JP6915639B2 - Thermosetting epoxy resin composition, adhesive film for forming an insulating layer and multilayer printed wiring board - Google Patents

Description

In the present invention, a thermosetting epoxy resin composition and a cured product thereof, which have a low dielectric loss tangent and are suitable for forming an insulating layer having a roughened surface with low roughness and high peel, and low roughness and high roughness. The present invention relates to a multilayer printed wiring board having a cured product layer having a roughened surface of a peel as an insulating layer.

As a conductor forming method that can cope with the increase in the number of layers and the density of the build-up layer of the multi-layer printed wiring board used with the miniaturization and high performance of electronic devices, after roughening the surface of the insulating layer, The additive method of forming a conductor layer by electroless plating and the semi-additive method of forming a conductor layer by electroless plating and electrolytic plating are known. In these methods, the adhesion between the surface of the insulating layer and the layer of the plated conductor is known. Is secured mainly by roughening the surface of the insulating layer to make it a surface having fine irregularities that exert an anchor effect.

The anchor effect due to the unevenness formed on the surface of the insulating layer increases as the surface roughness increases, and the adhesion to the plated conductor layer increases. However, if the surface roughness of the insulating layer is large, the surface portion to be removed when the thin film conductor layer formed on the roughened surface is partially removed by etching so as to form a predetermined wiring pattern. Since it is difficult to remove the conductor layer part that has entered the recess, it takes a long time for the etching process, and as a result, even the wiring pattern part that should be left is eroded, and the fine wiring is damaged or broken. The risk of etching increases. Therefore, in order to cope with the miniaturization and high density of wiring, the surface condition of the insulating layer is rough as fine as possible and the adhesion to the thin film conductor layer formed by plating can be sufficiently ensured. It is required to be a chemical surface.

Further, the insulating layer is also required to have a low coefficient of linear thermal expansion so that there is no difference in the coefficient of linear thermal expansion between the insulating layer and the conductor layer formed of a 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 the linear thermal expansion coefficient between the insulating layer and the conductor layer becomes large, and problems such as cracks are likely to occur between the insulating layer and the conductor layer.

Conventionally, an "active ester compound" is known as a curing agent used in a thermosetting resin composition for forming an insulating layer of an inner layer circuit board of a multilayer printed wiring board as described above, and such an "active ester compound" is known. "Active ester compounds containing a dicyclopentadienyldiphenol structure" have been mainly used. However, in recent years, the build-up layer of the multilayer printed wiring board has been remarkably increased in height and density, and many proposals have been made for epoxy resin compositions capable of forming a compatible insulating layer.

Patent Document 1 describes an insulating layer exhibiting low dielectric properties by using an active ester compound obtained by aryl esterifying a phenolic hydroxyl group in a phenol novolac resin as a curing agent for a thermosetting epoxy resin composition. It is described that a cured product to be formed can be obtained.

In Patent Document 2, although the roughness of the roughened surface obtained by roughening the surface of the cured product is relatively small, the roughened surface exhibits high adhesion to the plated conductor and has a linear thermal expansion rate. As an epoxy resin composition capable of forming an insulating layer having a small size, (A) epoxy resin, (B) active ester compound, (C) phenol resin having a triazine structure, (D) maleimide compound, and (E) phenoxy resin are used. The epoxy resin composition to be contained is described.

Further, Patent Document 3 describes a polyarylene oxy structure as a thermosetting epoxy resin composition that exhibits a low dielectric constant and a low dielectric loss tangent and provides a cured product having both excellent heat resistance and flame retardancy. An epoxy resin composition containing an active ester resin having an arylcarbonyl group in the aromatic nucleus of the structure as the main skeleton is described.

As described above, many proposals have been made for epoxy resin compositions suitable for forming an insulating layer of an inner layer circuit board, but a finely roughened surface having a low dielectric loss tangent and excellent adhesion to a plating layer. There is a growing demand for an epoxy resin composition that can form an insulating layer that has a well-balanced characteristic that can be used to increase the number of layers and densities of the build-up layer of a multilayer printed wiring board. There is.

Japanese Unexamined Patent Publication No. 07-082348 JP-A-2010-090238 Japanese Unexamined Patent Publication No. 2012-012534

INDUSTRIAL APPLICABILITY The present invention has a high multi-layered build-up layer of a multilayer printed wiring board, which exhibits a low dielectric loss tangent and can form a roughened surface having fine irregularities having excellent adhesion to a plating layer and etching properties. It is composed of a thermocurable epoxy resin composition capable of forming an insulating layer having well-balanced characteristics corresponding to high density, a printed wiring board having an insulating layer formed by the cured product, and the printed wiring board. It is an object of the present invention to provide a multilayer printed wiring board.
Further, in the present invention, an adhesive film for forming an insulating layer in which a resin composition layer composed of the above thermosetting epoxy resin composition is formed on a support film and the above thermosetting epoxy resin composition are used as a sheet-like reinforcing base material. It is an object of the present invention to provide an impregnated insulating layer forming prepreg.

As a result of diligent studies on the curing agents and compounded resins used in the thermosetting epoxy resin composition, the present inventors have among various resins known as resin components to be blended in the epoxy resin composition. The following invention was made after finding that the "active ester compound containing a naphthalene structure" is a resin component that can solve the above-mentioned problems when a specific amount thereof is blended in the resin composition. ..

