TW201446499A - Multilayer body, laminate, printed wiring board, method for producing multilayer body, and method for manufacturing laminate - Google Patents

Abstract

A multilayer body having one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layers contain a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (C).

Description

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

The present invention relates to a laminate, a laminate, and a method of manufacturing the same, and a printed wiring board suitable for use in a semiconductor package or a printed wiring board.

In recent years, the miniaturization, weight reduction, and multi-functionality of electronic equipment have been further developed. With this, the integration of LSI (large-scale integration) or wafer components has been progressing. Moreover, the form is also rapidly changing toward multiple pins and miniaturization. Therefore, in the laminated board, in order to increase the mounting density of electronic components, development of fine wiring has been advanced. As a manufacturing method of a multilayer wiring board which meets such requirements, there is a build-up type multilayer wiring board which uses an insulating resin not containing glass cloth instead of a prepreg as an insulating layer, and a through hole on one side ( The via hole is formed by connecting only the desired portion to form a wiring layer, and the multilayer wiring board is becoming mainstream as a method suitable for weight reduction, miniaturization, or miniaturization.

The multilayer wiring board of such a build-up type is produced by laminating an insulating resin film on an inner layer circuit board and hardening it by heating to form a build-up layer. After that, through the laser processing to form a through hole, borrow The roughening treatment and the smear treatment are performed by alkaline permanganic acid treatment or the like to perform electroless copper plating to form a via hole which can be interlayer-connected to the second circuit (see Patent Documents 1 to 3). Here, the adhesion between the resin and the electroless copper plating is ensured by the roughness (an anchoring effect) of the surface of the resin, and the surface roughness Ra is as large as 0.6 μm or more. According to this method, a fine circuit of 10 μm or less may cause a short circuit failure or an open circuit failure. Therefore, a multilayer wiring board cannot be manufactured with good yield. On the other hand, if the roughened shape is reduced, the adhesion to electroless copper plating is lowered, and defects such as wire peeling occur. Therefore, there is a need for a circuit board material that exhibits a higher adhesion to electroless copper plating on a smooth surface.

On the other hand, there is an increasing demand for thinning and weight reduction of electronic machinery, and the thickness and density of semiconductor packages and printed wiring boards are increasing. In order to cope with such thinning, high density, and stable mounting of electronic components, it is very important to suppress warpage generated during the assembly.

One of the main causes of warpage occurring on the semiconductor package during mounting is that the laminated board used in the semiconductor package has a thermal expansion coefficient which is different from that of the germanium wafer mounted on the surface of the laminated board. Therefore, in the case of a laminate for a semiconductor package, efforts have been made to bring the coefficient of thermal expansion close to the coefficient of thermal expansion of the tantalum wafer, that is, to lower the coefficient of thermal expansion. Moreover, since the elastic modulus of the laminated board also causes warpage, it is also effective to increase the elasticity of the laminated board to reduce warpage. In this way, in order to reduce the warpage of the laminated board, it is effective to reduce the expansion ratio of the laminated board and to improve the elasticity of the laminated board.

A method of reducing the thermal expansion rate of the laminated board and improving the elasticity of the laminated board can be considered in various ways, wherein the reduction is known for the laminated board. The resin has a coefficient of thermal expansion or is highly filled with an inorganic filler material in the resin. In particular, a highly filled inorganic filler is a technique that can be expected to lower the coefficient of thermal expansion and improve heat resistance or flame retardancy (Patent Document 4). However, since the filling amount of the inorganic filler is increased in this way, the insulation reliability is lowered or the adhesion between the resin and the wiring layer formed on the surface of the resin is insufficient, and the press forming at the time of manufacturing the laminated sheet is poor, so there is a limit in height filling. .

Moreover, attempts have been made to achieve a low coefficient of thermal expansion by selecting or modifying the resin. In general, for example, a method of increasing the crosslinking density of a resin for a wiring board to increase the Tg and lowering the coefficient of thermal expansion (Patent Documents 5 and 6). However, increasing the crosslinking density is to shorten the molecular chain between the functional groups. However, if the molecular chain is shortened to a certain extent or more, there is a problem that there is a limit in terms of the reaction, and the resin strength is lowered.

As a method different from the above, an attempt has been made to use a glass film as a layer having a coefficient of thermal expansion substantially equal to a coefficient of thermal expansion of an electronic component (a silicon wafer), and to laminate a resin and a glass film to thereby reduce thermal shock stress. (Patent Document 7) However, since the resin used has a low modulus of elasticity and a high coefficient of thermal expansion, it is not sufficient to reduce the warpage of the substrate.

As a constituent element of a laminated board having a smooth surface capable of forming a fine line, the glass film is generally considered to be effective, but it is generally considered that since the chemical adhesion between glass and copper is extremely insufficient, it is difficult to form a fine line.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent No. 3290296

Patent Document 2: Japanese Patent No. 3654581

Patent Document 3: Japanese Patent No. 3785749

Patent Document 4: Japanese Laid-Open Patent Publication No. 2004-182851

Patent Document 5: Japanese Laid-Open Patent Publication No. 2000-243864

Patent Document 6: Japanese Laid-Open Patent Publication No. 2000-114727

Patent Document 7: Japanese Patent No. 4657554

As described above, it is considered that since the surface of the glass is very smooth, it is effective for forming a fine line, but the chemical adhesion to electroless copper plating is very weak. Therefore, when a fine circuit of 10 μm or less is formed, a short-circuit defect or an open circuit failure occurs, and manufacturing cannot be performed with good yield. Further, the substrate obtained by the manufacturing methods of Patent Documents 4 to 6 has a low modulus of elasticity, so that it is not sufficient to reduce the warpage of the substrate.

Further, in Patent Document 7, the properties of the resin in the substrate in which the glass film and the resin are laminated are not disclosed at all. In Patent Document 7, it is generally considered that only the influence on the thermal expansion action of the substrate must be considered. That is, it is not considered at all that the adhesion of the electroless copper plating is promoted to form a multilayer wiring board in which a wiring layer is formed by a through hole to connect only a desired portion.

As apparent from the above, it is an object of the present invention to provide a laminated body, a laminated board, and the like, which have a high surface roughness Ra and exhibit high electroless copper plating. Adhesive, which increases line density. Further, it is an object to provide a printed wiring board using the same The laminate or laminate.

