KR102264708B1 - Laminated body, laminated board, multi-layer laminated board, printed wiring board, and production method for laminated board - Google Patents

Abstract

According to the present invention, there is provided a laminate comprising at least one resin composition layer and at least one glass substrate layer, wherein the resin composition layer consists of a resin composition including a thermosetting resin and an inorganic filler, and the glass substrate layer is the To provide a laminate in an amount of 10 to 95 vol% based on the entire laminate. In addition, a laminate comprising at least one cured resin layer and at least one glass substrate layer, wherein the cured resin layer consists of a cured product of a resin composition including a thermosetting resin and an inorganic filler, and the glass substrate layer A printed wiring board having a laminated sheet in an amount of 10 to 95% by volume with respect to the entire laminated sheet, the above laminated sheet, and wiring provided on the surface of the laminated sheet is provided. And, it provides the manufacturing method of the said laminated board including the resin cured material layer forming process of forming the resin cured material layer on the surface of a glass substrate.

Description

LAMINATED BODY, LAMINATED BOARD, MULTI-LAYER LAMINATED BOARD, PRINTED WIRING BOARD, AND PRODUCTION METHOD FOR LAMINATED BOARD

The present invention relates to laminates and laminates suitable for semiconductor packages or printed wiring boards, printed wiring boards, multilayer laminates, and methods for manufacturing laminates using the laminates.

In recent years, the demand for thickness reduction and weight reduction of electronic devices has become increasingly strong, and thickness reduction and density increase of a semiconductor package and a printed wiring board are progressing. In order to mount electronic components stably in response to these thickness reduction and density increase, it becomes important to suppress the curvature which arises at the time of mounting.

One of the main causes of warpage occurring in a semiconductor package during mounting is a difference in thermal expansion coefficient between a laminate used for a semiconductor package and a silicon chip mounted on the surface of the laminate. Therefore, in the laminated board for semiconductor packages, the effort of making a thermal expansion coefficient approach the thermal expansion coefficient of a silicon chip, ie, making it low thermal expansion, is made. Moreover, since the low elastic modulus of a laminated board also causes curvature, in order to reduce curvature, it is also effective to make a laminated board highly elastic. Thus, in order to reduce the curvature of a laminated board, low expansion coefficient and high elasticity-ization of a laminated board are effective.

Although various methods for making a laminated board low thermal expansion coefficient and high elasticity-ization are considered, especially, low thermal expansion coefficient-ization of resin for laminated boards, and high filling of the inorganic filler in resin are known. In particular, high filling of the inorganic filler is a method in which heat resistance and flame retardancy can be expected along with low thermal expansion coefficient (Patent Document 1). However, it is known that increasing the filling amount of the inorganic filler in this way causes a decrease in insulation reliability, a lack of adhesion between the resin and the wiring layer formed on the surface, and poor press molding at the time of manufacturing a laminate. have.

Moreover, by selection or improvement of resin, it is attempted to achieve low coefficient of thermal expansion. For example, the method of raising the crosslinking density of resin for wiring boards, raising Tg, and reducing a coefficient of thermal expansion is common (patent documents 2 and 3). However, while increasing the crosslinking density shortens the molecular chain between functional groups, shortening the molecular chain more than a certain amount has a limit from the viewpoint of reaction, and there is also a problem that the resin strength is lowered. For this reason, there is also a limit to lowering the coefficient of thermal expansion by the method of increasing the crosslinking density.

Thus, in the conventional laminated board, although high filling of an inorganic filler, and low thermal expansion and high elasticity-ization by employ|adoption of low thermal expansion resin have been attained, it is reaching|attaining a limit.

In addition, as a method different from the above, a glass film is used as a layer having a coefficient of thermal expansion substantially equal to that of an electronic component (silicon chip), and a resin and a glass film are pressed and laminated, thereby reducing thermal shock stress. Although the trial was made (patent document 4), since the elastic modulus of a resin layer was low and thermal expansion coefficient was high, it was insufficient to implement|achieve the low curvature of a board|substrate.

Japanese Patent Laid-Open No. 2004-182851 Japanese Patent Laid-Open No. 2000-243864 Japanese Patent Laid-Open No. 2000-114727 Patent No. 4657554

As mentioned above, since the board|substrate obtained by the manufacturing method of patent document 4 still had a low elastic modulus and a high thermal expansion coefficient, it was insufficient to implement|achieve the low warpage of a board|substrate.

The present invention has been made in view of these circumstances, has a low coefficient of thermal expansion and a high modulus of elasticity, can suppress warpage, and is less prone to cracking and laminates, laminates and multilayer laminates suitable for production of laminates and multilayer laminates, and these laminates And it aims at providing the printed wiring board using the multilayer laminated board, and the manufacturing method of this laminated board.

Patent document 4 is a board|substrate formed by laminating|stacking a glass film and resin. WHEREIN: There is no description that resin contains an inorganic filler. When it sees from description of patent document 4, it is thought that containing an inorganic filler in resin should be avoided.

That is, in patent document 4, it is made into the essential structure that the thermal expansion effect|action of the whole board|substrate is substantially determined by a glass film (claim 1 of patent document 4). In view of this, it is necessary to make the effect of the resin on the thermal expansion action of the substrate as small as possible, and for that purpose, it is necessary to suppress the elastic modulus of the resin low (for example, if the resin has a high modulus of elasticity, the resin of this high modulus can will be greatly affected by the action of thermal expansion of the whole). On the other hand, when resin contains an inorganic filler, resin will become high elastic modulus. Therefore, when it sees from description of patent document 4, it should avoid containing an inorganic filler in resin.

Moreover, when resin of patent document 4 contains an inorganic filler, an inorganic filler will become a starting point, and it will be considered that a glass substrate will break easily. Also from this point, it is estimated that patent document 4 avoids containing an inorganic filler in resin.

Currently, in the laminated board of a glass substrate layer and a resin layer like patent document 4, there is no example of the laminated board which made the inorganic filler contained in the resin layer.

However, surprisingly, as a result of intensive research conducted by the present inventors to solve the above problems, in a laminate including a cured resin material layer and a glass substrate layer, by containing an inorganic filler in the cured resin material layer, a low coefficient of thermal expansion and a high modulus of elasticity It has been found that a laminated sheet that is less prone to cracking by suppressing curvature is obtained.

The present invention has been completed based on this knowledge, and has the following [1] to [12] as the gist of the present invention.

[1] A laminate comprising at least one resin composition layer and at least one glass substrate layer, wherein the resin composition layer consists of a resin composition including a thermosetting resin and an inorganic filler, and the glass substrate layer is the laminate 10 to 95 vol% of the total laminate.

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

[3] The thermosetting resin is 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, or a dicyclopentadiene resin. , The laminate according to the above [1] or [2], wherein one or two or more selected from a silicone resin, a triazine resin, and a melamine resin.

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

[5] A laminate comprising at least one cured resin layer and at least one glass substrate layer, wherein the cured resin layer is made of a cured product of a resin composition including a thermosetting resin and an inorganic filler, and the glass substrate layer 10 to 95 vol% of the total amount of the laminate.

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

[7] The laminate according to [5] or [6], obtained by heating and pressurizing the laminate according to any one of [1] to [4].

[8] A multilayer laminate comprising a plurality of laminates, wherein at least one laminate is the laminate according to any one of [5] to [7].

[9] A printed wiring board comprising the laminate according to any one of [5] to [7], and wiring provided on a surface of the laminate.

[10] A printed wiring board comprising the multilayer laminate according to [8] and wiring provided on a surface of the multilayer laminate.