[1] The active ester compound (B) containing the naphthalene structure when the non-volatile component in the resin composition containing at least the epoxy resin (A) and the active ester compound (B) containing the naphthalene structure is 100% by mass. A thermosetting epoxy resin composition having a content of 0.1 to 30% by mass.
[2] The thermosetting epoxy resin composition according to [1], wherein the active ester compound (B) containing a naphthalene structure is an active ester compound having a polynaphthylene oxide structure and an arylcarbonyloxy group.
[3] The thermosetting according to [1] or [2], wherein the active ester compound (B) containing a naphthalene structure is an active ester compound in which an arylcarbonyloxy group is bonded to a naphthalene nucleus having a polynaphthylene oxide structure. Sex epoxy resin composition.
[4] The thermosetting epoxy resin composition according to 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], which further contains an inorganic filler.
[6] The thermosetting epoxy resin composition according to any one of [1] to [5], which further contains a thermoplastic resin.
[7] The thermosetting epoxy resin composition according to any one of [1] to [6], which is a resin composition for an insulating layer of a multilayer printed wiring board that forms a conductor layer by plating.
[8] An adhesive film for forming an insulating layer, which comprises a resin composition layer composed of the thermosetting epoxy resin composition according to any one of [1] to [7] on a support film.
[9] A prepreg for forming an insulating layer, wherein the thermosetting epoxy resin composition according to any one of [1] to [7] is impregnated in a sheet-like fiber base material.
[10] An insulator for a printed wiring board, which comprises a cured product of either the resin composition layer of the adhesive film for forming an insulating layer according to [8] or the prepreg for forming an insulating layer according to [9].
[11] An insulator for a printed wiring board having a conductor layer circuit patterned on an insulating layer made of the insulator for a printed wiring board according to [10].
[12] The surface roughness Ra of the insulating layer is 10 to 200 nm, Rq is 15 to 250 nm, and the peel strength of the insulating layer and the conductor layer is 0.35 kgf / cm or more. The insulator for a printed wiring board according to [10] or [11].
[13] A multilayer printed wiring board formed by laminating the insulator for a printed wiring board according to [11] or [12] in multiple layers.
[14] A semiconductor device using the multilayer printed wiring board according to [13].

The thermosetting epoxy resin composition exhibits a low dielectric loss tangent, can form a roughened surface having excellent adhesion to the plating layer, and has a high multi-layer and high build-up layer of the multilayer printed wiring board. It is a thermosetting epoxy resin composition capable of forming a cured product layer as an insulating layer having well-balanced characteristics corresponding to densification.
Further, the cured product obtained by curing the thermosetting epoxy resin composition is a case where fine irregularities having a surface roughness Ra of 10 to 200 nm and an Rq of 15 to 250 nm are formed by the surface roughening treatment. However, since it becomes a roughened surface having excellent adhesion to the plating layer, it is particularly useful as an insulating layer forming material in a multilayer printed wiring board.

Hereinafter, each of the thermosetting epoxy resin composition of the present invention, the adhesive film for forming an insulating layer, the prepreg for forming an insulating layer, the insulator for a printed wiring board, and the multilayer printed wiring board will be described in more detail.

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, and is also used for inorganic fillers, thermoplastic resins, and epoxy resins. A curing agent, a curing accelerator, and an additive used in the resin composition forming the insulating layer in the multilayer printed wiring board can be contained, if necessary.

<Epoxy resin (A)>
The epoxy resin (A) used in the thermosetting epoxy resin composition of the present invention is an epoxy resin usually used in a resin composition for forming an insulating layer in a multilayer printed wiring board, and is appropriately selected from the following. Can be used.

For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin. , Naftylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, Examples thereof include an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, and a halogenated epoxy resin.

Two or more kinds of epoxy resins (A) may be used in combination. When the non-volatile component of the epoxy resin (A) is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Further, it is preferable that one molecule has two or more epoxy groups and a liquid aromatic epoxy resin (liquid epoxy resin) is contained at a temperature of 20 ° C., and 3 in the liquid epoxy resin and one molecule. A mode having more than one epoxy group and containing a solid aromatic epoxy resin (solid epoxy resin) at a temperature of 20 ° C. is more preferable.
In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in its molecule. The epoxy equivalent (g / eq) is the molecular weight per epoxy group. By using a liquid epoxy resin and a solid epoxy resin as the epoxy resin, it is possible to form a film that exhibits sufficient flexibility and is excellent in handleability when the epoxy resin composition is used in the form of an adhesive film. At the same time, the breaking strength of the cured product of the epoxy resin composition is improved, and the durability of the multilayer printed wiring board is improved.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mixing ratio (liquid: solid state) is preferably in the range of 1: 0.1 to 1: 2 in terms of mass ratio. By using the liquid epoxy resin within such a range, when used in the form of an adhesive film, sufficient flexibility can be obtained, handleability is improved, and sufficient fluidity at the time of laminating can be obtained. Will be. On the other hand, by using a solid epoxy resin within such a range, the adhesiveness of the epoxy resin composition can be lowered, and when used in the form of an adhesive film, the degassing property at the time of vacuum lamination can be improved. In addition, it is possible to improve the peelability of the protective film and the support film during vacuum lamination and improve the heat resistance after curing.

