JP6269506B2 - LAMINATE, LAMINATE, PRINTED WIRING BOARD, LAMINATE MANUFACTURING METHOD, AND LAMINATE MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to a laminate suitable for a semiconductor package or a printed wiring board, a laminated board, a manufacturing method thereof, and a printed wiring board.

  In recent years, electronic devices have been further reduced in size, weight, and functionality, and accordingly, high integration of LSIs and chip parts has progressed. And the form is rapidly changing to a multi-pin and miniaturization. For this reason, in order to improve the mounting density of electronic components in the laminated board, development of fine wiring has been advanced. As a manufacturing method of multilayer wiring boards that meet these requirements, a build-up multilayer that uses insulating resin that does not contain glass cloth as an insulating layer instead of prepreg, and forms wiring layers while connecting only necessary parts with via holes. There is a wiring board and it is becoming mainstream as a technique suitable for weight reduction, miniaturization, and miniaturization.

  In such a build-up type multilayer wiring board, an insulating resin film is first laminated on an inner circuit board and cured by heating to form a build-up layer. After that, a via hole is formed by laser processing, and a roughening process and a smear process are performed by an alkali permanganate treatment or the like, and electroless copper plating is performed to form a via hole that enables interlayer connection with the second circuit. (See Patent Documents 1 to 3). Here, the adhesive strength between the resin and the electroless copper plating is secured by the roughness of the resin surface (anchor effect), and the surface roughness is 0.6 μm or more in terms of Ra, and the surface roughness. There was a big situation. With such a method, a short circuit or an open defect may occur in a fine circuit of 10 μm or less. Therefore, a multilayer wiring board cannot be manufactured with a high yield. On the other hand, when the roughened shape is reduced, the adhesive force with the electroless copper plating is reduced, and defects such as line peeling occur. Therefore, the wiring board material which shows electroless copper plating and high adhesive force on the smooth surface was needed.

  On the other hand, demands for thinner and lighter electronic devices are increasing, and semiconductor packages and printed wiring boards are becoming thinner and higher in density. In order to stably mount electronic components corresponding to these reductions in thickness and density, it is important to suppress warpage that occurs during mounting.

  One of the main causes of warpage occurring in the semiconductor package during mounting is a difference in thermal expansion coefficient between the laminated plate used in the semiconductor package and the silicon chip mounted on the surface of the laminated plate. For this reason, efforts are being made to bring the coefficient of thermal expansion close to the coefficient of thermal expansion of the silicon chip, that is, to lower the coefficient of thermal expansion, in the laminated sheet for semiconductor packages. Further, since the elastic modulus of the laminate also causes warping, it is effective to increase the elasticity of the laminate in order to reduce warpage. Thus, in order to reduce the warpage of the laminate, it is effective to reduce the expansion coefficient and increase the elasticity of the laminate.

  Various methods for lowering the thermal expansion coefficient and increasing the elasticity of the laminated board are conceivable. Among them, it is known to lower the thermal expansion coefficient of the resin for the laminated board and to increase the inorganic filler in the resin. In particular, the high filling of the inorganic filler is a technique that can be expected to improve heat resistance and flame retardancy as well as a low thermal expansion coefficient (Patent Document 4). However, increasing the filling amount of the inorganic filler in this manner causes a decrease in insulation reliability, insufficient adhesion between the resin and the wiring layer formed on the surface, and press molding failure during the production of the laminate. There is a limit to the high filling.

  In addition, attempts have been made to achieve a low coefficient of thermal expansion by selecting or improving the resin. For example, a method of increasing the crosslinking density of the resin for wiring boards and increasing the Tg to reduce the coefficient of thermal expansion is generally used (Patent Documents 5 and 6). However, increasing the crosslinking density shortens the molecular chain between the functional groups, but shortening the molecular chain beyond a certain level has a limit in terms of reaction, and causes a problem of causing a decrease in resin strength. It was.

  As a method different from the above, a heat shock stress is obtained by using a glass film as a layer having a coefficient of thermal expansion substantially matching that of an electronic component (silicon chip) and pressing and laminating the resin and the glass film. (Patent Document 7), however, since the elastic modulus of the resin used is low and the coefficient of thermal expansion is high, it is insufficient to realize low warpage of the substrate.

  The glass film described above is considered to be effective as a component of a laminate having a smooth surface so that fine wiring can be formed. However, since the chemical adhesion between glass and copper is very poor, fine wiring is formed. Is considered difficult.

Japanese Patent No. 3290296 Japanese Patent No. 3654851 Japanese Patent No. 378549 JP 2004-182851 A JP 2000-243864 A JP 2000-114727 A Japanese Patent No. 4657554

  As described above, since the surface of the glass is very smooth, it is thought that it is effective for forming fine wiring, but the chemical adhesive force with the electroless copper plating is very weak. Therefore, when a fine circuit of 10 μm or less is formed, a short circuit failure or an open failure occurs, and it cannot be manufactured with a high yield. Furthermore, since the board | substrate obtained by the manufacturing method of patent documents 4-6 was low in elasticity, it was inadequate to implement | achieve the low curvature of a board | substrate.

  Further, Patent Document 7 does not disclose at all about the properties of a resin in a substrate formed by laminating a glass film and a resin. In Patent Document 7, it is considered necessary to consider only the influence on the thermal expansion action of the substrate. That is, it is not considered at all to form a build-up type multilayer wiring board in which a wiring layer is formed while connecting only necessary portions by via holes by improving the adhesive force with electroless copper plating.

  As described above, the present invention provides a laminate and a laminate that can exhibit high adhesion to electroless copper plating even when the surface roughness Ra is small, and can increase the wiring density, and a method for manufacturing the same. With the goal. Moreover, it aims at providing the printed wiring board using the said laminated body or laminated board.

  As a result of investigations to solve the above problems, the present inventors have found that the problems can be solved by the present invention described below. That is, the present invention is as follows.

