JP2017071797A - Thermosetting epoxy resin composition, adhesive film for forming insulating layer and multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which can form a roughened surface that has a low dielectric loss tangent and is excellent in adhesiveness with a conductor layer, and can form an insulating layer having well-balanced characteristics of an increase in multilayering of build-up layers and an increase in density of a multilayer printed wiring board.SOLUTION: There is provided a thermosetting epoxy resin composition, where when a nonvolatile component in a resin composition containing at least an epoxy resin (A) and an active ester compound (B) containing a naphthalene structure is 100 mass%, a content of the active ester compound (B) containing the naphthalene structure is 0.1-30 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting epoxy resin composition suitable for forming an insulating layer having a low dielectric loss tangent and a low roughness and a high peel rough surface, a cured product thereof, and a low roughness, high 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.

  With the downsizing and high performance of electronic equipment, as a conductor formation method that can cope with the high build-up layer and high density of the build-up layer of the multilayer printed wiring board used, after roughening the insulating layer surface, The additive method for forming a conductor layer by electroless plating and the semi-additive method for forming a conductor layer by electroless plating and electrolytic plating are known. In these methods, the adhesion between the insulating layer surface and the plated conductor layer is known. Is ensured mainly by roughening the surface of the insulating layer to form a surface with fine irregularities that exhibits 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, when the roughness of the surface of the insulating layer is large, when the thin film conductor layer formed on the roughened surface is partially removed by etching so that a predetermined wiring pattern is formed, the surface portion to be removed Since the conductor layer portion that has entered the recess is in a state that is difficult to remove, the etching process takes a long time, and as a result, the wiring pattern portion that should be left is eroded and the fine wiring is damaged or disconnected. The risk of accidents increases. Therefore, in order to cope with the miniaturization and high density of the wiring, the surface state of the insulating layer should be as rough as possible to ensure sufficient adhesion with the thin film conductor layer formed by plating with the finest possible unevenness. It is required to be a conversion surface.

  The insulating layer is also required to have a low linear thermal expansion coefficient so as not to cause a difference in the linear thermal expansion coefficient 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 increases, and problems such as the occurrence of cracks between the insulating layer and the conductive layer are likely to occur.

  Conventionally, "active ester compound" is known as a curing agent used in the thermosetting resin composition for forming the insulating layer of the inner circuit board of the multilayer printed wiring board as described above, and such "active ester compound" "The active ester compound containing a dicyclopentadienyl diphenol structure" has been mainly used. However, in recent years, the build-up layer of a multilayer printed wiring board has been greatly increased in the number of layers and the density has been increased, and many proposals of an epoxy resin composition capable of forming a corresponding insulating layer have been made.

  Patent Document 1 discloses an insulating layer that exhibits low dielectric properties by using an active ester compound obtained by arylesterifying 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 body 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 coefficient. As an epoxy resin composition capable of forming an insulating layer having a small size, (A) an epoxy resin, (B) an active ester compound, (C) a phenol resin having a triazine structure, (D) a maleimide compound, and (E) a phenoxy resin The containing epoxy resin composition is described.

  Patent Document 3 discloses a polyaryleneoxy structure as a thermosetting epoxy resin composition that exhibits a low dielectric constant and a low dielectric loss tangent and gives 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 is described.

  As described above, many proposals for an epoxy resin composition suitable for the formation of an insulating layer of an inner circuit board have been made, but a fine rough surface having a low dielectric loss tangent and excellent adhesion to a plating layer. The demand for an epoxy resin composition capable of forming an insulating layer with a well-balanced property that can cope with higher multilayer and higher density build-up layers of multilayer printed wiring boards is increasing. Yes.

Japanese Patent Laid-Open No. 07-082348 JP 2010-090238 A JP 2012-012534 A

The present invention is capable of forming a multi-layered build-up layer of a multilayer printed wiring board that exhibits a low dielectric loss tangent and can form a roughened surface having fine irregularities excellent in adhesion and etching properties with a plating layer. A thermosetting epoxy resin composition capable of forming an insulating layer having a well-balanced characteristic capable of supporting high density, a printed wiring board having an insulating layer formed by the cured product, and the printed wiring board. An object of the present invention is to provide a multilayer printed wiring board.
In addition, the present invention provides an insulating layer-forming adhesive film in which a resin composition layer comprising the above thermosetting epoxy resin composition is formed on a support film, and the thermosetting epoxy resin composition as a sheet-like reinforcing substrate. An object of the present invention is to provide an impregnated prepreg for forming an insulating layer.