The inventors of the present invention have diligently studied to solve the above problems, and as a result, have found that the problem 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, and the resin composition layer contains a polybutadiene-modified polyamine resin containing a phenolic hydroxyl group ( C).

[2] The laminate according to [1], wherein the resin composition layer comprises a polyfunctional epoxy resin (A) and an epoxy resin hardener (B).

[3] The laminate according to the above [2], wherein the phenolic hydroxyl group-containing polybutylene is 100 parts by mass based on the total of the polyfunctional epoxy resin (A) and the epoxy resin hardener (B). The blending ratio of the olefin modified polyamine resin (C) is 4 to 40 parts by mass.

[4] The laminated body according to any one of [1] to [3] wherein the total 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], wherein the thickness of the glass substrate layer is 30 to 200 μm.

The laminate according to any one of the above aspects, wherein the polyfunctional epoxy resin (A) contained in the resin composition layer has a biphenyl structure.

[7] The layered body according to the above [6], wherein the polyfunctional epoxy resin (A) contained in the resin composition layer is an aralkyl type epoxy resin having a biphenyl structure.

[8] The laminate according to any one of [1] to [7] wherein The filler contains an inorganic filler (D) having an average primary particle diameter of 100 nm or less.

[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 laminate according to any one of [1] to [10] wherein the polybutadiene-modified polyamine resin (C) having a phenolic hydroxyl group has the following formula (i) Structural elements represented by (ii) and (iii): [wherein, a, b, c, x, y, and z are the average degrees of polymerization, respectively, and represent a = 2 to 10, b = 1 to 8, c = 3 to 20, and y + z with respect to x = 1 An integer from 2 to 300, and z ≧ 20 with respect to y = 1, and x = 1 to 100, y = 1 to 200; R, R' and R" are independently derived from aromatic diamine or aliphatic The divalent group of the diamine, and the plurality of R''' are each independently a divalent group derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having a carboxyl group at both terminals.

[12] A laminated board comprising one or more layers of a resin cured material layer and one or more layers of a glass substrate layer, wherein the layered body according to any one of [1] to [11] is subjected to a hardening treatment. .

[13] The laminate according to [12], wherein the storage elastic modulus at 40 ° C is 1 GPa to 70 GPa.

[14] The laminated board according to the above [12], 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 formed by providing a wiring 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], wherein a plurality of laminated boards are provided, and at least one of the above-mentioned 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 on a surface of a glass substrate to form a resin composition layer comprising: a polybutadiene modified polyamine containing a phenolic hydroxyl group; Resin (C).

[18] The method for producing a laminate according to [17], wherein the resin composition comprises a polyfunctional epoxy resin (A) and an epoxy resin curing agent (B).

[19] The method for producing a laminate according to the above [17], wherein the polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group has the following formula (i), Structural units represented by (ii) and (iii): [wherein, a, b, c, x, y, and z are the average degrees of polymerization, respectively, and represent a = 2 to 10, b = 1 to 8, c = 3 to 20, and y + z with respect to x = 1 An integer from 2 to 300, and z ≧ 20 with respect to y = 1, and x = 1 to 100, y = 1 to 200; R, R' and R" are independently derived from aromatic diamine or aliphatic The divalent group of the diamine, and the plurality of R''' are each independently a divalent group derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having a carboxyl group at both terminals.

[20] The method for producing a layered product according to any one of [17], wherein the resin composition layer is formed and then subjected to a drying treatment.

[21] A method for producing a laminated sheet, comprising: forming a film composed of a resin composition, and laminating the film on a glass substrate using a vacuum laminator or a roll laminator, and then applying a curing treatment to the film, the resin composition The composition comprises: a polybutadiene modified polyamine resin (C) containing a phenolic hydroxyl group.

[22] The method for producing a laminate according to [21], wherein the resin composition comprises a polyfunctional epoxy resin (A) and an epoxy resin curing agent (B).

[23] The method for producing a laminate according to [21], wherein the polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group has the following formula (i), Structural units represented by (ii) and (iii): [wherein, a, b, c, x, y, and z are the average degrees of polymerization, respectively, and represent a = 2 to 10, b = 1 to 8, c = 3 to 20, and y + z with respect to x = 1 An integer from 2 to 300, and z ≧ 20 with respect to y = 1, and x = 1 to 100, y = 1 to 200; R, R' and R" are independently derived from aromatic diamine or aliphatic The divalent group of the diamine, and the plurality of R''' are each independently a divalent group derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having a carboxyl group at both terminals.

[24] The method for producing a laminated board according to any one of [21], wherein the film is laminated and subjected to a pressing treatment before the hardening treatment.

According to the present invention, it is possible to provide a laminated body and a laminated board which exhibits high adhesion to electroless copper plating even if the surface roughness Ra is small, and the manufacturing method. Able to improve the line density. Further, it is possible to provide a printed wiring board using the laminated body or the laminated board.

Hereinafter, the laminated body, the laminated board, the manufacturing method of these, and the printed wiring board of this invention are demonstrated in detail.

In the present specification, the term "layered body" refers to a layered body in which a thermosetting resin (polyfunctional epoxy resin) which is a constituent component is not cured or semi-cured, and the term "laminate" means a constituent component thereof. That is, a laminate in which the thermosetting resin is cured or 90% or more of the thermosetting resin is cured. Further, the degree of hardening of the thermosetting resin can be measured by a reaction rate measured by a differential scanning calorimeter.

[Laminated and laminated boards]

The laminate of the present invention has one or more resin composition layers and one or more glass substrate layers, and the resin composition layer contains a polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group. The present invention comprises: a polyfunctional epoxy resin (A); an epoxy resin hardener (B); and a polybutadiene modified polyamine resin (C) containing a phenolic hydroxyl group, which has a formula (hereinafter) The structural units represented by i), (ii) and (iii).

Here, the resin composition layer of the present invention is present on the support in an unhardened or semi-hardened state (so-called B-stage state) before being formed as a part of the layer of the wiring board for the wiring board or the multilayer wiring board. On the glass substrate, etc.

Moreover, the laminated board of the present invention is obtained by heating the present invention Thereby, the resin composition layer is cured to form a resin cured layer.

Here, a layer having a low thermal expansion coefficient and a high modulus of elasticity similar to that of the tantalum wafer is used as the glass substrate layer, whereby warpage is suppressed and cracking is less likely to occur. In particular, such a laminate has a glass substrate layer having high heat resistance, whereby the thermal expansion property is remarkably low in a temperature region from 100 ° C to a Tg which does not reach the cured resin. Further, the resin cured layer contains an inorganic filler, whereby the resin cured layer becomes a layer having low thermal expansion and high elasticity, and the laminated sheet including the cured resin layer has lower thermal expansion and higher elastic modulus. The number of laminates.