In the epoxy resin composition of the present invention, when the non-volatile component of the epoxy resin composition is 100% by mass, the content of the epoxy resin (A) is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. It is by mass, more preferably 20 to 35% by mass. By setting the content of the epoxy resin (A) within this range, the curability of the epoxy resin composition tends to be improved.

<Active ester compound (B) containing naphthalene structure>
The "active ester compound (B) containing a naphthalene structure" in the thermosetting epoxy resin composition of the present invention has a function as a curing agent for the epoxy resin and when the surface of the cured resin is roughened. In addition, it is considered that it also contributes to the formation of fine irregularities having good adhesion to the plating layer.

The active ester compound (B) containing a naphthalene structure is not particularly limited as long as it has a naphthalene structure and an arylcarbonyloxy group, but an active ester compound having a polynaphthylene oxide structure and an arylcarbonyloxy group is preferable. An active ester compound in which an arylcarbonyloxy group is bonded to a naphthalene nucleus having a naphthylene oxide structure is more preferable. The polynaphthylene oxide structure may be a polynaphthylene oxide structure substituted with an alkyl group having 1 to 4 carbon atoms, or may have a polyphenylene oxide structure. The above-mentioned active ester compound can be produced by a condensation reaction of a compound having a naphthalene structure having a nuclear-substituted hydroxyl group and a carboxylic acid compound having a carboxyl group in a naphthalene nucleus or a benzene nucleus. Such an active ester compound is, for example, a compound included in "an active ester compound having a polyaryleneoxy structure as a main skeleton and esterified with an arylcarboxylic acid" described in Patent Document 3.

Specifically, the following general formula (1) can be mentioned.

〔式中、Ｒ１はそれぞれ独立に水素原子又は炭素数１〜４のアルキル基となり、好ましくは水素原子である。Ｒ２はそれぞれ独立に水素原子又は下記一般式（２）が挙げられる。Ｘはそれぞれ独立に水素、ベンゾイル基又はナフチルカルボニル基となり、好ましくはベンゾイル基である。ｎ及びｍはそれぞれ０〜５の整数であって、ｎ又はｍのいずれか一方は１以上の整数である。〕

[In the formula, R1 independently becomes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom. Each of R2 independently has a hydrogen atom or the following general formula (2). Each of X independently becomes a hydrogen, benzoyl group or naphthylcarbonyl group, and is preferably a benzoyl group. n and m are integers of 0 to 5, respectively, and either n or m is an integer of 1 or more. ]

〔式中、Ｒ１は上記と同様である。Ｘは上記と同様である。ｐは１又は２の整数である。なお、上記一般式（１）及び（２）のＸの少なくとも一つはベンゾイル基又はナフチルカルボニル基となる。〕

[In the formula, R1 is the same as above. X is the same as above. p is an integer of 1 or 2. At least one of X in the general formulas (1) and (2) is a benzoyl group or a naphthylcarbonyl group. ]

In the epoxy resin composition of the present invention, when the non-volatile component of the epoxy resin composition is 100% by mass, the content of the active ester compound (B) containing a naphthalene structure is 0.1 to 30% by mass. As a result, it is possible to form a roughened surface having a low dielectric loss tangent and fine irregularities having excellent adhesion to the plating layer and etching property. A more preferable range is 3 to 30% by mass, and even more preferably 5 to 28% by mass.

<Inorganic filler>
The epoxy resin composition of the present invention can further reduce the coefficient of linear thermal expansion and the dielectric loss tangent by further containing an inorganic filler. Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and barium titanate. Examples thereof include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable, and fused silica and spherical silica are more preferable in terms of reducing the surface roughness of the insulating layer. Spherical fused silica is preferable, and spherical fused silica is more preferable. These may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SOC2" and "SOC1" manufactured by Admatex Co., Ltd.

The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, and 2 μm or less from the viewpoint that the surface of the insulating layer becomes low roughness and fine wiring can be formed. Is even more preferable, 1 μm or less is even more preferable, 0.8 μm or less is particularly preferable, 0.6 μm or less is particularly preferable, and 0.4 μm or less is particularly preferable. On the other hand, when the resin composition is a resin varnish, 0.01 μm or more is preferable, 0.03 μm or more is more preferable, and 0. 05 μm or more is further preferable, 0.07 μm or more is further preferable, and 0.1 μm or more is particularly preferable. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, LA-950 or the like manufactured by HORIBA, Ltd. can be used. Inorganic fillers include aminosilane-based coupling agents, ureidosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, vinylsilane-based coupling agents, and styrylsilane-based coupling agents. , Acrylic silane coupling agent, isocyanate silane coupling agent, sulfide silane coupling agent, organosilazane compound, titanate coupling agent and other surface treatment agents to improve the moisture resistance and dispersibility. Is preferable. These may be used alone or in combination of two or more.

When the inorganic filler is blended, it depends on the characteristics required for the resin composition, but when the non-volatile component in the epoxy resin composition is 100% by mass, it is preferably 30 to 90% by mass. It is more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass. If the content of the inorganic filler is too small, the coefficient of linear thermal expansion of the cured product tends to be high, and if the content is too large, it becomes difficult to form an adhesive film when preparing an adhesive film, or the cured product becomes brittle. It tends to be.

