that the inorganic filler (D) was not added.

[Manufacture of prepreg]
The varnishes (G) and (H) were impregnated and coated on E glass cloths having different thicknesses, and dried by heating at 160 ° C. for 10 minutes to obtain prepregs. As the type of E glass cloth, IPC standards 1027, 1078 and 2116 of Asahi Kasei E-materials were used. A prepreg produced using these three types of glass cloth may be referred to as PP # 1027 (G), PP # 1078 (G), PP # 2116 (G), and PP # 1078 (H), respectively. Moreover, the resin content of each prepreg was 66, 54, 50, and 50 mass%, respectively.

[Examples 1 to 3, Comparative Example 1]
A glass film “trade name OA-10G” (manufactured by Nippon Electric Glass Co., Ltd.) having a thickness of 100 μm manufactured by an overflow molding method was prepared as a glass film to be a glass substrate layer (sometimes referred to as GF100 μm).
The glass film and the prepreg are overlapped as shown in Table 2, 12 μm electrolytic copper foils are placed one above the other, and pressed at a pressure of 3.0 MPa and a temperature of 235 ° C. for 120 minutes to obtain a copper-clad laminate. Produced.

[Example 4, Comparative Example 2]
(Adjustment of adhesive film varnish H)
Nippon Kayaku Co., Ltd. polyamide resin BPAM-155 (product name) dissolved in a dimethylacetamide solvent to a concentration of 10% is used as an epoxy resin, and Nippon Kayaku Co., Ltd. epoxy resin NC3000- 62.0 parts of H (trade name, concentration 100%), 23.5 parts of triazine-containing phenolic novolac resin LA-1356-60P (trade name, concentration 60%) manufactured by DIC Corporation as a curing agent, cured As an accelerator, 0.6 part of 2-phenylimidazole (trade name, concentration 100%) manufactured by Shikoku Kasei Kogyo Co., Ltd. and 8 parts of fumed silica AEROSIL R972 (trade name, concentration 100%) manufactured by Nippon Aerosil Co., Ltd. are used. 8 parts, polyester-modified polydimethylsiloxane BYK-310 (trade name) manufactured by BYK Chemie Japan 3.6 parts of 25% strength), further, dimethylacetamide solvent and add 314.3 parts dissolved, mixed, subjected to bead mill dispersion treatment to prepare a varnish H.

(Adjustment of adhesive film varnish I)
As an epoxy resin, 31.8 parts of NC3000-H (concentration: 100%) and as a curing agent, triazine-containing cresol novolak LA-3018-50P (trade name, concentration: 50%) manufactured by DIC Corporation, 7.2. As a phenol-containing resin containing phosphorus, HCA-HQ (trade name, concentration: 100%) manufactured by Sanko Co., Ltd., phenol novolac TD2131 (concentration 100%) manufactured by DIC Corporation, and Shikoku Kasei Kogyo as a curing accelerator 1-Cyanoethyl-2-phenylimidazolium trimellitate 2PZCNS-PW (trade name, concentration 100%) manufactured by Co., Ltd. in an aminosilane in a methyl isobutyl ketone solvent so that the solid content is 70% Silica filler treated with coupling agent SO-C2 (manufactured by Admafine Techno Co., Ltd., trade name) 78.6 parts, as additional solvent, methyl ethyl ketone was blended 42.7 parts, dissolution, mixing, subjected to bead mill dispersion treatment to prepare a varnish I.

<Manufacture of adhesive film>
The resin varnish H is dried to 5 μm after drying using a bar coater on the release-treated surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Co., Ltd.) having a thickness of 38 μm. And dried at 140 ° C. for 3 minutes. Subsequently, varnish I was coated on the varnish H layer so that Example 4 had a thickness of 25 μm after drying, and Comparative Example 2 had a thickness of 76 μm. Got.

<Manufacture of laminated board (resin cured product layer / glass substrate layer / resin cured product layer)>
As the glass substrate, an ultrathin glass film “OA-10G” (trade name, thickness 100 μm) manufactured by Nippon Electric Glass was used. The adhesive film is placed on both surfaces of the glass substrate so that the resin composition layer is in contact with the glass substrate, and a batch type vacuum pressure laminator “MVLP-500” (made by Meiki Co., Ltd., trade name) ) Was laminated by lamination. The degree of vacuum at this time was 30 mmHg (40.0 hPa) 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 and cured at 180 ° C. for 60 minutes to obtain a three-layer laminate (resin cured product layer / glass substrate layer / resin cured product layer).

