TW201945191A - Laminate sheet, printed wiring board, multilayer printed wiring board, laminate body, and method for producing laminate sheet - Google Patents

Abstract

A laminate sheet, including at least one layer of a glass substrate layer, at least one layer of a curable composite material layer containing a resin and a reinforcing material, and at least one layer of a resin sheet layer having a tensile elastic modulus of not more than 15 GPa.

Description

Laminated board, printed wiring board, multilayer printed wiring board, laminated body, and method for manufacturing laminated board

This invention relates to the manufacturing method of a laminated board, a printed wiring board, a multilayer printed wiring board, a laminated body, and a laminated board.

As a material for a (multi-layer) printed wiring board, an insulating layer composed of a prepreg or a hardened prepreg obtained by hardening the prepreg, or a coating obtained by laminating a metal wiring layer such as a copper foil is known. Copper laminate. Sometimes such an insulating layer or a copper-clad laminated board is laminated to form an optical waveguide as a glass layer for optical wiring.
However, when a glass layer is laminated on a hardened prepreg, warpage may occur during heating or the glass may break.
For example, in Patent Document 1, as a method for solving the problem of warping or cracking of a laminated plate obtained by curing a prepreg laminated glass layer, it is disclosed that the thickness of the prepreg layer after curing is 30 to 100 The product of the thermal expansion coefficient at ℃ becomes a constant value or less.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-120688

[Problems to be Solved by the Invention]

Although the technology disclosed in Patent Document 1 has a certain degree of improvement in warpage or cracking of a laminated plate obtained by curing a prepreg laminated glass layer, it is still not satisfactory. In addition, the technology disclosed in Patent Document 1 makes the product of the thickness of the prepreg after hardening and the coefficient of thermal expansion less than a certain value. Therefore, it is difficult to adopt this method when the thickness of the prepreg is thick or if several sheets are laminated. technology.
In view of the problems described above, the present invention has as a problem the following problem: to effectively solve the problem of warping or cracking when curing a prepreg laminated glass layer regardless of the thickness of the prepreg.
[Means for solving problems]

As a result of intensive research to solve the above-mentioned problems, the inventors of the present case have found that by coexisting a resin sheet containing resin as a main component, it is possible to improve warping or cracking when curing a prepreg laminated glass layer. Using this knowledge, the present invention has been completed.

That is, the present invention includes the following aspects.
[1]
A laminated board comprising:
At least one glass substrate layer,
A hardened composite material layer containing at least one resin and a reinforcing material, and at least one resin sheet layer having a tensile elastic modulus of 15 GPa or less.
[2]
The laminated board according to [1], wherein the resin sheet layer contains a thermosetting resin.
[3]
The laminated board according to [1] or [2], wherein the thickness of the resin sheet layer is 1 μm or more.
[4]
The laminated board according to any one of [1] to [3], wherein the thickness of the glass substrate layer is 10 to 500 μm.
[5]
The laminated board according to any one of [1] to [4], wherein the resin contained in the hardened composite material layer is selected from the group consisting of an epoxy resin, a phenol resin, a fluorene resin, and a melamine. Amine resin, cyanate resin, isocyanate resin, benzopyrene Resin, oxetane resin, amine resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, polysiloxane resin, three One or two or more resins in the group consisting of resin, modified polyphenylene ether resin, oligopolyphenylene ether resin, and melamine resin.
[6]
The laminated board according to any one of [1] to [5], wherein the reinforcing material contained in the hardened composite material layer is selected from the group consisting of glass fiber, polyimide fiber, polyester fiber, and polytetramethylene. At least one of the group consisting of a vinyl fluoride fiber and an aramid fiber.
[7]
The laminated board according to any one of [1] to [6], wherein the hardened composite material layer further contains an inorganic filler.
[8]
The laminated board according to [7], wherein the inorganic filler contained in the hardened composite material layer is selected from the group consisting of silicon oxide, aluminum oxide, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and nitrogen. At least one of the group consisting of aluminum nitride, silicon nitride, boron nitride, aluminum borate, and borosilicate glass.
[9]
The laminated board according to any one of [1] to [8], wherein the maximum value of the thermal expansion coefficient in the plane direction of the hardened composite material layer is 20 ppm / ° C or less.
[10]
The laminated board according to any one of [1] to [9], wherein the resin sheet layer is directly laminated on at least one side of the glass substrate layer.
[11]
The laminated board according to any one of [1] to [10], which includes two or more layers of the resin sheet layer, and the glass substrate layer is arranged between the two layers of the resin sheet layer.
[12]
The laminated board according to any one of [1] to [11], including only one layer of the glass substrate.
[13]
The laminated board according to any one of [1] to [12], further comprising at least one copper foil layer.
[14]
The laminated board according to any one of [1] to [13], which includes two or more layers of the hardened composite material.
[15]
A printed wiring board includes the laminated board according to any one of [1] to [14], and a conductor circuit provided on the laminated board.
[16]
A multilayer printed wiring board comprising:
At least one glass substrate layer,
A hardened composite material layer containing at least one of a resin and a reinforcing material,
At least one resin sheet layer with a tensile elastic modulus of 15 GPa or less, and at least two conductor circuit layers.
[17]
A laminated body comprising:
At least one glass substrate layer,
A composite material layer containing at least one uncured or semi-cured hardening resin and a reinforcing material, and at least one resin sheet layer having a tensile elastic modulus of 15 GPa or less.
[18]
A method for manufacturing a laminated body includes the following steps:
In the laminating step, at least one glass substrate layer, a composite material layer containing at least one uncured or semi-hardened thermosetting resin and a reinforcing material, and at least one resin sheet layer having a tensile elastic modulus of 15 GPa or less Layer to obtain a laminate;
In the heating and pressing step, the laminated body is heated and pressed.
[Effect of the invention]

According to the present invention, regardless of the thickness of the prepreg layer, a simple method can effectively improve the problem of warping or cracking of the glass laminated layer when the prepreg is hardened.

Hereinafter, the form for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the gist thereof.

[Laminated board]
The laminated board of this embodiment includes at least one glass substrate layer, at least one hardened composite material layer including a resin and a reinforcing material, and at least one resin sheet layer having a tensile elastic modulus of 15 GPa or less. Because of this structure, the laminated board of this embodiment can effectively improve the problem of warping or cracking when curing the laminated glass substrate layer without adjusting the thickness of the hardened composite material layer.

(Glass substrate layer)
The glass substrate layer is not particularly limited as long as it is a layer composed of a substrate including glass. Specific examples of the glass substrate layer include those obtained by implementing an optical wiring for an optical waveguide. In this embodiment, the type and application of the glass substrate layer are not limited. The material of the glass substrate is not particularly limited. For example, glass such as alkali metal silicate glass, alkali-free glass, and fused quartz can be used. Considering the viewpoint of making an optical waveguide, borosilicate glass is preferred. .

