HK1181714A - Laminated body, laminated board, multi-layer laminated board, printed wiring board, and production method for laminated board - Google Patents

Description

Laminate, multilayer laminate, printed wiring board, and method for producing laminate

Technical Field

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

Background

In recent years, demands for thinner and lighter electronic devices have been increasing, and semiconductor packages and printed wiring boards have been increasingly thinner and more densely packed. In order to stably mount electronic components in response to the reduction in thickness and the increase in density, it is important to suppress warpage generated during mounting.

One of the main causes of warpage in a semiconductor package at the time of mounting is a difference in thermal expansion coefficient between a laminated board used in the semiconductor package and a silicon wafer mounted on the surface of the laminated board. Therefore, in the laminate for semiconductor package, efforts have been made to make the thermal expansion coefficient close to that of the silicon wafer, that is, to lower the thermal expansion coefficient. Further, since the low elastic modulus of the laminated sheet is also a cause of bending, it is also effective to make the laminated sheet highly elastic in order to reduce bending. Therefore, in order to reduce the warpage of the laminated sheet, it is effective to make the expansion rate of the laminated sheet low and to make the laminated sheet highly elastic.

Various methods for reducing the thermal expansion coefficient and increasing the elasticity of the laminated sheet are conceivable, and in particular, reduction in the thermal expansion coefficient of the resin for the laminated sheet and increase in the filling of the inorganic filler in the resin are known. In particular, the high filling of the inorganic filler is a method of reducing the thermal expansion coefficient and expecting improvement of heat resistance and flame retardancy at the same time (patent document 1). However, it is known that the method of increasing the filling amount of the inorganic filler is limited in increasing the filling amount because insulation reliability is lowered, adhesion between the resin and the wiring layer formed on the surface is insufficient, and a pressure forming failure occurs during production of the laminated plate.

Further, attempts have been made to achieve a means for reducing the thermal expansion coefficient by selecting or improving a resin. For example, there are methods of increasing the crosslinking density and increasing Tg of a resin for a wiring board to lower the thermal expansion coefficient (patent documents 2 and 3). However, although increasing the crosslinking density shortens the molecular chains between the functional groups, shortening the molecular chains to a certain extent or more limits the reaction and also causes a problem of lowering the resin strength. Therefore, there is a limit to the method of increasing the crosslinking density to achieve a low thermal expansion coefficient.

In view of the above, conventional laminates have been limited in terms of achieving a low thermal expansion coefficient and high elasticity by high filling with an inorganic filler and using a resin having a low thermal expansion coefficient.

As a method different from the above, there has been attempted a method of using a glass film as a layer having a thermal expansion coefficient substantially equal to that of an electronic component (silicon wafer) and laminating a resin and the glass film by pressing to reduce a thermal impact stress (patent document 4).

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. 2004-182851

[ patent document 2] Japanese patent laid-open No. 2000-243864

[ patent document 3] Japanese patent laid-open No. 2000-114727

[ patent document 4] Japanese patent No. 4657554

Disclosure of Invention

[ problems to be solved by the invention ]

As described above, the substrate obtained by the manufacturing method of patent document 4 still has a low elastic modulus and a high thermal expansion coefficient, and therefore, is insufficient in realizing low warpage of the substrate.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a laminated plate and a multilayer laminated plate which have a low thermal expansion coefficient and a high elastic modulus and can suppress bending and prevent cracking, a laminated body suitable for manufacturing these laminated plate and multilayer laminated plate, a printed wiring board using these laminated plate and multilayer laminated plate, and a method for manufacturing the laminated plate.

[ means for solving the problems ]

Patent document 4 does not disclose any case where an inorganic filler is contained in a resin in a substrate in which a glass film and the resin are laminated. According to the description of patent document 4, it is conceivable that the case where an inorganic filler is contained in the resin should be avoided.

That is, in patent document 4, a glass film is an essential component for substantially determining the thermal expansion action of the entire substrate (claim 1 of patent document 4). Therefore, it is necessary to minimize the influence of the thermal expansion action of the resin on the substrate, and therefore, it is necessary to suppress the elastic modulus of the resin to be low (if the resin has a high elastic modulus, the thermal expansion action of the entire substrate is greatly influenced by the resin having the high elastic modulus). On the other hand, when the resin contains an inorganic filler, the resin has a high elastic modulus. Therefore, it is known from the description of patent document 4 that the resin should be prevented from containing an inorganic filler.

In addition, when the resin of patent document 4 contains an inorganic filler, it is conceivable that the inorganic filler serves as a starting point and the glass substrate is likely to be cracked. From this point, it is also presumed that patent document 4 avoids the inorganic filler contained in the resin.

At present, there is no example of a laminate of a glass substrate layer and a resin layer as in patent document 4, in which an inorganic filler is contained in the resin layer.

However, surprisingly, the inventors of the present invention have assiduously studied in order to solve the above-mentioned problems, and as a result, have found that a laminated plate having a low thermal expansion coefficient and a high elastic modulus, which is suppressed from bending and is less likely to crack, can be obtained by incorporating an inorganic filler into a resin cured layer in a laminated plate including the resin cured layer and a glass substrate layer.

The present invention has been completed based on this finding, and the gist thereof are as follows [1] to [12 ].

[1] A laminate comprising 1 or more resin composition layers and 1 or more glass substrate layers, wherein the resin composition layers are composed of a resin composition containing a thermosetting resin and an inorganic filler.

[2] The laminate according to [1], wherein the thickness of the glass substrate layer is 30 to 200 μm.

[3] The laminate according to [1] or [2], wherein the thermosetting resin is 1 or 2 or more selected from an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin, and a melamine resin.

[4] The laminate according to [1] to [3], wherein the inorganic filler is 1 or 2 or more selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass.

[5] A laminated board comprises 1 or more resin cured layers and 1 or more glass substrate layers, wherein the resin cured layers are formed by cured products of resin compositions containing thermosetting resins and inorganic filling materials.

[6] The laminate according to [5], wherein the dynamic storage elastic modulus at 40 ℃ is 10GPa to 70 GPa.

[7] The laminated plate according to [5] or [6], which is obtained by heating and pressing the laminated body according to any one of [1] to [4 ].

[8] A multilayer laminated plate comprising a plurality of laminated plates, at least one of the laminated plates being any one of the laminated plates recited in any one of [5] to [7 ].

[9] A printed wiring board having the laminated board described in any one of [5] to [7] and a wiring provided on a surface of the laminated board.

[10] A printed wiring board having the multilayer laminated board described in [8] and wiring provided on a surface of the multilayer laminated board.

[11] A method for producing a laminated plate comprising 1 or more resin cured layers composed of a cured product of a resin composition containing a thermosetting resin and an inorganic filler, and 1 or more glass substrate layers, wherein the method comprises a resin cured layer forming step of forming the resin cured layers on the surfaces of the glass substrates.