(resin composition)

As described above, the resin composition of the present invention is formed of a resin composition comprising: a polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group, preferably comprising: a polyfunctional ring Oxygen resin (A) (hereinafter, referred to as "(A) component)"; epoxy resin curing agent (B) (hereinafter, may be referred to as "(B) component)"; The polybutadiene modified polyamine resin (C) of a hydroxyl group (hereinafter may be referred to as "(C) component)"), which is represented by the formulas (i), (ii) and (iii) which will be described later. The structural unit.

Hereinafter, the components (A) to (C) will be described.

(C) ingredients:

Where a, b, c, x, y, and z are the average degrees of polymerization, respectively, and represent a = 2 to 10, b = 1 to 8, c = 3 to 20, and y + z = relative to x = 1 An integer from 2 to 300, and z ≧ 20 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''' It is independently a divalent group derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having a carboxyl group at both terminals.

In the resin composition, for example, the compounding ratio of the component (C) is preferably 4 parts by mass or more based on 100 parts by mass of the total of the resin component (excluding the component (C)) of the resin composition. In addition, when the component (A) and the component (B) are contained, it is preferably 4 to 40 parts by mass based on 100 parts by mass of the total. By blending in this ratio, it is possible to obtain a good adhesion strength to copper plating while maintaining good heat resistance.

The reason for obtaining such an effect is not necessarily clear, but is generally considered to be the reason as described below.

That is, since the (C) component is a polybutadiene modified polyfluorene containing a phenolic hydroxyl group Since the amine resin can react with the epoxy resin, the resin can be made toughened while maintaining good heat resistance of the epoxy resin. Further, since it has a large amount of amidino group, the adhesion of the guanamine group to copper is high, so that a high adhesion to copper plating is obtained.

Further, the polybutadiene-modified polyamine resin containing a phenolic hydroxyl group contains, for example, a phenolic hydroxyl group having good compatibility with an epoxy resin and a polybutadiene which is incompatible with an epoxy resin. When the blending ratio is 4 to 40 parts by mass based on 100 parts by mass of the total of the components (A) and (B), a fine sea-island structure can be formed more satisfactorily. By forming this sea-island structure, the amount of roughening of the sea layer and the island layer can be different by the roughening treatment, and a close shape can be formed during the roughening treatment. Since this shape is fine and has small deviation, it exhibits a high physical adhesion due to the anchoring effect, and the adhesion to copper plating is remarkably improved.

In addition, when the blending ratio of the component (C) is 4 parts by mass or more, the phase size (domain size) of the sea-island structure does not become excessive, and the Ra after the roughening treatment tends to be small. Further, the resin has high toughness and a more compact roughened shape, and a good tendency to adhere to copper plating can be obtained.

On the other hand, when the compounding ratio of the component (C) is 40 parts by mass or less, the phase region size of the sea-island structure does not become excessively large, and a good adhesion to electroless copper plating tends to be obtained. Further, it is possible to obtain good heat resistance, and it is also excellent in resistance to a chemical liquid in the roughening step.

In consideration of obtaining a better adhesion to copper plating, when the component (A) and the component (B) are contained, the compounding ratio of the component (C) is preferably 5 to 25 parts by mass based on 100 parts by mass of the total of the components. , further preferably 5 to 20 parts by mass, especially It is preferably 5 to 19 parts by mass.

Further, since the polyamine resin having a phenolic hydroxyl group and the acrylonitrile-butadiene modified polyamine resin containing a phenolic hydroxyl group are compared with a polybutadiene modified polyamine resin containing a phenolic hydroxyl group, Since the compatibility with the epoxy resin is more excellent, the sea-island structure is too tight, and it is difficult to form a fine shape after the roughening treatment, and the polybutadiene-modified polyamine resin having a phenolic hydroxyl group cannot be exhibited. Adhesion with copper plating. Further, when a nitrile group is introduced, the moisture absorption rate is increased, and the insulation property at the time of moisture absorption is also lowered.

The (C) component, that is, the polybutadiene-modified polyamine resin containing a phenolic hydroxyl group, is synthesized by, for example, a diamine and a dicarboxylic acid having a phenolic hydroxyl group and a dicarboxylic acid having no phenolic hydroxyl group. Acid and polybutadiene having a carboxyl group at both ends, in the presence of an organic solvent such as N-methyl-2-pyrrolidone (NMP), as a catalyst for the presence of a phosphite and a pyridine derivative Next, the carboxyl group and the amine group are subjected to polycondensation.

The weight average molecular weight of the component (C) is preferably from 60,000 to 250,000, more preferably from 80,000 to 200,000.

In the present invention, the diamine (diamine raw material) used in the production of the polybutadiene modified polyamine containing a phenolic hydroxyl group may be an aromatic diamine or an aliphatic diamine.

Specific examples of the aromatic diamine include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diamine mesitylene, diaminonitrobenzene, and Aminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyl diphenyl ether, methylene diamine, Methylene bis(dimethylaniline), methylene bis(methoxyaniline), Methylene bis(dimethoxyaniline), methylene bis(ethylaniline), methylene bis(diethylaniline), methylene bis(ethoxyaniline), methylene bis (two Ethoxyaniline), isopropylidenediphenylamine, diaminobenzophenone, diaminodimethylbenzophenone, diaminoguanidine, diaminodiphenyl sulfide, diamine II Methyl diphenyl sulfide, diaminodiphenylsulfone, diaminodiphenylsulfoxide, and diamine hydrazine.

Specific examples of the aliphatic diamine include ethylenediamine, propylenediamine, hydroxypropylenediamine, butanediamine, heptanediamine, hexamethylenediamine, diaminodiethylamine, diaminopropylamine, and a ring. Pentamethylenediamine, cyclohexanediamine, azapentanediamine, triazaundecadiamine, and the like. These aromatic and aliphatic diamines may be used alone or in combination of two or more.

In the present invention, when a polybutadiene-modified polyamine containing a phenolic hydroxyl group is produced, examples of the dicarboxylic acid containing a phenolic hydroxyl group include hydroxyisophthalic acid, hydroxyphthalic acid, and hydroxyl group. Terephthalic acid, dihydroxyisophthalic acid, dihydroxyterephthalic acid, etc., but are not limited thereto.

