TWI836345B - Thermosetting epoxy resin composition, adhesive film for insulating layer formation, prepreg for insulating layer formation, insulator for printed wiring board, multilayer printed wiring board and semiconductor device - Google Patents

Abstract

The present invention provides a thermosetting epoxy resin composition, which is characterized by a thermosetting epoxy resin containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, a thermoplastic resin and an inorganic filler. A composition, wherein when the non-volatile component in the resin composition is 100% by mass, the content of the naphthalene-containing active ester compound (B) is 0.1 to 30% by mass, and the average particle size of the inorganic filler is 0.01 Above μm and below 5μm.

Description

Thermosetting epoxy resin composition, adhesive film for forming an insulating layer, prepreg for forming an insulating layer, insulator for a printed wiring board, multilayer printed wiring board and semiconductor device

The present invention relates to a thermosetting epoxy resin composition having a low dielectric tangent and low roughness, which is suitable for forming an insulating layer having a roughened surface that can improve peel strength, and a cured product thereof, and a multilayer printed wiring board containing a cured product layer having a roughened surface that has a low roughness and can improve peel strength as an insulating layer.

As electronic devices become smaller and more powerful, the conductor formation methods that can correspond to the multi-layer and high-density increase in the multi-layer printed wiring boards used therein include an additive method in which the surface of the insulating layer is roughened and then the conductive layer is formed by electroless plating, and a semi-additive method in which the conductive layer is formed by electroless plating or electrolytic plating. In these methods, the adhesion between the surface of the insulating layer and the plated conductive layer is mainly ensured by roughening the surface of the insulating layer to form a fine concave-convex surface that exerts a fixing effect.

The fixing effect of the concave and convex formed on the surface of the insulating layer is greater as the surface roughness increases. The greater the roughness, the better the adhesion between the insulating layer and the plated conductive layer. However, when the surface roughness of the insulating layer is large, when the thin film conductive layer formed on the roughened surface is partially removed by etching to form a specific wiring pattern, the conductive layer portion that enters the concave portion of the insulating layer surface to be removed is difficult to remove, so the etching process requires a longer time. At the same time, due to its influence, the wiring pattern portion that should be retained is etched and the fine wiring is damaged, resulting in a higher risk of disconnection. Therefore, in order to cope with the miniaturization and high density of wiring, the surface state of the insulating layer is required to be a roughened surface with as fine an irregularity as possible and sufficient adhesion to the thin film conductor layer formed by plating.

In addition, the insulating layer is also required to have a low linear thermal expansion coefficient so as not to generate a difference in linear thermal expansion coefficient with the conductor layer formed by the wiring pattern formed on the surface of the insulating layer. When the linear thermal expansion coefficient of the insulating layer is high, the difference in linear thermal expansion coefficient with the conductor layer becomes larger, and problems such as cracking between the insulating layer and the conductor layer are likely to occur.

In the past, "active ester compounds" have been known as curing agents for thermosetting resin compositions used to form the insulating layer of the inner circuit board of the multilayer printed wiring board. As this "active ester compound", mainly Use "active ester compound containing dicyclopentadienyl diphenol structure". However, in recent years, the build-up of layers of multilayer printed wiring boards has significantly progressed toward higher layering and higher density, and there are many proposals for epoxy resin compositions that can form insulating layers that can cope with this situation.

Patent document 1 states that by using an active ester compound obtained by esterifying phenolic hydroxy aromatics in a novolac resin as a hardener for a thermosetting epoxy resin composition, a hardened material having an insulating layer exhibiting low dielectric properties can be obtained.

Patent Document 2 describes an epoxy resin composition containing (A) epoxy resin, (B) active ester compound, (C) phenol resin having a triazine structure, (D) maleimide compound, and (E) phenoxy resin as an epoxy resin composition that can form an insulating layer having a relatively small linear thermal expansion coefficient despite the relatively small roughness of the roughened surface of the hardened surface after roughening treatment.

Furthermore, Patent Document 3 describes an epoxy resin composition containing an active ester resin having a polyaryloxy structure as a main skeleton and an aromatic carbonyl group on the aromatic nucleus of the structure as a thermosetting epoxy resin composition that can provide a cured product having low dielectric constant and low dielectric tangent and excellent heat resistance and flame retardancy.

As mentioned above, there have been many proposals for epoxy resin compositions suitable for forming the insulating layer of the inner circuit board. However, it is possible to form a finely roughened surface with low dielectric tangent and excellent adhesion to the conductor layer. There is an increasing demand to form an epoxy resin composition having well-balanced insulating layer characteristics that can cope with the increase in layering and density of multilayer printed wiring boards.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 07-082348

[Patent Document 2] Patent Publication No. 2010-090238

[Patent Document 3] Japanese Patent Application Publication No. 2012-012534

The purpose of the present invention is to provide a thermosetting epoxy resin composition that exhibits low dielectric tangent and can form a roughened surface with fine irregularities that has excellent adhesion and etching properties to a conductive layer and can form an insulating layer that has well-balanced properties corresponding to the increased number of layers and high density in the build-up of a multi-layer printed wiring board, a printed wiring board having an insulating layer formed by the cured product thereof, and a multi-layer printed wiring board composed of the printed wiring board.

Furthermore, an object of the present invention is to provide an adhesive film for forming an insulating layer in which a resin composition layer composed of the above-mentioned thermosetting epoxy resin composition is formed on a supporting film and impregnated with the above-mentioned thermosetting epoxy resin composition. A prepreg for forming an insulating layer formed in a sheet-like reinforcing base material.