[Measurement]
About the laminated board obtained by said Example and comparative example, performance was measured and evaluated with the following method.
(1) Measurement of thickness of cured resin layer or cured fiber-containing resin layer The thickness of cured resin layer or cured fiber-containing resin layer is measured by holding the cured substrate vertically or horizontally and laminating. The thickness of a total of 10 places including a total of 8 places and 2 places in the central portion of the inner side of the plate 6 mm or more from 2 places on each side was measured with a micrometer to a unit of 0.01 mm. However, the measurement at one place was performed twice, and the average value was taken as the thickness of each point. A value obtained by subtracting the total thickness of the “glass substrate layers” included in the laminate from the average thickness thus obtained was defined as an average thickness d. The thickness of the glass substrate layer was measured in advance by the same method.
The thickness d thus obtained is shown in parentheses as the structure of the laminate of Table 2.

(2) Measurement of thermal expansion coefficient of resin cured product layer or fiber-containing resin cured product layer A test piece of 4 mm × 30 mm was cut out from a laminate composed only of a resin cured product layer or a fiber-containing resin cured product layer. 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., the load is 5 g, and the chuck distance is 10 mm. Each average thermal expansion coefficient in the range of ° C. was determined.
As a result, the average thermal expansion coefficient σ in the temperature range of 30 to 100 ° C. was 11 ppm / ° C. for all prepregs. All of the adhesive films were 33 ppm / ° C. Table 2 shows the product of the above average thickness d and the obtained average thermal expansion coefficient σ.

(3) Measurement of thermal expansion coefficient of laminated board A test piece of 4 mm x 30 mm was cut out from the laminated board. 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., the load is 5 g, and the chuck distance is 10 mm. Average thermal expansion coefficients in the range of ° C and in the range of 100 to 190 ° C were determined, respectively. The results are shown in Table 2.

(4) Measurement of storage elastic modulus of laminated board A test piece of 5 mm x 30 mm was cut out from the laminated board. When using a copper clad laminated board, after removing copper foil by being immersed in copper etching liquid, the test piece was cut out.
Storage elastic modulus at 40 ° C. was measured using a wide-area viscoelasticity measuring device (DVE-V4 type, manufactured by Rheology) under the conditions of 20 mm span, 10 Hz frequency, and 1 to 3 μm vibration displacement (stop excitation). . The results are shown in Table 2.

(5) Shape of cut surface A cross section of a test piece cut out by a wet cutting machine was observed with an optical microscope (× 10) and evaluated according to the following criteria.
○: No peeling at the center of the glass ×: Peeling at the center of the glass

  As is apparent from Table 2, Examples 1 to 4 of the present invention are conditions in which the product of the thickness d of the resin composition layer and the average thermal expansion coefficient σ in the temperature range of 30 ° C. to 100 ° C. is limited. By laminating underneath, a wiring board that does not break from the cut surface can be produced. Furthermore, the highly elastic laminated board was able to be obtained by adding an inorganic filler.

  From the above results, according to the present invention, a highly elastic laminate having high fracture toughness can be provided.

Claims (13)

A laminate including 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, and an average thickness d of the cured resin composition layer and an average value σ of a thermal expansion coefficient at 30 to 100 ° C. The product d · σ is 1000 μm · ppm · ° C. ⁻¹ or less. A laminate including one or more resin composition layers and one or more glass substrate layers,
The resin composition layer is made of a resin composition including a thermosetting resin and a fiber base material, and an average thickness d of the cured resin composition layer and an average value σ of a thermal expansion coefficient at 30 to 100 ° C. The product d · σ is 1000 μm · ppm · ° C. ⁻¹ or less.   The laminate according to claim 2, wherein the fiber substrate is one or more selected from glass fiber, polyimide fiber, polyester fiber, polytetrafluoroethylene fiber, and aramid resin.   The laminate according to claim 2 or 3, wherein the resin composition layer further contains an inorganic filler.   The said inorganic filler is 1 type (s) or 2 or more types selected from a silica, an alumina, a talc, a mica, aluminum hydroxide, magnesium hydroxide, a calcium carbonate, an aluminum borate, and a borosilicate glass. 4. The laminate according to 4.   The laminate according to any one of claims 1 to 5, wherein the glass substrate layer has a thickness of 30 to 200 µm.   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 6, wherein the laminate is one or more selected from a triazine resin and a melamine resin.   The laminated board obtained by heat-pressing the laminated body in any one of Claims 1-7.   A multilayer laminate comprising one or more laminates according to claim 8.   The printed wiring board which provided the circuit in the laminated board of Claim 8.   The multilayer printed wiring board which provided the circuit in the multilayer laminated board of Claim 9.   A method for producing a laminate comprising one or more cured resin layers made of a cured product of the resin composition and one or more glass substrate layers, wherein the cured resin layer is formed on the surface of the glass substrate layer. The manufacturing method of the laminated board which has a resin hardened | cured material layer formation process to do.   The method for producing a laminated board according to claim 12, wherein the resin cured product layer forming step is heating and pressing of an adhesive film made of the resin composition.