The thickness of the glass substrate layer is not limited, and may be appropriately set according to the application, and may be, for example, 1 to 1000 μm, 10 to 500 μm, or 50 to 500 μm.
The number of layers of the glass substrate layer is not limited, and only one layer may be provided, and multiple layers may be provided according to requirements.
In addition, the ratio of the glass substrate layer in the laminate is not limited. In the case where the glass substrate layer is used as the optical wiring, a certain degree of thickness is required. Considering the rigidity or thermal expansion of the laminate, the ratio of the glass substrate layer Great system is better. On the other hand, from the viewpoint of ease of processing or handling, it is preferable that the ratio of the glass substrate layer is not too large. Therefore, the ratio of the thickness of the glass substrate layer (the total thickness when the glass substrate layer is provided in multiple layers) to the thickness of the entire laminated board is preferably 5 to 70%, more preferably 10 to 70%, and still more preferably 15 to 70. %.

(Hardened composite material layer)
The hardened composite material layer is not particularly limited as long as it contains a resin and a reinforcing material. A typical hardened composite material layer includes a hardened prepreg obtained by impregnating a resin with a reinforcing material (fiber substrate, etc.) and hardening a semi-hardened prepreg.
The manufacturing method of the prepreg is not limited. For example, a resin composition containing a curable resin and an inorganic filler as required can be impregnated or coated on a fiber substrate, and then heated and dried for B-stage (half-step). Hardening). This B-stage conversion, in the case of a thermosetting resin, can usually be performed by heating and drying at a temperature of 100 to 200 ° C. for about 1 to 30 minutes. Alternatively, the resin composition can be produced by dissolving the resin composition in an organic solvent, impregnating or coating the fibrous substrate as a varnish, and removing the organic solvent by drying or the like. The organic solvent used in the preparation of the varnish is not particularly limited as long as it can dissolve the resin composition and disperse the inorganic filler, and examples thereof include ethanol, propanol, butanol, methylcythreon, Alcohol solvents such as butyl cyperidine, propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ester solvents such as ethyl acetate or γ-butyrolactone, and ethers such as tetrahydrofuran Solvents, aromatic solvents such as toluene, xylene, mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other nitrogen-containing solvents, dimethylsulfene Solvents containing sulfur atoms can be used singly or in combination of two or more.

The resin contained in the hardened composite material layer is not particularly limited, and for example, various known resins used for prepregs can be used. Specific examples of the resin contained in the hardened composite material layer are not limited to the following, and may be selected from the group consisting of an epoxy resin, a phenol resin, a fluorene imine resin, a maleimide resin, and a cyanate ester. Resin, isocyanate resin, benzopyrene Resin, oxetane resin, amine resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, polysiloxane resin, three Resin, modified polyphenylene ether resin, oligopolyphenylene ether resin, and melamine resin.
However, the resin in this embodiment means a resin in a solid state, and is not limited to a cured product of a curable resin such as a thermosetting resin or a photocurable resin, and may be a thermoplastic resin. Specific examples of the thermoplastic resin are not limited to the following, and examples thereof include polyamide, polyester, polycarbonate, polyether, polysulfide, and ketone resin. These resins may be used alone. , Can also be mixed and used.
These resins may be used alone or in combination.

Reinforcing materials are materials with higher physical strength than resins used in combination. Specific examples of the reinforcing material are not limited to the following, and include reinforcing fibers. The reinforcing fiber is not limited to the following, and for example, glass fibers such as E glass, D glass, NE glass, T glass, S glass, and Q glass, carbon fibers, basalt fibers, and inorganic fibers such as SiC fibers can be used. Organic fibers such as rhenium fiber, polyester fiber, polytetrafluoroethylene fiber, aramid fiber, and hemp fiber. Among them, preferred examples include glass fibers, polyimide fibers, polyester fibers, polytetrafluoroethylene fibers, and polyaramide fibers. In consideration of heat resistance, moisture resistance, and processability, the reinforcing material is preferably a surface treatment or mechanical fiber opening treatment by a surface treatment agent such as a silane coupling agent.
These reinforcing materials may be used singly or in combination.

The reinforcing fibers may be continuous fibers or discontinuous fibers.
Examples of continuous fibers include sheet-like or ribbon-like fibers such as woven fabrics, knitted fabrics, and non-woven fabrics, or rovings. In addition, the nonwoven fabric-based fibers are stacked in a three-dimensionally structured sheet, and examples thereof include a random mat, a paper material, and a felt.
In the case of non-continuous fibers, the aspect ratio should preferably be 5 or more, or 10 or 50 or more. The fiber length is not limited, and may be, for example, 0.001 mm to 10 mm.

The ratio in the hardened composite material layer of the reinforcing material is not limited, and may be, for example, 1 to 90% by mass. From the viewpoint of obtaining high mechanical strength, the range of more than 20% by mass and 70% by mass is more preferable, and the range of 25 to 55% by mass is more preferable.
The reinforcing material and the resin are preferably mixed, and the resin may be impregnated into the reinforcing material.

The hardened composite material layer contains various additives in addition to the resin and the reinforcing material as required.
Such additives are not limited, and examples thereof include inorganic fillers. The inorganic filler is not limited to the following, and examples thereof include silicon oxide, aluminum oxide, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon nitride, Inorganic fillers such as aluminum borate and borosilicate glass can be used alone or in combination. The particle size of the inorganic filler is not limited, and may be, for example, 0.01 to 200 μm. Although the content of the inorganic filler is not limited, considering that the maximum value of the thermal expansion coefficient in the surface direction of the hardened composite material layer becomes a desired value as described later, the total amount of the resin and the inorganic filler is preferably 5 to 75% by mass, more It is preferably 15 to 70% by mass, and more preferably 30 to 70% by mass.
However, when the reinforcing fiber is not used as the reinforcing material in this embodiment, for example, the inorganic filler may be used as the reinforcing material. On the other hand, when a reinforcing fiber is used as a reinforcing material in the present embodiment, the inorganic filler is used as an additive.