As a result of actively examining the hardeners or formulated resins used in thermosetting epoxy resin compositions, the inventors of the present invention have discovered that among various resins known as resin components formulated in epoxy resin compositions, when a "naphthalene-containing active ester compound" is formulated in a specific amount in the resin composition, it will become a means to solve the above-mentioned problem, and thus the following invention has been completed.

[1] A thermosetting epoxy resin composition comprising at least an epoxy resin (A) and an active ester compound (B) containing a naphthalene structure, wherein

When the non-volatile components in the aforementioned thermosetting epoxy resin composition are 100% by mass, the content of the aforementioned naphthalene-containing active ester compound (B) is 0.1 to 30% by mass.

[2] The thermosetting epoxy resin composition as described in [1], wherein the aforementioned active ester compound containing a naphthalene structure (B) is an active ester compound having a polyoxynaphthalene structure and an aromatic carbonyloxy group.

[3] The thermosetting epoxy resin composition according to [1] or [2], wherein the active ester compound (B) containing a naphthalene structure has an aryl group bonded to the naphthalene core of the polyoxynaphthalene structure. Active ester compound of carbonyloxy group.

[4] A thermosetting epoxy resin composition as described in any one of [1] to [3], wherein the epoxy resin (A) contains a liquid epoxy resin.

[5] The thermosetting epoxy resin composition according to any one of [1] to [4], further containing an inorganic filler.

[6] A thermosetting epoxy resin composition as described in any one of [1] to [5], which further contains a thermoplastic resin.

[7] A thermosetting epoxy resin composition as described in any one of [1] to [6], which is a resin composition for an insulating layer of a multi-layer printed wiring board in which a conductive layer is formed by coating.

[8] An adhesive film for forming an insulating layer, in which a resin composition composed of the thermosetting epoxy resin composition as described in any one of [1] to [7] is provided on a supporting film. Made up of layers.

[9] A prepreg for forming an insulating layer, which is obtained by impregnating a thermosetting epoxy resin composition as described in any one of [1] to [7] into a sheet-like fiber substrate.

[10] An insulator for a printed wiring board, which is formed by hardening either a resin composition layer with a film for forming an insulating layer as described in [8] or a prepreg for forming an insulating layer as described in [9].

[11] An insulator for a printed wiring board, which is formed by providing a patterned conductive layer on an insulating layer formed by the insulator for a printed wiring board as described in [10].

[12] The insulator for printed wiring boards according to [10] or [11], wherein the surface roughness Ra of the insulating layer is 10 to 200 nm, Rq is 15 to 250 nm, and the peeling strength of the insulating layer and the conductor layer is It is above 0.35kgf/cm.

[13] A multilayer printed wiring board in which a plurality of printed wiring boards according to [11] or [12] are laminated with insulators.

[14] A semiconductor device including the multilayer printed wiring board according to [13].

The thermosetting epoxy resin composition has a low dielectric tangent, can form a roughened surface with excellent adhesion to the conductor layer, and can be formed into a well-balanced structure that can be used as a multi-layer printed wiring board with built-up layers. The thermosetting epoxy resin composition of the hardened material layer of the insulating layer with more layered and high-density characteristics.

Furthermore, when the cured product obtained by curing the above-mentioned thermosetting epoxy resin composition is subjected to surface roughening treatment to form fine irregularities with a surface roughness Ra of 10 to 200 nm and Rq of 15 to 250 nm, it also becomes a roughened surface with excellent adhesion to the conductor layer, so it is particularly useful as an insulating layer forming material in a multi-layer printed wiring board.

The following is a further detailed description of the thermosetting epoxy resin composition, the adhesive film for forming an insulating layer, the prepreg for forming an insulating layer, the insulator for a printed wiring board, and the multi-layer printed wiring board of the present invention.

The thermosetting epoxy resin composition of the present invention contains an epoxy resin (A) and an active ester compound (B) containing a naphthalene structure as essential components. In addition, it may optionally contain an inorganic filler, a thermoplastic resin, and an epoxy resin compound. Hardeners, hardening accelerators, and additives used in resin compositions that form insulating layers in multilayer printed wiring boards.

〈Epoxy resin(A)〉

The epoxy resin (A) used in the thermosetting epoxy resin composition of the present invention is an epoxy resin commonly used in resin compositions for forming insulating layers in multi-layer printed wiring boards, and can be appropriately selected and used from the following examples.

That is, the epoxy resin (A) includes, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and phenolic novolak type epoxy resin. Resin, tertiary butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin Grease, cresol novolak type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, miscellaneous Cyclic epoxy resin, epoxy resin containing spiro rings, cyclohexanedimethanol-type epoxy resin, trimethylol-type epoxy resin, halogenated epoxy resin, etc.

Two or more types of epoxy resins (A) may be used in combination. When the non-volatile component of the epoxy resin (A) is taken as 100% by mass, the epoxy resin (A) is preferably in a form containing at least 50% by mass or more of an epoxy resin having two or more epoxy groups per molecule. Furthermore, a preferred form of the epoxy resin (A) is an aromatic epoxy resin (liquid epoxy resin) which contains two or more epoxy groups per molecule and is liquid at a temperature of 20°C. , a more preferable aspect is to contain the liquid epoxy resin and an aromatic epoxy resin (solid epoxy resin) that has three or more epoxy groups in one molecule and is solid at a temperature of 20°C.

In addition, in the present invention, the so-called aromatic epoxy resin means an epoxy resin having an aromatic cyclic skeleton in its molecule. And the so-called epoxy equivalent (g/eq) means the molecular weight per 1 epoxy group. By using a liquid epoxy resin and a solid epoxy resin as the epoxy resin, when the epoxy resin composition is used in the form of a film, a film showing sufficient flexibility and excellent workability can be formed, and the fracture strength of the cured product of the epoxy resin composition is improved, and the durability of the multi-layer printed wiring board is improved.