In the present invention, when a polybutadiene-modified polyamine containing a phenolic hydroxyl group is produced, a dicarboxylic acid (dicarboxylic acid raw material) which does not contain a phenolic hydroxyl group may be an aromatic dicarboxylic acid or a fat. The dicarboxylic acid may also be an oligomer having a carboxyl group at both ends. Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, diphenylic acid, methylene dibenzoic acid, thiodibenzoic acid, and carbonyl dibenzoic acid. , sulfobenzoic acid and naphthalene dicarboxylic acid.

As the aliphatic dicarboxylic acid, oxalic acid, malonic acid, and methyl group are mentioned. Malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth) acryloxy succinic acid, di(methyl) propylene oxy succinic acid And (meth) propylene methoxy methoxy malic acid, (meth) acryl decyl succinic acid, or (meth) acryl amide amino acid.

The polybutadiene having a carboxyl group at both ends, preferably having an average molecular weight of from 200 to 10,000, more preferably from 500 to 5,000.

As a commercial item of the polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group, BPAM-155 by Nippon Kayaku Co., Ltd. is mentioned.

(A) Ingredients:

The polyfunctional epoxy resin (A) is an epoxy resin having two or more epoxy groups in the molecule, and examples thereof include a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, and a phenol. An alkyl type epoxy resin or the like. Among these, it is preferable to contain an aralkyl novolak type epoxy resin as a polyfunctional epoxy resin.

The aralkyl novolac type epoxy resin is preferably an aralkyl novolac type epoxy resin having a biphenyl structure. The novolac type epoxy resin having a biphenyl structure is an aromatic ring aralkyl novolak type epoxy resin containing a biphenyl derivative in the molecule, and examples thereof include the following formula (1) (wherein p represents an epoxy resin represented by 1 to 5).

Furthermore, a plurality of epoxy trees represented by the above formula may be used in combination. fat. In addition, as a commercial item of this resin, NC-3000 (p 1.7 epoxy resin), NC-3000-H (p is 2.8 epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. are mentioned.

The proportion of the (A) polyfunctional epoxy resin in the proportion of the resin composition is preferably from 20 to 80% by mass, more preferably from 40 to 70% by mass. The blending amount of the component (A) is 20 to 80% by mass, whereby the adhesion strength to the circuit conductor and the solder heat resistance can be made good.

(B) Ingredients:

As the epoxy resin curing agent as the component (B), various phenol resins, acid anhydrides, amines, anthracene, and the like can be used. As the phenol resin, a novolak type phenol resin, a resol type phenol resin, or the like can be used. As the acid anhydride, phthalic anhydride, benzophenonetetracarboxylic dianhydride, methylhimic acid or the like can be used. As the amine, dicyandiamide, diaminodiphenylmethane, guanylurea or the like can be used. In order to improve reliability, a novolac type phenol resin is preferred.

The blending amount of the epoxy resin hardener is preferably from 0.5 to 1.5 equivalents based on the epoxy group. It is 0.5 to 1.5 equivalents with respect to the epoxy group, whereby the adhesion to the outer layer copper can be prevented from being lowered, and the glass transition temperature (Tg) or the insulation property can be prevented from being lowered.

Further, in addition to the curing agent, a reaction accelerator can be used as needed. A potential thermal hardener, that is, various imidazoles or BF ₃ amine complexes can be used as a reaction accelerator. From the viewpoint of storage stability of the resin composition or handleability of the B-stage (semi-hardened) resin composition and solder heat resistance, 2-phenylimidazole or 2-ethyl-4-methyl group is preferred. Imidazole is preferably used in an amount of 0.1 to 5.0% by mass based on the amount of the epoxy resin.

The resin composition preferably contains an inorganic filler (D) having an average primary particle diameter of 100 nm or less (hereinafter, referred to as "(D) component"). By containing the component (D), in addition to increasing the modulus of elasticity, heat resistance and laser processability can be improved.

Hereinafter, the component (D) will be described.

(D) Ingredients:

Examples of the inorganic filler (D) component include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and boron nitride. , aluminum borate, barium titanate, barium titanate, calcium titanate, barium titanate, titanium oxide, barium zirconate and calcium zirconate. Among them, gas phase cerium oxide is preferred.

The specific surface area of the inorganic filler is preferably 20 m ² /g or more from the viewpoint of forming a fine line on the resin composition layer. Moreover, the average primary particle diameter is preferably 100 nm or less from the viewpoint of reducing the surface shape after the roughening treatment in the plating process.

In the present specification, the "average primary particle diameter" means the average particle diameter of the non-aggregated monomer, and the average diameter of the non-aggregated particles, that is, the secondary particle diameter. The primary average particle diameter can be determined by, for example, a laser diffraction type particle size distribution analyzer.

Further, the inorganic filler is preferably subjected to a surface treatment by a surface treatment agent such as a decane coupling agent to improve moisture resistance, and is preferably subjected to a hydrophobization treatment to enhance dispersibility.

The content of the component (D) is preferably from 5 to 75 volumes in the resin composition. % is more preferably 15 to 70% by volume, still more preferably 30 to 70% by volume. When the content of the inorganic filler is 5% by volume or more in the resin composition, the effect of improving the modulus of elasticity is sufficient, and when it is 75% by volume or less, the surface shape after the roughening treatment can be maintained, and the surface shape can be prevented. The plating characteristics and the insulation reliability between the layers are lowered.

As a commercial product of an inorganic filler having an average primary particle diameter of 100 nm or less, AEROSIL R972 (trade name) manufactured by AEROSIL Co., Ltd. (Nippon Aerosil Co., Ltd.) and AEROSIL R202, Fuso Chemical Co. ., Ltd is an.) for manufacturing the PL-1 (trade name, specific surface area of 181m ² / g), and PL-7 (trade name, specific surface area of 36m ² / g) and the like.

The inorganic filler as described above may be used alone or in combination of two or more.

Further, in order to improve the dispersibility, the inorganic filler may be used by a known kneading method or dispersion method such as a kneader, a ball mill, a bead mill, a three-roll mill, or a nanomizer.

The resin composition of the present invention is obtained by blending the above-mentioned component (C) as an essential component, and can be suitably used in the component (A), the component (B), the component (D), and the general resin composition. Various additives such as a thixotropic agent, a surfactant, and a coupling agent. After sufficiently stirring the mixture, it was allowed to stand until no bubbles were formed, thereby obtaining a resin composition.