Examples of the additives other than the inorganic filler include flame retardant compounds or general additives. Specific examples of the flame-retardant compound are not limited to the following, and include bromine compounds such as 4,4'-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, melamine, and benzoguanamine Isobaric compounds, thorium-containing Cyclic compounds, and polysiloxane compounds. In addition, the general additives are not limited to the following, and examples thereof include elastomers, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, and tackifiers. Agents, flow regulators, lubricants, defoamers, dispersants, leveling agents, gloss agents, polymerization inhibitors, hardening accelerators, wetting and dispersing agents, surface treatment agents, etc.
Among them, in the case where the reinforcing material is an inorganic material or the resin composition contains an inorganic filler, it is suitable to use a wet dispersant or a surface treatment agent to improve the dispersibility in the resin composition. As the surface treatment agent, a silane coupling agent is well known, and specifically, it is not limited to the following, and examples thereof include γ-aminopropyltriethoxysilane, N-β- (aminoethyl)- γ-aminopropyltrimethoxysilane and other amine silane series, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other rings Ethoxysilane-based, γ-methacryloxypropyltrimethoxysilane, vinyl-tris (β-methoxyethoxy) silane, and other vinyl silane-based, N-β- (N-vinylbenzyl Cationic silanes such as aminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride and phenylsilanes. In addition, as for the wetting and dispersing agent, it can be used by users of general coatings, and a wetting and dispersing agent based on a copolymer substrate is preferable. Specific examples of commercially available products of such wetting and dispersing agents are not limited to the following, and examples include Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK Japan Co., Ltd., BYK-W903, BYK-W940, etc.
Examples of the hardening accelerator include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetoacetone, nickel octylate, and manganese octoate. Phenol compounds such as phenol, xylenol, cresol, resorcinol, catechol, octylphenol, nonylphenol, alcohols such as 1-butanol, 2-ethylhexanol, 2-methyl Imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, Imidazoles such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of these imidazole carboxylic acids or their anhydrides Derivatives such as dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, amines, phosphine compounds, phosphine oxide compounds, sulfonium salts Compounds, phosphorus compounds such as diphosphine compounds, epoxy-imidazole adduct compounds, benzamidine peroxide, benzamidine p-chloroperoxide, di (tertiary butyl) peroxide, peroxodicarbonate Peroxides such as propyl ester, di-2-ethylhexyl carbonate, Or azo compounds such as azobisisobutyronitrile.

Each of the above additives can be used alone or in combination of two or more according to demand.
In addition, the total content (ratio of components other than the resin and the reinforcing material) of the content of the hardened composite material layer of various additives is preferably 20% by mass or less.

The maximum value of the thermal expansion coefficient in the plane direction of the hardened composite material layer (value in the direction in which the thermal expansion coefficient becomes maximum, hereinafter sometimes referred to as "CTE of the hardened composite material layer") is preferably 20 ppm / ° C or less, more preferably 10 ppm / ° C or lower, more preferably 5 ppm / ° C or lower, further preferably 3 ppm / ° C or lower, and particularly preferably 1 ppm / ° C or lower. In addition, the thermal expansion coefficient can be obtained, for example, by measuring the linear expansion coefficient in the plane direction of 60 ° C. to 120 ° C. at a temperature of 10 ° C. per minute from 40 ° C. to 340 ° C. by a thermomechanical analysis device.
If the CTE of the hardened composite material layer is within the above-mentioned range, warpage of the laminate or cracking of the glass is unlikely to occur.
In addition, the CTE of the hardened composite material layer is, for example, as a resin, a reinforcing material, and an optional inorganic filler, from the specific examples of the resin, the reinforcing material, and the inorganic filler contained in the hardened composite material layer described above, respectively. It is appropriately selected and easily adjusted within the above range. In addition, regardless of the type of the resin, the reinforcing material, and the inorganic filler, for example, the amount of the resin, the reinforcing material, and the inorganic filler can be increased or decreased as appropriate within the respective ideal ranges described above, thereby easily Adjust to the above range.

In addition, the material constituting the hardened composite material layer (a resin composition including a resin, a reinforcing material, and an additive added as required) has a tensile elastic modulus (hereinafter, also referred to simply as "the tensile elastic modulus of the hardened composite material layer" ") Is not particularly limited, and considering the viewpoint of easier maintenance of the shape of the laminated plate by reducing thermal expansion, it is preferably more than 15 GPa, and more preferably 20 GPa or more. In addition, the tensile elastic modulus of the hardened composite material layer can be measured in accordance with IPC-TM-650 2.4.19. In addition, the tensile elastic modulus of the hardened composite material layer can be used as a resin, a reinforcing material, and an optional inorganic filler, respectively. The resin, the reinforcing material, and the inorganic filler contained in the hardened composite material layer can be individually used. A specific example is appropriately selected, and it is easy to adjust within the above range. In addition, regardless of the type of resin, reinforcing material, and inorganic filler, for example, the amount of resin, reinforcing material, and inorganic filler can be increased or decreased appropriately within the respective ideal ranges, and it is easy to adjust. Within the above range.

The thickness of the hardened composite material layer is not limited, and can be appropriately set according to the use thereof, the thickness of the glass substrate layer, and the like. For example, it can be 1 to 1000 μm, and from the viewpoint of practicality, it is preferably 10 to 200 μm. Generally speaking, a thicker layer of the hardened composite material is less likely to cause warpage in the laminate, and as a result, the glass tends to be less likely to crack. However, in the laminated board of the present embodiment, since the warpage or cracking of the glass is reduced by the resin sheet layer, the hardened composite material layer may be thin, for example, 200 μm or less, or 100 μm or less, and may further be 60 μm or less.
The number of layers of the hardened composite material layer is not limited, and a plurality of layers can be provided according to requirements. When multiple layers are provided, the thickness of each layer may be the same or different. When a plurality of layers are provided, they may be alternately laminated with a copper foil layer or the like described later.

(Resin sheet)
In this embodiment, as described above, the laminated board including the glass substrate layer and the hardened composite material layer further reduces the warpage of the laminated board or the cracking of the glass by further including the resin sheet layer.
Here, the resin sheet is a sheet containing a resin (polymer material) as a main component, and the content ratio (mass%) of the resin is larger than that of the hardened composite material layer.
The resin sheet layer may contain various additives such as inorganic fillers in addition to the resin. Considering the viewpoint of suppressing warpage of the laminated board and glass breakage, the content of the resin should be 20% by mass or more, and more preferably 50% by mass or more. It is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 98% by mass or more.
In addition, it is preferable that the resin sheet layer is composed of only a resin or only a resin and an inorganic filler.
In addition, the inorganic filler that has been described as being contained in the hardened composite material layer can also be used as the inorganic filler that can be contained in the resin sheet layer. In addition, the content of the inorganic filler in the resin sheet layer is not particularly limited, and may be, for example, the same as the content of the hardened composite material layer.