[12] The method for producing a laminated plate according to item [11], wherein the cured resin layer forming step is a step of applying the resin composition to the glass substrate, and then drying and curing the applied resin composition.

[13] The method of producing a laminated plate according to item [11], wherein the cured resin layer forming step is a step of laminating and curing a film made of the resin composition on the glass substrate using a vacuum laminator or a roll laminator.

[14] The method for producing a laminated plate according to item [11], wherein the cured resin layer forming step is a step of disposing a film made of the resin composition on the glass substrate, and then pressing and curing the film.

[ Effect of the invention ]

According to the present invention, it is possible to provide a laminated plate and a multilayer laminated plate which have a low thermal expansion coefficient and a high elastic modulus and are less likely to crack due to bending, a laminated body suitable for manufacturing these laminated plates and multilayer laminated plates, a printed wiring board using these laminated plates and multilayer laminated plates, and a method for manufacturing the laminated plate.

Drawings

FIG. 1 is a schematic sectional view illustrating the production method of examples 1 to 3.

Fig. 2 is a schematic cross-sectional view illustrating the manufacturing method of example 4.

[ description of symbols ]

1 a support film; 2 an interlayer insulating composition layer; 2a an interlayer insulating layer;

3 a resin film; 4a resin composition layer; 4a resin cured layer;

5a, 5b, 5c adhesive film; 6 a glass substrate layer; 7a, 7b are laminated.

Detailed Description

The laminate, the multilayer laminate, the printed wiring board, and the method for producing the laminate of the present invention will be described in detail below.

In the present invention, the laminate refers to a laminate in which the thermosetting resin as a component is uncured or semi-cured, and the laminate refers to a laminate in which the thermosetting resin as a component is cured.

[ laminate ]

The laminate of the present invention is a laminate including 1 or more resin composition layers and 1 or more glass substrate layers, the resin composition layers being composed of a resin composition containing a thermosetting resin and an inorganic filler.

The size of the laminate of the present invention is preferably selected from the range of 10mm to 1000mm in width and 10mm to 3000mm in length (when used in a roll form, the length is suitably applicable) from the viewpoint of workability. Particularly preferably, the width is 25mm to 550mm, and the length is 25mm to 550 mm.

The thickness of the laminate of the present invention is preferably selected in the range of 35 μm to 20mm depending on the application. The thickness of the laminate is more preferably 50 to 1000. mu.m, still more preferably 100 to 500. mu.m, and particularly preferably 110 to 300. mu.m.

In the laminate obtained by curing the resin composition layer of the laminate of the present invention as a resin cured layer, since the glass substrate layer has a low thermal expansion coefficient and a high elastic modulus similar to those of a silicon wafer, the laminate is a structure having a low thermal expansion coefficient and a high elastic modulus, and can be prevented from being bent and hardly causing cracks. In particular, since the laminate has a glass substrate layer having high heat resistance, it has remarkably low thermal expansion in a temperature range from 100 ℃ to less than Tg of a cured resin. In addition, since the resin cured layer contains an inorganic filler, the resin cured layer has a layer structure with a low coefficient of thermal expansion and a high elastic modulus, and the laminate including the resin cured layer is a material with a further low coefficient of thermal expansion and a further high elastic modulus.

< resin composition >

The resin composition of the present invention includes a thermosetting resin and an inorganic filler.

Thermosetting resin

The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. Among them, epoxy resins and cyanate resins are preferable because of their excellent moldability and electrical insulation properties.

Examples of the epoxy resin include bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, bisphenol F novolac type epoxy resins, stilbene type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenol methane type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracenes. Further, phosphorus-containing epoxy resins obtained by introducing a phosphorus compound into these epoxy resins can be cited. Among them, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy. 1 or 2 or more of them may be used in combination.

Examples of the cyanate ester resin include bisphenol type cyanate ester resins such as novolac type cyanate ester resin, bisphenol a type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethylbisphenol F type cyanate ester resin, and partial triazinated prepolymers thereof. Among them, a novolak type cyanate ester resin is preferable from the viewpoint of heat resistance and flame retardancy. 1 or 2 or more of them may be used in combination.

The content of the thermosetting resin in the resin composition is preferably in the range of 20 to 80% by mass, more preferably 40 to 80% by mass, even more preferably 50 to 80% by mass, and particularly preferably 60 to 75% by mass, based on the mass of the resin composition excluding the content of the inorganic filler.

Inorganic Filler Material

Examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass.

Among them, silica is preferable from the viewpoint of low thermal expansion, and spherical amorphous silica having a very small thermal expansion coefficient of about 0.6ppm/K and a small decrease in fluidity when a resin is highly filled is more preferable.

The spherical amorphous silica has a cumulative 50% particle diameter of 0.01 to 10 μm, preferably 0.03 to 5 μm.

Here, the cumulative 50% particle diameter means that when a cumulative power distribution curve based on the particle diameters is obtained with the entire volume of the powder as 100%, the particle diameter corresponding to exactly 50% by volume can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.

The content of the inorganic filler in the resin composition is preferably 5 to 75% by volume, more preferably 15 to 70% by volume, and still more preferably 30 to 70% by volume of the total amount in the resin composition. When the content of the inorganic filler is 5 to 75% by volume of the resin composition, the effect of reducing the thermal expansion coefficient is sufficient, and the composition has appropriate fluidity and is excellent in moldability. 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 the content is 75% by volume or less, the fluidity is increased and the moldability is good.

When expressed in mass%, for example, when the inorganic filler is silica, the content of silica in the resin composition is preferably 8 to 85 mass%, more preferably 24 to 82 mass%, and still more preferably 44 to 82 mass% of the resin composition.

In addition, the inorganic filler is made of silica (nanometer) having an average primary particle diameter of 1 μm or lessSilica), fine wiring can be formed on the resin cured layer of the laminate. As the nano silica, the specific surface area is preferably 20m²More than g. In addition, the average primary particle diameter is preferably 100nm or less from the viewpoint of reducing the surface shape after the roughening treatment in the plating process. The specific surface area can be measured by the BET method.

The "average primary particle diameter" referred to herein is not the average diameter of the aggregated particles, i.e., the secondary particle diameter, but is the average particle diameter of the unagglomerated monomer. The average primary particle diameter can be determined by measurement with a laser diffraction particle size distribution meter, for example. As such an inorganic filler, fumed silica is preferable.

The inorganic filler is preferably treated with a surface treatment agent such as a silane coupling agent for the purpose of improving moisture resistance, and is preferably subjected to hydrophobization for the purpose of improving dispersibility.

In the case where fine wiring is formed on the resin cured layer of the laminate, the content of the inorganic filler is preferably 20 mass% or less in the resin composition. When the blending amount is 20 mass% or less, a good surface shape after the roughening treatment can be maintained, and a reduction in plating characteristics and interlayer insulation reliability can be prevented. On the other hand, since the resin composition can be expected to have low thermal expansion and high elasticity by containing the inorganic filler, when low thermal expansion and high elasticity are important in forming fine wiring, the content of the inorganic filler is preferably 3 to 20% by mass, more preferably 5 to 20% by mass.