From the viewpoint of workability, the resin composition of the present invention is preferably mixed in a solvent to be diluted or dispersed to form a varnish. In the solvent, methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone. These solvents may be a single solvent or a mixed solvent.

The ratio of the solvent to the resin composition may be appropriately adjusted in accordance with the apparatus for forming the coating film of the resin composition, and it is preferable that the solid content of the resin composition other than the solvent is 8 to 40% by mass in the varnish. The mode adjusts the amount of solvent used.

The resin composition layer of the present invention is obtained by applying the above-mentioned resin composition (or a varnish containing the same) to a support film or a prepreg, and drying at 100 to 230 ° C for about 1 to 10 minutes. The thickness of the resin composition layer is preferably from 0.5 to 100 μm, more preferably from 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, or a polyimide film is preferably used. A non-roughened copper foil which is not roughened, a low-roughened copper foil having a surface roughness (Ra) of 0.4 μm or less, and an aluminum foil. Further, as the support film, a film whose surface has been subjected to release treatment may be used to make it easy to peel off from the resin.

(glass substrate layer)

From the viewpoint of the thickness reduction of the laminate or the workability, the thin glass film having a thickness of the glass substrate layer of 30 to 200 μm is preferably 50 to 150 μm in consideration of practicality such as ease of handling. Further, from the viewpoint of the reduction in thickness of the laminate, it is preferably 30 to 90 μm. Further, as the material of the glass substrate, glass such as decanoic acid-based glass, alkali-free glass, or quartz glass can be used. However, from the viewpoint of low thermal expansion property, a glass having a high bismuth component ratio is preferable.

The total thickness of the resin composition layer and the glass substrate layer is preferably 50 to 300 μm, more preferably 100 to 250 μm. By having a thickness of 50 to 300 μm, it is possible to reduce the thickness of products such as printed wiring boards.

The thermal expansion coefficient of the glass substrate layer is closer to the thermal expansion coefficient (about 3 ppm/° C.) of the tantalum wafer, and the warpage of the laminated body or the laminated sheet obtained by the laminated body is suppressed, so that it is preferably 8 ppm/ Below °C, more preferably 6 ppm/° C. or less, still more preferably 4 ppm/° C. or less.

The glass substrate layer preferably has a dynamic storage elastic modulus at 40 ° C as much as possible, and is preferably 20 GPa or more, more preferably 25 GPa or more, still more 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. The support film and the protective film will be described in detail in the description of the method for producing a layered product to be described later.

[Manufacturing method of laminated body]

The method for producing a layered product of the present invention can be produced by applying a resin composition onto a glass substrate or laminating a film composed of a resin composition on a glass substrate. From the standpoint of ease of production, among them, the method carried out by lamination is preferred.

Each manufacturing method will be described in detail below.

[Manufacturing method of laminated body by coating]

The production method by coating is a method of producing a laminate by applying the above-described resin composition onto the surface of a glass substrate to form a resin composition layer. For example, preparing the above resin composition in an organic solvent, preparing A varnish dispersed as an inorganic filler of any component. This varnish is applied onto a glass substrate, and the organic solvent is dried by heating or blowing hot air or the like to form a resin composition layer. This resin composition layer may be further semi-hardened. In this way, a laminate in which the resin composition layer is formed can be produced.

[Manufacturing method of laminated body by lamination]

The above-mentioned laminated body can be produced by laminating an adhesive film obtained by using the resin composition of the present invention and a glass substrate by pressure lamination such as vacuum lamination or roll lamination. This adhesive film will be described later. Further, vacuum lamination or roll lamination can be carried out using a commercially available vacuum laminator or roll laminator.

Further, as the polyfunctional epoxy resin (A) in the above resin composition, it is preferred to use a resin which melts at a temperature lower than that at the time of lamination. For example, when laminating using a vacuum laminator or a roll laminator, since it is usually carried out at less than 140 ° C, the polyfunctional epoxy resin (A) in the above resin composition is preferably lower than Melt at 140 ° C.

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

(adhesive film)

Preferably, when a laminate is produced using a vacuum laminator or a pressure laminator, the above resin composition is formed into an adhesive film.

As the adhesive film used in the present invention, a film having the following laminated structure is preferably used.

(1) Support film/resin composition layer

Moreover, it is also preferable to use a laminate structure having the following laminated structure in which the protective film is further laminated in the laminated structure of the above (1).

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

The protective film is formed on one side opposite to the support film with respect to the resin composition layer of the present invention, and is used to prevent foreign matter from adhering or being damaged.

Further, a material obtained by removing the support film and the protective film from the adhesive films may be referred to as an adhesive film body.

The adhesive film having the laminated structure of the above (1) and (2) can be produced according to a method known to those skilled in the art of the present invention.

As an example of the production of 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. Then, the support film is used as a support, and the varnish is applied, and the organic solvent is dried by heating or blowing hot air to form a resin composition layer.

As an example of the adhesive film of the above (2), the above resin composition is dissolved in an organic solvent to prepare a varnish in which any inorganic filler is dispersed. Then, the varnish is applied to any one of the support film and the protective film, and the other of the support film and the protective film is disposed on the varnish, and the varnish is organic by heating or blowing hot air or the like. The solvent is dried, whereby a resin composition layer can be formed.

As a coating device of the resin composition layer, the present invention can be used, such as a comma coater, a bar coater, an applicator coater, a roll coater, a gravure coater, and a die coater. A brushing device known to those skilled in the art is well-known in the technical field, and is preferably selected in accordance with the film thickness to be produced.

Further, in the above adhesive film, the resin composition layer may be semi-cured in advance.

The support film described above is a support for the production of an adhesive film. Moreover, when manufacturing a multilayer printed wiring board, it is generally finally peeled off or removed.

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

When the adhesive film has a protective film, after the protective film is removed, the adhesive film is pressurized and heated, and is crimped onto the glass substrate. As a condition for lamination, it is preferred to preheat the adhesive film and the glass substrate as needed, preferably at a crimping temperature (stacking temperature) of 60 ° C to 140 ° C, and preferably a crimping pressure of 1 to 11 kgf / Cm ² to laminate. Further, when a vacuum laminator is used, it is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type performed by a roll.

As described above, after the adhesive film is laminated on the glass substrate, it is cooled to near room temperature. The support film is peeled off as needed.