In addition, when a liquid epoxy resin and a solid epoxy resin are used together as the epoxy resin, the mixing ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1~ in terms of mass ratio. 1:2 range. By using liquid epoxy resin within this range, sufficient flexibility can be obtained when used in the form of a bonded film, workability can be improved, and sufficient fluidity can be obtained during lamination. Furthermore, by using a solid epoxy resin within this range, the adhesiveness of the epoxy resin composition is reduced, and when used in the form of an adherent film, the degassing properties during vacuum lamination can be improved. Moreover, the peelability of the protective film or support film during vacuum lamination is good, and the heat resistance after hardening can also be improved.

In the epoxy resin composition of the present invention, when the non-volatile components of the epoxy resin composition are taken as 100% by mass, the content of the epoxy resin (A) is preferably 10-50% by mass, more preferably 20-40% by mass, and even more preferably 20-35% by mass. By making the content of the epoxy resin (A) within this range, there is a tendency to improve the curability of the epoxy resin composition.

〈Active ester compound (B) containing naphthalene structure〉

The "naphthalene-containing active ester compound (B)" (naphthalene-type active ester compound) in the thermosetting epoxy resin composition of the present invention functions as a hardener for the epoxy resin, and is considered to be effective in roughening the resin. When hardening the surface of the object, it also helps to form fine unevenness with good adhesion to the conductor layer.

The active ester compound (B) containing a naphthalene structure is not particularly limited if it has a naphthalene structure and an aryl carbonyloxy group, but is preferably an active ester compound having a polyoxynaphthalene structure and an aryl carbonyloxy group, and more preferably an active ester compound having an aryl carbonyloxy group bonded to the naphthalene nucleus of the polyoxynaphthalene structure. The polyoxynaphthalene structure may also be a polyoxynaphthalene structure substituted by an alkyl group having 1 to 4 carbon atoms. The active ester compound as described above can be prepared by condensing a naphthalene structure compound having a core-substituted hydroxyl group with a carboxylic acid compound having a carboxyl group on a naphthalene nucleus or a benzene nucleus. The active ester compound is, for example, a compound included in the "active ester compound having a polyoxyaryloxy structure as the main skeleton and esterified with an aryl carboxylic acid" described in Patent Document 3.

Specific examples of the active ester compound (B) containing a naphthalene structure include compounds represented by the following general formula (1).

[式(1)中，R₁各獨立為氫原子或碳數1~4之烷基，較好為氫原子，R₂各獨立為氫原子或以下述通式(2)表示之1價基，X各獨立為氫原子、苯甲醯基或萘羰基，較好為苯甲醯基，n及m各獨立為0~5之整數，n或m之任一者為1以上之整數]。

[In formula (1), R ₁ is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, and R ₂ is each independently a hydrogen atom or a univalent group represented by the following general formula (2) , each of

[式(2)中，R₁係與上述相同，X係與上述相同，p為1或2之整數，又，上述通式(1)及通式(2)中之X中之至少一者為苯甲醯基或萘羰基]。

[In formula (2), R ₁ is the same as above, X is the same as above, p is an integer of 1 or 2, and at least one of X in the above general formula (1) and general formula (2) It is benzyl or naphthylcarbonyl].

In the thermosetting epoxy resin composition of the present invention, when the non-volatile components of the thermosetting epoxy resin composition are taken as 100% by mass, the content of the naphthalene structure-containing active ester compound (B) is 0.1 to 30% by mass. %. According to this, a roughened surface showing low dielectric tangent and having fine unevenness with excellent adhesion to the conductor layer and etching property can be formed. The content of the naphthalene structure-containing active ester compound (B) is preferably in the range of 3 to 30 mass %, and more preferably in the range of 5 to 28 mass %.

〈Inorganic filler〉

By further containing an inorganic filler in the thermosetting epoxy resin composition of the present invention, the linear thermal expansion coefficient or the dielectric tangent can be reduced. Examples of inorganic fillers include silica, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and barium titanate. , strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. Among them, amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica and other silicas are preferred, which further reduces the Regarding the surface roughness of the insulating layer, fused silica, spherical silica, and spherical fused silica are more preferred. These can be used 1 type or in combination of 2 or more types. An example of commercially available spherical fused silica is manufactured by ADMATECH Co., Ltd. "SOC2", "SOC1", etc.

The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of making the surface of the insulating layer low in roughness and enabling formation of fine wiring, it is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 2 μm. below, more preferably 1 μm or below, still more preferably 0.8 μm or below, more preferably 0.6 μm or below, still more preferably 0.4 μm or below. On the other hand, when the resin composition is used as a resin paint, from the viewpoint of preventing the paint from increasing in viscosity and reducing workability, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, and still more preferably 0.05 μm. Above, preferably 0.07 μm or more, further preferably 0.1 μm or more. The average particle size of the above-mentioned inorganic filler material can be determined by laser diffraction based on Mie scattering theory. Determination by scattering method. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction and scattering particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As a measurement sample, it is preferable to use one in which an inorganic filler is dispersed in water using ultrasonic waves. As a laser diffraction scattering particle size distribution measuring device, LA-950 manufactured by Horiba Manufacturing Co., Ltd. can be used. The inorganic filler is preferably an aminosilane coupling agent, a ureidoalkyl coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, a vinylsilane coupling agent, or styrene. Surface treatment agents such as silane-based coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, thioether silane coupling agents, organosilazane compounds, titanate coupling agents, etc. can be used to improve their resistance. Wet and dispersive. These can be used 1 type or in combination of 2 or more types.