[11] The method for producing a laminate according to any one of [5] to [7], including a resin cured material layer forming step of forming a cured resin material layer on the surface of a glass substrate.

[12] The method for producing a laminate according to [11], wherein the cured resin layer forming step is a step of applying the resin composition on the glass substrate, followed by drying and curing.

[13] The method for producing a laminate according to [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 laminate according to [11], wherein the cured resin layer forming step is a step of placing the film made of the resin composition on the glass substrate, then pressing and curing.

According to the present invention, a laminate and multilayer laminate having a low coefficient of thermal expansion and a high modulus of elasticity, curvature can be suppressed and cracking hardly occur, a laminate suitable for manufacturing these laminates and multilayer laminates, and these laminates and multilayer laminates The used printed wiring board and the manufacturing method of this laminated board can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing explaining the manufacturing method of Examples 1-2 and 4.
Fig. 2 is a schematic cross-sectional view for explaining the manufacturing method of Example 5;

Hereinafter, the manufacturing method of the laminated body, a laminated board, a multilayer laminated board, a printed wiring board, and a laminated board of this invention is demonstrated in detail.

In addition, in this invention, a laminated body means that the thermosetting resin which is its constituent component is uncured or semi-hardened, and a laminated board means that the thermosetting resin which is its constituent component is hardened|cured.

[Laminate]

The laminate of the present invention is a laminate including one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer consists of a resin composition containing a thermosetting resin and an inorganic filler, and the glass substrate layer It is 10-95 volume% with respect to this whole laminated body.

The size of the laminate of the present invention is preferably selected from the range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (when used by a roll, the length is appropriately applied) from the viewpoint of handleability. In particular, it is preferable that the range is 25 mm to 550 mm in width and 25 mm to 550 mm in length.

It is preferable that the thickness of the laminated body of this invention is selected from the range of 35 micrometers - 20 mm according to the use. The thickness of the laminate is more preferably 50 to 1000 µm, still more preferably 100 to 500 µm, still more preferably 120 to 300 µm.

The laminate obtained by curing the resin composition layer of the laminate of the present invention to form a cured resin layer has a glass substrate layer having a low thermal expansion coefficient and a high modulus of elasticity similar to that of a silicon chip, so that it has a low coefficient of thermal expansion and a high modulus of elasticity, The curvature is suppressed and it becomes a thing which a crack is hard to generate|occur|produce. In particular, since this laminated board has a glass substrate layer with high heat resistance, it has remarkably low thermal expansibility in the temperature range from 100 degreeC to less than Tg of a cured resin material. Further, since the cured resin layer contains an inorganic filler, the cured resin layer has a low coefficient of thermal expansion and a high modulus of elasticity, and the laminate including the cured resin layer has a lower coefficient of expansion and a high modulus of elasticity. do.

<Resin composition>

The resin composition of this invention contains a thermosetting resin and an inorganic filler.

≪Thermosetting resin≫

There is no restriction|limiting in particular as a thermosetting resin, For example, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dish Chlopentadiene resin, silicone resin, triazine resin, and melamine resin are mentioned. Among these, an epoxy resin and a cyanate resin are preferable at the point excellent in a moldability and electrical insulation.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F type epoxy resin, and bisphenol F type epoxy resin. Rock-type epoxy resin, stilbene-type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolphenol methane-type epoxy resin, biphenyl-type epoxy resin, xylylene-type epoxy resin, biphenyl aralkyl-type epoxy and diglycidyl ether compounds of polycyclic aromatics such as resin, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin, alicyclic epoxy resin, polyfunctional phenol, and anthracene. Moreover, the phosphorus containing epoxy resin which introduce|transduced the phosphorus compound into these epoxy resins is mentioned. Among these, a biphenyl aralkyl type epoxy resin and a naphthalene type epoxy resin are preferable from a viewpoint of heat resistance and a flame retardance. These can be used 1 type or in mixture of 2 or more types.

As cyanate resin, for example, bisphenol-type cyanate resin, such as novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, and tetramethylbisphenol F-type cyanate resin, these were partially triazine-formed. and prepolymers. Among these, a novolak-type cyanate resin is preferable from a viewpoint of heat resistance and a flame retardance. These can be used 1 type or in mixture of 2 or more types.

The content of the thermosetting resin contained in the resin composition is preferably in the range of 20 to 80 mass %, more preferably 40 to 80 mass %, with respect to the mass obtained by subtracting the content of the inorganic filler from the total amount of the resin composition, 50 -80 mass % is more preferable, and 60-75 mass % is still more preferable.

≪Inorganic filling material≫

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

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

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

Here, the cumulative 50% particle diameter is the particle diameter at a point exactly equivalent to 50% of the volume when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the powder as 100%, and the particle size distribution using the laser diffraction scattering method It can be measured with a measuring device or the like.

5-75 volume% of the total amount of a resin composition is preferable, as for content of the inorganic filler in a resin composition, it is more preferable that it is 15-70 volume%, It is more preferable that it is 30-70 volume%. When content of an inorganic filler is 5-75 volume% of a resin composition, the reduction effect of a thermal expansion coefficient becomes enough, and it has moderate fluidity|liquidity and is excellent in a moldability. That is, if content of an inorganic filler is 5 volume% or more, the reduction effect of a thermal expansion coefficient will become sufficient thing, and if it is 75 volume% or less, fluidity|liquidity will increase and moldability will become favorable.

When expressing in mass %, for example, when an inorganic filler is silica, it is preferable that content of silica in a resin composition is 8-85 mass % of a resin composition, It is more preferable that it is 24-82 mass %, 44 It is more preferable that it is -82 mass %.

Moreover, fine wiring can be formed on the resin cured material layer of a laminated board by using silica (nano silica) whose average primary particle diameter is 1 micrometer or less for an inorganic filler. As nanosilica, it is preferable that a specific surface area is 20 m<2>/g or more. Moreover, it is preferable that an average primary particle diameter is 100 nm or less from a viewpoint of making small the surface shape after the roughening process in a plating process. This specific surface area can be measured by the BET method.

In addition, the "average primary particle diameter" as used herein is not the average diameter of the aggregated particles, that is, the secondary particle diameter, but means the average particle diameter in a single unit that is not aggregated. The said average primary particle diameter can be measured and calculated|required with a laser diffraction type particle size distribution analyzer, for example. As such an inorganic filler, fumed silica is preferable.

Moreover, in order to improve moisture resistance, it is preferable to process with surface treating agents, such as a silane coupling agent, and, as for an inorganic filler, in order to improve dispersibility, it is preferable that it is hydrophobized.

When forming fine wiring on the resin cured material layer of a laminated board, as content of an inorganic filler, it is preferable that it is 20 mass % or less in a resin composition. When a compounding quantity is 20 mass % or less, the favorable surface shape after a roughening process can be maintained, and the fall of a plating characteristic and the insulation reliability between layers can be prevented. On the other hand, since low thermal expansion and high elasticity of the resin composition can be expected by containing the inorganic filler, when low thermal expansion and high elasticity are also important with fine wiring formation, the content of the inorganic filler is 3 to 20 mass%. It is preferable, and it is more preferable to set it as 5-20 mass %.

≪Other ingredients≫

To this resin composition, in addition to the above components, a curing agent, a curing accelerator, a thermoplastic resin, an elastomer, a flame retardant, a UV absorber, an antioxidant, a photopolymerization initiator, an optical brightener, an adhesive improving agent, and the like can be added.