<Thermoplastic resin>
The epoxy resin composition of the present invention can further improve the mechanical strength of the cured product by further containing a thermoplastic resin, and can further improve the film molding ability when used in the form of an adhesive film. .. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin. Phenoxy resin and polyvinyl acetal resin are particularly preferable. Each of these thermoplastic resins may be used alone, or two or more kinds may be used in combination. The weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 20000, more preferably in the range of 12000 to 100,000. The weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is obtained by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K manufactured by Showa Denko Corporation as a column. -804 L can be measured using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

When the thermoplastic resin is blended, when the non-volatile component in the epoxy resin composition is 100% by mass, it is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. Within this range, the effects of improving the film forming ability and the mechanical strength can be exhibited, and further, the melt viscosity can be increased and the roughness of the surface of the insulating layer after the wet roughening step can be lowered.

<Hardener for epoxy resin>
In the epoxy resin composition of the present invention, a more general curing agent for epoxy resin can also be used. Examples of the epoxy resin curing agents that can be used include 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 Kayaku Co., Ltd., trade name], SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 [Nippon Steel Chemical Co., Ltd., trade name], LA7052, LA7054, Phenolic curing agents such as LA3018, LA1356 [DIC Co., Ltd., trade name], Fa, Pd [Shikoku Kasei Co., Ltd., trade name], HFB2006M [Showa Polymer Co., Ltd., trade name], etc. Benzoxazine-based curing agents, methylhexahydrohydride phthalic acid, methylnadic acid anhydrides, acid anhydride-based curing agents such as hydride methylnadic acid anhydrides, PT30, PT60, BA230S75 [Lonza Japan Co., Ltd., trade name ] And the like, such as cyanate ester-based curing agents.

<Curing accelerator>
The epoxy resin composition of the present invention can efficiently adjust the curing time and the curing temperature by further containing a curing accelerator. Examples of the curing accelerator include organic phosphine compounds such as TPP, TPP-K, TPP-S, and TPTP-S [Hokuko Kagaku Kogyo Co., Ltd., trade name], Curesol 2MZ, 2E4MZ, Cl1Z, Cl1Z-CN, Cl1Z. -Imidazole compounds such as CNS, Cl1Z-A, 2MZ-OK, 2MA-OK, 2PHZ [Shikoku Kasei Kogyo Co., Ltd., trade name], Novacure [Asahi Kasei Kogyo Co., Ltd., trade name], Fuji Cure [Fuji Kasei Kogyo (Fuji Kasei Kogyo Co., Ltd.) Amine Adduct Compounds, Trade Name], 1,8-diazabicyclo [5,4,0] undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) Examples thereof include amine compounds such as phenol and 4-dimethylaminopyridine, organic metal complexes such as cobalt, copper, zinc, iron, nickel, manganese and tin, or organic metal salts. Two or more kinds of curing accelerators may be used in combination. When the curing accelerator is blended, when the total amount of the epoxy resin contained in the epoxy resin composition is 100% by mass (nonvolatile component), it is preferably used in the range of 0.05 to 1% by mass.

The epoxy resin composition of the present invention may optionally contain various resin additives other than those described above as long as the effects of the present invention are exhibited. Examples of the resin additive include organic fillers such as silicon powder, nylon powder, fluorine powder and rubber particles, thickeners such as Orben and Benton, silicone-based, fluorine-based and polymer-based defoaming agents or leveling agents. Adhesion-imparting agents such as imidazole, thiazole, triazole, and silane coupling agents, colorants such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, and carbon black, metal hydroxides, phosphorus-containing compounds, etc. Flame-retardant agents and the like can be mentioned.

The epoxy resin composition of the present invention is appropriately mixed with the above components, and if necessary, kneaded or kneaded by a kneading means such as a three-roll, ball mill, bead mill, sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be adjusted by mixing. Further, it can be adjusted as a resin varnish by further adding an organic solvent.

In the epoxy resin composition of the present invention, since a roughened surface showing low dielectric loss tangent and excellent adhesion to the plating layer can be formed, a resin composition (plating) for forming a conductor layer by plating. It can be suitably used as a resin composition for an insulating layer of a multilayer printed wiring board that forms a conductor layer), and is further suitable as a resin composition for a build-up layer of a multilayer printed wiring board.

The resin composition of the present invention has a composition particularly suitable as an insulating layer forming material for a multilayer printed wiring board, such as a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin. , Can be used in a wide range of applications where a resin composition is required. The form of the resin composition of the present invention is not particularly limited, but can be applied to sheet-like laminated materials such as adhesive films and prepregs, and circuit boards (for laminated boards, multilayer printed wiring boards, etc.). The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but industrially, it is generally used for forming an insulating layer as a form of a sheet-like laminated material such as an adhesive film or a prepreg. Used.

<Sheet-like laminated material>
(Adhesive film for forming an insulating layer)
The adhesive film for forming an insulating layer of the present invention is characterized by having a resin composition layer made of a thermosetting epoxy resin composition on a support film. A method known to those skilled in the art, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied to a support using a die coater or the like, and further heated or blown with hot air. It can be produced by drying the organic solvent to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitol such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Two or more kinds of organic solvents may be used in combination.

The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, the resin composition layer is formed by drying the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.

The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of thinning, 15 to 80 μm is more preferable.