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

[1] Active ester compound (B) having the naphthalene structure when the nonvolatile component in the resin composition containing at least the epoxy resin (A) and the active ester compound (B) having a naphthalene structure is 100% by mass The thermosetting epoxy resin composition whose content is 0.1-30 mass%.
[2] The thermosetting epoxy resin composition according to [1], wherein the active ester compound (B) having 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) having a naphthalene structure is an active ester compound in which an arylcarbonyloxy group is bonded to a naphthalene nucleus of a polynaphthylene oxide structure. 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], further containing an inorganic filler.
[6] The thermosetting epoxy resin composition according to any one of [1] to [5], further containing 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 in which a conductor layer is formed by plating.
[8] An adhesive film for forming an insulating layer, comprising a resin composition layer comprising 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 printed wiring boards, comprising a cured product of any of the resin composition layer of the adhesive film for forming an insulating layer according to [8] and the prepreg for forming an insulating layer according to [9].
[11] A printed wiring board insulator having a conductor layer circuit patterned on an insulating layer made of the printed wiring board insulator 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, [10] The insulator for a printed wiring board according to [11].
[13] A multilayer printed wiring board formed by multilayering the printed wiring board insulator according to [11] or [12].
[14] A semiconductor device using the multilayer printed wiring board according to [13].

The thermosetting epoxy resin composition exhibits a low dielectric loss tangent and can form a roughened surface with excellent adhesion to the plating layer. It is a thermosetting epoxy resin composition capable of forming a cured product layer that becomes an insulating layer having a well-balanced characteristic capable of coping with densification.
Moreover, the hardened | cured material formed by hardening | curing the said thermosetting epoxy resin composition is a case where fine unevenness | corrugation whose surface roughness Ra is 10-200 nm and Rq is 15-250 nm is formed by the surface roughening process. In addition, 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, 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 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 in addition, for inorganic fillers, thermoplastic resins, and epoxy resins. The additive used for the resin composition which forms the insulating layer in a hardening | curing agent, a hardening accelerator, and a multilayer printed wiring board can be contained as needed.

<Epoxy resin (A)>
The epoxy resin (A) used in the thermosetting epoxy resin composition of the present invention is an epoxy resin that is usually used in a resin composition for forming an insulating layer in a multilayer printed wiring board, and is appropriately selected from those listed below. 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 Naphthylene 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 butadiene structure, Alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogen Epoxy resins.

Two or more epoxy resins (A) may be used in combination. When the nonvolatile component of the epoxy resin (A) is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule. Furthermore, an embodiment having two or more epoxy groups in one molecule and containing a liquid aromatic epoxy resin (liquid epoxy resin) at a temperature of 20 ° C. is preferable. An embodiment having at least 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 the 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 an epoxy resin, when the epoxy resin composition is used in the form of an adhesive film, a film exhibiting sufficient flexibility and excellent handleability can be formed. 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.

  Moreover, when using together a liquid epoxy resin and a solid epoxy resin as an epoxy resin, the mixture ratio (liquid: solid state) has the preferable range of 1: 0.1-1: 2 by mass ratio. By using a liquid epoxy resin within such a range, when used in the form of an adhesive film, sufficient flexibility is obtained, handling is improved, and sufficient fluidity can be obtained during lamination. It becomes like this. On the other hand, by using a solid epoxy resin within such a range, the tackiness of the epoxy resin composition can be reduced, and when used in the form of an adhesive film, the deaeration during vacuum lamination can be improved. In addition, the peelability of the protective film and the support film can be improved during vacuum lamination, and the heat resistance after curing can be improved.

In the epoxy resin composition of the present invention, when the nonvolatile 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%. It is mass%, More preferably, it is 20-35 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 containing naphthalene structure (B)>
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 the surface of the cured resin is roughened. In addition, it is considered that it contributes to the formation of fine irregularities with 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 active ester compound as described above can be produced by a condensation reaction between a compound having a naphthalene structure having a nucleus-substituted hydroxyl group and a carboxylic acid compound having a carboxyl group in a naphthalene nucleus or a benzene nucleus. Such active ester compounds are, for example, compounds included in “active ester compounds having a polyaryleneoxy structure as a main skeleton and esterified with an arylcarboxylic acid” described in Patent Document 3.