As an example of a hardening|curing agent, For example, when using an epoxy resin, polyfunctional phenol compounds, such as a phenol novolak and cresol novolak; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; acid anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, and maleic anhydride copolymer; Polyimides can be used. Several types of these hardening|curing agents can also be used together.

Examples of the curing accelerator include imidazoles and derivatives thereof as curing accelerators for epoxy resins; organophosphorus compounds; secondary amines, tertiary amines, and quaternary ammonium salts are mentioned.

As an example of a ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned.

As antioxidant, the antioxidant of a hindered phenol type and styrenated phenol is mentioned.

As an example of a photoinitiator, photoinitiators, such as benzophenones, benzyl ketals, and a thioxanthone type, are mentioned.

Examples of the optical brightener include optical brighteners such as stilbene derivatives.

As an example of an adhesive improving agent, the adhesive improving agent of urea compounds, such as urea silane, and a silane coupling agent is mentioned.

<Resin composition layer>

The resin composition layer contains the above-described resin composition. In addition, semi-hardened|cured material is also contained in the resin composition layer other than the unhardened|cured material of a resin composition.

The size of the resin composition layer of the present invention is preferably selected from a range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (when using with a roll, the length is appropriately applied). In particular, it is preferable from the viewpoint of handling property that it is the range of 25 mm - 550 mm in width and 25 mm - 550 mm in length.

It is preferable that the thickness per layer of the resin composition layer of this invention is selected in the range of 3 micrometers - 200 micrometers. From the viewpoint of low thermal expansion and high elastic modulus of the laminate and laminate, the thickness per layer of the resin composition is preferably 3 to 150 μm, more preferably 3 to 100 μm, still more preferably 5 to 50 μm. And, it is more preferable that it is 5-30 micrometers.

<Glass substrate layer>

The thickness per layer of the glass substrate layer is preferably 30 to 200 µm from the viewpoint of thinning the laminate and workability, and in consideration of practicality such as ease of handling, the thickness is more preferably 50 to 150 µm, 80 to 120 μm is more preferable.

The thickness of the glass substrate layer here refers to the average thickness of the glass substrate layer. The average thickness of a glass substrate layer can be measured using well-known thickness measuring instruments, such as a micrometer and a film thickness measuring instrument. For example, in the case of a rectangular or square glass substrate layer, the thickness of a square and a center can be measured using a micrometer, and the average value can be calculated|required as the average thickness of a glass substrate layer. Moreover, although glass, such as an alkali silicate type glass, an alkali free glass, and a quartz glass, can be used as a raw material of a glass substrate layer, a viewpoint of low thermal expansibility to borosilicate glass is preferable.

It is preferable that the magnitude|size of the glass substrate layer of this invention is selected from width 10mm - 1000mm, and length 10mm - 3000mm (when using with a roll, length is suitably applied). In particular, it is more preferable from the point of handleability that it is the range of 25 mm - 550 mm in width and 25 mm - 550 mm in length.

The coefficient of thermal expansion of the glass substrate layer is closer to the thermal expansion coefficient of the silicon chip (about 3 ppm/° C.), so the warpage of the laminate or the laminate obtained from the laminate may be suppressed, but it is preferably 8 ppm/° C. or less, more preferably Preferably it is 6 ppm/degreeC or less, More preferably, it is 4ppm/degreeC or less.

Although it is so good that the storage elastic modulus in 40 degreeC of this glass substrate layer is large, Preferably it is 20 GPa or more, More preferably, it is 25 GPa or more, More preferably, it is 30 GPa or more.

10-95 volume% is preferable with respect to the whole laminated body, as for this glass substrate layer, 15-90 volume% is more preferable, 20-85 volume% is still more preferable. When the content of the glass substrate is 10 vol% or more, it is advantageous in obtaining a laminate of low thermal expansibility and high elasticity, and conversely, when the content of the glass substrate is 95 vol% or less, it becomes advantageous from the viewpoint of workability and handling properties (easiness of handling). .

<Composition layer for interlayer insulation>

The laminate of the present invention may have a composition layer for interlayer insulation in order to improve the adhesiveness of the conductor layer described later.

That is, as mentioned later, when manufacturing a printed wiring board using the laminated body of this invention, a conductor layer may be formed by plating etc. with respect to the surface of the laminated board formed by hardening|curing a laminated body. Moreover, it is set as the laminated body or laminated board provided with the metal foil which has metal foil (conductor layer) on the surface. In these cases, the conductor layer may be formed on the above-mentioned resin composition layer or a cured resin layer obtained by curing the same, but an interlayer insulation composition layer or an interlayer insulation layer obtained by curing the same is further formed on the resin composition layer or cured resin material layer. It can also be formed and a conductor layer can also be formed on it. In this case, the adhesiveness between a laminated board and a conductor layer becomes favorable by using the thing with high adhesiveness of a conductor layer as an interlayer insulation composition layer.

Moreover, as mentioned later, after forming a via hole with respect to a laminated board, a desmear process may be performed. In this case, by forming the composition layer for interlayer insulation excellent in desmear resistance, it is prevented that the surface of the laminate (that is, the interlayer insulation layer formed by curing the composition layer for interlayer insulation) has excessively large irregularities, It becomes possible to form a fine wiring pattern on the surface.

As a structure in the case where the laminate has the composition layer for interlayer insulation in this way, for example,

Glass substrate layer/resin composition layer/composition layer for interlayer insulation

It may be a three-layer structure such as

Composition layer for interlayer insulation/resin composition layer/glass substrate layer/resin composition layer/composition layer for interlayer insulation

It may be a five-layer structure such as In addition, the description "glass substrate layer/resin composition layer/composition layer for interlayer insulation" means that the glass substrate layer, the resin composition layer, and the composition layer for interlayer insulation are laminated in this order. The same applies to the notation regarding the five-layer structure.

In addition to the above examples, any configuration in which the composition for interlayer insulation can be disposed between the conductor layer and the laminate of the present invention is not particularly limited to the above examples.

There is no limitation in particular as a material of this composition layer for interlayer insulation, For example, although it may be the above-mentioned resin composition, it is preferable to select resin from a viewpoint of the adhesive improvement of a conductor layer. In addition, the composition layer for interlayer insulation may contain the inorganic filler, and may not contain it.

<Adhesive layer>

Moreover, although the laminated body of this invention has a resin composition layer containing a thermosetting resin and an inorganic filler, other than that, it may have an adhesive layer containing a thermosetting resin and not containing an inorganic filler. A contact bonding layer is arrange|positioned between a glass substrate layer and a resin composition layer, for example, and can be used for the objective of improving the adhesiveness of both layers.

<Ratio of each layer in the laminate>

The resin composition layer of the present invention has a low coefficient of thermal expansion and from the viewpoint of obtaining a laminate having a high modulus of elasticity, with respect to the entire laminate, it is preferably 5 to 60 vol%, more preferably 5 to 55 vol%, more preferably 10 to It is still more preferable that it is 50 volume%, and it is still more preferable that it is 20-40 volume%.

It is preferable that it is 20-90 volume% with respect to the whole laminated body from a viewpoint of obtaining the laminated board of the low thermal expansion coefficient and high elastic modulus, as for the glass substrate layer of this invention, It is more preferable that it is 30-85 volume%, It is more preferable, 35- It is still more preferable that it is 80 volume%, and it is still more preferable that it is 40-75 volume%.

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 3 to 10 vol%, based on the entire laminate. more preferably.

When the laminate has an adhesive layer, the adhesive layer is preferably 1 to 20% by volume, more preferably 2 to 15% by volume, and still more preferably 3 to 10% by volume, based on the entire laminate.