[1] A laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C).
[2] The laminate according to [1], wherein the resin composition layer includes a polyfunctional epoxy resin (A) and an epoxy resin curing agent (B).
[3] The blending ratio of the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) is 4 to 40 parts by mass with respect to 100 parts by mass in total of the polyfunctional epoxy resin (A) and the epoxy resin curing agent (B). The laminate according to [2].
[4] The laminate according to any one of [1] to [3], wherein the combined thickness of the resin composition layer and the glass substrate layer is 50 to 300 μm.
[5] The laminate according to any one of [1] to [4], wherein the glass substrate layer has a thickness of 30 to 200 μm.
[6] The laminate according to any one of [2] to [5], wherein the polyfunctional epoxy resin (A) contained in the resin composition layer has a biphenyl structure.
[7] The laminate according to [6], wherein the polyfunctional epoxy resin (A) contained in the resin composition layer is an aralkyl epoxy resin having a biphenyl structure.
[8] The laminate according to any one of [1] to [7], which contains an inorganic filler (D) having an average primary particle size of 100 nm or less as the inorganic filler.
[9] The laminate according to [8], wherein the inorganic filler (D) is fumed silica.
[10] The laminate according to [8] or [9], wherein the inorganic filler (D) is subjected to a surface treatment.

[11] The phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) according to any one of [1] to [10], which has a structural unit represented by the following formulas (i), (ii), and (iii): Laminated body.
[Wherein, a, b, c, x, y and z are average degree of polymerization, respectively, and a = 2 to 10, b = 1 to 8, c = 3 to 20, and y = 1 to z = 1. = 2 to 300, z ≧ 20 with respect to y = 1, x = 1 to 100, and y = 1 to 200. R, R ′ and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and a plurality of R ′ ″ are each independently an aromatic dicarboxylic acid, aliphatic It is a divalent group derived from dicarboxylic acid or an oligomer having carboxyl groups at both ends. ]
[12] A laminate including one or more cured resin layers and one or more glass substrate layers, the laminate obtained by curing the laminate according to any one of [1] to [11] Board.
[13] The laminate according to [12], wherein the storage elastic modulus at 40 ° C. is 1 GPa to 70 GPa.

[14] The laminated plate according to [12] or [13], wherein the surface roughness (Ra) of the cured resin layer after the roughening treatment is 0.4 μm or less.
[15] A printed wiring board in which wiring is provided on at least one surface of the laminated board according to any one of [12] to [14].
[16] The printed wiring board according to [15], including a plurality of laminated boards, wherein at least one of the laminated boards is a laminated board according to any one of [12] to [14].

[17] A method for producing a laminate, which comprises applying a resin composition containing a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) to the surface of a glass substrate to form a resin composition layer.
[18] The method for producing a laminate according to [17], wherein the resin composition contains a polyfunctional epoxy resin (A) and an epoxy resin curing agent (B).

[19] The laminate according to [17] or [18], wherein the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) has a structural unit represented by the following formulas (i), (ii), and (iii): Manufacturing method.
[Wherein, a, b, c, x, y and z are average degree of polymerization, respectively, and a = 2 to 10, b = 1 to 8, c = 3 to 20, and y = 1 to z = 1. = 2 to 300, z ≧ 20 with respect to y = 1, x = 1 to 100, and y = 1 to 200. R, R ′ and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and a plurality of R ′ ″ are each independently an aromatic dicarboxylic acid, aliphatic It is a divalent group derived from dicarboxylic acid or an oligomer having carboxyl groups at both ends. ]

[20] The method for producing a laminate according to any one of [17] to [19], wherein a drying process is performed after the resin composition layer is formed.
[21] A film made of a resin composition containing a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) is prepared, and the film is laminated on a glass substrate using a vacuum laminator or a roll laminator, and then the film is cured. The manufacturing method of the laminated board which gives.
[22] The method for producing a laminated board according to [21], wherein the resin composition contains a polyfunctional epoxy resin (A) and an epoxy resin curing agent (B).

[23] The laminate according to [21] or [22], wherein the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) has a structural unit represented by the following formulas (i), (ii) and (iii): Manufacturing method.
[Wherein, a, b, c, x, y and z are average degree of polymerization, respectively, and a = 2 to 10, b = 1 to 8, c = 3 to 20, and y = 1 to z = 1. = 2 to 300, z ≧ 20 with respect to y = 1, x = 1 to 100, and y = 1 to 200. R, R ′ and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and a plurality of R ′ ″ are each independently an aromatic dicarboxylic acid, aliphatic It is a divalent group derived from dicarboxylic acid or an oligomer having carboxyl groups at both ends. ]
[24] The method for manufacturing a laminated board according to any one of [21] to [23], in which a press treatment is performed after the film is laminated and before the curing treatment.

  ADVANTAGE OF THE INVENTION According to this invention, even if surface roughness Ra is small, it shows high adhesiveness with respect to electroless copper plating, and provides the laminated body and laminated board which can be wiring high density, and these manufacturing methods. it can. Moreover, the printed wiring board using the said laminated body or laminated board can be provided.

Hereinafter, the laminate, the laminate, the production method thereof, and the printed wiring board of the present invention will be described in detail.
In the present specification, the “laminate” means that the thermosetting resin (polyfunctional epoxy resin) that is a component is uncured or semi-cured, and “laminate” It means that the thermosetting resin as a constituent component is cured, or 90% or more of the thermosetting resin is cured. The degree of cure of the thermosetting resin can be measured by the reaction rate measured from a differential scanning calorimeter.