The type of resin contained in the resin sheet layer is not limited, and may be a thermoplastic resin, a thermosetting resin, or a photocurable resin. Although there are differences in the degree depending on the type of resin, any resin has the effect of reducing the warpage and glass breakage of the laminated board. In view of practicality, the resin sheet layer preferably contains a thermosetting resin.
Specific examples of the resin contained in the resin sheet layer are not limited to the following, and examples thereof include bismaleimide resin, fluorimide resin, epoxy resin, maleimide resin, and cyanate ester. Resin, acrylic resin, methacrylic resin, isocyanate resin, citraconiline resin, benzopyrene Resin, oxetane resin, phenolic resin, silicone resin, three Thermosetting or photocurable resins such as resins, modified polyphenylene ether resins, oligopolyphenylene ether resins, and melamine resins.

In addition, if the material constituting the resin sheet layer (a resin alone or a resin composition containing a resin and additives added as required) has a tensile elastic modulus (hereinafter, sometimes referred to as "the tensile elastic modulus of the resin sheet layer" "." Is 15 GPa or less, the effect of reducing the warpage of the laminate and cracking the glass is improved. The tensile elastic modulus is preferably 10 GPa or less, more preferably 5 Gpa or less, further preferably 1 GPa or less, and more preferably 0.5 GPa or less. In addition, the tensile elastic modulus can be measured in accordance with IPC-TM-650 2.4.19. The tensile elastic modulus of the resin sheet layer is, for example, a resin to be used and an inorganic filler to be used arbitrarily, as appropriate, from specific examples of the resin and the inorganic filler contained in each of the resin sheets described above. Choose and easily adjust to the above range. In addition, regardless of the type of resin and inorganic filler, for example, the amount of resin and inorganic filler used can be appropriately increased or decreased within the aforementioned ideal ranges, etc., and it is easy to stretch the elastic sheet of the resin sheet. The amount is adjusted to the above range.

The thickness of the resin sheet layer is not limited, and may be, for example, 1 μm or more. A thicker resin sheet tends to have a higher effect of reducing warpage of the laminate and cracking the glass. Therefore, considering the viewpoint of suppressing warpage and cracking of the laminated board, the thickness may be 1 to 1,000 μm, 5 μm or more, 10 μm or more, 30 μm or more, or 40 μm or more.
In addition, the number of layers of the resin sheet layer is not limited, and may be one layer or multiple layers. It is preferable that two or more resin sheet layers are disposed on both sides of the glass substrate layer to sandwich the glass substrate layer. In other words, the glass substrate layer is preferably arranged between two or more resin sheet layers.

The maximum value of the thermal expansion coefficient in the surface direction of the resin sheet layer (the value in the direction in which the thermal expansion coefficient becomes maximum; hereinafter sometimes referred to as "CTE of the resin sheet layer") is not limited, and may be, for example, 1 to 200 ppm / ° C.

(Other layers)
The laminated board of this embodiment may include other layers in addition to the glass substrate layer, the hardened composite material layer, and the resin sheet layer. For such other layers, an adhesive layer, metal foil such as copper or aluminum may be mentioned Layers, conductor circuit layers, and various layers commonly used in electrical insulation materials. In view of practicality, it is preferable to include at least one copper foil layer as the metal foil layer.
In addition, the thickness of the metal foil layer is not particularly limited, but is preferably 2 to 70 μm, and more preferably 3 to 35 μm.

(Layer appearance)
In the laminated board of this embodiment, the lamination order of the glass substrate layer, the hardened composite material layer, the resin sheet layer, and the metal layer included in accordance with the requirements is not limited, and even if laminated in any order, a reduced laminated board can be obtained Effect of warping, glass breakage. That is, the laminated state in this embodiment is not particularly limited, and the laminated board in this embodiment may be a single-layer or multi-layer glass substrate layer and a single-layer or multi-layer hardened composite The material layer and the resin sheet layer which is a single layer or a plurality of layers are obtained by laminating them in an arbitrary arrangement (arbitrary stacking order). In consideration of practicality, the resin sheet layer may be directly laminated on at least one side of the glass substrate layer. From the viewpoint of more effectively preventing warpage or cracking when the glass substrate is laminated on the hardened composite material layer, it is preferable to include two or more resin sheet layers, and the glass substrate layer is arranged between the two resin sheet layers. That is, the resin sheet layer exists on both sides of the glass substrate layer in a state of sandwiching the glass substrate layer.
In addition, the resin sheet layer may be laminated directly on the glass substrate layer, or may be laminated on the glass substrate layer via other layers such as a hardened composite material layer or a copper foil layer.
Among the specific laminated states described above, the laminated board of this embodiment may be one including two or more hardened composite material layers, or may include only one glass substrate layer.

[Manufacturing method of laminated board]
The manufacturing method of the laminated board of this embodiment is not limited. For example, a glass substrate, a plate-shaped molded body of a hardened composite material, and a resin sheet can be prepared in advance, and these (and further, other layers such as copper foil layers according to requirements) can be laminated to form a stack of this embodiment. Shelf.
Here, in the resin sheet, a unit having a structure as described below can be prepared together with a support film or a protective film which is an arbitrary member.
(1) Support film / resin sheet The resin sheet should be prepared in a state where the support film has been laminated on one side. The support film is not limited to the following, and examples thereof include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, and polycarbonates. , Polyimide, and further metal foils such as release paper, copper foil, and aluminum foil. When a metal foil is used for the support film, a laminated one may be used as it is. In this case, examples of the metal foil include rolled copper and electrolytic copper foil, and a thickness of 2 to 36 μm is generally used. When using a thin copper foil, in order to improve workability, a copper foil with a carrier may be used. The support film may be subjected to a mold release treatment in addition to the extinction treatment and the corona treatment. The support film is used as a support when manufacturing a resin sheet. When a laminated sheet is manufactured using the resin sheet with the support film thus attached, the support film can be left as it is, but usually when manufacturing a printed wiring board or a multilayer printed wiring board , Which will be stripped or removed at the end.
(2) Support film / resin sheet / protective film The protective film is formed on the opposite side of the support film from the resin sheet, and is used by the user for the purpose of preventing foreign matter from adhering or scratching. When using such a resin sheet with a support film and a protective film to manufacture a laminated board, the support film or the protective film can be retained as it is. However, when a printed wiring board or a multilayer printed wiring board is manufactured, it is usually Wait for peeling or removing.

The resin sheet having the laminated structure (1) and (2) can be produced by a known method. Specifically, a coating device known to those skilled in the art such as a notch wheel coater, a rod coater, a contact coater, a roll coater, a gravure coater, and a die coater can be used. A resin (or a resin composition) is manufactured by coating on a support film or the like. When the resin is a hardening resin, it should be hardened or semi-hardened.
In addition, the glass substrate, the hardened composite plate-shaped molded body, and the resin sheet can be bonded to other layers such as a metal foil layer (for example, a copper foil layer is bonded to one side or both sides of the hardened composite material plate). Is the so-called copper-clad laminate, etc.). In addition, when the metal foil layer is provided, if the surface of the metal foil is flash-etched in advance, and then subjected to roughening such as CZ treatment, the adhesion with other layers can be improved.