Other ingredients

In addition to the above components, a curing agent, a curing accelerator, a thermoplastic resin, an elastomer, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightener, an adhesion improver, and the like may be added to the resin composition.

Examples of the curing agent include, for example, in the case of using an epoxy resin, a polyfunctional phenol compound such as phenol novolac or cresol novolac; amine compounds such as dicyandiamide, diaminodiphenylmethane and diaminodiphenylsulfone; anhydrides such as phthalic anhydride, pyromellitic dianhydride, maleic anhydride, and maleic anhydride copolymers; and (3) a polyimide. Several of these curing agents may be used in combination.

Examples of the curing accelerator include imidazoles and derivatives thereof as curing accelerators for epoxy resins; an organic phosphorus compound; secondary amines, tertiary amines and quaternary ammonium salts.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.

Examples of the antioxidant include hindered phenol-based and styrenated phenol-based antioxidants.

Examples of the photopolymerization initiator include photopolymerization initiators of the benzophenone type, the benzyl ketal type, and the thioxanthone type.

Examples of the fluorescent whitening agent include fluorescent whitening agents such as stilbene derivatives.

Examples of the adhesion improving agent include urea compounds such as urea silane and adhesion improving agents such as silane coupling agents.

< layer of resin composition >

The resin composition layer is composed of the resin composition described above. The resin composition layer contains a semi-cured product in addition to an uncured product of the resin composition.

The size of the resin composition layer of the present invention is preferably selected from the range of 10mm to 1000mm in width and 10mm to 3000mm in length (when used in a roll form, the length is suitably applicable). From the viewpoint of workability, the width is particularly preferably in the range of 25mm to 550mm and the length is preferably in the range of 25mm to 550 mm.

The thickness of each 1 layer of the resin composition layer of the present invention is preferably selected in the range of 3 μm to 200 μm. From the viewpoint of low thermal expansion and high elastic modulus of the laminate and the laminated plate, the thickness of each 1 layer of the resin composition is preferably 3 to 150 μm, more preferably 3 to 100 μm, further preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

< glass substrate layer >

The thickness of each 1 glass substrate layer is preferably 30 to 200 μm from the viewpoint of the reduction in thickness of the laminate and the workability, and in view of the practical use such as ease of handling, the thickness is more preferably 50 to 150 μm, and particularly preferably 80 to 120 μm.

The thickness of the glass substrate layer as referred to herein means the average thickness of the glass substrate layer. The average thickness of the glass substrate layer can be measured using a known thickness measuring device such as a micrometer or a film thickness measuring instrument. For example, in the case of a rectangular or square glass substrate layer, the thickness at the 4 corners and the center is measured using a micrometer, and the average value thereof is determined as the average thickness of the glass substrate layer. As a material of the glass substrate layer, glass such as alkali silicate glass, alkali-free glass, and quartz glass can be used, but borosilicate glass is preferable from the viewpoint of low thermal expansion.

The size of the glass substrate layer of the present invention is preferably selected from the range of 10mm to 1000mm in width and 10mm to 3000mm in length (when used in a roll form, the length is suitably applicable). From the viewpoint of workability, the width is particularly preferably in the range of 25mm to 550mm and the length is preferably in the range of 25mm to 550 mm.

The coefficient of thermal expansion of the glass substrate layer is preferably 8 ppm/DEG C or less, more preferably 6 ppm/DEG C or less, and even more preferably 4 ppm/DEG C or less, although the bending of the laminate or the laminate obtained from the laminate can be suppressed as the coefficient of thermal expansion of the silicon wafer is closer (about 3 ppm/DEG C).

The larger the storage elastic modulus at 40 ℃ of the glass substrate layer, the better, but it is preferably 20GPa or more, more preferably 25GPa or more, and still more preferably 30GPa or more.

< composition layer for interlayer insulation >

The laminate of the present invention may have an interlayer insulating composition layer for improving adhesion between the conductor layers described later.

That is, as will be described later, when a printed wiring board is manufactured using the laminate of the present invention, a conductor layer may be formed by plating or the like on the surface of a laminate obtained by curing the laminate. In addition, a metal foil-equipped laminate or a laminate plate having a metal foil (conductor layer) on the surface thereof may be formed. In these cases, although the conductor layer may be formed on the resin composition layer or the cured resin layer, a layer of the composition for interlayer insulation or an interlayer insulation layer after curing may be further formed on the resin composition layer or the cured resin layer, and the conductor layer may be formed thereon. In this case, the interlayer insulating composition layer is made of a material having high adhesion to the conductor layer, and thus the adhesion between the laminated plate and the conductor layer is improved.

As described later, after the laminated plate is formed with the through-hole, desmearing treatment may be performed. In this case, by providing a material having excellent anti-smear property as the interlayer insulating composition layer in advance, it is possible to prevent the surface of the laminated board (i.e., the interlayer insulating layer formed by curing the interlayer insulating composition layer) from having excessively large unevenness, and to form a precise wiring pattern on the surface.

When the laminate has a layer of the interlayer insulating composition, for example

May have a 3-layer structure of a glass substrate layer/a resin composition layer/an interlayer insulating composition layer,

the structure may have a 5-layer structure of interlayer insulating composition layer/resin composition layer/glass substrate layer/resin composition layer/interlayer insulating composition layer. The expression "glass substrate layer/resin composition layer/interlayer insulating composition layer" means that the glass substrate layer, the resin composition layer and the interlayer insulating composition layer are laminated in this order. The same applies to the 5-layer structure.

In addition to the above examples, the interlayer insulating composition may be disposed between the conductor layer and the laminate of the present invention, and is not limited to the above examples.

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

< adhesive layer >

The laminate of the present invention may further include an adhesive layer containing a thermosetting resin and no inorganic filler, in addition to the resin composition layer containing a thermosetting resin and an inorganic filler. For example, an adhesive layer may be disposed between the glass substrate layer and the resin composition layer, and used for the purpose of improving the adhesiveness between the two layers.

< ratio of layers in laminate >

The resin composition layer of the present invention is preferably 5 to 60 vol%, more preferably 5 to 55 vol%, further preferably 10 to 50 vol%, and particularly preferably 20 to 40 vol% based on the total volume of the laminate, from the viewpoint of obtaining a laminate having a low thermal expansion coefficient and a high elastic modulus.

From the viewpoint of obtaining a laminate having a low thermal expansion coefficient and a high elastic modulus, the glass substrate layer of the present invention is preferably 20 to 90 vol%, more preferably 30 to 85 vol%, further preferably 35 to 80 vol%, and particularly preferably 40 to 75 vol% based on the total laminate.

When the laminate has an interlayer insulating layer, the interlayer insulating layer is preferably 1 to 20 vol%, more preferably 2 to 15 vol%, and still more preferably 3 to 10 vol% of the entire laminate.