[Laminate and laminate]
The laminate of the present invention is a laminate having one or more resin composition layers and one or more glass substrate layers, and the resin composition layer includes a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C). Preferably, the polyfunctional epoxy resin (A), the epoxy resin curing agent (B), and a phenolic hydroxyl group-containing polybutadiene having a structural unit represented by the following formulas (i), (ii), and (iii) It is a resin composition containing a modified polyamide resin (C).
Here, the resin composition layer according to the present invention is an uncured or semi-cured state on a support or a glass substrate (so-called a so-called semi-cured state (so-called “so-called”)) before being made a part of a layer of a wiring board laminate or multilayer wiring board. B stage state).
Moreover, the laminated board of this invention is obtained by hardening the resin composition layer by heating the laminated body of this invention, and setting it as a resin cured material layer.
Here, by using a glass substrate layer having a low thermal expansion coefficient and a high elastic modulus as much as those of a silicon chip, warpage is suppressed and cracking is difficult to occur. In particular, such a laminate has a glass substrate layer with high heat resistance, and thus has a low thermal expansion in a temperature range from 100 ° C. to less than Tg of the cured resin. Moreover, by including an inorganic filler in the cured resin layer, the cured resin layer becomes low thermal expansion and high elasticity, and the laminate including the cured resin layer has lower expansion and high elasticity. It will be rate.

(Resin composition)
As described above, the resin composition according to the present invention contains a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C), preferably a polyfunctional epoxy resin (A) (hereinafter referred to as “component (A)”). ), Epoxy resin curing agent (B) (hereinafter sometimes referred to as “component (B)”), and phenol having a structural unit represented by (i), (ii), and (iii) described later It is formed of a resin composition containing a functional hydroxyl group-containing polybutadiene-modified polyamide resin (C) (hereinafter sometimes referred to as “component (C)”).
Hereinafter, components (A) to (C) will be described.

Component (C):

  In the formula, a, b, c, x, y, and z are average polymerization degrees, respectively, and a + 2 = 2 to a = 2-10, b = 1-8, c = 3-20, and x = 1. An integer of ˜300 ((y + z) / x) is shown, and z ≧ 20 (z / y) with respect to y = 1. R, R ′ and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and a plurality of R ′ ″ are each independently an aromatic dicarboxylic acid, aliphatic It is a divalent group derived from dicarboxylic acid or an oligomer having carboxyl groups at both ends.

  In the resin composition, the blending ratio of the component (C) is preferably, for example, 4 parts by mass or more with respect to a total of 100 parts by mass of the resin component (excluding the component (C)) of the resin composition. Moreover, when (A) component and (B) component are included, it is preferable that it is 4-40 mass parts with respect to these 100 mass parts in total. By mix | blending in this ratio, plating copper and favorable adhesive strength are obtained, maintaining favorable heat resistance.

The reason why such an effect is obtained is not necessarily clear, but the following reason can be considered.
That is, since the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) can react with the epoxy resin, the resin can be toughened while maintaining good heat resistance of the epoxy resin. Furthermore, since it has many amide groups with high adhesiveness with copper, high adhesive force with plated copper can be obtained.
Moreover, since the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin contains a phenolic hydroxyl group that is compatible with the epoxy resin and a polybutadiene that is incompatible with the epoxy resin, the blending ratio thereof is, for example, (A) component and (B ) In the case of 4 to 40 parts by mass with respect to 100 parts by mass in total of the components, a fine sea-island structure can be formed better. By forming this sea-island structure, it is possible to form a dense shape during the roughening process by utilizing the fact that the amount of roughening between the sea layer and the island layer differs during the roughening process. Since this shape is fine and has little variation, it exhibits a high physical adhesive force due to the anchor effect, and the adhesiveness with the plated copper is remarkably improved.

In addition, when the mixture ratio of (C) component is 4 mass parts or more, the domain size of a sea island structure does not become large too much, and there exists a tendency for Ra after a roughening process to become small. In addition, the toughness of the resin is high, and a finer rough shape is obtained, and a good adhesive force with the plated copper tends to be obtained.
On the other hand, when the blending ratio of the component (C) is 40 parts by mass or less, the domain size of the sea-island structure does not become too large and good adhesive strength with the electroless plated copper tends to be obtained. Moreover, favorable heat resistance is obtained and it exists in the tendency which is excellent also in the tolerance to the chemical | medical solution at the time of a roughening process.

  In consideration of obtaining better adhesiveness with the plated copper, the blending ratio of the component (C) is 5 with respect to 100 parts by mass in total when the component (A) and the component (B) are included. It is more preferably ˜25 parts by mass, further preferably 5 to 20 parts by mass, and particularly preferably 5 to 19 parts by mass.

  The phenolic hydroxyl group-containing polyamide resin and the phenolic hydroxyl group-containing acrylonitrile-butadiene modified polyamide resin have better compatibility with the epoxy resin than the phenolic hydroxyl group-containing polybutadiene modified polyamide resin. Therefore, it is difficult to form a fine shape after the roughening treatment, and the adhesive strength with the plated copper as much as the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin cannot be exhibited. In addition, when a nitrile group is introduced, the moisture absorption rate is increased, and the insulating property during moisture absorption is also lowered.

The (C) component phenolic hydroxyl group-containing polybutadiene-modified polyamide resin includes, for example, diamine, phenolic hydroxyl group-containing dicarboxylic acid, dicarboxylic acid not containing phenolic hydroxyl group, and polybutadiene having carboxyl groups at both ends. It is synthesized by polycondensation of a carboxyl group and an amino group in an organic solvent such as 2-pyrrolidone (NMP) in the presence of a phosphite ester and a pyridine derivative as a catalyst.
The weight average molecular weight of the component (C) is preferably 60,000 to 250,000, and more preferably 80,000 to 200,000.

In the present invention, the diamine (diamine raw material) used for producing the phenolic hydroxyl group-containing polybutadiene-modified polyamide may be an aromatic diamine or an aliphatic diamine.
Specific examples of aromatic diamines include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylene Diamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), isopropylidenedianiline, Diaminobenzophenone, diaminodimethylbenzophenone, diamino Ntorakinon, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, diaminofluorene and the like.

  Specific examples of the aliphatic diamine include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, and triazaundecadiamine. Etc. These aromatic and aliphatic diamines may be used alone or in combination of two or more.

  In the present invention, examples of the phenolic hydroxyl group-containing dicarboxylic acid used in the production of the phenolic hydroxyl group-containing polybutadiene-modified polyamide include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, dihydroxyterephthalic acid, and the like. It is not limited to these.