<Support film and protective film>

Said laminated body may have a support body film and a protective film on the surface. These support film and protective film are demonstrated in detail in description of the manufacturing method of the following laminated body.

[Method for producing a laminate]

There is no restriction|limiting in particular in the manufacturing method of the said laminated body, The lamination with respect to the glass substrate of the film which consists of a resin composition, application|coating to the glass substrate of a resin composition, etc. can manufacture. Among these, the method by lamination is preferable at the point which is easy to produce.

Next, each manufacturing method is demonstrated in detail.

<The manufacturing method of the laminated body by lamination>

Said laminated body can be suitably manufactured by laminating the adhesive film using the said resin composition, and a glass substrate by pressure lamination like vacuum lamination or roll lamination. This adhesive film is mentioned later. In addition, vacuum lamination and roll lamination can be performed using commercially available vacuum laminators and roll laminators.

In addition, as the thermosetting resin in the above-mentioned resin composition and the above-mentioned composition for interlayer insulation, those that melt at the temperature at the time of lamination or less are suitably used. For example, when laminating using a vacuum laminator or a roll laminator, the thermosetting resin in the resin composition and the interlayer insulation composition are preferably melted at 140° C. or less, since it is generally performed at 140° C. or less. Do.

First, the said adhesive film is demonstrated, and then the lamination method using this adhesive film is demonstrated.

≪Adhesive film≫

When manufacturing a laminated body using a vacuum laminator or a pressure laminator, it is common to manufacture the above-mentioned resin composition as an adhesive film.

As an adhesive film used for this invention, what has the following laminated structure is used suitably.

(1) Support film/resin composition layer

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

Moreover, in the laminated structure of said (1) and (2), what has the laminated structure after further laminating|stacking a protective film is used suitably.

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

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

A protective film is formed on the opposite side to a support body film with respect to the resin composition layer of this invention, and is used for the objective of preventing adhesion of a foreign material and a flaw.

In addition, the thing except a support film and a protective film from these adhesive films may be called an adhesive film main body.

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

As an example of manufacturing the adhesive film of said (1), the above-mentioned resin composition is melt|dissolved in an organic solvent, and the varnish in which the inorganic filler was disperse|distributed is manufactured. Then, what is necessary is just to form a resin composition layer by making a support body film into a support body, apply|coating this varnish, and drying the organic solvent by heating, hot air spraying, etc.

As an example of manufacturing the adhesive film of (2), the composition layer for interlayer insulation is melt|dissolved in an organic solvent, and a varnish is manufactured. Then, the composition layer for interlayer insulation is formed by apply|coating a varnish to a support body film, and drying the organic solvent by heating, hot-air spraying, etc. Thereafter, 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 manufacturing the adhesive film of (3), the above-mentioned resin composition is melt|dissolved in an organic solvent, and the varnish in which the inorganic filler was disperse|distributed is manufactured. Then, this varnish is apply|coated with respect to one of a support film and a protective film, the other of a support film and a protective film is arrange|positioned on this varnish, and the organic solvent of this varnish is dried by heating, hot-air spraying, etc. to a resin composition layer should be formed.

As an example of manufacturing the adhesive film of the above (4), a varnish is prepared by dissolving the above-described composition for interlayer insulation in an organic solvent, this varnish is applied to the support film, and the organic solvent is dried by heating or hot air spraying. By doing so, a composition layer for interlayer insulation is formed. Then, the surface on the side of the composition for interlayer insulation of this laminate and the surface on the side of the resin composition layer of the laminate prepared in advance as in (1) are brought into contact with each other, using a pressure laminator such as a vacuum laminator or a roll laminator to be described later. Laminate. As another example, a varnish is used on the support film to form an interlayer insulating layer, then a varnish for a resin composition is applied thereon, a protective film is placed thereon, and the organic solvent of this varnish is removed by heating or hot air spraying. What is necessary is just to form a resin composition layer by making it dry.

Coating apparatuses known to those skilled in the art, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater, can be used as the coating apparatus for the interlayer insulation composition layer and the resin composition layer, and It is preferable to select it appropriately.

Further, in the above-described adhesive film, the interlayer insulation composition layer and the resin composition layer may be semi-cured.

Said support body film becomes a support body at the time of manufacturing an adhesive film, When using normally, when manufacturing a multilayer printed wiring board, it peels or removes.

Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, Moreover, metal foils, such as a release paper, copper foil, and aluminum foil, etc. are mentioned. When copper foil is used for a support body film, copper foil can be used as a conductor layer as it is, and circuit formation can also be carried out. In this case, as copper foil, a rolled copper, an electrolytic copper foil, etc. are mentioned, The thing with a thickness of 2 micrometers - 36 micrometers is generally used. When using a thin copper foil, in order to improve workability, copper foil provided with a carrier may be used.

The support film may be subjected to a mold release treatment other than a matte treatment and a corona treatment.

The thickness of a support body film is 10 micrometers - 150 micrometers normally, Preferably they are 25-50 micrometers. When it is thinner than 10 micrometers, handling becomes difficult. On the other hand, since the support film is usually finally peeled or removed as described above, it is not preferable from the viewpoint of energy saving when the thickness exceeds 150 µm.

In addition, said protective film peels before lamination or hot pressing. In addition, as a protective film, the same material as a support film can also be used and a different material can also be used. 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-described adhesive film≫

Next, an example of the lamination method using the above-mentioned adhesive film is demonstrated.

When an adhesive film has a protective film, after removing a protective film, it pressure-bonds to a glass substrate, pressurizing and heating an adhesive film. As for the lamination conditions, it is preferable to preheat the adhesive film and the glass substrate as necessary, and to laminate at a pressing temperature (lamination temperature) of preferably 60° C. to 140° C. and a pressing pressure of preferably 1 to 11 kgf/cm 2 . . In addition, when using a vacuum laminator, it is preferable to perform lamination under reduced pressure of 20 mmHg (26.7 hPa) or less of air pressure. In addition, a batch type may be sufficient as the method of lamination, and the continuous type with a roll may be sufficient as it.

After laminating an adhesive film on a glass substrate as mentioned above, it cools to room temperature vicinity. The support film is peeled off as needed.

<The manufacturing method of the laminated body by application|coating>

There is no restriction|limiting in particular in the manufacturing method of the laminated body by application|coating. For example, the above-described resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed. This varnish is apply|coated to a glass substrate, and a resin composition layer is formed by drying the organic solvent by heating, hot air spraying, etc. This resin composition layer can also be made semi-hardened further. In this way, a laminate can be manufactured.

[Laminate]

The laminate of the present invention is a laminate including one or more cured resin material layers and one or more glass substrate layers, wherein the cured resin material layer is a cured product of a resin composition including a thermosetting resin and an inorganic filler, A glass substrate layer is 10-95 volume% with respect to the said whole laminated board.

It is preferable that this laminated board has the structure which made the resin composition layer of the above-mentioned laminated body into the resin cured material layer.

The size of the laminate of the present invention is preferably selected from a range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (when using a roll, the length is suitably applied). In particular, it is more preferable from the point of handleability that it is the range of 25 mm - 550 mm in width and 25 mm - 550 mm in length.

It is preferable that the thickness of the laminated board of this invention is selected in the range of 36 micrometers - 20 mm according to the use. The thickness of a laminated board becomes like this. More preferably, it is 50-1000 micrometers, More preferably, it is 100-500 micrometers, More preferably, it is 120-300 micrometers.