Lamination can be performed by laminating all the layers included in the laminated board at the same time, or by forming a laminated body (unit) obtained by laminating a glass substrate and a resin sheet in advance, or by laminating a plurality of hardened composite material plates (and metal foil layers). ) The laminated body (unit) obtained by laminating, and the like is laminated together at the end, and the layers contained in the laminated board are sequentially laminated.

When lamination is performed, pressure lamination such as vacuum lamination or roll lamination may be performed, and the respective layers may be pressure-bonded (lamination method). Vacuum lamination or roll lamination can be performed using a commercially available vacuum laminator or roll laminator.
As an example of the lamination method, a case where a resin sheet is laminated on a glass substrate will be described as an example. When the resin sheet is supplied in a state where a support film is provided on one side and a protective film is provided on the other side, the protective film is removed, and then the resin sheet is pressure-bonded to a glass substrate while being pressed and heated. The lamination conditions are based on preheating the resin sheet and the glass substrate according to the requirements. The lamination is preferably performed at a compression temperature (lamination temperature) of 40 ° C to 175 ° C and a compression pressure of 0.5 to 11 kgf / cm ² . In addition, when a vacuum laminator is used, it is preferable to perform lamination under a reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, the lamination method may be a batch method or a continuous method by a roller. As described above, after the resin sheet is laminated on the glass substrate, it is cooled to around room temperature. The support film is peeled as required.
In addition, during lamination, the layers can be fixed by pressing (pressing). When performing lamination, a support film may be added to the outermost surface and then lamination is performed. Considering the viewpoint of forming a laminated board having a uniform thickness, this pressing method is preferable, and in view of preventing the cracking of the glass substrate that may occur during pressing, the laminating conditions should be appropriately adjusted. As for specific pressing conditions, for example, a method generally used when producing a laminated board for a printed wiring board and a multilayer board can be adopted. Specifically, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, or an autoclave molding machine can be used, at a temperature of 180 to 350 ° C, a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm ² Conditions for lamination.
The above-mentioned layers are legal or oppressive, and only one of them may be performed, or both. In addition, all can be performed under heating. If the heating temperature is set to be higher than the melting temperature of the resin in the hardened composite material layer, it is better because the layers are firmly pressed.

(Manufacturing of laminated body and laminated board using the laminated body)
In addition, for the hardened composite material layer, a plate-shaped formed body made of a resin composition containing an unhardened or semi-hardened hardening resin, a reinforcing material, and an additive added as required, or an unhardened hardening material is prepared. A semi-hardened plate-shaped molded body made of a resin composition containing a resin, a reinforcing material, and an additive added according to demand (prepreg) is obtained by mixing it with a glass substrate and a resin sheet, a copper foil according to demand, or The hardened composite material plates and the like are laminated, and a laminated body (that is, at least one layer of a glass substrate, at least one layer of an unhardened or semi-hardened hardening resin and a reinforcing material, and at least one layer are first obtained. (A laminate of one or more layers of copper foil and / or one or more layers of hardened composite material as required), and then the hardening of the composite material layer is performed by heating or light irradiation The resin is hardened, and the laminated board of this embodiment can also be made.
As described above, the laminated system of this embodiment includes at least one glass substrate layer, a composite material layer including at least one layer of an unhardened or semi-hardened hardening resin and a reinforcing material, and at least one layer having a tensile elastic modulus of 15 GPa or less. With the resin sheet layer of this embodiment, the laminate of this embodiment can be ideally used to produce the laminate of this embodiment. That is, the method for manufacturing a laminated board according to this embodiment includes the following steps: a laminating step in which at least one layer of a glass substrate layer, at least one layer containing an unhardened or semi-hardened thermosetting resin and a reinforcing material The material layer and at least one resin sheet layer having a tensile elastic modulus of 15 GPa or less are laminated to obtain a laminated body; in the heating and pressing step, the laminated body is heated and pressed.
In the above method, if the above-mentioned lamination or compression bonding is performed after lamination, it is preferable because the layers of the laminated board are in close contact with each other, so that peeling does not easily occur. When laminating or laminating, heating or light irradiation for curing the curable resin may be performed simultaneously.
In this embodiment, it is preferable that a thermosetting resin is used as the curable resin in the laminate, and after the laminate is obtained, it is preferably heated and pressurized by lamination and / or pressing.

As described above, the laminated system of this embodiment includes: a composite material layer containing an unhardened or semi-hardened hardening resin and a reinforcing material; in the manufacturing process of the laminated board, the composite material layer becomes a hardened composite material layer. In addition, "unhardened", "semi-hardened", and "hardened" are those that can be easily distinguished by their appearance or physical properties.
After becoming the hardened composite material layer, that is, considering the viewpoint that it is easier to maintain the shape of the laminated plate by reducing the thermal expansion of the laminated plate of this embodiment, in terms of the tensile elastic modulus of the composite material layer, It should be more than 15GPa, more preferably more than 20GPa.
Here, the "tensile elastic modulus of the composite material layer" in the present specification means that the composite material layer is subjected to temperature by using a multi-stage press, a multi-stage vacuum press, a continuous forming machine, or an autoclave forming machine. The meaning of a specific value of the tensile elastic modulus of the "hardened composite material layer" obtained by pressing and curing at a temperature of 180 to 350 ° C, a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm ² is performed. That is, by measuring the hardened composite material layer obtained as described above in accordance with IPC-TM-650 2.4.19, the tensile elastic modulus of the composite material layer can be specified. In addition, by appropriately selecting, as the resin to be used, specific examples of the resin contained in the hardened composite material layer, or appropriately increasing or decreasing the amount of the inorganic filler used, the composite material layer can be easily formed. The tensile elastic modulus is adjusted within the above range.

By forming a pattern (or providing a conductor circuit on the laminated board) or through holes in the laminated board of this embodiment, a (multilayer) printed wiring board can be manufactured.

[Printed wiring board]
The printed wiring board of this embodiment includes the laminated board of this embodiment and a conductor circuit provided on the laminated board.
The manufacturing method of a printed wiring board is not limited, and an example of the manufacturing method of a printed wiring board is demonstrated below.
First, a laminated board of this embodiment having a metal foil layer on the surface is prepared, and when there is no thin metal layer, a conductor is formed on the hardened composite material layer equivalent to the laminated board by dry plating or wet plating. Floor. For dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the case of wet plating, the surface of the hardened composite material layer is first subjected to permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. The oxidant is roughened to form a convex anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (basic permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Then, a conductive layer is formed by a method of combining electroless plating and electrolytic plating. In addition, the conductive layer may be formed with a plating resist having a reverse pattern, and the conductive layer may be formed only by electroless plating.
Thereafter, a pattern can be formed on the conductor layer using, for example, a known subtractive method, a semi-additive process, or the like.