When the laminate has an adhesive layer, the adhesive layer is preferably 1 to 20 vol%, more preferably 2 to 15 vol%, and still more preferably 3 to 10 vol% of the entire laminate.

< support film and protective film >

The laminate may have a support film or a protective film on the surface thereof. These support film and protective film will be described in detail in the following description of the method for producing the laminate.

[ method for producing laminate ]

The method for producing the laminate is not particularly limited, and the laminate can be produced by laminating a film made of a resin composition on a glass substrate, coating a resin composition on a glass substrate, or the like. Among them, a lamination-based method is preferable in view of ease of production.

Next, each manufacturing method will be described in detail.

< method for producing laminated body by lamination >

The laminate can be suitably produced by laminating an adhesive film using the resin composition and a glass substrate by pressure lamination such as vacuum lamination or roll lamination. This adhesive film will be described later. The vacuum lamination and the roll lamination can be performed by using a commercially available vacuum laminator or roll laminator.

As the thermosetting resin in the resin composition and the interlayer insulating composition, a composition that melts at a temperature equal to or lower than the temperature at the time of lamination is suitably used. For example, when the laminate is laminated by using a vacuum laminator or a roll laminator, it is generally performed at 140 ℃ or lower, and therefore, the thermosetting resin in the resin composition and the interlayer insulating composition are preferably melted at 140 ℃ or lower.

First, the adhesive film will be described, and then, a lamination method using the adhesive film will be described.

Adhesive film

When a laminate is produced using a vacuum laminator or a pressure laminator, the resin composition is generally prepared as an adhesive film.

As the adhesive film used in the present invention, the following laminated structure is suitably used.

(1) Support film/resin composition layer

(2) Support film/composition layer for interlayer insulation/resin composition layer

In the laminated structures of (1) and (2), the following laminated structure having a protective film laminated thereon is more preferably used.

(3) Support film/resin composition layer/protective film

(4) Support film/composition layer for interlayer insulation/resin composition layer/protective film

The protective film is formed on the opposite side of the support film to the thermosetting resin composition layer of the present invention, and is used for preventing adhesion and damage of foreign matter.

The structure obtained by removing the support film and the protective film from the adhesive film may be referred to as an adhesive film body.

The adhesive film having the laminated structure of (1) to (4) can be produced by a method known to those skilled in the art.

As an example of the production of the adhesive film of the above (1), a varnish in which an inorganic filler is dispersed can be prepared by dissolving the above resin composition in an organic solvent. Then, the varnish is applied to the support film as a support, and the organic solvent is dried by heating and blowing hot air to form a resin composition layer.

As an example of the production of the adhesive film of (2), a varnish was prepared by dissolving the interlayer insulating composition layer in an organic solvent. Then, a varnish is applied to the support film, and the organic solvent is dried by heating, blowing hot air, or the like, thereby forming an interlayer insulating composition layer. Then, a resin composition layer may be formed on the surface of the interlayer insulating composition layer in the same manner as in (1) above.

As an example of the production of the adhesive film of (3), a varnish in which an inorganic filler is dispersed is prepared by dissolving the resin composition in an organic solvent. Then, the varnish may be applied to one of the support film and the protective film, the other of the support film and the protective film may be disposed on the varnish, and the organic solvent of the varnish may be dried by heating, blowing heat, or the like, thereby forming a resin composition layer.

As an example of the production of the adhesive film of the above (4), a varnish is prepared by dissolving the above-mentioned composition for interlayer insulation in an organic solvent, the varnish is applied to the above-mentioned support film, and the organic solvent is dried by heating, blowing hot air or the like to form a composition layer for interlayer insulation. Then, the surface of the laminate on the side of the interlayer insulating composition may be brought into contact with the surface of the laminate on the side of the resin composition layer previously produced as in the above (1), and the laminate may be laminated by using a pressing laminator such as a vacuum laminator or a roll laminator to be described later. As another example, the interlayer insulating layer may be formed by applying varnish to the support film, applying varnish for the resin composition thereon, disposing a protective film thereon and thereon, and drying an organic solvent of the varnish by heating, blowing hot air or the like to form the resin composition layer.

As the coating device for the interlayer insulating composition layer and the resin composition layer, a coating device known to those skilled in the art, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater, may be used, and is preferably selected as appropriate according to the film thickness to be produced.

In the adhesive film, the interlayer insulating composition layer and the resin composition layer may be semi-cured in advance.

The support film serves as a support when the adhesive film is produced, and is usually peeled off or removed when used in the production of a multilayer printed wiring board.

Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET") and polyethylene naphthalate, polycarbonates and polyimides, and further include release paper, metal foils such as copper foil and aluminum foil. When a copper foil is used as the support film, a circuit can be formed using the copper foil as a conductor layer as it is. In this case, the copper foil includes rolled copper, electrolytic copper foil and the like, and a copper foil having a thickness of 2 μm to 36 μm is generally used. When a copper foil having a small thickness is used, a copper foil with a carrier can be used to improve workability.

The support film may be subjected to a mold release treatment in addition to the matte treatment and the corona treatment.

The thickness of the support film is usually 10 to 150 μm, preferably 25 to 50 μm. When the thickness is thinner than 10 μm, handling is difficult. On the other hand, the support film is usually finally peeled or removed as described above, and if the thickness exceeds 150 μm, it is not preferable from the viewpoint of energy saving.

The protective film is peeled off before being laminated and hot-pressed. The protective film may be made of the same material as the support film or a different material. The thickness of the protective film is not particularly limited, and may be the same as that of the support film, but is more preferably in the range of 1 to 40 μm.

Lamination method Using the above adhesive film

Next, an example of a lamination method using the above adhesive film will be described.

In the case where the adhesive film has a protective film, the adhesive film is pressed against the glass substrate while being pressurized and heated after the protective film is removed. The lamination conditions include preheating the adhesive film and the glass substrate as needed, and the pressure bonding temperature (lamination temperature) is preferably 60 to 140 ℃, and the pressure bonding pressure is preferably 1 to 11kgf/cm²The lamination is preferably performed under such conditions. When a vacuum laminator is used, lamination is preferably performed under reduced pressure of not more than 20mmHg (26.7hPa) in terms of air pressure. The lamination 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, the substrate is cooled to near room temperature. The support film is peeled off as necessary.

< method for producing laminate by coating >

There is no particular limitation on the method of manufacturing the coating-based laminate. For example, the resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed. The varnish is applied to a glass substrate, and the organic solvent is dried by heating, blowing hot air, or the like, thereby forming a resin composition layer. The resin composition layer may be further semi-cured. In this manner, a laminate can be produced.

[ laminated sheet ]

The laminate of the present invention is a laminate including 1 or more resin cured layers made of a cured product of a resin composition containing a thermosetting resin and an inorganic filler, and 1 or more glass substrate layers.