The detail of this glass substrate layer and a resin composition is as having demonstrated with the description regarding the above-mentioned laminated body.

<Cured resin layer>

The thickness of this cured resin layer is preferably 3 to 200 µm. If it is 3 micrometers or more, the crack of a laminated board is suppressed. If it is 200 micrometers or less, the thickness of a glass substrate becomes large relatively, and low thermal expansion rate-ization and high elastic modulus-ization of a laminated board are attained. 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, still more preferably 5 to 30 μm. However, since the appropriate range of the thickness of a resin hardened|cured material layer differs with the thickness of a glass substrate layer, the number of layers, and the kind of resin hardened|cured material layer, and the number of layers, it is also possible to adjust suitably.

The storage elastic modulus in 40 degreeC of this cured resin layer becomes like this. Preferably it is 1-80 GPa. A glass substrate layer is protected as it is 1 GPa or more, and the crack of a laminated board is suppressed. If it is 80 GPa or less, the stress by the difference of the thermal expansion coefficient of a glass substrate layer and a cured resin layer is suppressed, and the curvature and crack of a laminated board are suppressed. From this point of view, the storage elastic modulus of the cured resin layer is more preferably 3 to 70 GPa, still more preferably 5 to 60 GPa, still more preferably 10 to 50 GPa, even more preferably 20 to 50 GPa. .

You may have metal foil, such as copper, aluminum, and nickel, on one side or both surfaces of a laminated board. Metal foil will not restrict|limit especially if it is used for an electrical insulation material use.

<Interlayer Insulation Layer>

The laminate may have an interlayer insulating layer. This interlayer insulating layer is obtained by hardening of the composition layer for interlayer insulation in the above-mentioned laminated body, for example.

As a structure in the case where the laminated sheet has an interlayer insulating layer in this way, for example,

Glass substrate layer/cured resin layer/interlayer insulating layer

It may be a three-layer structure such as

Interlayer insulating layer/cured resin layer/glass substrate layer/cured resin layer/interlayer insulating layer

It may be a five-layer structure such as In addition to the above examples, any configuration in which the composition for interlayer insulation can be disposed between the conductor layer and the laminate of the present invention is not particularly limited to the above examples.

<Characteristics of laminated board>

The storage modulus at 40°C of the laminate is preferably from 10 to 70 GPa, more preferably from 20 to 60 GPa, still more preferably from 25 to 50 GPa, even more preferably from the viewpoint of suppressing warpage and cracking of the laminate. preferably 25 to 45 GPa.

The average coefficient of thermal expansion in the range of 50 to 120° C. of the laminate is preferably 1 to 10 ppm/° C., more preferably 2 to 8 ppm/° C., further preferably from the viewpoint of suppressing warpage and cracking of the laminate. is 2 to 6 ppm/°C, and even more preferably 2 to 5 ppm/°C.

The average coefficient of thermal expansion in the range of 120 to 190° C. of the laminate is preferably 1 to 15 ppm/° C., more preferably 2 to 10 ppm/° C., further preferably from the viewpoint of suppressing warpage and cracking of the laminate. It is 2-8 ppm/degreeC, More preferably, it is 2-6ppm/degreeC.

<Ratio of each layer in the laminated board>

The cured resin layer of the present invention is preferably 5 to 60 vol%, more preferably 5 to 55 vol%, more preferably 5 to 55 vol%, based on the entire laminate from the viewpoint of obtaining a laminate having a low coefficient of thermal expansion and a high modulus of elasticity. It is still more preferable that it is 50 volume%, and it is still more preferable that it is 20-40 volume%.

It is preferable that it is 20-90 volume% with respect to the whole laminated board from a viewpoint of obtaining the laminated board of low thermal expansion coefficient and high elastic modulus, as for the glass substrate layer of this invention, It is more preferable that it is 30-85 volume%, It is more preferable, 35-80 It is more preferable that it is volume %, and it is still more preferable that it is 40-75 volume %.

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 furthermore, 3 to 10 vol%, based on the entire laminate. desirable.

When a laminated board has an adhesive layer, it is preferable that it is 1-20 volume% with respect to the whole laminated board, and, as for an adhesive bond layer, it is more preferable that it is 2-15 volume%, It is still more preferable that it is 3-10 volume%.

[Method for manufacturing laminated board]

There is no restriction|limiting in particular in the manufacturing method of the said laminated board. Next, the specific example of the manufacturing method of a laminated board is demonstrated.

<Example of production by heat curing of laminate>

The laminate obtained by said lamination WHEREIN: After peeling a support body film as needed, a laminated board can be manufactured by heat-hardening a resin composition layer.

The conditions of heat curing are selected from the range of 20 minutes - 80 minutes at 150 degreeC - 220 degreeC, More preferably, they are 30 minutes - 120 minutes at 160 degreeC - 200 degreeC. When the support body film to which the mold release process was given is used, after heat-hardening, the support body film can also be peeled.

According to this method, since it is not necessary to pressurize at the time of manufacture of a laminated board, generation|occurrence|production of a crack at the time of manufacture is suppressed.

<Production example by press method>

In addition, the laminated board which concerns on this invention can be manufactured by the press method.

For example, a laminated board can be manufactured by heating, pressurizing, and hardening|curing the laminated body obtained by the above-mentioned lamination by the press method.

In addition, the adhesive film body formed by removing the support film or protective film from the above-described adhesive film and/or the adhesive film and a glass substrate are stacked, heated, pressurized and cured by a press method to produce a laminate. .

Moreover, a laminated board can also be manufactured by coating and drying a resin composition on a glass substrate, superimposing what was made into a B-stage state, heating, pressurizing, and hardening by the press method.

[Multilayer laminate and manufacturing method thereof]

The multilayer laminate of the present invention is a multilayer laminate comprising a plurality of laminates, and at least one laminate is the laminate of the present invention described above.

There is no restriction|limiting in particular in the manufacturing method of this multilayer laminated board.

For example, what is necessary is just to laminate|stack the above-mentioned laminated board in multiple numbers through the adhesive film main body formed by removing a support film and a protective film from the above-mentioned adhesive film, and just to make it multilayer.

Alternatively, a multilayer laminate can also be manufactured by stacking a plurality of (for example, 2 to 20 sheets) of the above-described laminate and performing lamination molding. Specifically, using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., it can be molded 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.

[Printed wiring board and its manufacturing method]

The printed wiring board of this invention has the above-mentioned laminated board or multilayer laminated board, and the wiring provided in the surface of a laminated board or a multilayer laminated board.

Next, the manufacturing method of this printed wiring board is demonstrated.

<Formation of via holes, etc.>

If necessary, the above-described laminated sheet is punched by a method such as a drill, laser, plasma, or a combination thereof to form a via hole or a through hole. As a laser, a carbon dioxide gas laser, a YAG laser, a UV laser, an excimer laser, etc. are generally used. After formation of a via hole etc., you may desmear using an oxidizing agent. As the oxidizing agent, permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid (i.e., a mixture of hydrogen peroxide and sulfuric acid), nitric acid are suitable, and sodium hydroxide aqueous solution (alkaline permanganate) such as potassium permanganate and sodium permanganate aqueous solution) is more suitable.

<Formation of Conductor Layer>

Then, a conductor layer is formed on the resin cured material layer on the surface of a laminated board by dry plating or wet plating.

As dry plating, well-known methods, such as vapor deposition, sputtering, and ion plating, can be used.