When preparing inorganic fillers, their content varies with the properties required of the thermosetting epoxy resin composition, but the content of inorganic fillers is preferably 30-90% by mass, more preferably 40-80% by mass, and even more preferably 50-70% by mass, based on the non-volatile components in the thermosetting epoxy resin composition as 100% by mass. If the content of inorganic fillers is too low, the linear thermal expansion rate of the cured product tends to increase. If the content is too high, it will be difficult to form a film when preparing the adhesive film, making the cured product brittle.

〈Thermoplastic resin〉

The thermosetting epoxy resin composition of the present invention can improve the mechanical strength of the cured product by further containing a thermoplastic resin, and can also improve the film forming ability when used in the form of a film. Thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamide imide resins, polyether imide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins, preferably phenoxy resins and polyvinyl acetal resins. These thermoplastic resins can be used alone or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 200000, and more preferably in the range of 12000 to 100000. The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) (polystyrene conversion). Specifically, the weight average molecular weight measured by GPC can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation (Co., Ltd.) as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko (Co., Ltd.) as a column, chloroform as a mobile phase, etc., at a column temperature of 40°C, and calculated using a calibration line of standard polystyrene.

When preparing thermoplastic resin, the mixing amount is preferably 0.1~10 mass%, and more preferably 0.5~5 mass%, based on the non-volatile components in the thermosetting epoxy resin composition as 100 mass%. Within this range, the film forming ability or mechanical strength can be improved, thereby reducing the increase in melt viscosity or the roughness of the insulating layer surface after the wet roughening step.

〈Hardening agent for epoxy resin〉

The thermosetting epoxy resin composition of the present invention may further use a general hardener for epoxy resins. Examples of hardeners for epoxy resins that can be used are TD2090, TD2131 [DIC Co., Ltd., trade name], MEH-7600, MEH-7851, MEH-8000H [Meiwa Kasei Co., Ltd., trade name], NHN, CBN, GPH-65, GPH-103 [Nippon Chemical Co., Ltd., trade name], SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 [Nippon Steel Chemical Co., Ltd., trade name], LA7052 , LA7054, LA3018, LA1356 [DIC Co., Ltd., trade name] and other phenolic hardeners, F-a, P-d [Shikoku Kasei Co., Ltd., trade name], HFB2006M [Showa Polymer Co., Ltd., trade name], etc. Benzoxazine-based hardeners, methylhexahydrophthalic anhydride, methylnadic anhydride (methylnadic anhydride), hydrogenated methylnadic anhydride and other anhydride-based hardeners, PT30, PT60, BA230S75 [Japanese LONZA Co., Ltd. ), trade name] and other cyanate ester hardeners.

〈Hardening accelerator〉

The thermosetting epoxy resin composition of the present invention further contains hard Chemical accelerator can effectively adjust the hardening time and hardening temperature. Examples of curing accelerators include organic phosphine compounds such as TPP, TPP-K, TPP-S, TPTP-S [Hokuko Chemical Industry Co., Ltd., trade name], Curezol 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, Imidazole compounds such as C11Z-A, 2MZ-OK, 2MA-OK, 2PHZ [Shikoku Chemical Industry Co., Ltd., trade name], Novacure [Asahi Kasei Industry Co., Ltd., trade name], Fujicure [Fuji Chemical Industry Co., Ltd., Trade name] and other amine adduct compounds, 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2, Amine compounds such as 4,6-gins(dimethylaminomethyl)phenol and 4-dimethylaminopyridine, organic metal complexes or organic metal salts such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. . Two or more types of hardening accelerators may be used in combination. When formulating a hardening accelerator, when the total amount of epoxy resin contained in the epoxy resin composition is taken as 100 mass % (non-volatile components), it is preferably used in the range of 0.05 to 1 mass %.

The thermosetting epoxy resin composition of the present invention may also contain various other resin additives other than those mentioned above within the scope of exerting the effect of the present invention. The resin additives may include, for example, organic fillers such as silicon powder, nylon powder, fluorine powder, rubber particles, thickeners such as Orben and Benton, polysilicone, fluorine, polymer defoamers or leveling agents, imidazole, thiazole, triazole, silane coupling agents and other adhesion agents, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, and flame retardants such as metal hydroxides and phosphorus-containing compounds, etc.

The thermosetting epoxy resin composition of the present invention can be appropriately mixed with the above ingredients, and optionally ground with a three-axis roller, a ball mill, or beads. It is prepared by kneading or mixing with mixing means such as machines and sand mills, or with mixing means such as super mixers and planetary mixers. Then, an organic solvent is further added to prepare a resin paint.

Since the thermosetting epoxy resin composition of the present invention has a low dielectric tangent and can form a roughened surface with excellent adhesion to the conductor layer, it can be preferably used as a resin composition for forming a conductor layer by plating. (a resin composition for the insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating), and furthermore, it is preferably used as a resin composition for a build-up layer of a multilayer printed wiring board.

The thermosetting epoxy resin composition of the present invention is particularly suitable as an insulating layer forming material for multilayer printed wiring boards, and can be used in solder resists, underfill materials, die bonding materials, semiconductor sealing materials, buried hole resins, There are a wide range of applications requiring resin compositions such as parts embedded in resin. Moreover, the form of the resin composition of the present invention is not particularly limited, but it can be applied to sheet-like laminates such as adhesive films and prepregs, and circuit boards (laminated board applications, multilayer printed wiring board applications, etc.). The resin composition of the present invention can also be coated on a circuit substrate in a paint state to form an insulating layer. However, industrially, it is generally used in the form of a thin laminate such as a film or prepreg to form an insulating layer.