  Specifically, the thing of the following general formula (1) is 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 formula, R1 becomes a hydrogen atom or a C1-C4 alkyl group each independently, Preferably it is a hydrogen atom. R2 is independently a hydrogen atom or the following general formula (2). Each X is independently hydrogen, benzoyl group or naphthylcarbonyl group, preferably benzoyl group. n and m are each an integer of 0 to 5, and one of n and 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。〕

[Wherein, R1 is the same as above. X is the same as above. p is an integer of 1 or 2. In addition, 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 nonvolatile 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 that exhibits a low dielectric loss tangent and has fine irregularities excellent in adhesion to the plating layer and etching properties. As a more preferable range, it is 3-30 mass%, More preferably, it is 5-28 mass%.

<Inorganic filler>
The epoxy resin composition of the present invention can reduce the linear thermal expansion coefficient and 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, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable. In particular, fused silica and spherical silica are more preferable in terms of reducing the surface roughness of the insulating layer. Preferably, spherical fused silica is more preferable. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs 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 more preferably 2 μm or less from the viewpoint that the surface of the insulating layer has low roughness and enables fine wiring formation. Is more preferably 1 μm or less, still more preferably 0.8 μm or less, particularly preferably 0.6 μm or less, and particularly preferably 0.4 μm or less. On the other hand, when the resin composition is a resin varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. 05 μm or more is more preferable, 0.07 μm or more is further more preferable, and 0.1 μm or more is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used. Inorganic fillers include amino silane coupling agents, ureido silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, silane coupling agents, vinyl silane coupling agents, and styryl silane coupling agents. Surface treatment with surface treatment agents such as acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, organosilazane compounds, titanate coupling agents, etc. to improve its moisture resistance and dispersibility Are preferred. These may be used alone or in combination of two or more.

  When blending an inorganic filler, it varies depending on the properties required for the resin composition, but when the nonvolatile component in the epoxy resin composition is 100% by mass, it is preferably 30 to 90% by mass, More preferably, it is 40-80 mass%, and it is still more preferable that it is 50-70 mass%. If the content of the inorganic filler is too small, the linear thermal expansion coefficient of the cured product tends to increase. If the content is too large, it becomes difficult to form a film when preparing an adhesive film, or the cured product is brittle. Tend 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 also 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, polyetheretherketone resin, and polyester resin. In particular, phenoxy resin and polyvinyl acetal resin are preferable. These thermoplastic resins may 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 8,000 to 200,000, and more preferably in the range of 12,000 to 100,000. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  When mix | blending a thermoplastic resin, when the non-volatile component in an epoxy resin composition is 100 mass%, 0.1-10 mass% is preferable and 0.5-5 mass% is more preferable. Within this range, the effect of improving the film forming ability and mechanical strength can be exhibited, and the melt viscosity can be increased and the roughness of the insulating layer surface after the wet roughening step can be reduced.

<Curing agent for epoxy resin>
The epoxy resin composition of the present invention may further use a general curing agent for epoxy resins. Examples of the epoxy resin curing agent that can be used include TD2090, TD2131 [DIC Corporation, trade name], MEH-7600, MEH-7851, MEH-8000H [Maywa Kasei Co., 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 Corporation, trade name], Fa, Pd [Shikoku Kasei Co., trade name], HFB2006M [Showa Polymer Co., trade name], etc. Benzoxazine-based curing agents, methyl hexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride Acid anhydride curing agents such as acid anhydrides, PT30, PT60, BA230S75 [Lonza Japan Ltd., trade name] cyanate ester-based curing agent, such as and the like.

<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, TPTP-S [Hokuko Chemical Co., Ltd., trade name], Curesol 2MZ, 2E4MZ, Cl1Z, Cl1Z-CN, Cl1Z. -CNS, Cl1Z-A, 2MZ-OK, 2MA-OK, 2PHZ [Shikoku Kasei Kogyo Co., Ltd., trade name] and other imidazole compounds, Novacure [Asahi Kasei Kogyo Co., Ltd., trade name], Fujicure [Fuji Kasei Kogyo ( Co., Ltd., trade name, etc.], amine adduct compounds such as 1,8-diazabicyclo [5,4,0] undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) Amine compounds such as phenol and 4-dimethylaminopyridine, cobalt, copper, zinc, iron, nickel, manganese, tin, etc. Machine metal complex or organic metal salt, and the like. Two or more curing accelerators may be used in combination. When the curing accelerator is blended, it is preferably used in the range of 0.05 to 1% by mass when the total amount of the epoxy resin contained in the epoxy resin composition is 100% by mass (nonvolatile component).