[Manufacturing method of laminated board]

Next, a specific example of the method of manufacturing the laminated board will be described.

(Production example by heat hardening of laminate)

In the laminate obtained by the above-described lamination, the resin film layer may be subjected to a hardening treatment after peeling off the support film as necessary to obtain a resin cured layer, thereby producing a laminate.

The heat curing condition is selected from the range of 150 ° C to 220 ° C for 20 minutes to 80 minutes, more preferably 160 ° C to 200 ° C, and 30 minutes to 120 minutes. When the support film to which the mold release treatment has been applied is used, the support film may be peeled off after heat curing.

According to this method, since the pressurization is not required when the laminated board is manufactured, cracking at the time of manufacture is suppressed.

The thickness of the cured resin layer is preferably 5 to 200 μm. When it is 5 μm or more, cracking of the laminated board can be suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate is relatively increased, so that the thermal expansion coefficient of the laminated plate can be lowered and the elastic modulus of the laminated plate can be improved. From this point of view, the thickness of the resin cured layer is more preferably from 10 to 150 μm, still more preferably from 10 to 100 μm.

However, since the appropriate range of the thickness of the cured resin layer differs depending on the thickness of the glass substrate layer, the number of layers, and the number of layers of the cured resin layer, it is not limited to the above range.

The laminated plate has a storage elastic modulus at 40 ° C, preferably 1 to 80 GPa. If it is 1 GPa or more, the glass substrate can be protected, and the crack of the laminated board can be suppressed. When the thickness is 80 GPa or less, the stress caused by the difference in thermal expansion coefficient between the glass substrate and the cured resin layer is suppressed, and warpage and cracking of the laminated sheet are suppressed. From this point of view, the storage elastic modulus of the resin cured layer is more preferably from 3 to 70 GPa, still more preferably from 5 to 60 GPa.

It may also have a metal foil such as copper or aluminum on one or both sides of the laminate. If the metal foil is used as an electrical insulating material, it is not particularly limited.

(manufacturing example implemented by the pressing method)

Moreover, the laminated board of this invention can be manufactured by the press method.

For example, the laminated body obtained by laminating the above-described laminate can be cured by heating and pressing by a pressing method before the hardening treatment, thereby producing a laminated sheet.

Further, the adhesive film main body formed by removing the support film or the protective film from the above-mentioned adhesive film and/or the adhesive film can be laminated on the glass substrate, and heated and pressed by a pressing method to be hardened. Manufacturing laminates.

Further, the resin composition can be applied to the glass substrate and dried to form a B-stage state, and the laminate can be produced by heating and pressing by a pressing method.

[Multilayer laminate and its manufacturing method]

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

The method for producing the multilayered laminate is not particularly limited.

For example, the adhesive film body formed by removing the support film or the protective film from the above-mentioned adhesive film may be formed by laminating a plurality of the above-mentioned laminated plates.

Further, it is also possible to manufacture a multilayer laminated board by laminating a plurality of laminated sheets (for example, 2 to 20 sheets) and laminating them. Specifically, it can be formed in a range 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, using a multi-stage pressing, a multi-stage vacuum pressing, a continuous molding machine, an autoclave molding machine, or the like.

[Printed circuit board and its manufacturing method]

The printed wiring board of the present invention is formed by providing a wiring on at least one surface of the laminated board of the present invention. Further, there is a case where a plurality of laminated boards (multilayer printed wiring boards) are included. In this case, at least one laminated board is the laminated board of the present invention.

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

(forming through holes, etc.)

The above-mentioned laminated plate may be opened to form a through hole or a through hole by a method such as a drill, a laser, a plasma, or the like. As a laser, Carbon dioxide lasers or YAG (yttrium aluminum garnet) lasers, UV lasers, and excimer lasers are commonly used. It is also possible to perform desmear treatment using an oxidizing agent after forming a through hole or the like. As the oxidizing agent, permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, and nitric acid are preferred, and potassium permanganate or permanganic acid is more preferred. Aqueous sodium hydroxide solution (alkaline permanganic acid aqueous solution) such as sodium.

(forms a line pattern)

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

When the circuit processing is performed by the plating method on the resin cured layer of the laminated board or the multilayer wiring board of the present invention, the roughening treatment is first performed. As the roughening liquid at this time, 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 fluoroboric acid roughening liquid can be used. As the roughening treatment, for example, first, an aqueous solution of diethylene glycol monobutyl ether and NaOH as a swelling liquid is heated to 70 ° C, and the laminate or the multilayer wiring board is immersed for 5 minutes. Next, an aqueous solution of KMnO ₄ and NaOH as a roughening liquid was heated to 80 ° C, and immersed for 10 minutes. Next, it is immersed in an aqueous hydrochloric acid solution such as tin chloride (SnCl ₂ ) as a neutralizing solution at room temperature for 5 minutes to carry out neutralization.

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. A fine line can be formed by being 0.4 μm or less.

After the roughening treatment, a plating catalyst application treatment for adhering palladium is performed. Plating catalyst treatment, impregnated with palladium chloride-based plating catalyst solution In progress. Next, the following electroless plating treatment is performed: 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 underlayer for the plating process. .

Next, after the plating resist is formed, a plating treatment is performed to form a circuit of a desired thickness at a desired position. The electroless plating solution used in the electroless plating treatment can be a known electroless plating solution, and is not particularly limited. A known anti-plating agent can also be used as the plating resist, and is not particularly limited. Further, the plating treatment can also be carried out by a known method, and is not particularly limited. These platings are preferably copper plated. Further, an electroless plating layer at an unnecessary position can be etched away to form an outer layer circuit.

[Multilayer printed wiring board and method of manufacturing the same]

As one aspect of the above-described printed wiring board, as described above, a plurality of laminated boards in which a line pattern is formed may be laminated as a multilayer printed wiring board.

In the production of the multilayer printed wiring board, a plurality of laminated layers in which the above-described wiring patterns are formed are laminated via the above-mentioned adhesive film main body, thereby multilayering. Thereafter, formation of through holes or blind via holes by drilling or laser processing, and formation of interlayer lines by plating or conductive paste are performed. In this way, a multilayer printed wiring board can be manufactured.

[Laminated sheet and multi-layer laminate with metal foil, and manufacturing method of the same]

The laminated board of the present invention and the multi-layer laminated board obtained by using the laminated board may be a metal foil-clad laminated board and a multi-layer laminated board which have a metal foil such as copper or aluminum on one or both sides.