〈Laminar laminated material〉

(Adhesive film for insulating layer formation)

The adhesive film for forming an insulating layer of the present invention is characterized by providing a resin composition layer made of a thermosetting epoxy resin composition on the supporting film. The adhesive film for forming the insulating layer can be formed using a method known in the art. For example, the resin composition is dissolved in an organic solvent to prepare a resin paint, and a die nozzle coater is used to apply the resin paint on the support, and then It is produced by drying the organic solvent by heating or blowing hot air to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetate esters such as cellosolve, carbitols such as butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Amide solvents, etc. Organic solvents can also be used in combination of two or more types.

The drying conditions are not particularly limited, but the resin composition layer is preferably dried until the organic solvent content is 10 mass% or less, preferably 5 mass% or less. The amount of organic solvent in the paint also varies with the boiling point of the organic solvent. For example, a resin composition can be formed by drying paint containing 30 to 60% by mass of organic solvent at 50 to 150°C for about 3 to 10 minutes. layer.

The thickness of the resin composition layer formed in the film for forming the insulating layer is preferably greater than the thickness of the laminate. The thickness of the conductor layer of the circuit substrate is usually in the range of 5 to 70 μm, so the resin composition layer is preferably 10 to 100 μm thick. From the perspective of thin filmization, 15 to 80 μm is more preferred.

Examples of the support include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyester films such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate, polycarbonate films, polyimide films, and the like. Release paper or metal foils such as copper foil and aluminum foil may also be used. Among them, plastic films are preferred in terms of versatility, and polyethylene terephthalate films are more preferred. The support and the protective film described below may also be subjected to surface treatments such as surface modification (MAD) treatment and corona treatment. In addition, the film can also be removed by using a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

A protective film may be further laminated on the surface of the resin composition layer that is not in close contact with the support body according to the support body. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, dirt and the like can be prevented from adhering to the surface of the resin composition layer.

The insulating layer forming adhesive film having the above-mentioned structure can also be rolled into a roll and stored.

(Prepreg for insulating layer formation)

The prepreg for forming an insulating layer of the present invention is characterized by impregnating a sheet-like fiber base material with a thermosetting epoxy resin composition. That is, it can be produced by impregnating a sheet-shaped reinforcing base material with the thermosetting epoxy resin composition of the present invention using a thermal melting method or a solvent method, and then heating and semi-hardening the composition. As the sheet-like reinforcing base material, prepreg fibers made of commonly used fibers such as glass cloth or aramid fiber can be used. Furthermore, the prepreg for forming an insulating layer of the present invention is preferably provided on a support.

The hot melt method is a method of manufacturing a prepreg by temporarily coating the resin composition on a support without dissolving it in an organic solvent, and then laminating it on a thin sheet-like reinforcing substrate, or directly coating the resin composition on a thin sheet-like reinforcing substrate with a die-mouth coater. The solvent method is the same as the method of manufacturing the bonding film for forming the insulating layer, which is to dissolve the resin in an organic solvent to prepare a resin varnish, immerse the thin sheet-like reinforcing substrate in the varnish, impregnate the resin varnish in the thin sheet-like reinforcing substrate, and then dry it. In addition, the prepreg for forming the insulating layer of the present invention can also be prepared by continuously heat-laminating the insulating layer forming adhesive film from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support body or a protective film can also be used in the same manner as the above-mentioned insulating layer forming adhesive film.

As described above, the insulator for printed wiring boards formed by the cured product of the resin composition layer of the aforementioned insulating layer-forming film and the insulator for printed wiring boards formed by the cured product of the aforementioned insulating layer-forming prepreg are suitable as insulating layers for multi-layer printed wiring boards. In addition, it is more preferable to provide a patterned conductor layer (circuit) on the insulating layer formed by the insulator for printed wiring boards. Moreover, it is preferable to provide a multi-layer printed wiring board formed by laminating a plurality of insulators for printed wiring boards provided with the conductor layer (circuit).

〈Multilayer printed wiring board using sheet laminate material〉

Next, an example of a method of manufacturing a multilayer printed wiring board using the sheet-like laminated material manufactured as described above will be described.

First, a thin sheet of laminating material is laminated on one or both sides of a circuit substrate using a vacuum laminator. Examples of substrates used for circuit substrates include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In addition, the circuit substrate referred to herein refers to a substrate on which a patterned conductor layer (circuit) is formed on one or both sides of the substrate as described above. In addition, a multi-layer printed wiring board formed by alternately laminating conductor layers and insulating layers, where one or both sides of the outermost layer of the multi-layer printed wiring board are patterned conductor layers (circuits) are also included in the circuit substrate referred to herein. The surface of the conductor layer can also be roughened in advance by blackening treatment, copper etching, etc.

In the above-mentioned lamination, if the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit substrate may be preheated as necessary, and the sheet-like laminate material may be laminated to the circuit substrate while being pressed and heated. superior. Among the sheet-like laminated materials of the present invention, it is preferable to laminate them on a circuit substrate under reduced pressure using a vacuum lamination method. Lamination conditions are not particularly limited, but for example, the pressing temperature (lamination temperature) is preferably 70 to 140°C, and the pressing pressure (lamination pressure) is preferably 1 to 11 kgf/cm ² (9.8 ×10 ⁴ ~107.9 × 10 ⁴ N/m ² ), the pressing time (laminating time) is preferably set to 5 to 180 seconds, and the air pressure is set to 20mmHg (26.7hPa) or less for lamination under reduced pressure conditions. In addition, the lamination method may be a batch type or a continuous type using a roller. Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum coater manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., and a drum dry coater manufactured by Hitachi Kogyo Co., Ltd. Fabric machines, vacuum laminators manufactured by Hitachi AIC Co., Ltd., etc.