  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 olben and benton, silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, Adhesion imparting agents such as imidazole, thiazole, triazole, silane coupling agents, coloring agents such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black, metal hydroxides, phosphorus-containing compounds, etc. The flame retardant of No. can be mentioned.

  The epoxy resin composition of the present invention is appropriately mixed with the above components, and if necessary, 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. Moreover, it can adjust also as a resin varnish by adding an organic solvent.

  In the epoxy resin composition of the present invention, a roughened surface having a low dielectric loss tangent and excellent adhesion to a plating layer can be formed. Therefore, a resin composition for forming a conductor layer by plating (plating) 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 also suitable as a resin composition for a build-up layer of a multilayer printed wiring board.

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

<Sheet laminated material>
(Insulating layer forming adhesive film)
The adhesive film for forming an insulating layer according to the present invention has a resin composition layer made of a thermosetting epoxy resin composition on a support film. Methods known to those skilled in the art, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater, etc., and further heating or blowing hot air, etc. Thus, the organic solvent can be dried 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 carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an 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 polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

(Insulating layer forming prepreg)
The prepreg for forming an insulating layer according to the present invention is characterized in that a sheet-like fiber base material is impregnated with a thermosetting epoxy resin composition. That is, the resin composition of the present invention can be produced by impregnating a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. As a sheet-like reinforcement base material, what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example. And what formed the prepreg on the support body is suitable.

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

  As described above, the printed wiring board insulator made of a cured product of either the resin composition layer of the insulating layer forming adhesive film or the prepreg for forming the insulating layer is suitable as an insulating layer for a multilayer printed wiring board. It is. It is more preferable to have a conductor layer circuit patterned on an insulating layer made of the printed wiring board insulator. In addition, a multilayer printed wiring board formed by laminating a plurality of printed wiring board insulators having the conductor layer circuit is preferable.

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

  First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated as necessary, and the sheet-like laminate material is pressurized and Laminate to 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 suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

  After laminating the sheet-like laminated material on the circuit board, after cooling to near room temperature, if the support is peeled off, it is peeled off, and the resin composition is thermally cured to form a cured product, thereby forming 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 preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary.

Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for 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 metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in the range of 1 to 15 kgf / cm 2, and the second stage press has the temperature of 150 to 200 ° C. and the pressure is in the range of 1 to 40 kgf / cm 2 It is preferred to do so. The time for each stage is preferably 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

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

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

  Next, a roughening process is performed on the surface of the insulating layer. In the case of dry-type roughening treatment, plasma treatment or the like can be mentioned. It is done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor on the surface of the insulating layer. The swelling treatment with 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 liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU (ABUTEC Japan). 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 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. it 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 permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  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, and even more preferably 100 nm or less in terms of Ra value when forming fine wiring. Moreover, in order to ensure the anchor effect of a roughening surface, it is preferable that it is 10 nm or more. The Ra value is a kind of numerical value representing the surface roughness, and is called arithmetic average roughness. Specifically, the absolute value of the height changing in the measurement region is determined from the surface that is the average line. Measured and arithmetically averaged. For example, using WYKONT 3300 manufactured by Bee Coins Instruments Co., Ltd., a VSI contact mode and a numerical value obtained with a measurement range of 121 μm × 92 μm using a 50 × lens can be obtained.

  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 surface of the insulating layer is dense and smooth, and the peel strength is Found to stabilize. In order to obtain a dense and smooth insulating layer surface, the Rq value is preferably 250 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and even more preferably 100 nm or less. 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 representing the surface roughness, and is called root mean square roughness. Specifically, the absolute value of the height changing in the measurement region is the average line. It represents the root mean square measured from

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It becomes a printed wiring board.