Examples of the support include a polyolefin film such as polyethylene, polypropylene, and polyvinyl chloride, a polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), a polyester film such as polyethylene naphthalate, a polycarbonate film, and a polyimide film. Various plastic films can be mentioned. Further, a release paper, a metal foil such as a copper foil or an aluminum foil may be used. Among them, a plastic film is preferable, and a polyethylene terephthalate film is more preferable from the viewpoint of versatility. The support and the protective film described later may be subjected to surface treatment such as mud treatment and corona treatment. Further, the mold release treatment may be performed with a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, or a fluororesin-based mold 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 similar to the support can be further laminated on the surface of the resin composition layer where the support is not in close contact. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The adhesive film can also be rolled up and stored.

(Prepreg for forming an insulating layer)
The prepreg for forming an insulating layer of the present invention is characterized in that a thermosetting epoxy resin composition is impregnated in a sheet-like fiber base material. That is, it can be produced by impregnating a sheet-shaped reinforcing base material with the resin composition of the present invention by a hot melt method or a solvent method, and heating and semi-curing the resin composition. As the sheet-shaped reinforcing base material, for example, those made of fibers commonly used as prepreg fibers such as glass cloth and aramid fibers can be used. A prepreg formed on the support is preferable.

In the hot melt method, the resin composition is once coated on the support without being dissolved in an organic solvent and then laminated on the sheet-shaped reinforcing base material, or directly coated on the sheet-shaped reinforcing base material by a die coater. This is a method of manufacturing a prepreg. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as an adhesive film, a sheet-shaped reinforcing base material is immersed in the varnish, and the sheet-shaped reinforcing base material is impregnated with the resin varnish. It is a method of drying. It can also be prepared by continuously heat laminating the adhesive film from both sides of the sheet-shaped reinforcing base material under heating and pressure conditions. A support, a protective film, or the like can be used in the same manner as the adhesive film.

As described above, an insulator for a printed wiring board made of a cured product of any one of the resin composition layer of the adhesive film for forming an insulating layer and the prepreg for forming an insulating layer is suitable as an insulating layer for a multilayer printed wiring board. Is. Further, it is more preferable to have a conductor layer circuit patterned on the insulating layer made of the printed wiring board insulator. Further, a multilayer printed wiring board formed by laminating multiple layers of insulators for a printed wiring board having the conductor layer circuit is preferable.

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

First, the sheet-shaped laminated material is laminated (laminated) on one side or both sides of the circuit board using a vacuum laminator. Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. Here, the circuit board means a circuit board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. Further, in a multi-layer printed wiring board in which conductor layers and insulating layers are alternately laminated, one or both sides of the outermost layer of the multi-layer printed wiring board is a conductor layer (circuit) in which a pattern is processed. It is included in the circuit board mentioned above. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching or the like.

In the above lamination, when the sheet-shaped laminated material has a protective film, after removing the protective film, the sheet-shaped laminated material and the circuit board are preheated as necessary, and the sheet-shaped laminated material is pressurized and pressed. Laminate on the circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating conditions are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure (lamination pressure) is preferably 1 to 11 kgf / cm ² (9.8 ×). 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the crimping time (lamination time) is preferably 5 to 180 seconds, and the lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the laminating method may be a batch method or a continuous method using a roll. Vacuum laminating can be done using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by Nichigo Morton Co., Ltd., vacuum pressurized laminators manufactured by Meiki Seisakusho Co., Ltd., roll-type dry coaters manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like can be mentioned.

After laminating the sheet-like laminated material on the circuit board, it is cooled to around room temperature, and then the support is peeled off when peeled off, and the resin composition is thermoset to form a cured product on the circuit board. An insulating layer can be formed. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, and more preferably 160 ° C. to 210. It is selected in the range of 30 to 120 minutes at ° C. If the support is not peeled off after forming the insulating layer and before curing, it can be peeled off here if necessary.

Further, the sheet-shaped laminated material can be laminated on one side or both sides of the circuit board by using a vacuum press machine. The laminating step of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a heated metal plate such as a SUS plate from the support layer side. The pressing conditions are such that the degree of decompression is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ^-3 MPa or less. Although heating and pressurization can be performed in one step, it is preferable to divide the conditions into two or more steps from the viewpoint of controlling the exudation of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and a pressure of 1 to 15 kgf / cm2, and the second stage press has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm2. It is preferable to do so. The time of each step is preferably 30 to 120 minutes. By thermosetting the resin composition layer in this way, an insulating layer can be formed on the circuit board. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 manufactured by Meiki Seisakusho Co., Ltd. and VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.).

The dielectric loss tangent of the insulating layer is preferably 0.009 or less, more preferably 0.006 or less. The lower the dielectric loss tangent, the better, and there is no particular lower limit, but it is 0.001 or more, 0.003 or more, and the like.

Next, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. The drilling can be performed by, for example, a known method such as a drill, a laser, or a plasma, or a combination of these methods if necessary, but the most common drilling is a laser such as a carbon dioxide laser or a YAG laser. The method. If the support is not peeled off before the drilling process, it will be peeled off here.

Next, the surface of the insulating layer is roughened. In the case of dry roughening treatment, plasma treatment and the like can be mentioned, and in the case of wet roughening treatment, swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent and neutralization treatment with a neutralizing liquid can be performed in this order. Be done. The wet roughening treatment is preferable in that smears in the via holes can be removed while forming uneven anchors on the surface of the insulating layer. The swelling treatment with the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling solution include an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P and Swelling Dip Securiganth SBU manufactured by Atotech Japan Co., Ltd. be able to. The roughening treatment with 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 permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd. and Dozing Solution Security P. The neutralization treatment with a neutralizing solution is carried out by immersing in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably 35 to 45 ° C. for 3 to 8 minutes). The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include Reduction Solusin Securigant P manufactured by Atotech Japan Co., Ltd.