The size of the laminate of the present invention is preferably selected from the range of 10mm to 1000mm in width and 10mm to 3000mm in length (when used in a roll form, the length is suitably applicable). From the viewpoint of workability, the width is particularly preferably in the range of 25mm to 550mm and the length is preferably in the range of 25mm to 550 mm.

The thickness of the laminate of the present invention is preferably selected in the range of 36 μm to 20mm depending on the application. The thickness of the laminated plate is more preferably 50 to 1000 μm, still more preferably 100 to 500 μm, and particularly preferably 120 to 300 μm.

The laminate is preferably a laminate in which the resin composition layer of the laminate is formed as a cured resin layer.

The details of the glass substrate layer and the resin composition are the same as those described above for the laminate.

< layer of cured resin >

The thickness of the resin cured layer is preferably 3 to 200 μm. If the thickness is 3 μm or more, cracks in the laminated sheet are suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate layer becomes large, and a low thermal expansion coefficient and a high elastic modulus of the laminate can be achieved. From this viewpoint, the thickness of the cured resin layer is more preferably 3 to 150 μm, still more preferably 3 to 100 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm. However, the thickness of the resin cured layer may be appropriately adjusted in various ranges depending on the thickness and the number of layers of the glass substrate layer and the type and the number of layers of the resin cured layer.

The resin cured layer preferably has a storage elastic modulus of 1 to 80GPa at 40 ℃. When the thickness is 1GPa or more, the glass substrate layer is protected and cracks in the laminated plate are suppressed. When the thickness is 80GPa or less, stress due to a difference in thermal expansion coefficient between the glass substrate layer and the resin cured layer is suppressed, and bending and cracking of the laminate are suppressed. From this viewpoint, the storage elastic modulus of the cured resin layer is preferably 3 to 70GPa, more preferably 5 to 60GPa, still more preferably 10 to 50GPa, and particularly preferably 20 to 50 GPa.

The laminate may have a metal foil of copper, aluminum, nickel or the like on one surface or both surfaces thereof. The metal foil may be used for the purpose of an electrical insulating material, and is not particularly limited.

< interlayer insulating layer >

The laminate may have an interlayer insulating layer. The interlayer insulating layer can be obtained by, for example, curing the interlayer insulating composition layer of the laminate.

In the case where the laminate has an interlayer insulating layer, for example,

may have a 3-layer structure of a glass substrate layer/a resin cured layer/an interlayer insulating layer,

the structure may have a 5-layer structure of interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer.

In addition to the above examples, the interlayer insulating composition may be disposed between the conductor layer and the laminate of the present invention, and is not limited to the above examples.

< characteristics of laminated sheet >

The storage elastic modulus of the laminated sheet at 40 ℃ is preferably 10 to 70GPa, more preferably 20 to 60GPa, even more preferably 25 to 50GPa, and particularly preferably 25 to 45GPa, from the viewpoint of suppressing the bending and cracking of the laminated sheet.

From the viewpoint of suppressing the warpage and cracks of the laminated sheet, the average coefficient of thermal expansion of the laminated sheet in the range of 50 to 120 ℃ is preferably 1 to 10 ppm/DEG C, more preferably 2 to 8 ppm/DEG C, still more preferably 2 to 6 ppm/DEG C, and particularly preferably 2 to 5 ppm/DEG C.

From the viewpoint of suppressing the warpage and cracks of the laminated plate, the average coefficient of thermal expansion of the laminated plate in the range of 120 to 190 ℃ is preferably 1 to 15 ppm/DEG C, more preferably 2 to 10 ppm/DEG C, still more preferably 2 to 8 ppm/DEG C, and particularly preferably 2 to 6 ppm/DEG C.

< ratio of layers in laminated sheet >

From the viewpoint of obtaining a laminated sheet having a low thermal expansion coefficient and a high elastic modulus, the resin cured product layer of the present invention is preferably 10 to 60 vol%, more preferably 15 to 55 vol%, further preferably 20 to 50 vol%, and particularly preferably 20 to 40 vol% with respect to the entire laminated sheet.

From the viewpoint of obtaining a laminated sheet having a low thermal expansion coefficient and a high elastic modulus, the glass substrate layer of the present invention is preferably 20 to 90 vol%, more preferably 30 to 85 vol%, further preferably 35 to 80 vol%, and particularly preferably 40 to 75 vol% based on the entire laminated sheet.

When the laminate has an interlayer insulating layer, the interlayer insulating layer is preferably 1 to 20 vol%, more preferably 2 to 15 vol%, and still more preferably 3 to 10 vol% of the entire laminate.

When the laminated sheet has an adhesive layer, the adhesive layer is preferably 1 to 20 vol%, more preferably 2 to 15 vol%, and still more preferably 3 to 10 vol% of the entire laminated sheet.

[ method for producing laminated plate ]

The method for producing the laminated plate is not particularly limited. A specific example of the method for producing a laminated plate will be described below.

< production example by Heat curing of laminate >

In the laminate obtained by the above lamination, the support film is peeled off as necessary, and then the resin composition layer is heated and cured to produce a laminate.

The conditions for the heat curing may be selected from the range of 20 to 80 minutes at 150 to 220 ℃, and more preferably from 30 to 120 minutes at 160 to 200 ℃. In the case of using the support film subjected to the mold release treatment, the support film may be peeled off after being cured by heating.

This method eliminates the need for pressing during the production of the laminated sheet, and thus can suppress the occurrence of cracks during the production.

< production example by Press Molding method >

In addition, the laminate of the present invention may be manufactured by a press-fitting method.

For example, a laminated plate can be produced by heating, pressing, and curing a laminated body obtained by laminating the layers by a press method.

The adhesive film and/or the support film and the protective film are removed from the adhesive film to form an adhesive film main body, and the adhesive film main body is stacked on a glass substrate and cured by heating and pressing by a press-fit method, thereby manufacturing a laminated plate.

Further, a laminate can also be produced by laminating a material obtained by applying and drying a resin composition to a glass substrate to form a B-stage state, and curing the material by heating and pressing the material by a press-fit method.

[ multilayer laminated plate and method for producing the same ]

The multilayer laminated plate of the present invention is a multilayer laminated plate including a plurality of laminated plates, and at least one of the laminated plates is the aforementioned laminated plate of the present invention.

The method for producing the multilayer laminated sheet is not particularly limited.

For example, the laminate may be multilayered by laminating a plurality of layers through an adhesive film main body obtained by removing the support film and the protective film from the adhesive film.

Further, a plurality of the laminated bodies (for example, 2 to 20 sheets) are laminated and molded to produce a multilayer laminated plate. Specifically, the molding can be performed at a temperature of about 100 to 250 ℃, a pressure of about 2 to 100MPa, and a heating time of about 0.1 to 5 hours by using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, or the like.

[ printed Wiring Board and method for producing the same ]

The printed wiring board of the present invention has the above-described laminated board or multilayer laminated board, and a wiring provided on the surface of the laminated board or multilayer laminated board.