  In the present invention, the dicarboxylic acid not containing a phenolic hydroxyl group (dicarboxylic acid raw material) used for the production of a phenolic hydroxyl group-containing polybutadiene-modified polyamide is an oligomer having a carboxyl group at both ends, whether aromatic dicarboxylic acid or aliphatic dicarboxylic acid. But you can. Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, sulfonylbenzoic acid, and naphthalenedicarboxylic acid.

  Aliphatic dicarboxylic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth) acryloyloxysuccinic acid, di (meth) acryloyl Examples thereof include oxysuccinic acid, (meth) acryloyloxymalic acid, (meth) acrylamide succinic acid, and (meth) acrylamide malic acid.

  The polybutadiene having carboxyl groups at both ends preferably has a number average molecular weight of 200 to 10,000, more preferably an oligomer having a molecular weight of 500 to 5,000.

  As a commercial product of the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C), there is BPAM-155 manufactured by Nippon Kayaku Co., Ltd.

(A) component:
The polyfunctional epoxy resin as component (A) is an epoxy resin having two or more epoxy groups in the molecule, such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, an aralkyl epoxy resin, and the like. It is done. Especially, it is preferable that an aralkyl novolak type epoxy resin is included as a polyfunctional type epoxy resin.

  The aralkyl novolac type epoxy resin is preferably an aralkyl novolac type epoxy resin having a biphenyl structure. The novolak type epoxy resin having a biphenyl structure refers to an aralkyl novolak type epoxy resin containing an aromatic ring of a biphenyl derivative in the molecule. For example, the following formula (1) (wherein p is 1 to 5) An epoxy resin represented by

  In addition, you may use the epoxy resin represented by the said formula combining multiple types. Moreover, as a commercial item of the said resin, Nippon Kayaku Co., Ltd. NC-3000 (p is 1.7 epoxy resin), NC-3000-H (p is 2.8 epoxy resin), etc. are mentioned. .

  (A) It is preferable that the compounding quantity of a polyfunctional epoxy resin is 20-80 mass% in the ratio in a resin composition, and it is more preferable that it is 40-70 mass%. (A) When the compounding quantity of a component is 20-80 mass%, adhesive strength with a circuit conductor and solder heat resistance can be made into a favorable state.

(B) component:
As the epoxy resin curing agent as component (B), various phenol resins, acid anhydrides, amines, hydragits and the like can be used. As the phenol resin, a novolac type phenol resin, a resol type phenol resin, or the like can be used. As the acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, or the like can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. In order to improve reliability, a novolac type phenol resin is preferable.

  It is preferable that the compounding quantity of an epoxy resin hardening | curing agent is 0.5-1.5 equivalent with respect to an epoxy group. By being 0.5-1.5 equivalent with respect to an epoxy group, the fall of adhesiveness with outer layer copper can be prevented, and a Tg (glass transition temperature) and insulation fall can also be prevented.

In addition to the curing agent, a reaction accelerator can be used as necessary. As the reaction accelerator, various imidazoles and BF ₃ amine complexes which are latent thermosetting agents can be used. 2-phenylimidazole and 2-ethyl-4-methylimidazole are preferable from the viewpoints of storage stability of the resin composition, handleability of the B-staged (semi-cured) resin composition, and solder heat resistance. It is preferable that it is 0.1-5.0 mass% with respect to the compounding quantity of an epoxy resin.

The resin composition preferably contains an inorganic filler (D) having an average primary particle size of 100 nm or less (hereinafter sometimes referred to as “component (D)”). By containing the component (D), in addition to increasing the elastic modulus, the heat resistance and laser processability can be improved.
Hereinafter, the component (D) will be described.

(D) component:
Examples of the inorganic filler (D) include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples thereof include barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, fumed silica is preferable.
The inorganic filler preferably has a specific surface area of 20 m ² / g or more from the viewpoint of forming fine wiring on the resin composition layer. Further, from the viewpoint of reducing the surface shape after the roughening treatment in the plating process, the average primary particle size is preferably 100 nm or less.

  In the present specification, the “average primary particle size” refers to the average particle size of aggregated particles, that is, not the secondary particle size, but the average particle size of single particles that are not aggregated. The primary average particle size can be determined by measuring with a laser diffraction particle size distribution meter, for example.

  Furthermore, the inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance, and is preferably hydrophobized to improve dispersibility. .

  As content of (D) component, it is preferable that it is 5-75 volume% in a resin composition, It is more preferable that it is 15-70 volume%, It is further more preferable that it is 30-70 volume%. If the content of the inorganic filler is 5% by volume or more in the resin composition, the effect of improving the elastic modulus is sufficient, and if it is 75% by volume or less, a good surface shape after the roughening treatment is maintained. It is possible to prevent deterioration of plating characteristics and interlayer insulation reliability.

Commercially available inorganic fillers having an average primary particle size of 100 nm or less include AEROSIL R972 (trade name) and AEROSIL R202 manufactured by Nippon Aerosil Co., Ltd., PL-1 manufactured by Fuso Chemical Co., Ltd. (trade name, specific surface area of 181 m ² / g) and PL-7 (trade name, specific surface area 36 m ² / g).
Only one kind of inorganic filler as described above may be used, or two or more kinds may be used in combination.
Further, these inorganic fillers may be used by a known kneading method or dispersion method such as a kneader, ball mill, bead mill, three rolls, or nanomizer for the purpose of improving dispersibility.

  The resin composition according to the present invention is obtained by blending the component (C) described above as an essential component, and is also used for the components (A), (B), (D), and ordinary resin compositions. Various additives such as a thixotropic agent, a surfactant, and a coupling agent can be appropriately blended. After sufficiently stirring them, the resin composition can be obtained by standing until there are no bubbles.

It is preferable from the viewpoint of workability that the resin composition according to the present invention is mixed in a solvent and diluted or dispersed to form a varnish. Examples of the solvent include methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like. Can be used. These solvents may be used alone or in a mixed system.
The ratio of the solvent to the resin composition may be appropriately adjusted according to the equipment for forming the coating film of the resin composition, but the solvent is used so that the solid content of the resin composition excluding the solvent is 8 to 40% by mass in the varnish. It is preferable to adjust the amount used.