After laminating the sheet-like laminate material on the circuit substrate, after cooling to near room temperature, the support body can be peeled off to form a hardened material by thermally curing the resin composition, thereby forming an insulating layer on the circuit substrate. The thermal curing conditions can be appropriately selected according to the type and content of the resin components in the resin composition, but it is preferably selected within the range of 20 minutes to 180 minutes at 150℃~220℃, and more preferably 30 minutes to 120 minutes at 160℃~210℃. After the insulating layer is formed, if the support body is not peeled off before curing, it can also be peeled off at this time as needed.

In addition, a vacuum press can be used to laminate the sheet-like laminate material on one or both sides of the circuit board. The lamination step of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press. For example, it can be performed by pressurizing a heated metal plate such as a SUS plate from the support layer side. The pressurizing condition is set to a reduced pressure condition of usually 1× ^10-2 MPa or less, preferably 1× ^10-3 MPa or less. Heating and pressurizing can also be performed in one stage, but from the perspective of controlling resin seepage, it is better to perform it in two or more stages. For example, it is preferred that the first stage of pressurization is performed at a temperature of 70 to 150°C and a pressure of 1 to 15 kgf/ ^cm2 , and the second stage of pressurization is performed at a temperature of 150 to 200°C and a pressure of 1 to 40 kgf/ ^cm2 . Each stage is preferably performed for 30 to 120 minutes. By thermally curing the resin composition layer, an insulating layer can be formed on the circuit board. Examples of commercially available vacuum heat presses include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.) and VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.).

The dielectric tangent of the insulating layer is preferably less than 0.009, and more preferably less than 0.006. The lower the dielectric tangent, the better. Although there is no lower limit, it is set to be greater than 0.001, greater than 0.003, etc.

Then, the insulating layer formed on the circuit substrate is drilled to form through holes and through holes. Perforation processing can be carried out by conventional methods such as drilling machines, lasers, plasmas, etc., and these methods can be combined as needed. However, the most commonly used method is to use lasers such as carbon dioxide laser and YAG laser for perforation processing. . If the support is not peeled off before the perforation process, it will be peeled off at this time.

Next, the surface of the insulating layer is roughened. The dry roughening treatment is a plasma treatment, etc. The wet roughening treatment is a method of sequentially performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid. Wet roughening treatment is better in that it can form concave and convex anchors on the surface of the insulation layer and remove smear in the through holes. The swelling treatment using the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80°C for 5 to 20 minutes (preferably at 55 to 70°C for 8 to 15 minutes). Examples of the swelling solution include an alkaline solution, a surfactant solution, and the like, and an alkaline solution is preferred. Examples of the alkaline solution include a sodium hydroxide solution, a potassium hydroxide solution, and the like. Commercially available swelling agents include, for example, Swelling Dip Securiganth P and Swelling Dip Securiganth SBU manufactured by Japan ATOTECH Co., Ltd. The roughening treatment using an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80° C. for 10 to 30 minutes (preferably at 70 to 80° C. for 15 to 25 minutes). Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Moreover, the permanganate concentration in the alkaline permanganic acid solution is preferably 5 to 10% by weight. Commercially available oxidizing agents include, for example, Concentrate. manufactured by Japan ATOTECH Co., Ltd. Compact CP, Dozing Solution Securiganth P and other alkaline permanganic acid solutions. The neutralization treatment using the neutralizing liquid is performed by immersing in the neutralizing liquid at 30 to 50°C for 3 to 10 minutes (preferably 3 to 8 minutes at 35 to 45°C). The neutralizing solution is preferably an acidic aqueous solution, and commercially available products include, for example, Reduction Solution Securiganth P manufactured by Japan ATOTECH Co., Ltd.

From the viewpoint of forming fine wiring, the roughness of the roughened surface of the insulating layer surface is preferably 200 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less. And to ensure the anchoring effect of the roughened surface, it is better to have a thickness of 10nm or more. In addition, the so-called Ra value is a type of numerical value indicating surface roughness, and is called arithmetic mean roughness. Specifically, the absolute value of the change height of the surface from the average line is measured in the measurement area and the arithmetic average is obtained. . For example, WYKONT 3300 manufactured by Veeco Instruments can be used to determine the value using the VSI contact mode with a 50x lens and a measurement range of 121 μm × 92 μm.

In addition, since the root mean square roughness (Rq value) reflects the local state of the insulating layer surface, it is found that the peel strength can be stabilized by grasping the Rq value to confirm that the insulating layer surface is dense and smooth. In order to make the insulating layer surface dense and smooth, the Rq value is preferably 250nm or less, more preferably 200nm or less, more preferably 150nm or less, and even more preferably 100nm or less. From the perspective of stabilizing the peel strength, it is preferably 15nm or more, and more preferably 30nm or more. The so-called Rq value is a kind of numerical value that indicates surface roughness, which is called root mean square roughness. Specifically, it is the absolute value of the height variation of the surface from the average line measured in the measurement area and expressed as the root mean square.

Next, a conductive layer is formed on the insulating layer by dry plating or wet plating. Dry plating can use known methods such as evaporation, sputtering, and ion plating. Examples of wet plating include a method of forming a conductive layer by combining electroless plating and electrolytic plating, a method of forming a plating resist with a pattern opposite to that of the conductive layer, and a method of forming a conductive layer only by electroless plating. As for the subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to the artisan can be used, and a multi-layer printed wiring board can be manufactured by repeating the above series of steps several times and layering in multiple stages.