Next, a method for manufacturing the printed wiring board will be described.

< formation of Via hole and the like >

If necessary, the laminated plate may be perforated by a drill, a laser, plasma, or a combination thereof to form a through hole or a through hole. As the laser, a carbonic acid gas laser, a YAG laser, a UV laser, an excimer laser, or the like is generally used. After forming the through-hole or the like, desmearing treatment may be performed using an oxidizing agent. As the oxidizing agent, permanganate (potassium permanganate, sodium permanganate, or the like), dichromate, ozone, hydrogen peroxide/sulfuric acid (i.e., a mixture of hydrogen peroxide and sulfuric acid), and nitric acid are suitably used, and an aqueous sodium hydroxide solution (alkaline aqueous permanganate solution) of potassium permanganate, sodium permanganate, or the like is more preferable.

< formation of conductor layer >

Next, a conductor layer is formed on the resin cured layer on the surface of the laminated plate by dry plating or wet plating.

As the dry plating, a known method such as vapor plating, sputtering, ion plating, or the like can be used.

In the case of wet plating, first, the surface of the resin cured layer is roughened with an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate, or the like), dichromate, ozone, hydrogen peroxide/sulfuric acid, or nitric acid, to form a rough surface (anchor) having irregularities. As the oxidizing agent, a sodium hydroxide aqueous solution (alkaline permanganic acid aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. The roughening treatment may be combined with the above-described desmearing treatment. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Further, the conductive layer can be formed by electroless plating alone by forming the plating prevention layer in a pattern opposite to the conductive layer.

When a support film made of a metal foil is used as the laminate, the step of forming the conductor layer can be omitted.

< formation of Wiring Pattern >

As a method of forming the pattern thereafter, for example, a known subtractive process (subtractive process), a semi-additive process, or the like can be used.

[ multilayer printed Wiring Board and method for producing the same ]

As one mode of the above-described printed wiring board, a multilayer printed wiring board can be obtained by laminating a plurality of laminated boards each having a wiring pattern formed thereon as described above.

When manufacturing the multilayer printed wiring board, the multilayer board having the wiring pattern formed thereon is multilayered through the adhesive film body. Then, a through hole or a blind via hole is formed by drill processing or laser processing, and an interlayer wiring is formed by plating or conductive paste. In this manner, a multilayer printed wiring board can be manufactured.

Laminate with metal foil, multilayer laminate, and methods for producing them

The laminate and the multilayer laminate may be a metal foil-clad laminate or a multilayer laminate having a metal foil of copper, aluminum, nickel or the like on one or both surfaces.

The method for producing the metal foil-clad laminate is not particularly limited. For example, a metal foil can be used as the support film as described above, whereby a metal foil-clad laminate can be produced. In addition, a laminate with a metal foil can be produced by laminating one or more (for example, 2 to 20) laminates obtained by the above lamination or coating, and laminating the laminates in a structure in which a metal foil is disposed on one surface or both surfaces of the laminates.

The molding conditions can be applied to a method of using a laminated sheet or a multilayer sheet for an electrical insulating material, and for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like is used to perform molding at a temperature of about 100 to 250 ℃, a pressure of about 2 to 100MPa, and a heating time of about 0.1 to 5 hours.

< method for evaluating thermal expansion coefficient >

The thermal expansion coefficient of the laminated plate can be measured by using a Thermal Mechanical Analyzer (TMA), a temperature-dependent three-dimensional displacement measuring Device (DIC), a laser interference method, or the like.

< method for evaluating elastic modulus >

The elastic modulus of the laminate sheet can be measured as a static elastic modulus in addition to the storage elastic modulus by a wide-area viscoelasticity measuring apparatus. The flexural modulus can be determined by performing a 3-point bending test or the like.

[ examples ]

The present invention will be described in more detail below with reference to 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.

Fig. 1 is a schematic cross-sectional view illustrating the manufacturing method of example 1 and example 2. Fig. 2 is a schematic cross-sectional view illustrating the manufacturing method of example 4.

[ example 1]

< production of resin film (laminate of interlayer insulating composition layer 2 and support film 1) 3 >

To 135.4 parts of a polyamide resin "BPAM-155" (trade name) produced by Nippon Kabushiki Kaisha dissolved in a dimethylacetamide solvent at a concentration of 10%, 62.0 parts of an epoxy resin "NC 3000-H" (trade name, concentration 100%) produced by Nippon Kabushiki Kaisha was added as a thermosetting resin, 23.5 parts of a triazine-containing phenol novolak resin "LA-1356-60P" (trade name, concentration 60%) produced by DIC Kabushiki Kaisha was added as a curing agent, 0.6 part of 2-phenylimidazole "2 PZ" (trade name, concentration 100%) produced by Nippon Kabushiki Kaisha was used as a curing accelerator, 8.8 parts of fumed silica "AEROSIL R972" (trade name, concentration 100%, average particle diameter of primary particles: 16nm, specific surface area by BET method: 110. + -. 20m²/g) as an inorganic filler, 3.6 parts of polyester-modified polydimethylsiloxane "BYK-310" (trade name, concentration 25%) manufactured by BYK Chemie Japan K.K. was used as another component, and 314.3 parts of dimethylacetamide solvent was further added thereto, followed by dissolution and mixing, and dispersion treatment with a bead mill was performed to prepare a varnish.

As the support film 1, a polyethylene terephthalate film (PET film) having a thickness of 38 μm was used, and the varnish was coated and dried by a comma coater. The coating thickness was set to 5 μm, and the drying temperature was set; by setting the drying time to 3 minutes at 140 ℃, a resin film 3 having a width of 270mm, in which the interlayer insulating composition layer 2 was formed on the support film 1, was obtained (fig. 1 (a)).

< production of varnish for resin composition layer >

31.8 parts of an epoxy resin "NC 3000-H" (trade name, concentration 100%) manufactured by Nippon chemical Co., Ltd as a thermosetting resin, 7.2 parts of a triazine-containing cresol novolak "LA-3018-50P" (trade name, concentration; 50%) manufactured by DIC as a curing agent, 5.1 parts of an HCA-HQ "(trade name, concentration 100%) manufactured by Sanko corporation as a phosphorus-containing phenolic resin, 4.4 parts of a phenol novolak" TD2131 "(concentration 100%) manufactured by DIC, and a curing accelerator were mixed together0.1 part of 1-cyanoethyl-2-phenylimidazolium tris (mellitic acid) salt "2 PZCNS-PW" (trade name, concentration 100%) manufactured by SiKogyo chemical industries, and silica filler "SO-C2" (trade name, concentration 100%) manufactured by アドマフアインテクノ K, as an inorganic filler, which was treated with an aminosilane coupling agent in a methyl isobutyl ketone solvent SO that the solid content was 70% (solid content, average particle diameter of primary particles: 500nm, specific surface area by BET method: 6.8m²78.6 parts/g), and then 42.7 parts of methyl ethyl ketone was added as an additional solvent, and the mixture was dissolved and mixed to carry out a bead mill dispersion treatment, thereby preparing a varnish for a resin composition layer.