  The peel strength between the insulating layer and the conductor layer is preferably 0.35 kgf / cm or more, and more preferably 0.4 kgf / cm or more so that the insulating layer and the conductor layer are sufficiently adhered to each other. The upper limit of the peel strength is preferably as high as possible and is not particularly limited, but is generally 1.5 kgf / cm or less, 1.2 kgf / cm or less, 1.0 kgf / cm or less, 0.8 kgf / cm or less. 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 in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for 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 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).

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not restrict | limited by these Examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”.

Measurement Method / Evaluation Method <Measurement of Peeling Strength (Peel Strength) of Plating Conductor Layer, Arithmetic Average Roughness (Ra), Root Mean Square Roughness (Rq)>

(1) Surface treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminated board with inner layer circuit (copper foil thickness 18μm, remaining copper ratio 60%, substrate thickness 0.3mm, Matsushita Electric Works, Ltd.) Both surfaces of R5715ES) were immersed in CZ8100 manufactured by Mec Co., Ltd., and the copper surface was roughened.

(2) Lamination of adhesive film The adhesive film prepared in each example and each comparative example was prepared on both sides of a laminate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.). Laminated. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

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

(4) Roughening treatment The laminated plate is immersed in a swelling dip secu-ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 10 minutes at 60 ° C., and then used as a roughening solution. Soaked 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. -It was immersed in securigant P for 5 minutes at 40 ° C. The laminate after the roughening treatment was designated as sample A.

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

(6) Arithmetic average roughness (Ra value), root mean square roughness (Rq value) measurement For sample A, using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoins Instruments), VSI contact mode, Ra and Rq values were obtained from numerical values obtained using a 50 × lens with a measurement range of 121 μm × 92 μm. And it was set as the measured value by calculating | requiring the average value of 10 each.

(7) Measurement of peel strength (peel strength) of plated conductor layer Cut the conductor layer of sample B into a 10 mm wide and 100 mm long part, peel off one end, and grasping tool (TS Co., Ltd.) -E, auto-comb 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 thermally 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 a test piece having a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technology Co., Ltd. were used. The dielectric loss tangent (tan δ) was measured by the cavity resonance method at a measurement frequency of 5.8 GHz. Two test pieces were measured, 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 biphenyl type epoxy resin (epoxy equivalent 291; “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) (Hereinafter abbreviated as “MEK”) 15 parts and 15 parts of cyclohexanone were heated and dissolved with stirring. Thereto, 43 parts of a naphthalene type active ester compound [“EXB9411-65BK” manufactured by DIC Corporation, an active ester equivalent of 272, a solid solution of 65% toluene], a curing accelerator [manufactured by Guangei Chemical Industry Co., Ltd., “4 -Dimethylaminopyridine "] 0.15 parts, spherical silica [average particle size 0.5 μm," SO-C2 "with phenylaminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.18% per unit mass] 100 Part and 15 parts of phenoxy resin (YL6954BH30, MEK solution with a solid content of 30% by mass, weight average molecular weight 40000) were mixed and dispersed uniformly 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 resin thickness after drying was 40 μm, and 80 to 120 ° C. (average (100 ° C.) for 6 minutes to obtain a sheet-like adhesive film.

Example 2
Example 1 except that 43 parts of the naphthalene-type active ester compound (“EXB9411-65BK” manufactured by DIC Corporation, active ester equivalent 272, 65% solids toluene solution) in Example 1 was changed to 80 parts. A resin varnish was prepared in the same manner as described 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 (“EXB9411-65BK” manufactured by DIC Corporation, active ester equivalent 272, 65% solids toluene solution) in Example 1 was changed to 20 parts. A resin varnish was prepared in the same manner as described 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; “NC3000H” manufactured by Nippon Kayaku Co., Ltd.] is added to 15 parts of naphthol type epoxy resin [epoxy equivalent 332, “ESN475V” manufactured by Nippon Steel Chemical Co., Ltd.] 15 And 15 parts of cyanate ester resin ("BA230S75" manufactured by Lonza Corporation, methyl ethyl ketone solution with a solid content of 75%) and a curing catalyst [3% cyclohexanone diluted solution of zinc naphthenate mineral spirit solution (metal content 8%)] A resin varnish was produced in 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 Corporation, toluene solution having an active ester equivalent of 272 and a solid content of 65%) 43 parts of active ester compound [“HPC8000-65T manufactured by DIC Corporation”) ”, 35 parts by weight toluene solution with an active ester equivalent of 223 and a solid content of 65%], and spherical silica (“ SO-C2 ”with an average particle size of 0.5 μm, phenylaminosilane treatment, manufactured by Admatechs, unit mass) The carbon amount per 0.18%] was changed to 100 parts, and the curing accelerator [Guangei Chemical Industry Co., Ltd., “4-dimethylaminopyridine”] 0.15 parts was changed to 0.1 parts. A resin varnish was prepared in exactly the same manner as in Example 1 except that. 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 (“EXB9411-65BK” manufactured by DIC Corporation, active ester equivalent 272, 65% solids toluene solution) in Example 1 was changed to 95 parts. A resin varnish was prepared in the same manner as described above. Next, an adhesive film was obtained in the same manner as in Example 1.