In order to make the insulating layer and the conductive layer fully adhered, the peel strength of the insulating layer and the conductive layer is preferably above 0.35kgf/cm, and more preferably above 0.4kgf/cm. The upper limit of the peel strength is as high as possible, and although there is no special restriction, it is generally below 1.5kgf/cm, below 1.2kgf/cm, below 1.0kgf/cm, below 0.8kgf/cm, etc. The insulating layer of the insulator for the printed wiring board of the present invention has low roughness and high peel strength between the insulating layer and the conductive layer, so it can be used as a multi-layer printed wiring board.

〈Semiconductor devices〉

Semiconductor devices can be manufactured by using the multilayer printed wiring board of the present invention. That is, the semiconductor device of the present invention includes the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed wiring board of the present invention. The so-called "conducting part" refers to "the part in the multilayer printed wiring board that conducts electrical signals." Its location can be on the surface or in a buried location. Moreover, if the semiconductor wafer is half There are no special restrictions on electrical circuit components whose conductors are made of materials.

The semiconductor chip mounting method when manufacturing the semiconductor device of the present invention is not particularly limited as long as it enables the semiconductor chip to effectively function. Specific examples include metal wire bonding mounting method, flip chip mounting method, mounting method using bump build-up layer (BBUL), mounting method using anisotropic conductive film (ACF), mounting method using non-conductive film (NCF), etc.

[Example]

The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited by these examples and the like. In the following description, "parts" and "%" mean "parts by mass" and "% by mass".

Measurement method. Evaluation method

〈Measurement of peel strength (peel strength), arithmetic average roughness (Ra), and root mean square roughness (Rq) of the laminate〉

(1) Treatment of the bottom layer of the laminate

The glass cloth base material epoxy resin with the inner circuit formed on both sides of the copper-laminated laminate (copper foil thickness 18 μm, residual copper rate 60%, substrate thickness 0.3mm, R5715ES manufactured by Panasonic Electric Co., Ltd.) was immersed in Merck on both sides In CZ8100 manufactured by Co., Ltd., the copper foil surface is roughened.

(2)Lamination of subsequent films

The adhesive films prepared in each of the following Examples and Comparative Examples were laminated on both sides of the above-mentioned laminate using a batch-type vacuum pressure laminator MVLP-500 [trade name manufactured by Meiki Seisakusho Co., Ltd.]. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of resin composition

The PET film is peeled off from the laminated adhesive film, and the resin composition is cured at 170°C for 30 minutes to form an insulating layer.

(4) Roughening treatment

The above laminate with the insulating layer formed thereon was immersed in Swelling Dip Securiganth P containing diethylene glycol monobutyl ether of Japan ATOTECH Co., Ltd. as a swelling liquid at 60°C for 10 minutes, and then immersed in roughening solution at 80°C. Concentrate. Liquid manufactured by Japan ATOTECH Co., Ltd. Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) for 20 minutes, and finally immersed in Reduction Solution Securiganth P manufactured by Japan ATOTECH Co., Ltd. as a neutralizing solution at 40° C. for 5 minutes. The laminate after roughening treatment was used as sample A.

(5) Conductor layer formation using semi-additive process

In order to form a circuit on the surface of the insulating layer, the laminate of sample A was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After heating at 150° C. for 30 minutes and annealing, an etching resist pattern was formed. After the pattern was formed by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 180° C. for 60 minutes. This laminate was designated as sample B.

(6) Determination of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value)

For sample A, the Ra and Rq values were calculated using a non-contact surface roughness meter (WYKONT3300 manufactured by Veeco Instruments) in VSI contact mode with a 50x lens and a measurement range of 121 μm × 92 μm. Next, the numerical value obtained by calculating the average value of 10 points was used as the measured value.

(7) Determination of the peel strength of the conductor layer

An incision was made on part of the conductor layer of sample B to enclose a range of 10 mm in width and 100 mm in length, and one end of the short strip conductor layer was clamped with a peeling jig (TSI Co., Ltd., AUTOCOM type testing machine AC-50C-SL) , at room temperature, measure the load (kgf/cm) when peeling 35mm in the vertical direction at a speed of 50mm/min.

〈Measurement of dielectric tangent〉

The adhesive films obtained in each of the following Examples and Comparative Examples were thermally cured at 190° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The hardened material was cut into a test piece with a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method dielectric measuring device manufactured by Kanto Applied Electronics Development Co., Ltd. CP521 and network analyzer E8362B manufactured by Agilent Technology Co., Ltd. used the cavity resonance method to measure the dielectric tangent (tanδ) at a measuring frequency of 5.8GHz. Measurement was performed on two test pieces, and the average value was calculated.

Implementation Example 1

While stirring 15 parts of methyl ethyl ketone (hereinafter referred to as "MEK") and 15 parts of copper cyclohexane, liquid bisphenol A-type epoxy resin (epoxy equivalent: 180, "828US" manufactured by Mitsubishi Chemical Co., Ltd. ) and 15 parts of biphenyl-type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), while heating to dissolve. Then, 43 parts of a naphthalene-type active ester compound ["EXB9411-65BK" manufactured by DIC Co., Ltd., active ester equivalent 272, solid content 65% toluene solution] and a hardening accelerator [manufactured by Kwangyoung Chemical Industry Co., Ltd. "4-dimethylaminopyridine"] 0.15 parts, spherical silica [average particle size 0.5 μm, "SO-C2" treated with phenylamine silane, manufactured by ADMATECHS Co., Ltd., amount of carbon per unit mass 0.18%] 100 parts of phenoxy resin (YL6954BH30, MEK solution with solid content of 30% by mass, weight average molecular weight 40000), 15 parts are evenly dispersed with a high-speed rotating kneader to make resin paint. Next, the resin varnish was applied to a polyethylene terephthalate (thickness 38 μm, hereinafter referred to as "PET") film using a die nozzle coater so that the dried resin thickness became 40 μm. Dry at 80~120℃ (average 100℃) for 6 minutes to obtain a flaky adhesive film.