[Multilayer printed wiring board]
In addition, the multilayer printed wiring board refers to a printed wiring board including a plurality of layers of conductor circuits. That is, the multilayer printed wiring board of this embodiment includes at least one glass substrate layer, a hardened composite material layer including at least one resin and a reinforcing material, at least one resin sheet layer having a tensile elastic modulus of 15 GPa or less, Conductor circuit layer of at least two layers. The manufacturing method of the multilayer printed wiring board is not particularly limited. For example, a plurality of printed wiring boards forming the above-mentioned wiring pattern can be laminated to form a multilayer, and then drilled or laser processed. A through hole or a via hole is formed, and the interlayer wiring is formed by plating or a conductive paste.
During lamination, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used, 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. Range. In addition, as for the laser used in forming the through hole or the through hole, a carbon dioxide laser, a YAG laser, a UV laser, an excimer laser, and the like can be used.
[Example]

Next, this embodiment will be described in more detail by way of examples. This embodiment is not limited in any way by these examples.

[Materials used]
1. Glass substrate layer As a glass substrate layer, the following glass plate (4) (made by Schott AG) was used.

[Table 1]

2. Prepreg In the substitution (comparison) of resin sheet layers and production of laminated board units, the following prepregs (2A) to (2E) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were used.

[Table 2]

3. Resin sheet layer As the resin sheet layer, the following resin sheets (3a) to (3a-3) and (3b) to (3c) (all manufactured by Designer Molecules Inc.) and (3d) (ADFLEMA by NAMICS CORPORATION) were used. ). In the state of these commercially available resin sheets, a support film made of PET or the like is affixed on both sides, and the support film is peeled off when used in the production of a laminated board.

In addition, as the resin sheets (3a) to (3a-3), individual resin sheets each composed of a polyimide resin having a maleimide terminal and represented by the following structural formula (I) were used.
In addition, as the resin sheet (3b), an individual resin sheet composed of a polyimide-based resin having a maleimide terminal was used.

[Chemical 1]

(In the formula (I), n represents an integer of 1 to 10.)

In addition, for the resin sheet (3c), a single resin sheet composed of a bismaleimide-based resin represented by the following structural formula (II) and a polyfluorene-imide-based resin having a maleimide terminal is used.

[Chemical 2]

For the resin sheet (3d), a single resin sheet obtained from an OPE resin composed of an oligopolyphenylene ether and a styrene butadiene-based elastomer described in Japanese Patent No. 4825286 is used.

In addition, the maximum value of the thermal expansion coefficient in the surface direction of the resin sheet layer (referred to as "CTE" in the table) was raised from 40 ° C to 340 at 10 ° C per minute in a thermomechanical analysis device (manufactured by TA Instruments, Inc.). ℃, and measured the linear expansion coefficient in the plane direction at 60 ° C to 120 ° C. In addition, the tensile elastic modulus of the resin sheet is measured in accordance with IPC-TM-650 2.4.19. The measurement results are shown in Table 3 below.

[table 3]

4. Hardened composite material layer In the laminated plates of Examples and Comparative Examples, as the hardened composite material layer, a double-sided copper-clad laminated plate (1A) obtained by bonding copper foils to both sides of a cured prepreg was used. To (1E) (copper foil / cured prepreg / copper foil) (manufactured by Mitsubishi Gas Chemical Co., Ltd.).

In addition, the maximum value of the thermal expansion coefficient of the hardened composite material layer (hardened prepreg) in the plane direction (referred to simply as "CTE" in the table) was measured in a thermomechanical analysis device (manufactured by TA Instruments, Inc.) at 10 per minute. The temperature was raised from 40 ° C to 340 ° C, and the linear expansion ratio of the glass cloth of the reinforcing material in the plane direction of 60 ° C to 120 ° C was measured. Here, the hardened prepreg included in the double-sided copper-clad laminate is subjected to the above measurement after the copper foil is removed by etching on the entire surface.
In addition, the tensile elastic modulus of the hardened composite material layer is measured in accordance with IPC-TM-650 2.4.19. The measurement results are shown in Table 4 below.

[Table 4]

5. Copper foil layer In the laminates of the examples and comparative examples, the following copper foil (5) (manufactured by Mitsui Metals Industry Co., Ltd.) was further laminated as the copper foil layer.

[table 5]

[Construction unit]
Regarding the constituent units used to manufacture the laminates of the examples and / or comparative examples, the following laminates were prepared.

1. Glass substrate layer unit with resin sheet layer (resin sheet layer / glass substrate layer / resin sheet layer)
The resin sheet (3) was laminated on both sides of the glass plate (4) to obtain glass (10a) to (10d) with a resin sheet attached thereto having a structure shown in Figs. 1 and 6.
In addition, when laminating, only one of the supporting films attached to both sides of the resin sheet is peeled off, and the resin sheet and the glass plate are laminated so that the side not covered with the supporting film faces the glass plate, and The vacuum laminator was laminated under conditions of 100 ° C. and 0.13 MPa for 30 seconds to be crimped.

[TABLE 6]

2. Glass substrate layer unit with prepreg (prepreg / glass substrate layer / prepreg)
The prepreg (2) was laminated on both sides of the glass plate (4) to obtain glass (11A) and (11B) with a prepreg having a structure shown in Table 7.
In addition, at the time of lamination, prepregs were laminated on both sides of a glass plate, and laminated on a vacuum laminator at 100 ° C. and 0.13 MPa for 30 seconds for pressure bonding.

[TABLE 7]

3.4 Plywood unit (copper foil / hardened prepreg / copper laminate / hardened prepreg / copper foil)
The above-mentioned copper foil (5), prepreg (2), and copper-clad laminate (1) were laminated to obtain a structure shown in Fig. 2 and Table 8 in which four layers of copper foil were bonded to three layers. Four layers (15A) to (15E) of hardened composite material layers.
In addition, at the time of lamination, the two sides of the copper foil of the copper-clad laminated board are subjected to roughening treatment (CZ treatment), and then overlapped in the order of copper foil / prepreg / copper-clad laminate / prepreg / copper foil. In a vacuum laminator, the 4-layer boards (15A) to (15C) and (15E) were heated from 25 ° C at 7 ° C / min. After maintaining at 110 ° C for 30 minutes, the temperature was raised again at 7 ° C / min. The prepreg (2) was hardened by pressing at 220 ° C for 90 minutes and a pressure of 3.2 MPa. In addition, the 4-layer board (15D) was heated from 25 ° C at 10 ° C / min. After being maintained at 125 ° C for 20 minutes, it was heated at 2.5 ° C / min. After being maintained at 145 ° C for 10 minutes, it was again 2.5 ° C / min. The prepreg (2D) was hardened by heating and pressing at 220 ° C for 110 minutes and a pressure of 3.2 MPa.