The resin composition layer according to the present invention is obtained by applying the above-described resin composition (or varnish containing the same) on a support film or prepreg and drying at 100 to 230 ° C. for about 1 to 10 minutes. can get. The thickness of the resin composition layer is preferably 0.5 to 100 μm, and more preferably 1 to 50 μm.
As the support film to be used, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide film, a Teflon (registered trademark) film, a polyimide film, a non-roughened copper foil or a surface roughness (Ra) of 0 is used. A low-roughened copper foil, aluminum foil or the like having a thickness of 4 μm or less is preferable. Moreover, you may use for these support body films the surface by which the mold release process was carried out in order to make peeling with resin easy.

(Glass substrate layer)
As the thickness of the glass substrate layer, a thin glass film having a thickness of 30 to 200 μm is preferable from the viewpoint of thinning the laminate and workability, and the thickness is 50 considering practicality such as ease of handling. -150 micrometers is more preferable. Furthermore, it is preferable to set it as 30-90 micrometers from a viewpoint of thickness reduction of a laminated body. Further, as a material for the glass substrate, glass such as alkali silicate glass, non-alkali glass, and quartz glass can be used, and glass having a high silicon content is preferable from the viewpoint of low thermal expansion.

  The total thickness of the resin composition layer and the glass substrate layer is preferably 50 to 300 μm, and more preferably 100 to 250 μm. When the thickness is 50 to 300 μm, a product such as a printed wiring board can be thinned.

As the thermal expansion coefficient of the glass substrate layer is closer to the thermal expansion coefficient (about 3 ppm / ° C.) of the silicon chip, warpage of the laminate or a laminate obtained from the laminate may be suppressed, but preferably 8 ppm / ° C. It is below, More preferably, it is 6 ppm / degrees C or less, More preferably, it is 4 ppm / degrees C or less.
The larger the dynamic storage elastic modulus of this glass substrate layer at 40 ° C., the better. However, it is preferably 20 GPa or more, more preferably 25 GPa or more, and further preferably 30 GPa or more.

(Support film and protective film)
The laminate of the present invention may have a support film or a protective film on its surface. About these support body films and protective films, it demonstrates in detail in description of the manufacturing method of the below-mentioned laminated body.

[Manufacturing method of laminate]
The manufacturing method of the laminated body of this invention can be manufactured by the application | coating to the glass substrate of a resin composition, the lamination to the glass substrate of the film which consists of a resin composition, etc. Among these, the method using lamination is preferable from the viewpoint of easy production.
Each manufacturing method will be described in detail below.

[Method for producing laminate by coating]
The production method by coating is a method for producing a laminate by coating the above-described resin composition on the surface of a glass substrate to form a resin composition layer. For example, the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler as an optional component is dispersed. The resin composition layer is formed by applying the varnish to a glass substrate and drying the organic solvent by heating or blowing hot air. This resin composition layer may be further semi-cured. Thus, the laminated body in which the resin composition layer was formed can be manufactured.

[Manufacturing method of laminate by lamination]
Said laminated body can be manufactured by laminating | stacking the adhesive film using the resin composition which concerns on this invention, and a glass substrate by pressure lamination like vacuum lamination and roll lamination. This adhesive film will be described later. Moreover, vacuum lamination and roll lamination can be performed using a commercially available vacuum laminator and roll laminator.

  As the polyfunctional epoxy resin (A) in the resin composition, those that melt at a temperature equal to or lower than the temperature at the time of lamination are suitably used. For example, when laminating using a vacuum laminator or a roll laminator, since it is generally performed at 140 ° C. or lower, the polyfunctional epoxy resin (A) in the above resin composition is preferably melted at 140 ° C. or lower. .

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

(Adhesive film)
When manufacturing a laminated body using a vacuum laminator or a pressurization laminator, it is preferable that said resin composition is 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 In the laminated structure of (1), those having the following laminated structure in which a protective film is further laminated are also preferably used.

(2) Support Film / Resin Composition Layer / Protective Film The protective film is formed on the side opposite to the support film with respect to the resin composition according to the present invention, and is used for the purpose of preventing the adhesion and scratches of foreign matters. Is.
In addition, what remove | excluded the support body film and the protective film from these adhesive films may be called an adhesive film main body.

The adhesive film having the laminated structure of (1) and (2) can be produced according to a method known to those skilled in the art.
As an example for producing the adhesive film of the above (1), the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed. Next, the resin composition layer may be formed by applying the varnish using the support film as a support and drying the organic solvent by heating, hot air blowing, or the like.
As an example for producing the adhesive film of the above (2), the above resin composition is dissolved in an organic solvent, and a varnish in which an arbitrary inorganic filler is dispersed is prepared. Next, this varnish is applied to either the support film or the protective film, the other of the support film and the protective film is placed on the varnish, and the organic solvent of the varnish is removed by heating, hot air blowing, or the like. What is necessary is just to form a resin composition layer by making it dry.

As the coating device for these resin composition layers, 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, a die coater, etc. can be used. It is preferable to select appropriately.
In the above adhesive film, the resin composition layer may be semi-cured.
The above support film serves as a support when producing an adhesive film, and is usually finally peeled off or removed when producing a multilayer printed wiring board.

Next, an example of a laminating method using the above adhesive film will be described.
When the adhesive film has a protective film, after removing the protective film, the adhesive film is pressure-bonded to the glass substrate while being pressurized and heated. The lamination is preferably performed by preheating the adhesive film and the glass substrate as necessary, and laminating at a pressure bonding temperature (laminating temperature) of preferably 60 ° C. to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm ² . Moreover, when using a vacuum laminator, it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll.
As described above, after the adhesive film is laminated on the glass substrate, it is cooled to around room temperature. The support film is peeled off as necessary.

[Manufacturing method of laminate]
Next, a specific example of a method for manufacturing a laminated board will be described.