In the case of wet plating, first, the surface of the cured resin layer of the laminate is roughened with an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, form the anchor of As an oxidizing agent, sodium hydroxide aqueous solution (alkaline aqueous permanganic acid aqueous solution), such as potassium permanganate and sodium permanganate, is especially used preferably. This roughening process may serve also as said desmear process. Then, a conductor layer is formed by the method which combined electroless-plating and electroplating. Moreover, the plating resist of the reverse pattern to a conductor layer can be formed, and a conductor layer can also be formed only by electroless plating.

In addition, when using what has a support body film containing metal foil on the surface as a laminated body, the formation process of this conductor layer can be abbreviate|omitted.

<Formation of wiring pattern>

As a method of subsequent pattern formation, a well-known subtractive method, a semi-additive method, etc. can be used, for example.

[Multilayer printed wiring board and manufacturing method thereof]

As one aspect of the printed wiring board described above, a plurality of laminated boards on which wiring patterns are formed as described above may be laminated to form a multilayer printed wiring board.

In order to manufacture this multilayer printed wiring board, the laminated board in which the above-mentioned wiring pattern was formed is multilayered by laminating|stacking in multiple numbers via the above-mentioned adhesive film. Thereafter, a through hole or a blind via hole is formed by drilling or laser processing, and an interlayer wiring is formed by plating or an electrically conductive paste. In this way, a multilayer printed wiring board can be manufactured.

[Laminate and multilayer laminates provided with metal foil, and their manufacturing method]

In addition, the above-mentioned laminated board and multilayer laminated board may be a laminated board and a multilayer laminated board provided with the metal foil which has metal foil, such as copper, aluminum, nickel, on one side or both surfaces.

There is no restriction|limiting in particular in the manufacturing method of this laminated board provided with metal foil. For example, a laminated board provided with metal foil can be manufactured by using metal foil as a support film as mentioned above. Further, by laminating one or more laminates (for example, 2 to 20) of the laminate obtained by the above-described lamination or coating, and laminating and molding in a configuration in which a metal foil is disposed on one side or both sides thereof, a laminated sheet provided with a metal foil can also be manufactured.

As the molding conditions, the method of a laminated sheet or multilayer sheet for an electrical insulation material can be applied, for example, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250°C, and a pressure of 2 It can be molded in a range of about 100 MPa to about 100 MPa and a heating time of about 0.1 to 5 hours.

<Evaluation method of thermal expansion coefficient>

The coefficient of thermal expansion of the laminate can be measured using an apparatus such as a thermal mechanical analysis (TMA), a temperature-dependent three-dimensional displacement measuring apparatus (DIC: Digital Image Correlation), or a laser interferometry.

<Evaluation method of elastic modulus>

The elastic modulus of a laminated board can measure a bending elastic modulus as a static elastic modulus including the measurement of the storage elastic modulus by a wide area viscoelasticity measuring apparatus. A bending elastic modulus can be calculated|required by performing a three-point bending test, etc.

Example

Next, although an Example and a comparative example are used to demonstrate this invention further in detail, this invention is not limited to these description.

In addition, in an Example and a comparative example, "part" and "%" mean "mass part" and "mass %", respectively.

1 is a schematic cross-sectional view explaining the manufacturing method of Examples 1-2 and 4. Fig. 2 is a schematic cross-sectional view for explaining the manufacturing method of Example 5;

[Example 1]

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

To 135.4 parts of a polyamide resin "BPAM-155" (product name) manufactured by Nippon Kayaku Co., Ltd. dissolved in a dimethylacetamide solvent to a concentration of 10%, an epoxy resin manufactured by Nippon Kayaku Co., Ltd. as a thermosetting resin 62.0 parts of "NC3000-H" (brand name, concentration 100%), 23.5 parts of DIC Corporation triazine-containing phenolic novolac resin "LA-1356-60P" (trade name, concentration 60%) as a curing agent (trade name, concentration 60%) 0.6 parts of 2-phenylimidazole "2PZ" (trade name, concentration 100%) manufactured by Shikoku Chemical Co., Ltd. as a curing accelerator, and fumed silica "AEROSIL R972" manufactured by Nippon Aerosil Corporation as an inorganic filler ( Brand name, concentration 100%, average particle diameter of primary particles: 16 nm, specific surface area by BET method: 110 ± 20 m 2 /g) of 8.8 parts, polyester modified by BYK Chemi Japan Co., Ltd. as other ingredients After adding 3.6 parts of polydimethylsiloxane "BYK-310" (brand name, density|concentration 25%), 314.3 parts of dimethylacetamide solvents were further added, melt|dissolution, mixing, and a bead mill dispersion process were performed, and the varnish was produced.

As the support film 1, using a polyethylene terephthalate film (PET film) having a thickness of 38 µm, this varnish was coated and dried with a comma coater. The coating thickness was set to 5 μm, and the drying temperature; By setting it so that it might become 140 degreeC and drying time of 3 minutes, the 270-mm-width resin film 3 formed by forming the composition layer 2 for interlayer insulation on the support body film 1 was obtained (FIG.1(a)).

<Production of varnish for resin composition layer>

31.8 parts of epoxy resin "NC3000-H" (trade name, concentration 100%) manufactured by Nippon Kayaku Co., Ltd. as a thermosetting resin, and triazine-containing cresol novolac "LA-3018-50P" manufactured by DIC Corporation as a curing agent (brand name, concentration: 50%) 7.2 parts and phosphorus-containing phenolic resin "HCA-HQ" (trade name, concentration: 100%) manufactured by Sanko Corporation 5.1 parts, DIC Corporation phenol novolac " TD2131" (concentration 100%) 4.4 parts, 1-cyanoethyl-2-phenylimidazolium trimellitate "2PZCNS-PW" manufactured by Shikoku Kasei Kogyo Co., Ltd. as a curing accelerator (brand name, concentration 100%) Silica filler "SO-C2" manufactured by Admapine Techno, Ltd., which was treated with an aminosilane coupling agent in a methyl isobutyl ketone solvent so as to have a solid content of 70% as an inorganic filler in 0.1 parts of an inorganic filler (trade name, concentration 100%, 1 Average particle diameter of tea particles: 500 nm, specific surface area by BET method: 6.8 m 2 /g) of 78.6 parts, after each blending, 42.7 parts of methyl ethyl ketone as an additional solvent is further blended, dissolved, mixed, and beads Mill dispersion processing was performed and the varnish for resin composition layers was produced.

<Production of adhesive film (support film (1)/composition layer for interlayer insulation (2)/resin composition layer (4)) (5a)>

By forming the resin composition layer 4 on the resin film 3, the adhesive film 5a was manufactured.

As a method, using the resin film 3 (support film 1 / interlayer insulation composition layer 2), a varnish for resin composition layer is applied to the interlayer insulation composition layer 2 side by a comma coater. dry Set the coating thickness to be 20 μm (interlayer insulation composition layer 2; 5 μm, resin composition layer 4; 15 μm setting), set the drying temperature to 105° C., and set the drying time to 1.2 minutes to set the resin composition layer ( By setting it as 4), the adhesive film 5a of width 270mm was obtained (FIG.1(b)).

<Production of laminated board (interlayer insulating layer/cured resin layer/glass substrate layer/cured resin layer/interlayer insulating layer)>

As the glass substrate layer 6, the ultra-thin glass film "OA-10G" (trade name, 100 micrometers in thickness, 250 x 250 mm) manufactured by Nippon Denki Glass was used. On both surfaces of this glass substrate layer 6, the above-described adhesive film 5a is placed so that its resin composition layer 4 is in contact with the glass substrate layer 6, and a batch type vacuum pressurization laminator "MVLP-500" ( It laminated|stacked by lamination using the Meiki Corporation make, brand name (FIG. 1(c), (d)). The vacuum degree at this time was 30 mmHg or less, the temperature was set to 90 degreeC, and the pressure was set to 0.5 MPa.