[TABLE 8]

4.10-layer board unit (copper foil / hardened prepreg / 4-layer board / hardened prepreg / 4-layer board / hardened prepreg / copper foil)
The above-mentioned copper foil (5), prepreg (2), and 4-layer board (15) were laminated to obtain 10 layers of copper foil bonded to 9 layers of hardened composite having the structure shown in Figs. 3 and 9 10-layer boards (16A) to (16E) of the material layer. In addition, at the time of lamination, the copper foil on both sides of the copper-clad laminate is roughened (CZ treatment), and then the copper foil / prepreg / 4-layer board / prepreg / 4-layer board / prepreg is used. The order of copper / copper foils was overlapped. The 10-layer boards (16A) to (16C) and (16E) were heated from 25 ° C at 7 ° C / min in a vacuum laminator, maintained at 110 ° C for 30 minutes, and then again at 7 ° C. The temperature was raised / min, and pressure bonding was performed at 220 ° C for 90 minutes and 3.2 MPa to harden the prepreg (2). In addition, the 10-layer board (16D) was heated from 25 ° C at 10 ° C / min. After being maintained at 125 ° C for 20 minutes, it was heated at 2.5 ° C / min. After being maintained at 145 ° C for 10 minutes, it was again 2.5 ° C / min. The prepreg (2D) was hardened by heating and pressing at 220 ° C for 110 minutes and a pressure of 3.2 MPa.

[TABLE 9]

[Example 1]
Using the above-mentioned 10-layer board unit and the glass substrate layer unit provided with a resin sheet layer, a laminated board (20A) corresponding to this embodiment having 20 layers of copper foil having the structure shown in Fig. 4 and Table 10 was manufactured.
Specifically, the 10-layer board (16A) and the glass (10) with a resin sheet layer are overlapped in the order of the 10-layer board (16A) / the glass (10a) with a resin sheet / 10-layer board (16A), and the vacuum is applied. The laminator starts to heat up from 25 ° C at 7 ° C / min. After maintaining at 110 ° C for 30 minutes, it raises the temperature again at 7 ° C / min and presses at 220 ° C for 90 minutes and 3.2 MPa to harden the resin sheet. Laminate the layers.

[Examples 2 to 13]
In the same manner as in Example 1, the laminates (20A ') to (20A-3) of Examples 2 to 13 having 20 layers of copper foil having the constitution shown in Table 10 were produced.

[TABLE 10]

[Comparative Example 1]
Using the above-mentioned 10-layer board unit and the glass substrate layer unit provided with a prepreg, a laminated board (24A) of a comparative example having 20 layers of copper foil having a structure shown in Table 11 was produced.
Specifically, the 10-layer board (16A) and the glass with prepreg (13) are overlapped in the order of 10-layer board (16A) / glass with prepreg (11A) / 10-layer board (16A). The vacuum laminator started to heat up from 25 ° C at 7 ° C / min. After maintaining at 110 ° C for 30 minutes, the temperature was increased again at 7 ° C / min. The compression was performed at 220 ° C for 90 minutes and 3.2 MPa. The prepreg contained in the glass substrate layer unit of the body is hardened, and the layers are bonded together.

[Comparative Example 2]
Using the above-mentioned 10-layer board unit and the glass substrate layer unit provided with a prepreg, a laminated board (24B) of a comparative example having 20 layers of copper foil having a structure shown in Table 11 was produced.
Specifically, the 10-layer board (16B) and the glass (11B) with the prepreg are overlapped in the order of the 10-layer board (16B) / the glass with the prepreg (11B) / 10-layer board (16B). The vacuum press was heated from 25 ° C at 7 ° C / min, and maintained at 110 ° C for 30 minutes, and then heated again at 7 ° C / min, and pressed at 220 ° C for 90 minutes and 3.2 MPa, so that a pre-immersion was attached. The prepreg contained in the glass substrate layer unit of the body is hardened, and the layers are bonded together.

[TABLE 11]

[Example 14]
Using the above-mentioned 10-layer board unit, the glass substrate layer unit with a resin sheet layer, and the glass substrate layer unit with a prepreg, a laminated board (25A) of Example 14 having 20 layers of copper foil having a structure shown in Table 12 was produced .
Specifically, the 10-layer board (16A), the glass (10) with a resin sheet, and the glass (11A) with a prepreg are divided into 10-layer board (16A) / glass with a resin sheet (10) / attachment The order of the prepreg glass (11A) / glass with resin sheet (10) / 10 layer board (16A) was superimposed, and the temperature was raised from 25 ° C in a vacuum laminator at 7 ° C / min, and maintained at 110 ° C for 30 After several minutes, the temperature was raised again at 7 ° C./min, and compression bonding was performed at 220 ° C. for 90 minutes and 3.2 MPa to harden the resin sheet and the prepreg, and bond the layers.

[TABLE 12]

[Evaluation method]
In order to evaluate the laminated plates of Examples and Comparative Examples, the following methods were used.
1. Number of samples with glass breakage, etc. Prepare six pieces of laminated plates for each of the examples and comparative examples. Observe with visual inspection and optical microscope to calculate any of glass breakage, substrate warpage, and peeling. The number of samples in which the situation occurred.

2. Fracture toughness test For the laminated plates of each of the Examples and Comparative Examples, a cross section was cut with a wet cutter (cutting speed: 1 mm / sec), and the cross section was observed with a laser microscope (magnification 25 times) to confirm whether it occurred. The cracking of the glass was evaluated according to the following criteria.
〇: No peeling occurred in the center of the glass ×: No peeling occurred in the center of the glass

3. Moisture absorption and heat resistance test For each of the examples and comparative examples, three laminates were prepared, and a protective tape with a width of 25 mm was pasted on one half of each of the laminates and subjected to an etching treatment to produce copper foil. A sample obtained by etching 3/4 of the whole surface. Then, three samples were set in a PCT (Pressure Cooker Test) tester in which pure water was placed, and they were made to absorb moisture at 121 ° C., 0.1 MPa × 5 h. The surface moisture of the hygroscopic sample was wiped off and immersed in a solder bath at 260 ° C for 1 minute. The three samples after the immersion were visually observed, and the number of samples in which any one of the glass breakage, the substrate warpage, and the peeling occurred in the center of the glass was counted.