(Production example by heat curing of laminate)
In the laminate obtained by the above-described laminate, a laminate can be produced by peeling the support film as necessary and then curing the resin composition layer to obtain a cured resin layer. .

The conditions for heat curing are selected in the range of 20 to 80 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C. When a support film subjected to a release treatment is used, the support film may be peeled off after being cured by heating.
According to this method, since it is not necessary to pressurize at the time of manufacture of a laminated board, it is controlled that a crack arises at the time of manufacture.

The thickness of the cured resin layer is preferably 5 to 200 μm. If the thickness is 5 μm or more, cracking of the laminate is suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate is relatively increased, so that the thermal expansion coefficient and the high elastic modulus of the laminated plate can be reduced. From this viewpoint, the thickness of the cured resin layer is more preferably 10 to 150 μm, and further preferably 10 to 100 μm.
However, the appropriate range of the thickness of the cured resin layer varies depending on the thickness of the glass substrate layer, the number of layers, and the number of layers of the cured resin layer, and thus is not limited to the above range.

The storage elastic modulus of this laminate at 40 ° C. is preferably 1 to 80 GPa. A glass substrate is protected as it is 1 GPa or more, and the crack of a laminated board is suppressed. When it is 80 GPa or less, stress due to the difference in coefficient of thermal expansion between the glass substrate and the cured resin layer is suppressed, and warpage and cracking of the laminate are suppressed. From this viewpoint, the storage elastic modulus of the cured resin layer is more preferably 3 to 70 GPa, and further preferably 5 to 60 GPa.
You may have metal foil, such as copper and aluminum, on the single side | surface or both surfaces of a laminated board. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.

(Production example by press method)
Moreover, the laminated board which concerns on this invention can be manufactured by the press method.
For example, a laminate can be produced by curing a laminate obtained by the above-described laminate by heating and pressurizing by a pressing method before performing a curing treatment.
In addition, by overlapping the adhesive film body described above and / or the adhesive film body obtained by removing the support film and the protective film from the adhesive film, and the glass substrate, by heating, pressing and curing by a press method, Laminates can also be manufactured.
Furthermore, a laminated board can also be manufactured by applying and drying a resin composition on a glass substrate and superimposing them in a B-stage state, followed by heating and pressing by a pressing method and curing.

[Multi-layer laminate and its manufacturing method]
The multilayer laminate of the present invention is a multilayer laminate including a plurality of laminates, and at least one laminate is the aforementioned laminate of the present invention.
There is no restriction | limiting in particular in the manufacturing method of this multilayer laminated board.
For example, a plurality of the above-described laminated plates may be laminated to form a multilayer through an adhesive film body obtained by removing the support film and the protective film from the above-described adhesive film.
Moreover, a multilayer laminated board can also be manufactured by laminating | stacking several laminated bodies (for example, 2-20 sheets) and carrying out lamination | stacking shaping | molding. Specifically, using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., the temperature is about 100 to 250 ° C., the pressure is about 2 to 100 MPa, and the heating time is about 0.1 to 5 hours. Can be molded.

[Printed wiring board and manufacturing method thereof]
The printed wiring board of the present invention is formed by providing wiring on at least one surface of the laminated board of the present invention. Further, there may be a configuration (multilayer printed wiring board) including a plurality of laminated boards. In that case, at least one laminated board is the laminated board of the present invention.
Next, a method for manufacturing this printed wiring board will be described.

(Formation of via holes)
The above laminated plate is drilled by a method such as drilling, laser, plasma, or a combination thereof as necessary to form a via hole or a through hole. As the laser, a carbon dioxide laser, YAG laser, UV laser, excimer laser, or the like is generally used. After forming the via hole or the like, desmear treatment may be performed using an oxidizing agent. As the oxidizing agent, permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid are suitable, and potassium permanganate, sodium permanganate A sodium hydroxide aqueous solution (alkaline permanganic acid aqueous solution) such as the above is more preferable.

(Formation of wiring pattern)
As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.
When circuit processing is carried out by plating on the cured resin layer of the laminated board or multilayer wiring board of the present invention, first, roughening treatment is performed. As the roughening liquid in this case, an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, or a borofluoric acid roughening liquid should be used. Can do. As the roughening treatment, for example, as a swelling liquid, an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated to 70 ° C., and the laminate or multilayer wiring board is immersed for 5 minutes. Next, as a roughening liquid, an aqueous solution of KMnO ₄ and NaOH is heated to 80 ° C. and immersed for 10 minutes. Subsequently, it is neutralized by immersing it in a neutralizing solution, for example, an aqueous hydrochloric acid solution of stannous chloride (SnCl ₂ ) at room temperature for 5 minutes.
Here, the surface roughness (Ra) of the cured resin layer after the roughening treatment is, for example, preferably 0.45 μm or less, preferably 0.40 μm or less, and preferably 0.38 μm or less. Fine wiring can be achieved when the thickness is 0.4 μm or less.

  After the roughening treatment, a plating catalyst application treatment for adhering palladium is performed. The plating catalyst treatment is performed by immersing in a palladium chloride plating catalyst solution. Next, an electroless plating treatment is performed by immersing in an electroless plating solution to deposit an electroless plating layer (conductor layer) having a thickness of 0.3 to 1.5 μm on the entire surface of the plating process primer layer.

  Next, after forming a plating resist, electroplating is performed to form a circuit with a desired thickness at a desired location. As the electroless plating solution used for the electroless plating treatment, a known electroless plating solution can be used, and there is no particular limitation. As the plating resist, a known plating resist can be used, and there is no particular limitation. Also, the electroplating treatment can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Furthermore, the outer layer circuit can be formed by etching away the electroless plating layer at unnecessary portions.

[Multilayer printed wiring board and manufacturing method thereof]
As one form of the printed wiring board described above, a multilayer printed wiring board may be formed by laminating a plurality of laminated boards on which wiring patterns are formed as described above.
In order to manufacture this multilayer printed wiring board, a multilayer is formed by laminating a plurality of laminated boards on which the above-described wiring pattern is formed via the adhesive film main body described above. Thereafter, through holes or blind via holes are formed by drilling or laser processing, and interlayer wiring is formed by plating or conductive paste. In this way, a multilayer printed wiring board can be manufactured.