After cooling to room temperature, the support film 1 was peeled off, and it hardened|cured for 60 minutes in the dryer set at 180 degreeC. By this hardening, the composition layer 2 for interlayer insulation and the resin composition layer 4 became the interlayer insulation layer 2a and the resin cured material layer 4a, respectively. In this way, a laminated plate (interlayer insulating layer/cured resin layer/glass substrate layer/cured resin layer/interlayer insulating layer) 7a having a five-layer structure was obtained (FIG. 1(e)).

[Example 2]

<Production of adhesive film (support film/composition layer for interlayer insulation/resin composition layer) (5b)>

The adhesive film 5a of Example 1 except that the coating thickness of the varnish was set to 40 µm (interlayer insulation composition layer 2; 5 µm, resin composition layer 4; 35 µm setting) instead of 20 µm ) and the same operation was performed to obtain an adhesive film 5b having a size of 250 mm x 250 mm.

<Production of laminated board (interlayer insulating layer/cured resin layer/glass substrate layer/cured resin layer/interlayer insulating layer)>

The same operation as in Example 1 was performed except that the above-described adhesive film 5b was used instead of the adhesive film 5a, and a laminated plate having a five-layer structure (interlayer insulating layer/cured resin layer/glass substrate layer/resin film) was performed. cargo layer/interlayer insulating layer).

[Example 3]

<Production of laminated board (interlayer insulating layer / cured resin layer / interlayer insulating layer / cured resin layer / glass substrate layer / cured resin layer / interlayer insulating layer / cured resin layer / interlayer insulating layer) >

As a glass substrate, the ultra-thin glass film "OA-10G" (trade name, 100 micrometers in thickness, 250 x 250 mm) made from Nippon Denki Glass was used. On both surfaces of this glass substrate, the above-described adhesive film 5b was placed so that the cured resin material layer was in contact with the glass substrate, and a batch type vacuum pressurized laminator "MVLP-500" (manufactured by Meiki Corporation, trade name) was applied. laminated by lamination. The vacuum degree at this time was 30 mmHg or less, the temperature was set to 90 degreeC, and the pressure was set to 0.5 MPa. After cooling to room temperature, the support film was peeled.

The above-mentioned adhesive film 5b is placed on the interlayer insulation composition layer exposed by peeling of the support film so that the cured resin material layer is in contact, and a batch type vacuum pressurization laminator "MVLP-500" (Meiki Co., Ltd.) It laminated|stacked by lamination using the company make, brand name). The vacuum degree at this time was 30 mmHg or less, the temperature was 65 degreeC, and the pressure was set to 0.5 MPa.

After cooling to room temperature, the support film is peeled off and cured for 60 minutes in a dryer set at 180°C, whereby a 9-layered laminated plate (interlayer insulating layer/cured resin layer/interlayer insulating layer/cured resin layer/glass substrate) layer/cured resin layer/interlayer insulating layer/cured resin layer/interlayer insulating layer) was obtained.

[Example 4]

<Production of adhesive film (support film/composition layer for interlayer insulation/resin composition layer) (5c)>

The adhesive film 5a of Example 1 except that the coating thickness of the varnish was set to 30 µm (interlayer insulation composition layer 2; 5 µm, resin composition layer 4; 25 µm setting) instead of 20 µm ) and the same operation was performed to obtain an adhesive film 5c having a width of 270 mm.

<Production of laminated board (interlayer insulating layer/cured resin layer/glass substrate layer/cured resin layer/interlayer insulating layer)>

The same operation as in Example 1 was performed except that the above-described adhesive film 5c was used instead of the adhesive film 5a, and a thickness of 150 μm was used instead of 100 μm as the glass substrate 6, and a five-layer structure was obtained. A laminate (interlayer insulating layer/cured resin layer/glass substrate layer/cured resin layer/interlayer insulating layer) was obtained.

[Example 5]

<Production of varnish for resin composition layer>

To 135.4 parts of a polyamide resin "BPAM-155" (product name) manufactured by Nippon Kayaku Co., Ltd. dissolved in a dimethylacetamide solvent to a concentration of 10%, an epoxy resin manufactured by Nippon Kayaku Co., Ltd. as a thermosetting resin 62.0 parts of "NC3000-H" (brand name, concentration 100%), 23.5 parts of DIC Corporation triazine-containing phenolic novolac resin "LA-1356-60P" (trade name, concentration 60%) as a curing agent (trade name, concentration 60%) 0.6 parts of 2-phenylimidazole "2PZ" (trade name, concentration 100%) manufactured by Shikoku Chemical Co., Ltd. as a curing accelerator, and fumed silica "AEROSIL R972" manufactured by Nippon Aerosil Corporation as an inorganic filler ( Brand name, concentration 100%, average particle diameter of primary particles: 16 nm, specific surface area by BET method: 110 ± 20 m / g) of 4.8 parts, as other ingredients, polyester modified by BYK Chemi Japan Co., Ltd. After adding 1.7 parts of polydimethylsiloxane "BYK-310" (a brand name, density|concentration of 25%), 66.3 parts of dimethylacetamide solvents were further added. Thereafter, a uniform resin varnish was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).

<Preparation of adhesive film (support film (1)/resin composition layer (4) (5d)>)

The adhesive film 5d was manufactured by forming the resin composition layer 4 on the support body film 1 (FIG.2(a)).

As a method, a resin varnish is applied to the release-treated surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec, trade name), which is a support film, using a comma coater so that the thickness after drying becomes 20 μm, It was dried at 140 degreeC for 5 minutes, and the resin composition layer 4 formed the width 270mm adhesive film 5d in which the support body film 1 was contained.

<Production of laminated board (cured resin layer/glass substrate layer/cured resin layer)>

As the glass substrate layer 6, the ultra-thin glass film "OA-10G" (trade name, 150 micrometers in thickness, 250 x 250 mm) manufactured by Nippon Denki Glass was used. On both surfaces of this glass substrate layer 6, the above-described adhesive film 5d is placed so that its resin composition layer 4 is in contact with the glass substrate layer 6, and a batch type vacuum pressurization laminator "MVLP-500" ( It laminated|stacked by lamination using the Meiki Corporation make, brand name (FIG.2(b), (c)). The vacuum degree at this time was 30 mmHg or less, the temperature was 120 degreeC, and the pressure was set as 0.5 MPa.

After cooling to room temperature, the support film 1 was peeled off, and it hardened|cured for 60 minutes in the dryer set at 180 degreeC. By this hardening, the resin composition layer 4 became the resin hardened|cured material layer 4a. In this way, a laminated sheet (cured resin material layer/glass substrate layer/cured resin material layer) 7b having a three-layer structure was obtained (FIG. 2(d)).

[Comparative Example 1]

<Production of resin film>

Except not having added the inorganic filler (fumed silica), operation similar to the resin film 3 of Example 2 was performed, and the resin film was manufactured.

<Production of varnish>

Except not having added an inorganic filler (silica filler), operation similar to the varnish for resin composition layers of Example 2 was performed, and the varnish was manufactured.

<Production of adhesive film C>

The same operation as in Example 2 was performed except that the above resin film and varnish were used instead of the resin film 3 and the varnish for the resin composition layer of Example 2, and the adhesive film (support film/composition layer for interlayer insulation/resin) composition layer) was prepared.