The roughness of the roughened surface obtained by roughening the surface of the insulating layer is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less in terms of forming fine wiring. Further, in order to secure the anchor effect of the roughened surface, it is preferably 10 nm or more. The Ra value is a kind of numerical value indicating the surface roughness, which is called the arithmetic mean roughness. Specifically, the absolute value of the height that changes in the measurement region is calculated from the surface that is the average line. It is measured and arithmetically averaged. For example, it can be obtained by using a WYKONT3300 manufactured by B-Coin Sturments Co., Ltd. and using a VSI contact mode and a 50x lens to obtain 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 can be confirmed by grasping the Rq value that the insulating layer surface is dense and smooth, and the peel strength is high. Found to stabilize. The Rq value is preferably 250 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, and even more preferably 100 nm or less in order to obtain a dense and smooth insulating layer surface. Further, from the viewpoint of stabilizing the peel strength, 15 nm or more is preferable, and 30 nm or more is more preferable. The Rq value is a kind of numerical value indicating the surface roughness, which is called the root mean square roughness, and specifically, the surface whose absolute value of the height changing in the measurement region is the average line. It represents the root mean square measured from.

Then, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as thin film deposition, sputtering, and ion plating can be used. Examples of wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a pattern opposite to that of the conductor layer, and a method of forming a conductor layer only by electroless plating. Be done. As a method for forming a pattern thereafter, for example, a subtractive method, a semi-additive method, etc. known to those skilled in the art can be used. It becomes a printed wiring board.

The peel strength of the insulating layer and the conductor layer is preferably 0.35 kgf / cm or more, and more preferably 0.4 kgf / cm or more in order to keep the insulating layer and the conductor layer in close contact with each other. The higher the upper limit of the peel strength, the better, and there is no particular limitation, but generally, it is 1.5 kgf / cm or less, 1.2 kgf / cm or less, 1.0 kgf / cm or less, 0.8 kgf / cm or less, and the like. In the present invention, since it has low roughness and high peel, it can be suitably used as a build-up layer of a multilayer printed wiring board.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of the multilayer printed wiring board of the present invention. The "conduction point" is a "place for transmitting an electric signal in the multilayer printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. In the following description, "parts" and "%" mean "parts by mass" and "% by mass".

Measurement method / evaluation method <Measurement of peeling strength (peel strength) of plated conductor layer, arithmetic mean roughness (Ra), root mean square roughness (Rq)>

(1) Base treatment of laminated board Glass cloth base material with inner layer circuit Epoxy resin double-sided copper-clad laminated board (copper foil thickness 18 μm, residual copper ratio 60%, substrate thickness 0.3 mm, Matsushita Electric Works Co., Ltd. Both sides of R5715ES (manufactured by R5715ES) were immersed in CZ8100 manufactured by MEC Co., Ltd. to roughen the copper surface.

(2) Laminating of Adhesive Films The adhesive films produced in each example and each comparative example are used on both sides of a laminated board using a batch type vacuum pressure laminator MVLP-500 [manufactured by Meiki Seisakusho Co., Ltd., trade name]. Laminated in. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions of 170 ° C. for 30 minutes.

(4) Neutralization treatment The laminated board is immersed in a swelling liquid, Atotech Japan Co., Ltd.'s diethylene glycol monobutyl ether-containing Swelling Dip Securigan P, at 60 ° C. for 10 minutes, and then as a roughening liquid, Atotech Japan. Immerse in Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd.'s reduction sholysin. -Immersed in securigant P at 40 ° C. for 5 minutes. The laminated board after this roughening treatment was used as sample A.

(5) Plating formation by the semi-additive method In order to form a circuit on the surface of the insulating layer, the laminated board _{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 to perform annealing treatment, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. Next, the annealing treatment was performed at 180 ° C. for 60 minutes. This laminated board was used as sample B.

(6) Measurement of Arithmetic Mean Roughness (Ra Value) and Root Mean Square Roughness (Rq Value) For Sample A, use a non-contact surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments) in VSI contact mode. The Ra and Rq values were determined from the numerical values obtained by setting the measurement range to 121 μm × 92 μm with a 50x lens. Then, the average value of 10 points was obtained and used as the measured value.

(7) Measurement of Peeling Strength (Peel Strength) of Plated Conductor Layer Make a notch in the conductor layer of sample B with a width of 10 mm and a length of 100 mm, and peel off one end of the grip tool (TS Co., Ltd.). E, Autocom type tester AC-50C-SL), and the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature was measured.

<Measurement of dielectric loss tangent>
The adhesive films obtained in each Example and each Comparative Example were heat-cured at 190 ° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into test pieces having a width of 2 mm and a length of 80 mm, and a cavity resonator permittivity measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8632B manufactured by Azilent Technology Co., Ltd. were used. The dielectric constant tangent (tan δ) was measured at a measurement frequency of 5.8 GHz by the cavity resonance method. Measurements were made on the two test pieces, and the average value was calculated.