[Laminated plate with metal foil and multilayer laminated plate, and production methods thereof]
The laminate of the present invention and the multilayer laminate using the laminate may be a laminate with a metal foil and a multilayer laminate having a metal foil such as copper or aluminum on one side or both sides.
There is no restriction | limiting in particular in the manufacturing method of this laminated sheet with metal foil. For example, as described above, a laminate with a metal foil can be produced by using a metal foil as the support film. In addition, by laminating one or a plurality (for example, 2 to 20) of laminates obtained by the above-described lamination or coating, and laminating and forming the metal foil on one or both sides, a metal foil is obtained. A laminated board can also be manufactured.
The molding conditions can be applied to a laminated plate for an electrical insulating material or a multilayer plate, for example, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250 ° C., a pressure of 2 Molding can be performed in a range of about 100 MPa and a heating time of about 0.1 to 5 hours.

  EXAMPLES Next, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples.

(Example 1) (Preparation of resin varnish A)
After blending 91.4 g of N, N-dimethylacetamide (DMAc) with 10.2 g of the phenolic hydroxyl group-containing polybutadiene-modified polyamide (Nippon Kayaku Co., Ltd., trade name: BPAM-155) as component (C), 12. A) Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., trade name: NC-3000H) 40.0 g, component (B) Bisphenol A novolak (Mitsubishi Chemical Co., trade name: YLH129) 6 g, 0.4 g of 2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2PZ) as a curing accelerator, and 3.6 g of fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) as component (D) After the addition, it was diluted with a mixed solvent consisting of DMAc and methyl ethyl ketone (solid content concentration of about 25% by mass). Thereafter, resin varnish A was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Co., Ltd.).

(Manufacture of adhesive film)
The resin varnish A is dried to 12 μm by using a bar coater on the release treatment surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Co., Ltd.) having a thickness of 38 μm. It was applied and dried at 140 ° C. for 10 minutes to form a resin composition layer.

(Manufacture of laminated board (cured resin layer / glass substrate layer / cured resin layer))
As the glass substrate, an ultrathin glass film “OA-10G” (trade name, thickness 100 μm) manufactured by Nippon Electric Glass was used. On both surfaces of this glass substrate, the prepared adhesive film was placed so that the resin composition layer was in contact with the glass substrate, and a batch-type vacuum pressure laminator “MVLP-500” (made by Meiki Co., Ltd., trade name) ) Was laminated by lamination. The degree of vacuum at this time was 30 mmHg (40.0 hPa) or less, the temperature was set to 90 ° C., and the pressure was set to 0.5 MPa.
After cooling to room temperature, the support film was peeled off and cured in a dry atmosphere set at 180 ° C. for 60 minutes to obtain a three-layer laminate (resin cured product layer / glass substrate layer / resin cured product layer). .

(Example 2) (Preparation of resin varnish B)
Resin varnish B was obtained in the same manner as resin varnish A except that the composition shown in Table 1 below was used.

(Manufacture of adhesive film)
Manufactured in the same manner as in Example 1 except that the resin varnish B was used.

(Manufacture of laminated board (cured resin layer / glass substrate layer / cured resin layer))
The same operation as in Example 1 was performed except that the above adhesive film was used in place of the adhesive film of Example 1, and a three-layer laminate (resin cured product layer / glass substrate layer / resin cured product layer) was obtained. Obtained.

(Example 3) (Preparation of resin varnish C)
A resin varnish C was obtained in the same manner as the resin varnish A except that the composition shown in Table 1 was used.

(Manufacture of adhesive film)
Manufactured in the same manner as in Example 1 except that the resin varnish C was used.

(Manufacture of laminated board (cured resin layer / glass substrate layer / cured resin layer))
The same operation as in Example 1 was performed except that the above adhesive film was used in place of the adhesive film of Example 1, and a three-layer laminate (resin cured product layer / glass substrate layer / resin cured product layer) was obtained. Obtained.

(Example 4) (Preparation of resin varnish D)
A resin varnish D was obtained in the same manner as the resin varnish A except that the formulation shown in Table 1 was used.

(Manufacture of adhesive film)
Manufactured in the same manner as in Example 1 except that the resin varnish D was used.

(Manufacture of laminated board (cured resin layer / glass substrate layer / cured resin layer))
The same operation as in Example 1 was performed except that the above adhesive film was used in place of the adhesive film of Example 1, and a three-layer laminate (resin cured product layer / glass substrate layer / resin cured product layer) was obtained. Obtained.

(Example 5) (Preparation of resin varnish E)
Resin varnish E was obtained in the same manner as resin varnish A except that the composition shown in Table 1 below was used.

(Manufacture of adhesive film)
Manufactured in the same manner as in Example 1 except that the resin varnish E was used.

(Manufacture of laminated board (cured resin layer / glass substrate layer / cured resin layer))
The same operation as in Example 1 was performed except that the above adhesive film was used in place of the adhesive film of Example 1, and a three-layer laminate (resin cured product layer / glass substrate layer / resin cured product layer) was obtained. Obtained.

In order to chemically roughen a laminate having a cured resin layer and a glass substrate layer, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, NaOH: 5 g / L was prepared as a swelling liquid and heated to 70 ° C. Immersion treatment was performed for 5 minutes. Next, an aqueous solution of KMnO ₄ : 60 g / L and NaOH: 40 g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 10 minutes. Subsequently, it was neutralized by immersing in an aqueous solution of a neutralizing solution (SnCl ₂ : 30 g / L, HCl: 300 ml / L) at room temperature for 5 minutes.