<Production of laminated board (interlayer insulating layer/cured resin layer/glass substrate layer/cured resin layer/interlayer insulating layer)>

The same operation as in Example 2 was performed except that the above adhesive film was used instead of the adhesive film 5a of Example 2, and a laminated plate having a five-layer structure (interlayer insulating layer/cured resin layer/glass substrate layer/resin film) was performed. cargo layer/interlayer insulating layer).

[Reference Example 1]

Next, a laminate using a general prepreg as a laminate for a semiconductor package or a printed wiring board is generally manufactured as follows.

<Preparation of a solution of a resin composition having an unsaturated maleimide group>

4,4'-bis(4-aminophenoxy)biphenyl: 69.10 g, bis(4) in a reaction vessel having a heating and cooling volume of 2 liters with a water meter equipped with a thermometer, a stirring device, and a reflux cooling tube -Maleimidephenyl)sulfone: 429.90 g, p-aminophenol: 41.00 g, and propylene glycol monomethyl ether: 360.00 g were added, and reacted at reflux temperature for 2 hours to obtain a solution of a resin composition having an acidic substituent and an unsaturated maleimide group. got it

<Production of varnish containing thermosetting resin composition>

(1) a solution of a resin composition having an unsaturated maleimide group as described above as the curing agent (A);

(2) as the thermosetting resin (B), a bifunctional naphthalene type epoxy resin [Dainippon Ink Chemical Co., Ltd. product, trade name: HP-4032D];

(3) as modified imidazole (C), isocyanate mask imidazole [manufactured by Daiichi Kogyo Seyaku Co., Ltd., trade name: G8009L];

(4) As an inorganic filler (D), fused silica [manufactured by Admatex Co., Ltd., trade name: SC2050-KC, concentration 100%, average particle diameter of primary particles: 500 nm, specific surface area by BET method: 6.8 m2/g],

(5) as the phosphorus-containing compound (E) imparting flame retardancy, a phosphorus-containing phenol resin [manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ, phosphorus content of 9.6% by mass];

(6) as the chemically harmonizable compound (F), crosslinked acrylonitrile butadiene rubber (NBR) particles [manufactured by JSR Corporation, trade name: XER-91];

(7) as a diluent solvent, methyl ethyl ketone

was mixed at the mixing ratio (parts by mass) shown in Table 1 using , to prepare a uniform varnish (G) having a resin content (sum of the resin components) of 65% by mass.

<Production of prepreg containing thermosetting resin composition>

The said varnish (G) was respectively impregnated and coated on E glass cloth from which thickness differs, and it heat-dried at 160 degreeC for 10 minutes, and obtained the prepreg. The kind of E glass cloth produced the prepreg of 250 mm x 250 mm using IPC standard 2116 of Asahi Kasei Materials. The resin content of the produced prepreg was 50 mass %. Three of these prepregs were combined, an electrolytic copper foil having a thickness of 12 µm was placed up and down, and pressed at a pressure of 3.0 MPa and a temperature of 235°C for 120 minutes to produce a copper clad laminate.

[Measure]

About the laminated board obtained by the said Example, a comparative example, and a reference example, the performance was measured and evaluated by the following method.

(1) Measurement of coefficient of thermal expansion

A 4 mm x 30 mm test piece was cut out from the laminated board. When using a copper clad laminated board, after removing copper foil by immersing in copper etching liquid, the test piece was cut out.

It evaluated by observing the thermal expansion characteristic of less than Tg of a test piece using the TMA test apparatus (made by DuPont, TMA2940). Specifically, measured by a tensile method at a temperature increase rate of 5 ° C / min, 1st run, measurement range 20 to 200 ° C, 2nd run measurement range -10 to 280 ° C, weight 5 g, between chucks 10 mm, 50 to 120 ° C range And the average coefficient of thermal expansion in the range of 120-190 degreeC was calculated|required, respectively. The results are shown in Table 2.

(2) Measurement of storage modulus

A 4 mm x 30 mm test piece was cut out from the laminated board. When using a copper clad laminated board, after removing copper foil by immersing in copper etching liquid, the test piece was cut out.

Using a wide area viscoelasticity measuring device (manufactured by Rheology, DVE-V4 type), the distance between spans is 20 mm, the frequency is 10 Hz, and the vibration displacement is 1 to 3 µm (stop excitation) at 40°C. The tensile storage modulus was measured. The results are shown in Table 2.

As is clear from Table 2, Examples 1 to 5 of the present invention are excellent in low thermal expansibility at 50 to 120°C and high elasticity at 40°C. In addition, even in the high-temperature region of 120 to 190° C., while the coefficient of thermal expansion is increased in Reference Example 1 compared to the low-temperature region (50 to 120° C.), in Examples 1 to 5, the low thermal expansion property of about the same degree as the low temperature region know that you have Therefore, Example 1 of this invention maintains low thermal expansion property not only in a low-temperature area|region but also in a high-temperature area|region.

1: support film
2: Interlayer insulation composition layer
2a: interlayer insulating layer
3: resin film
4: resin composition layer
4a: cured resin layer
5a, 5b, 5c, 5d: adhesive film
6: Glass substrate layer
7a, 7b: laminate

Claims (14)

A laminate comprising one or more resin composition layers and one or more glass substrate layers,
The resin composition layer consists of a resin composition including a thermosetting resin and an inorganic filler,
The inorganic filler is silica having an average primary particle size of 1 μm or less,
The content of silica in the resin composition is 44 to 82% by mass,
The thickness per layer of the resin composition layer is 3 to 35 μm,
The glass substrate layer is 40 to 75 volume % with respect to the entire laminate,
A laminate having a thickness of 30 to 120 μm of the glass substrate layer. The laminate according to claim 1, wherein the glass substrate layer has a thickness of 50 to 120 µm. According to claim 1, wherein the thermosetting resin is 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, dicyclo One or two or more types of laminates selected from pentadiene resins, silicone resins, triazine resins and melamine resins. delete A laminate comprising at least one cured resin layer and at least one glass substrate layer,
The cured resin layer consists of a cured product of a resin composition including a thermosetting resin and an inorganic filler,
The inorganic filler is silica having an average primary particle size of 1 μm or less,
The content of silica in the cured resin layer is 44 to 82% by mass,
The thickness per layer of the cured resin layer is 3 to 35 μm,
The glass substrate layer is 40 to 75 volume % with respect to the entire laminate,
A laminate having a thickness of 30 to 120 μm of the glass substrate layer. The laminate according to claim 5, wherein the laminate has a storage elastic modulus at 40°C of 10 GPa to 70 GPa. The laminated board obtained by heating the laminated body in any one of Claims 1-3. A multi-layer laminate comprising a plurality of laminates,
A multilayer laminate, wherein at least one laminate is the laminate according to claim 7. The printed wiring board which has the laminated board of Claim 7 and the wiring provided in the surface of the said laminated board. A printed wiring board comprising the multilayer laminate according to claim 8 and wiring provided on a surface of the multilayer laminate. The manufacturing method of the laminated board of Claim 5 including the resin hardened|cured material layer formation process of forming a resin hardened|cured material layer on the surface of a glass substrate. The method for manufacturing a laminate according to claim 11, wherein the step of forming the cured resin layer is a step of applying the resin composition on the glass substrate, followed by drying and curing. The method for producing a laminate according to claim 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. The method for manufacturing a laminate according to claim 11, wherein the cured resin layer forming step is a step of placing the film made of the resin composition on the glass substrate, then pressing and curing the film.

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