There is no particular limitation on the method of manufacturing the metal foil-clad laminate. For example, as described above, a metal foil can be used as the support film, whereby a metal foil-clad laminate can be produced. Further, it is also possible to laminate one or a plurality of sheets (for example, 2 to 20 sheets) by laminating or brushing the above-mentioned laminated body, and to form a metal foil on one or both sides thereof, thereby forming a laminate. A laminate with metal foil is produced.

The forming conditions can be applied to a laminate or a multilayer board for an electrical insulating material. For example, multi-stage pressing, multi-stage vacuum pressing, continuous forming machine, and autoclave forming machine can be used at a temperature of about 100 to 250 ° C and a pressure of 2 to 100 MPa. It is formed in the range of about 0.1 to 5 hours from the left and right and the heating time.

(Example)

Next, the present invention will be specifically described by way of examples, but the scope of the invention is not limited to the examples.

(Example 1) (Preparation of resin varnish A)

Formulated with 91.4 g of N,N-dimethyl group in 10.2 g of the component (C), which is a polybutadiene-modified polydecylamine (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155) containing a phenolic hydroxyl group. After acetaminophen (DMAc), 40.0 g of the component (A), which is a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000H), and 12.6 g of the component (B) are added. Bisphenol A novolak resin (manufactured by Mitsubishi Chemical Corporation, trade name: YLH129), 0.4 g of 2-phenylimidazole (a product manufactured by Shikoku Chemicals Corporation) as a hardening accelerator Name: 2PZ) and 3.6g of (D) component, gas phase cerium oxide (manufactured by Nippon Aerosil Co., Ltd., trade name: R972), and then by DMAc and methyl ethyl ketone The mixed solvent is diluted to form a solid The concentration is about 25% by mass). After that, a resin varnish A was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).

(manufacturing adhesive film)

A bar coater was used on a release-treated surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Corporation, trade name) having a thickness of 38 μm. The resin varnish A was applied so as to be 12 μm after drying, and dried at 140 ° C for 10 minutes to form a resin composition layer.

(Production of laminate (resin cured layer / glass substrate layer / resin cured layer))

A very thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used as a glass substrate. On both sides of the glass substrate, the adhesive film formed by arranging the resin composition layer against the glass substrate, and using a batch type vacuum pressure laminating machine "MVLP-500" (Ming Machine Co., Ltd. Meiki Co., Ltd.), manufactured by trade name, laminated by lamination. The degree of vacuum at this time was set to 30 mmHg (40.0 hPa) or less, the temperature was 90 ° C, and the pressure was 0.5 MPa.

After cooling to room temperature, the support film was peeled off and cured in dry air set at 180 ° C for 60 minutes to obtain a laminate having a three-layer structure (resin cured layer/glass substrate layer/resin cured layer).

(Example 2) (Preparation of resin varnish B)

In the same manner as the resin varnish A, except for the preparation of the following Table 1. Operation, obtaining resin varnish B.

(manufacturing adhesive film)

The resin varnish B was produced in the same manner as in Example 1 except that the resin varnish B was used.

(Production of laminate (resin cured layer / glass substrate layer / resin cured layer))

A laminate of a three-layer structure (resin cured layer/glass substrate layer/resin cured layer) was obtained in the same manner as in Example 1 except that the above-mentioned adhesive film was used instead of the adhesive film of Example 1.

(Example 3) (Preparation of resin varnish C)

A resin varnish C was obtained in the same manner as in the resin varnish A except for the preparation of the following Table 1.

(manufacturing adhesive film)

The resin varnish C was used in the same manner as in Example 1 except that the resin varnish C was used.

(Production of laminate (resin cured layer / glass substrate layer / resin cured layer))

A laminate of a three-layer structure (resin cured layer/glass substrate layer/resin cured layer) was obtained in the same manner as in Example 1 except that the above-mentioned adhesive film was used instead of the adhesive film of Example 1.

(Example 4) (Preparation of resin varnish D)

A resin varnish D was obtained in the same manner as in the resin varnish A except for the preparation of the following Table 1.

(manufacturing adhesive film)

The resin varnish D was used in the same manner as in Example 1 except that the resin varnish D was used.

(Manufacturing laminate (resin hardened layer / glass substrate layer / resin hardened) Physical layer))

A laminate of a three-layer structure (resin cured layer/glass substrate layer/resin cured layer) was obtained in the same manner as in Example 1 except that the above-mentioned adhesive film was used instead of the adhesive film of Example 1.

(Example 5) (Preparation of resin varnish E)

A resin varnish E was obtained in the same manner as in the resin varnish A except for the preparation of the following Table 1.

(manufacturing adhesive film)

The resin varnish E was used in the same manner as in Example 1 except that the resin varnish E was used.

(Production of laminate (resin cured layer / glass substrate layer / resin cured layer))

A laminate of a three-layer structure (resin cured layer/glass substrate layer/resin cured layer) was obtained in the same manner as in Example 1 except that the above-mentioned adhesive film was used instead of the adhesive film of Example 1.

Units are mass parts as long as they are not specifically stated

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

[manufacturing circuit board]

In order to form a circuit layer on a wiring board having a resin cured layer and a glass substrate layer, first, HS-202B (manufactured by Hitachi Chemical Co., Ltd.) as a catalyst for electroless plating containing PdCl ₂ is used at room temperature. The immersion treatment was carried out for 10 minutes and washed with water, and further immersed in a plating solution CUST-201 (manufactured by Hitachi Chemical Co., Ltd.) for electroless copper plating at room temperature for 15 minutes to further perform copper sulfate 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 the position where the plating conductor is not required to be removed by etching, the oxide film on the copper surface is first removed by a #600 polishing roll, and then a resist is formed, followed by etching, and then the resist is removed to form a circuit. A circuit board of a hardened layer and a glass substrate layer.

[Adhesion strength to outer circuit]

A part of the circuit layer of the wiring board obtained in each example was formed by etching of copper, and a portion having a width of 10 mm and a length of 100 mm was formed, and one end of the circuit layer/resin interface was peeled off, and clamped by a jig. The load at the time of peeling at room temperature at a tensile speed of about 50 mm/min toward the vertical direction.

[Surface roughness of resin cured layer]

The surface of the cured resin layer exposed by removing copper of a part of the circuit layer of the wiring board obtained in each example by an etching treatment was measured using a Micromap MN5000 model manufactured by Ryoka Systems Inc. Roughness Ra.