< production of adhesive film (support film 1/interlayer insulating composition layer 2/resin composition layer 4)5a >

On the resin film 3, the adhesive film 5a is produced by forming the resin composition layer 4.

As a method, using the resin film 3 (the support film 1/the interlayer insulating composition layer 2), a varnish for the resin composition layer was applied to the interlayer insulating composition layer 2 side by a comma coater and dried. The adhesive film 5a having a width of 270mm was obtained by forming the resin composition layer 4 at a coating thickness of 40 μm (2: 5 μm for the interlayer insulating composition layer and 4: 35 μm for the resin composition layer), a drying temperature of 105 ℃ and a drying time of 1.2 minutes (FIG. 1 (b)).

< production of laminate (interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer) >

As the glass substrate layer 6, an extremely thin glass film "OA-10G" (trade name, thickness 100 μm, 250 mm. times.250 mm) made by Nippon electric glass was used. The adhesive films 5a were disposed on both surfaces of the glass substrate layer 6 so that the resin composition layer 4 was in contact with the glass substrate layer 6, and laminated by lamination using a batch-type vacuum pressure laminator "MVLP-500" (trade name, manufactured by nomenclatu co., ltd.) (fig. 1(c), (d)). The vacuum degree at this time was set to 30mmHg or less, the temperature was set to 90 ℃ and the pressure was set to 0.5 MPa.

After cooling to room temperature, the support film 1 was peeled off and cured in a dry gas set at 180 ℃ for 60 minutes. By this curing, the interlayer insulating composition layer 2 and the resin composition layer 4 become an interlayer insulating layer 2a and a resin cured layer 4a, respectively. Thus, a laminated board 7a having a 5-layer structure (interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer) was obtained (fig. 1 (e)).

[ example 2]

< production of adhesive film (support film/interlayer insulating composition layer/resin composition layer) 5b >

An adhesive film 5b was obtained in the same manner as the adhesive film 5a of example 1, except that the coating thickness of the varnish was set to 30 μm instead of 40 μm (2: 5 μm for the interlayer insulating composition layer, 4: 25 μm for the resin composition layer).

< production of laminate (interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer) >

As the glass substrate layer 6, an extremely thin glass film "OA-10G" (trade name, thickness 50 μm, 250 mm. times.250 mm) made by Nippon electric glass was used. A laminated plate having a 5-layer structure (interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer) was obtained in the same manner as in example 1, except that the adhesive film 5b was used on both surfaces of the glass substrate layer 6.

[ example 3]

< production of laminate (interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer) >

A laminated plate having a 5-layer structure (interlayer insulating layer/glass substrate layer/resin cured layer/interlayer insulating layer) was obtained in the same manner as in example 2, except that an extremely thin glass film "OA-10G" (trade name, thickness 150 μm, 250mm × 250mm) made of japan electric glass was used as the glass substrate layer 6.

[ example 4]

< production of varnish for resin composition layer >

To 135.4 parts of a polyamide resin "BPAM-155" (trade name) made by Nippon chemical Co., Ltd dissolved in a dimethylacetamide solvent at a concentration of 10%, 62.0 parts of a thermosetting epoxy resin "NC 3000-H" (trade name, concentration 100%) made by Nippon chemical Co., Ltd, 23.5 parts of a triazine-containing phenolic novolak resin "LA-1356-60P" (trade name, concentration 60%) made by Nippon chemical Co., Ltd, 0.6 part of 2-phenylimidazole "2 PZ" (trade name, concentration 100%) made by Nippon chemical industry Co., Ltd as a curing agent, 4.8 parts of a fumed silica "ROSIL R" (trade name, concentration 100%) made by Nippon AEROSIL Co., Ltd as an inorganic filler, and 4.8 parts of a polyester-modified polydimethylsiloxane "BYK-310" (trade name) made by BYK-Chemi Japan, as other components were added, concentration 25%) 1.7 parts, and 66.3 parts of dimethylacetamide solvent was further added thereafter. Thereafter, a uniform resin varnish was obtained using a disperser (Nanomizer, trade name, manufactured by Jitian Kogyo Co., Ltd.).

< production of adhesive film (support film 1/resin composition layer 4)5c >

The adhesive film 5c is produced by forming the resin composition layer 4 on the support film 1 (fig. 2 (a)).

As a method, a resin varnish was applied to a release-treated surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, trade name, Lintec) as a support film, so that the thickness after drying was 20 μm, and the resin varnish was dried at 140 ℃ for 5 minutes to form an adhesive film 5c having a width of 270mm and comprising the resin composition layer 4 and the support film 1.

< production of laminated Board (resin cured layer/glass substrate layer/resin cured layer) >

As the glass substrate layer 6, an extremely thin glass film "OA-10G" (trade name, thickness 150 μm, 250 mm. times.250 mm) made by Nippon electric glass was used. The adhesive films 5c were disposed on both surfaces of the glass substrate layer 6 so that the resin composition layer 4 was in contact with the glass substrate layer 6, and laminated by lamination using a batch-type vacuum pressure laminator "MVLP-500" (trade name, manufactured by nomenclatu co., ltd.) (fig. 2(b), (c)). The vacuum degree at this time was set to 30mmHg or less, the temperature was set to 120 ℃ and the pressure was set to 0.5 MPa.

After cooling to room temperature, the support film 1 was peeled off and cured in a dry gas set at 180 ℃ for 60 minutes. By this curing, the resin composition layer 4 becomes a resin cured layer 4 a. Thus, a laminated plate (resin cured layer/glass substrate layer/resin cured layer) 7b having a 3-layer structure was obtained (fig. 2 (d)).

Comparative example 1

< production of resin film >

A resin film was produced in the same manner as in resin film 3 of example 1, except that the inorganic filler (fumed silica) was not added.

< production of varnish >

A varnish was produced in the same manner as the varnish for the resin composition layer of example 1, except that the inorganic filler (silica filler) was not added.

< production of adhesive film >

An adhesive film (support film/interlayer insulating composition layer/resin composition layer) was produced in the same manner as in example 1, except that the resin film and varnish described above were used instead of the resin film 3 and varnish for resin composition layer in example 1.

< production of laminate (interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer) >

The same operation as in example 1 was carried out, except that the above adhesive film was used in place of the adhesive film 5a of example 1, to obtain a laminated board having a 5-layer structure (interlayer insulating layer/resin cured layer/glass substrate layer/resin cured layer/interlayer insulating layer).

[ reference example 1]

Next, a laminate using a prepreg, which is a general laminate for semiconductor packages and printed wiring boards, is produced as follows.