Example 1
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "828US" manufactured by Mitsubishi Chemical Corporation) and 15 parts of biphenyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.) are methyl ethyl ketone. (Hereinafter abbreviated as "MEK") 15 parts and 15 parts of cyclohexanone were heated and dissolved with stirring. There, 43 parts of a naphthalene-type active ester compound ["EXB9411-65BK" manufactured by DIC Co., Ltd., an active ester equivalent of 272, a toluene solution having a solid content of 65%], and a curing accelerator [manufactured by Koei Chemical Industry Co., Ltd., "4". -Dimethylaminopyridine "] 0.15 parts, spherical silica [average particle size 0.5 μm, phenylaminosilane treated" SO-C2 ", manufactured by Admatex Co., Ltd., carbon content per unit mass 0.18%] 100 15 parts of phenoxy resin (YL6954BH30, MEK solution having a solid content of 30% by mass, weight average molecular weight 40,000) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Next, the resin varnish was applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) with a die coater so that the dried resin thickness would be 40 μm, and the temperature was 80 to 120 ° C. (average). It was dried at 100 ° C. for 6 minutes to obtain a sheet-shaped adhesive film.

Example 2
Example 1 except that 43 parts of the naphthalene-type active ester compound of Example 1 [“EXB9411-65BK” manufactured by DIC Co., Ltd., active ester equivalent 272, toluene solution having a solid content of 65%] was changed to 80 parts. A resin varnish was prepared in exactly the same manner as above. Next, an adhesive film was obtained in the same manner as in Example 1.

Example 3
Example 1 except that 43 parts of the naphthalene-type active ester compound of Example 1 [“EXB9411-65BK” manufactured by DIC Co., Ltd., active ester equivalent 272, toluene solution having a solid content of 65%] was changed to 20 parts. A resin varnish was prepared in exactly the same manner as above. Next, an adhesive film was obtained in the same manner as in Example 1.

Example 4
15 parts of the biphenyl type epoxy resin of Example 1 [epoxy equivalent 291 and "NC3000H" manufactured by Nippon Kayaku Co., Ltd.], 15 parts of the naphthol type epoxy resin [epoxy equivalent 332, "ESN475V" manufactured by Nippon Steel Chemical Co., Ltd.] 15 parts of cyanate ester resin (“BA230S75” manufactured by Ronza, methyl ethyl ketone solution with 75% solid content) and curing catalyst [3% cyclohexanone diluted solution of zinc naphthenate mineral spirit solution (metal content 8%)] A resin varnish was prepared in exactly the same manner as in Example 3 except that 0.03 part was added. Next, an adhesive film was obtained in the same manner as in Example 1.

Comparative Example 1
43 parts of the naphthalene-type active ester compound of Example 1 [“EXB9411-65BK” manufactured by DIC Co., Ltd., active ester equivalent 272, toluene solution having a solid content of 65%] was added to the active ester compound [“HPC8000-65T” manufactured by DIC Co., Ltd. , Active ester equivalent 223, solid content 65% toluene solution] changed to 35 parts, spherical silica [average particle size 0.5 μm, phenylaminosilane treatment "SO-C2", manufactured by Admatex Co., Ltd., unit mass Carbon amount per 0.18%] 100 parts was changed to 90 parts, and curing accelerator [manufactured by Koei Chemical Industry Co., Ltd., "4-dimethylaminopyridine"] 0.15 parts was changed to 0.1 parts. Except for this, a resin varnish was produced in exactly the same manner as in Example 1. Next, an adhesive film was obtained in the same manner as in Example 1.

Comparative Example 2
Example 1 except that 43 parts of the naphthalene-type active ester compound of Example 1 [“EXB9411-65BK” manufactured by DIC Co., Ltd., active ester equivalent 272, toluene solution having a solid content of 65%] was changed to 95 parts. A resin varnish was prepared in exactly the same manner as above. Next, an adhesive film was obtained in the same manner as in Example 1.

Measurement results of the peel strength of the plated conductor layer of the evaluation sample using the adhesive films produced in Examples and Comparative Examples, the surface roughness (Ra value) and (Rq value) after the roughening treatment, and the dielectric loss tangent of the evaluation sample. Table 1 shows the evaluation results of flexibility.

As shown in Table 1, the cured product of the epoxy resin composition of Comparative Example 1 in which the active ester compound containing a naphthalene structure in the epoxy resin composition of Example 1 was changed to an active ester compound outside the scope of the present invention The values of Ra and Rq after the 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. Regardless, the adhesion to the plating layer (peel strength) is smaller than that of Example 1, and the value of the dielectric loss tangent is large.
Further, in the epoxy resin composition of Comparative Example 2, since the blending amount of the active ester compound containing the naphthalene structure is larger than the range of the present invention, the adhesion (peel strength) with the plating layer is improved in Examples. It is smaller than the one in 1.
As is clear from the results of the above Examples and Comparative Examples, the epoxy resin composition of the present invention has well-balanced characteristics that can cope with high multi-layer and high-density build-up layers of the multilayer printed wiring board. An epoxy resin composition capable of forming an insulating layer made of a cured product.