[Manufacture of wiring boards]
In order to form a circuit layer on a wiring board having a cured resin layer and the glass substrate layer, first, a catalyst for electroless plating containing PdCl ₂ HS-202B (manufactured by Hitachi Chemical Co., Ltd.), room temperature -10 It was immersed in water for a minute, washed with water, immersed in a plating solution CUST-201 (manufactured by Hitachi Chemical Co., Ltd.) for electroless copper plating at room temperature for 15 minutes, and further subjected to copper sulfate electrolytic plating. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 35 μm.

  Next, in order to remove unnecessary portions of the plating conductor by etching, first, the oxide film on the copper surface is removed by polishing with # 600, followed by forming an etching resist, then etching, and then removing the etching resist. Then, circuit formation was performed to produce a wiring board having a cured resin layer and a glass substrate layer.

[Adhesion strength with outer layer circuit]
A part having a width of 10 mm and a length of 100 mm is formed on a part of the circuit layer of the wiring board obtained in each example by a copper etching process. One end of the circuit layer is peeled off at the circuit layer / resin interface, and is gripped with a gripper. The tensile load was about 50 mm / min, and the load when peeled off at room temperature was measured.

[Surface roughness of cured resin layer]
For the resin cured material layer surface exposed by etching and removing a part of the copper of the circuit layer of the wiring board obtained in each example, a surface roughness Ra is used using a Ryoka System Co., Ltd. micromap MN5000 type. It was measured.

[288 ° C solder heat resistance]
The multilayer wiring board produced in each example was cut into 25 mm squares, floated in a solder bath adjusted to 288 ± 2 ° C., and the time until blistering was examined.

[Storage modulus]
A test piece of 5 mm × 30 mm was cut out from the laminate.
Using a wide-area viscoelasticity measurement device (DVE-V4, manufactured by Rheology), measuring the tensile storage modulus at 40 ° C under the conditions of 20 mm span, 10 Hz frequency, and 1-3 μm vibration displacement (stop excitation) did. The results are shown in Table 2.

As is apparent from Table 2, Examples 1 to 5 of the present invention show electroless copper plating and high adhesion on a smooth resin surface. Furthermore, since Examples 1-3 are excellent also in 288 degreeC solder heat resistance, it turns out that a wiring board in consideration of the environment can be manufactured. Furthermore, from Examples 1, 2, 4 and 5, by adding an inorganic filler, it was possible to obtain a highly elastic laminate that could not be achieved in Patent Document 7.
From the above results, according to the present invention, it is possible to provide a highly elastic laminate having high adhesion to electroless copper plating.

Claims (15)

A laminate obtained by curing a laminate having one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer is a polyfunctional epoxy resin (A), epoxy resin curing agent (B) and only contains phenolic hydroxyl group-containing polybutadiene modified polyamide resin (C), and phenolic hydroxyl group-containing polybutadiene modified polyamide resin (C) is a compound represented by the following formula (i), (ii) and (iii) A laminate having a storage unit and a storage elastic modulus at 40 ° C. of 1 GPa to 70 GPa .

[Wherein, a, b, c, x, y and z are average degree of polymerization, respectively, and a = 2 to 10, b = 1 to 8, c = 3 to 20, and y = 1 to z = 1. = 2 to 300, z ≧ 20 with respect to y = 1, x = 1 to 100, and y = 1 to 200. R, R ′ and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and a plurality of R ′ ″ are each independently an aromatic dicarboxylic acid, aliphatic It is a divalent group derived from dicarboxylic acid or an oligomer having carboxyl groups at both ends. ] The blending ratio of the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) is 4 to 40 parts by mass with respect to a total of 100 parts by mass of the polyfunctional epoxy resin (A) and the epoxy resin curing agent (B). Item 2. The laminated sheet according to item 1 . The laminated plate according to claim 1 or 2 , wherein a total thickness of the resin composition layer and the glass substrate layer is 50 to 300 µm. Laminate according to any one of claims 1 to 3 the thickness of the glass substrate layer is 30 to 200 [mu] m. The laminated board of any one of Claims 1-4 in which the polyfunctional epoxy resin (A) contained in the said resin composition layer has a biphenyl structure. The laminate according to claim 5 , wherein the polyfunctional epoxy resin (A) contained in the resin composition layer is an aralkyl epoxy resin having a biphenyl structure. The laminated board of any one of Claims 1-6 containing the inorganic filler (D) with an average primary particle diameter of 100 nm or less as an inorganic filler. The laminate according to claim 7 , wherein the inorganic filler (D) is fumed silica. The laminate according to claim 7 or 8 , wherein the inorganic filler (D) is subjected to a surface treatment. The laminate according to any one of claims 1 to 9, wherein the surface roughness (Ra) of the cured resin layer after the roughening treatment is 0.4 µm or less. The printed wiring board by which wiring is provided in the at least one surface of the laminated board of any one of Claims 1-10 . It includes a plurality of stacked plates, printed wiring board according to claim 11 at least one of said laminate is a laminate according to any one of claims 1 to 10. A film composed of a resin composition containing a polyfunctional epoxy resin (A), an epoxy resin curing agent (B) and a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C) is prepared, and the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin ( C) has a structural unit represented by the following formulas (i), (ii) and (iii),
The manufacturing method of the laminated board whose storage elastic modulus in 40 degreeC is 1 GPa-70 GPa by laminating | stacking the said film on a glass substrate using a vacuum laminator or a roll laminator, and giving the said film a hardening process.

[Wherein, a, b, c, x, y and z are average degree of polymerization, respectively, and a = 2 to 10, b = 1 to 8, c = 3 to 20, and y = 1 to z = 1. = 2 to 300, z ≧ 20 with respect to y = 1, x = 1 to 100, and y = 1 to 200. R, R ′ and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and a plurality of R ′ ″ are each independently an aromatic dicarboxylic acid, aliphatic It is a divalent group derived from dicarboxylic acid or an oligomer having carboxyl groups at both ends. ] The manufacturing method of the laminated board of Claim 13 which contains an inorganic filler (D) with an average primary particle diameter of 100 nm or less as an inorganic filler in a resin composition. The manufacturing method of the laminated board of Claim 13 or 14 which performs a press process after giving the said hardening process after laminating | stacking the said film.