Example 2

The rest are the same as Example 1 except that 43 parts of the naphthalene-type active ester compound ["EXB9411-65BK" manufactured by DIC Co., Ltd., active ester equivalent: 272, solid content 65% toluene solution] in Example 1 was changed to 80 parts. Exactly the same, making resin paint. Then, an adhesive film was obtained in the same manner as in Example 1.

Example 3

The rest were the same as in Example 1, except that 43 parts of the naphthalene-type active ester compound ["EXB9411-65BK" manufactured by DIC Co., Ltd., active ester equivalent: 272, solid content 65% toluene solution] was changed to 20 parts. Exactly the same, making resin paint. Then, an adhesive film was obtained in the same manner as in Example 1.

Example 4

The resin varnish was prepared in exactly the same manner as in Example 3, except that 15 parts of the biphenyl epoxy resin [epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.] in Example 1 was replaced with 15 parts of naphthol epoxy resin [epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel Chemical Co., Ltd.], and 15 parts of cyanate resin ("BA230S75" manufactured by LONZA, 75% solid content methyl ethyl ketone solution) and 0.03 parts of a curing catalyst [3% cyclohexanone dilution of zinc cycloalkanoate mineral oil solution (metal content 8%)] were added. Then, a bonding film was obtained in the same manner as in Example 1.

Comparative example 1

The resin paint was prepared in exactly the same manner as in Example 1 except that 43 parts of the naphthalene-type active ester compound [DIC (Co., Ltd.) "EXB9411-65BK", active ester equivalent 272, 65% solid content toluene solution] was replaced with 35 parts of the active ester compound [DIC (Co., Ltd.) "HPC8000-65T", active ester equivalent 223, 65% solid content toluene solution], 100 parts of spherical silica [average particle size 0.5μm, phenylaminosilane treated "SO-C2", ADMATECHS (Co., Ltd.), carbon content per unit mass 0.18%] was changed to 90 parts, and 0.15 parts of the curing accelerator [Guangrong Chemical Industry (Co., Ltd.) "4-dimethylaminopyridine"] was changed to 0.1 parts. Then, the film is obtained in the same manner as in Example 1.

Comparison Example 2

The remaining contents of Example 1 were the same as in Example 1, except that 43 parts of the naphthalene-type active ester compound ["EXB9411-65BK" manufactured by DIC Co., Ltd., active ester equivalent: 272, solid content 65% toluene solution] was changed to 95 parts. Exactly the same, making resin paint. Then, an adhesive film was obtained in the same manner as in Example 1.

The measurement results of the conductor layer peeling strength, surface roughness (Ra value) and (Rq value) after roughening treatment, and the dielectric tangent of the evaluation sample using the film-adhered evaluation samples produced in the Examples and Comparative Examples are shown. in Table 1.

As shown in Table 1, the cured product of the epoxy resin composition of Example 1 in which the active ester compound containing a naphthalene structure in the epoxy resin composition of Example 1 is changed to an active ester compound outside the scope of the present invention, although the values of Ra and Rq after roughening treatment are much larger than the values of Ra and Rq of the roughened surface formed on the surface of the cured product of the epoxy resin composition of Example 1, the adhesion (peeling strength) with the conductive layer is smaller than that of Example 1, and the value of the dielectric tangent becomes larger.

In addition, the epoxy resin composition of Comparative Example 2 contains a naphthalene-containing active ester compound in an amount exceeding the scope of the present invention, so the adhesion (peel strength) to the conductor layer is smaller than that of Example 1.

From the results of the above Examples and Comparative Examples, it can be understood that the epoxy resin composition of the present invention can be formed into a well-balanced structure that has the characteristics of more layers and higher density corresponding to the build-up of multilayer printed wiring boards. An epoxy resin composition that is an insulating layer made of hardened material.

Claims (4)

A multilayer printed wiring board, which is a multilayer printed wiring board with a conductor layer formed on an insulating layer, characterized in that the insulating layer contains at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, and an inorganic filler A cured product obtained by thermally curing a thermosetting epoxy resin composition of a material and a thermoplastic resin. The epoxy resin (A) includes a liquid epoxy resin and a solid epoxy resin. The average particle size of the inorganic filler is When the diameter is 0.01 μm or more and 5 μm or less, and the non-volatile component in the resin composition is 100 mass%, the content of the naphthalene-containing active ester compound (B) is 0.1 to 30 mass%. Compound (B) is an active ester compound with a polyoxynaphthalene structure. The surface roughness Ra of the insulating layer is 10~200nm, Rq is 15~250nm, and the peeling strength of the insulating layer and the conductor layer is 0.35kgf/cm or more. . The multilayer printed wiring board of claim 1, wherein the active ester compound (B) containing a naphthalene structure is an active ester compound having a polyoxynaphthalene structure and an arylcarbonyloxy group. The multilayer printed wiring board of claim 1 or 2, wherein the active ester compound (B) containing a naphthalene structure is an active ester compound having an aryl carbonyloxy group bonded to the naphthalene core of the polyoxynaphthalene structure. A semiconductor device characterized by use as claimed The multi-layer printed wiring board of item 1 or 2.