4. Solder floating test For each of the Examples and Comparative Examples, three laminated boards were prepared, and these laminated boards were directly used and floated in a solder bath at 280 ° C for 30 minutes (n = 3). The three floating samples were visually observed, and the number of samples in which any one of glass breakage, substrate warpage, and peeling occurred in the center of the glass was counted.

Table 13 shows the number of samples with glass breakage, etc., the fracture toughness, moisture absorption and heat resistance tests, and solder float test results for the laminated plates of Examples 1 to 14 and Comparative Examples 1 and 2.

[TABLE 13]

From the comparison between Example 1 and Examples 8 to 10 and Comparative Example 1, it can be confirmed that the laminated board obtained by laminating the glass substrate layer on the hardened composite material layer (hardened prepreg) and the prepreg, and the resin sheet Coexistence of layers does not depend on the type or physical properties of the resin constituting the resin sheet, and can reduce the cracking of glass. In addition, from the results of Examples 11 to 14, it was confirmed that this effect was similarly exhibited regardless of the thickness or arrangement of the resin sheet layer.

In addition, with respect to the hardened composite material layer (hardened prepreg) and prepreg contained in the laminated board, the thinner one tends to cause glass cracking. However, the results of Examples 1, 2, and 4 also confirmed that According to this embodiment, even when the thickness of the hardened composite material layer is thin, a laminated plate with high fracture toughness with few glass cracks can be realized.

In addition, from the results of Examples 1 and 3, 5 to 7, for the hardened composite material layer (hardened prepreg) and prepreg contained in the laminated board, it can be confirmed that the CTE or the elastic modulus is not related. Coexistence of the resin sheet layer can suppress glass breakage.

This application is based on a Japanese patent application filed in the Japanese Patent Office on April 24, 2018 (Japanese Patent Application No. 2018-083290), the contents of which are incorporated herein by reference.
[Industrial availability]

As described above, the laminated sheet of the present invention which contains a resin sheet in addition to the hardened composite material layer (hardened prepreg) and the glass substrate layer, although the hardened composite material layer and the glass substrate layer are laminated, the glass is broken less.
Therefore, the laminated board of the present invention can be used in various applications that are likely to be exposed to high temperatures. For example, it can be suitably used in the manufacture of (multi-layer) printed wiring boards, etc., and can be particularly suitably used as a material for manufacturing incorporated light. Material for wiring (multilayer) printed wiring boards.

(1) ‧‧‧ Copper clad laminate

(2) ‧‧‧ Prepreg

(3) ‧‧‧ resin sheet

(4) ‧‧‧ glass plate

(5) ‧‧‧copper foil

(10) ‧‧‧Glass with resin sheet

(15) ‧‧‧4 layers

(16a) ‧‧‧10-layer board

[Fig. 1] Fig. 1 is a schematic diagram of a glass substrate layer unit with a resin sheet layer in the embodiment.

[Fig. 2] Fig. 2 is a schematic diagram of a 4-layer board unit in the embodiment.

[Fig. 3] Fig. 3 is a schematic diagram of a 10-layer board unit in the embodiment.

[FIG. 4] FIG. 4 is a schematic diagram illustrating a laminated board according to an embodiment of the present invention.

Claims (18)

A laminated board comprising: At least one glass substrate layer, A hardened composite material layer containing at least one of a resin and a reinforcing material, and A resin sheet layer having a tensile elastic modulus of at least one layer of 15 GPa or less. For example, the laminated board of the scope of application for the first item, wherein the resin sheet layer contains a thermosetting resin. For example, the laminated board according to item 1 or 2 of the patent application scope, wherein the thickness of the resin sheet layer is 1 μm or more. For example, the laminated board according to item 1 or 2 of the patent application scope, wherein the thickness of the glass substrate layer is 10 to 500 μm. For example, the laminated board according to item 1 or 2 of the patent application scope, wherein the resin contained in the hardened composite material layer is selected from the group consisting of epoxy resin, phenol resin, fluorene imine resin, maleimide resin, Cyanate resin, isocyanate resin, benzopyrene Resin, oxetane resin, amine resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, polysiloxane resin, three One or two or more resins in the group consisting of resin, modified polyphenylene ether resin, oligopolyphenylene ether resin, and melamine resin. For example, the laminated board according to item 1 or 2 of the patent scope, wherein the reinforcing material contained in the hardened composite material layer is selected from the group consisting of glass fiber, polyimide fiber, polyester fiber, and polytetrafluoroethylene fiber. And at least one of the group consisting of aramid fibers. For example, the laminated board according to item 1 or 2 of the patent application scope, wherein the hardened composite material layer further contains an inorganic filler. For example, the laminated board according to item 7 of the application, wherein the inorganic filler contained in the hardened composite material layer is selected from the group consisting of silicon oxide, aluminum oxide, talc, mica, aluminum hydroxide, magnesium hydroxide, and carbonic acid. At least one of the group consisting of calcium, aluminum nitride, silicon nitride, boron nitride, aluminum borate, and borosilicate glass. For example, the laminated board according to item 1 or 2 of the scope of patent application, wherein the maximum value of the thermal expansion coefficient in the plane direction of the hardened composite material layer is 20 ppm / ° C or lower. For example, the laminated board according to item 1 or 2 of the patent application scope, wherein the resin sheet layer is directly laminated on at least one side of the glass substrate layer. For example, the laminated board according to item 1 or 2 of the patent application scope includes two or more layers of the resin sheet, and the glass substrate layer is disposed between the two layers of the resin sheet. For example, the laminated board according to item 1 or 2 of the patent application scope includes only one layer of the glass substrate. For example, the laminated board according to item 1 or 2 of the patent application scope further includes at least one copper foil layer. For example, the laminated board according to item 1 or 2 of the patent application scope includes two or more layers of the hardened composite material. A printed wiring board includes a laminated board such as item 1 or 2 of the scope of patent application, and a conductor circuit provided on the laminated board. A multilayer printed wiring board comprising: At least one glass substrate layer, A hardened composite material layer containing at least one of a resin and a reinforcing material, At least one resin sheet having a tensile elastic modulus of 15 GPa or less, and Conductor circuit layer of at least two layers. A laminated body comprising: At least one glass substrate layer, A composite material layer containing at least one layer of an unhardened or semi-hardened hardening resin and a reinforcing material, and A resin sheet layer having a tensile elastic modulus of at least one layer of 15 GPa or less. A method for manufacturing a laminated body includes the following steps: In the laminating step, at least one glass substrate layer, a composite material layer containing at least one layer of an unhardened or semi-hardened thermosetting resin and a reinforcing material, and at least one resin sheet layer having a tensile elastic modulus of 15 GPa or less are stacked. Layer to obtain a laminate; In the heating and pressing step, the laminated body is heated and pressed.