[288°C solder heat resistance]

The multilayer wiring board produced in each example was cut into 25 mm squares and floated in a solder bath adjusted to 288 ± 2 ° C, and the time until expansion occurred was investigated.

[Storage Elastic Modulus]

A test piece of 5 mm × 30 mm was cut out from the laminate.

Using a wide-area viscoelasticity measuring device (manufactured by Rheology Co., Ltd., DVE-V4 type), the measurement was carried out at 40 ° C with a span of 20 mm, a frequency of 10 Hz, and a vibration displacement of 1 to 3 μm (stopping vibration). Stretch storage elastic modulus. The results are shown in Table 2.

As is apparent from Table 2, Examples 1 to 5 of the present invention exhibited high adhesion to electroless copper plating on the surface of a smooth resin. Further, in implementation In Examples 1 to 3, since the solder heat resistance at 288 ° C was also excellent, it was found that a circuit board in consideration of the environment can be manufactured. Further, from Examples 1, 2, 4 and 5, by adding an inorganic filler, a highly elastic laminated sheet which cannot be obtained in Patent Document 7 can be obtained.

As is apparent from the above results, according to the present invention, it is possible to provide a laminated board having high elasticity which is highly adhesive to electroless copper plating.

Claims (24)

A laminated body comprising one or more resin composition layers and one or more glass substrate layers, and the resin composition layer contains a polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group. The laminate according to claim 1, wherein the resin composition layer comprises a polyfunctional epoxy resin (A) and an epoxy resin hardener (B). The laminate according to claim 2, wherein the phenolic hydroxyl group-containing polybutadiene is modified with respect to 100 parts by mass of the total of the polyfunctional epoxy resin (A) and the epoxy resin hardener (B). The blending ratio of the polyamide resin (C) is 4 to 40 parts by mass. The laminate according to any one of claims 1 to 3, wherein the resin composition layer and the glass substrate layer have a total thickness of 50 to 300 μm. The laminate according to any one of claims 1 to 4, wherein the glass substrate layer has a thickness of 30 to 200 μm. The laminate according to any one of claims 2 to 5, wherein the polyfunctional epoxy resin (A) contained in the resin composition layer has a biphenyl structure. The laminate according to claim 6, wherein the polyfunctional epoxy resin (A) contained in the resin composition layer is an aralkyl ring having a biphenyl structure. Oxygen resin. The laminate according to any one of claims 1 to 7, wherein the inorganic filler contains an inorganic filler (D) having an average primary particle diameter of 100 nm or less. The laminate according to claim 8, wherein the inorganic filler (D) is gas phase cerium oxide. The laminate according to claim 8 or 9, wherein the inorganic filler (D) is subjected to a surface treatment. The laminate according to any one of claims 1 to 10, wherein the polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group has the following formula (i), (ii) and (iii) the structural unit represented: [wherein, a, b, c, x, y, and z are the average degrees of polymerization, respectively, and represent a = 2 to 10, b = 1 to 8, c = 3 to 20, and y + z with respect to x = 1 An integer from 2 to 300, and z ≧ 20 with respect to y = 1, and x = 1 to 100, y = 1 to 200; R, R' and R" are independently derived from aromatic diamine or aliphatic The divalent group of the diamine, and the plurality of R''' are each independently a divalent group derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having a carboxyl group at both terminals. A laminated board comprising one or more layers of a resin cured layer and one or more layers of a glass substrate, and is obtained by subjecting the layered body according to any one of claims 1 to 11 to a hardening treatment. The laminate according to claim 12, wherein the storage elastic modulus at 40 ° C is 1 GPa to 70 GPa. The laminate according to claim 12, wherein the surface roughness (Ra) of the cured resin layer after the roughening treatment is 0.4 μm or less. A printed wiring board formed by providing a wiring on at least one surface of a laminated board according to any one of claims 12 to 14. The printed wiring board according to claim 15, wherein the plurality of laminated boards are included, and at least one of the foregoing laminated boards is the laminated board according to any one of claims 12 to 14. A method for producing a laminate, which comprises applying a resin composition on a surface of a glass substrate to form a resin composition layer comprising: a polybutadiene-modified polyamine resin containing a phenolic hydroxyl group (C) ). The method for producing a laminate according to claim 17, wherein the resin composition comprises a polyfunctional epoxy resin (A) and an epoxy resin curing agent (B). The method for producing a laminate according to claim 17 or 18, wherein the polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group has the following formulas (i), (ii) and Iii) the structural unit represented: [wherein, a, b, c, x, y, and z are the average degrees of polymerization, respectively, and represent a = 2 to 10, b = 1 to 8, c = 3 to 20, and y + z with respect to x = 1 An integer from 2 to 300, and z ≧ 20 with respect to y = 1, and x = 1 to 100, y = 1 to 200; R, R' and R" are independently derived from aromatic diamine or aliphatic The divalent group of the diamine, and the plurality of R''' are each independently a divalent group derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having a carboxyl group at both terminals. The method for producing a layered product according to any one of claims 17 to 19, wherein after the resin composition layer is formed, a drying treatment is applied. A method for producing a laminated board, comprising: forming a film composed of a resin composition, and laminating the film on a glass substrate using a vacuum laminator or a roll laminator, and then applying a curing treatment to the film, the resin composition comprising: A polybutadiene modified polyamine resin (C) containing a phenolic hydroxyl group. The method for producing a laminate according to claim 21, wherein the resin composition comprises a polyfunctional epoxy resin (A) and an epoxy resin curing agent (B). The method for producing a laminate according to claim 21 or 22, wherein the polybutadiene-modified polyamine resin (C) containing a phenolic hydroxyl group has the following formulas (i), (ii) and Iii) the structural unit represented: [wherein, a, b, c, x, y, and z are the average degrees of polymerization, respectively, and represent a = 2 to 10, b = 1 to 8, c = 3 to 20, and y + z with respect to x = 1 An integer from 2 to 300, and z ≧ 20 with respect to y = 1, and x = 1 to 100, y = 1 to 200; R, R' and R" are independently derived from aromatic diamine or aliphatic The divalent group of the diamine, and the plurality of R''' are each independently a divalent group derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an oligomer having a carboxyl group at both terminals. The method for producing a laminated board according to any one of claims 21 to 23, wherein after the film is laminated and before the hardening treatment, a pressing treatment is applied.