< production of solution of resin composition having unsaturated Maleimide group >

To a 2-liter reaction vessel equipped with a thermometer, a stirring device, a reflux cooling tube and a moisture meter and capable of heating and cooling was placed 4, 4' -bis (4-aminophenoxy) biphenyl: 69.10g, bis (4-maleimidophenyl) sulfone: 429.90g, p-aminophenol: 41.00g, and propylene glycol monomethyl ether: 360.00g, at a reflux temperature for 2 hours, to thereby obtain a solution of a resin composition having an acidic substituent and an unsaturated maleimide group.

< production of varnish containing thermosetting resin composition >

(1) As the curing agent (A), a solution of the resin composition having the unsaturated maleimide group is used,

(2) as the thermosetting resin (B), a 2-functional naphthalene type epoxy resin [ manufactured by Dainippon ink chemical industry Co., Ltd., trade name, HP-4032D ] was used,

(3) as the modified imidazole (C), isocyanate-blocked imidazole (Japanese: イソシアネ - トマスクイミダゾ - ル) (product name of first Industrial pharmaceutical Co., Ltd.: G8009L ] is provided,

(4) as the inorganic filler (D), fused silica (manufactured by Admatech, trade name: SC2050-KC, concentration 70%, average of primary particlesAverage particle size: 500nm, specific surface area based on BET method: 6.8m²/g〕，

(5) As the phosphorus-containing compound (E) for imparting flame retardancy, a phosphorus-containing phenol resin [ manufactured by mitrochoech corporation, trade name: HCA-HQ, phosphorus content 9.6% by mass),

(6) as the compound (F) which can be chemically coarsened, crosslinked nitrile rubber (NBR) particles [ [ product name manufactured by JSR (ltd.): XER-91) of the formula (I),

(7) as the diluting solvent, methyl ethyl ketone was used,

by mixing the components at the mixing ratios (parts by mass) shown in table 1, a uniform varnish (G) having a resin content (total of resin components) of 65 mass% was produced.

[ Table 1]

TABLE 1

	Mass portion of
		Curing agent (A)	50
Thermosetting resin (B)	49.5
		Modified imidazole (C)	0.5
Inorganic filler (D)	40
		Phosphorus-containing Compound (E)	3
Compound (F)	1

< production of prepreg comprising thermosetting resin composition >

E glass cloths of different thicknesses were each impregnated with the above varnish (G) and dried at 160 ℃ for 10 minutes by heating, to obtain prepregs of 250 mm. times.250 mm. Regarding the type of E glass cloth, IPC standard 2116 of japan asahi chemical イ - マテリアルズ was used, and the resin content of the prepreg was 50 mass%. Three prepregs were combined, and electrolytic copper foils having a thickness of 12 μm were placed in the vertical direction, and pressed at a pressure of 3.0MPa and a temperature of 235 ℃ for 120 minutes to produce a copper-clad laminate.

[ measurement ]

The performance of the laminated sheets obtained in the above examples, comparative examples and reference examples was measured and evaluated by the following method.

(1) Determination of the coefficient of thermal expansion

A test piece of 4 mm. times.30 mm was cut out from the laminated sheet. In the case of using a copper-clad laminate, the copper foil was removed by immersing in a copper etching solution, and then a test piece was cut out.

Evaluation was performed by observing thermal expansion characteristics smaller than Tg of the test piece using a TMA test apparatus (manufactured by DuPont, TMA 2940). Specifically, the average thermal expansion coefficients in the range of 50 to 120 ℃ and the range of 120 to 190 ℃ were determined by a tensile method using a temperature rise rate of 5 ℃/min for the first round in the measurement range of 20 to 200 ℃, a weight of 5g for the second round in the measurement range of-10 to 280 ℃, and a distance of 10mm between clamps. The results are shown in table 2.

(2) Determination of storage modulus of elasticity

Test pieces of 5mm × 30mm were cut out from the laminated sheet. In the case of using a copper-clad laminate, the test piece was cut out by immersing in a copper etching solution and removing the copper foil.

The tensile storage modulus at 40 ℃ was measured using a wide range viscoelasticity measuring apparatus (model DVE-V4, manufactured by レオロジ Co., Ltd.) under the conditions of a pitch of 20mm, a frequency of 10Hz, and a vibration displacement of 1 to 3 μm (stop oscillation (Japanese: ストツプ oscillation)). The results are shown in Table 2.

[ Table 2]

TABLE 2

As is clear from Table 2, examples 1 to 4 of the present invention are excellent in low thermal expansion at 50 to 120 ℃ and high elasticity at 40 ℃. It is also found that in the high temperature region of 120 to 190 ℃, the low thermal expansion property of examples 1 to 4 is almost the same as that in the low temperature region, compared to the case where the thermal expansion coefficient is increased in the low temperature region (50 to 120 ℃) in reference example 1. Therefore, examples 1 to 4 of the present invention maintained low thermal expansion not only in the low temperature region but also in the high temperature region.

Claims (14)

1. A laminate comprising 1 or more resin composition layers and 1 or more glass substrate layers, wherein the resin composition layers are composed of a resin composition containing a thermosetting resin and an inorganic filler.

2. The laminate according to claim 1,

the thickness of the glass substrate layer is 30-200 mu m.

3. The laminate according to claim 1 or 2,

the thermosetting resin is 1 or more than 2 selected from epoxy resin, phenolic 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 and melamine resin.

4. The laminate according to any one of claims 1 to 3,

the inorganic filler is 1 or more than 2 selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate and borosilicate glass.

5. A laminated board comprising 1 or more resin cured layers and 1 or more glass substrate layers, wherein the resin cured layers are formed from a cured product of a resin composition containing a thermosetting resin and an inorganic filler.

6. The laminate panel of claim 5,

the storage elastic modulus at 40 ℃ is 10 GPa-70 GPa.

7. The laminated plate according to claim 5 or 6, wherein the laminated plate is obtained by heating the laminate according to any one of claims 1 to 4.

8. A multi-layer laminate comprising a plurality of laminates, wherein at least one laminate is a laminate as claimed in any one of claims 5 to 7.

9. A printed wiring board having the laminated board according to any one of claims 5 to 7 and a wiring provided on a surface of the laminated board.

10. A printed wiring board having the multilayer laminated board according to claim 8 and wiring provided on a surface of the multilayer laminated board.

11. A method for producing a laminated plate including 1 or more resin cured layers composed of a cured product of a resin composition containing a thermosetting resin and an inorganic filler, and 1 or more glass substrate layers, the method comprising a resin cured layer forming step of forming the resin cured layers on the surfaces of the glass substrates.

12. The method of manufacturing a laminated plate according to claim 11,

the resin cured product layer forming step is a step of applying the resin composition on the glass substrate, and then drying and curing the resin composition.

13. The method of manufacturing a laminated plate according to claim 11,

the cured resin layer forming step is a step of laminating and curing a film made of the resin composition on the glass substrate using a vacuum laminator or a roll laminator.

14. The method of manufacturing a laminated plate according to claim 11,

the resin cured product layer forming step is a step of disposing a film made of the resin composition on the glass substrate, and then pressing and curing the film.