Claims (10)

A multi-layer printed wiring board in which a conductor layer is formed on an insulating layer.
The insulating layer is an insulation obtained by thermosetting a thermosetting epoxy resin composition containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, a thermoplastic resin, and an inorganic filler. It ’s a layer,
When the non-volatile component in the thermosetting epoxy resin composition is 100% by mass, the content of the active ester compound (B) containing the naphthalene structure is 0.1 to 30% by mass.
The average particle size of the inorganic filler is 0.01 μm or more and 5 μm or less.
The arithmetic average surface roughness Ra of the insulating layer is 10 to 200 nm, and the root mean square roughness Rq is 15 to 250 nm.
The peel strength of the insulating layer and the conductor layer is 0.35 kgf / cm (3.43 N / cm) or more.
A multilayer printed wiring board in which the dielectric loss tangent of the insulating layer is 0.009 or less. A multi-layer printed wiring board in which a conductor layer is formed on an insulating layer.
The insulating layer is an insulating layer obtained by thermosetting a thermosetting epoxy resin composition containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, and a thermoplastic resin.
When the non-volatile component in the thermosetting epoxy resin composition is 100% by mass, the content of the active ester compound (B) containing the naphthalene structure is 0.1 to 30% by mass.
As the epoxy resin (A), a liquid epoxy resin at a temperature of 20 ° C. and a solid epoxy resin at a temperature of 20 ° C. are used in combination.
The arithmetic average surface roughness Ra of the insulating layer is 10 to 200 nm, and the root mean square roughness Rq is 15 to 250 nm.
The peel strength of the insulating layer and the conductor layer is 0.35 kgf / cm (3.43 N / cm) or more.
A multilayer printed wiring board in which the dielectric loss tangent of the insulating layer is 0.009 or less. A multi-layer printed wiring board in which a conductor layer is formed on an insulating layer.
The insulating layer is an insulation obtained by thermosetting a thermosetting epoxy resin composition containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, a thermoplastic resin, and an inorganic filler. It ’s a layer,
When the non-volatile component in the thermosetting epoxy resin composition is 100% by mass, the content of the active ester compound (B) containing the naphthalene structure is 0.1 to 30% by mass.
The content of the inorganic filler is 30 to 90% by mass,
The arithmetic average surface roughness Ra of the insulating layer is 10 to 200 nm, and the root mean square roughness Rq is 15 to 250 nm.
The peel strength of the insulating layer and the conductor layer is 0.35 kgf / cm (3.43 N / cm) or more.
A multilayer printed wiring board in which the dielectric loss tangent of the insulating layer is 0.009 or less. A semiconductor device using the multilayer printed wiring board according to any one of claims 1 to 3. A thermosetting epoxy resin composition containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, a thermoplastic resin, and an inorganic filler.
When the non-volatile component in the thermosetting epoxy resin composition is 100% by mass, the content of the active ester compound (B) containing the naphthalene structure is 0.1 to 30% by mass.
The average particle size of the inorganic filler is 0.01 μm or more and 5 μm or less.
The thermosetting epoxy resin composition was cured under curing conditions of 170 ° C. for 30 minutes, and the roughened cured product had an arithmetic average surface roughness Ra of 10 to 200 nm and a root mean square roughness Rq of 15 to 250 nm. And
The peel strength of the cured product and the conductor layer formed on the cured product is 0.35 kgf / cm (3.43 N / cm) or more.
A thermosetting epoxy resin composition having a dielectric loss tangent of 0.009 or less of the cured product. A thermosetting epoxy resin composition containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, and a thermoplastic resin.
When the non-volatile component in the thermosetting epoxy resin composition is 100% by mass, the content of the active ester compound (B) containing the naphthalene structure is 0.1 to 30% by mass.
As the epoxy resin (A), a liquid epoxy resin at a temperature of 20 ° C. and a solid epoxy resin at a temperature of 20 ° C. are used in combination.
The thermosetting epoxy resin composition was cured under curing conditions of 170 ° C. for 30 minutes, and the roughened cured product had an arithmetic average surface roughness Ra of 10 to 200 nm and a root mean square roughness Rq of 15 to 250 nm. And
The peel strength of the cured product and the conductor layer formed on the cured product is 0.35 kgf / cm (3.43 N / cm) or more.
A thermosetting epoxy resin composition having a dielectric loss tangent of 0.009 or less of the cured product. The thermosetting epoxy resin composition according to claim 6, further containing an inorganic filler. A thermosetting epoxy resin composition containing at least an epoxy resin (A), an active ester compound (B) containing a naphthalene structure, a thermoplastic resin, and an inorganic filler.
When the non-volatile component in the thermosetting epoxy resin composition is 100% by mass, the content of the active ester compound (B) containing the naphthalene structure is 0.1 to 30% by mass, and the content of the inorganic filler is Is 30 to 90% by mass,
The thermosetting epoxy resin composition was cured under curing conditions of 170 ° C. for 30 minutes, and the roughened cured product had an arithmetic average surface roughness Ra of 10 to 200 nm and a root mean square roughness Rq of 15 to 250 nm. And
The peel strength of the cured product and the conductor layer formed on the cured product is 0.35 kgf / cm (3.43 N / cm) or more.
A thermosetting epoxy resin composition for forming an insulating layer of a multilayer printed wiring board, wherein the cured product has a dielectric loss tangent of 0.009 or less. The thermosetting epoxy resin composition according to claim 5 or 8, wherein the epoxy resin (A) contains a liquid epoxy resin at a temperature of 20 ° C. The thermosetting epoxy resin composition according to claim 7, wherein the content of the inorganic filler is 30 to 90% by mass when the non-volatile component in the thermosetting epoxy resin composition is 100% by mass.