  Measurement results of peel strength, plating surface roughness (Ra value) and (Rq value) after the roughening treatment, and dielectric loss tangent of the evaluation sample, using the adhesive films produced in Examples and Comparative Examples 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 was In addition, the Ra and Rq values after the roughening treatment are much larger than the Ra and Rq values of the roughened surface formed on the surface of the cured product of the epoxy resin composition of Example 1. Regardless, the adhesion (peel strength) to the plating layer is smaller than that of Example 1, and the numerical value of the dielectric loss tangent is large.
In addition, the epoxy resin composition of Comparative Example 2 has an adhesiveness (peel strength) with the plating layer as a result of the amount of the active ester compound containing a naphthalene structure exceeding the range of the present invention. It is smaller than one.
As is clear from the results of the above Examples and Comparative Examples, the epoxy resin composition of the present invention has a well-balanced characteristic that can cope with the increase in the number of layers and the increase in the density of the build-up layer of the multilayer printed wiring board. An epoxy resin composition capable of forming an insulating layer made of a cured product.

Claims (16)

Inclusion of active ester compound (B) containing naphthalene structure when non-volatile component in resin composition containing at least epoxy resin (A) and active ester compound (B) containing naphthalene structure is 100% by mass The amount is 0.1-30% by mass,
The thermosetting epoxy resin composition whose active ester compound (B) containing the said naphthalene structure is an active ester compound which has a polynaphthylene oxide structure and an arylcarbonyloxy group.   The thermosetting epoxy resin composition of Claim 1 whose active ester compound (B) containing the said naphthalene structure is an active ester compound which the arylcarbonyloxy group couple | bonded with the naphthalene nucleus of the polynaphthylene oxide structure.   The thermosetting epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (A) contains a liquid epoxy resin at a temperature of 20 ° C.   Furthermore, the thermosetting epoxy resin composition of any one of Claims 1-3 containing an inorganic filler.   The thermosetting epoxy resin composition of Claim 4 whose content of an inorganic filler is 30-90 mass% when the non-volatile component in a resin composition is 100 mass%.   Furthermore, the thermosetting epoxy resin composition of any one of Claims 1-5 containing a thermoplastic resin.   The thermosetting epoxy resin composition of Claim 6 whose content of a thermoplastic resin is 0.1-10 mass% when the non-volatile component in a resin composition is 100 mass%.   The thermosetting epoxy resin according to any one of claims 1 to 7, wherein the content of the epoxy resin (A) is 10 to 50% by mass when the nonvolatile component in the resin composition is 100% by mass. Composition.   The thermosetting epoxy resin composition according to any one of claims 1 to 8, which is a resin composition for an insulating layer of a multilayer printed wiring board on which a conductor layer is formed by plating.   An adhesive film for forming an insulating layer, comprising a resin composition layer comprising the thermosetting epoxy resin composition according to any one of claims 1 to 9 on a support film.   A prepreg for forming an insulating layer, wherein the thermosetting epoxy resin composition according to any one of claims 1 to 9 is impregnated in a sheet-like fiber base material.   The insulator for printed wiring boards which consists of a hardened | cured material in any one of the resin composition layer of the adhesive film for insulating layer formation of Claim 10, and the prepreg for insulating layer formation of Claim 11.   The insulator for printed wiring boards which has the conductor layer circuit patterned on the insulating layer which consists of an insulator for printed wiring boards of Claim 12.   The insulating layer has an arithmetic average roughness Ra of 10 to 200 nm, a root mean square roughness Rq of 15 to 250 nm, and a peel strength of the insulating layer and the conductor layer of 0.35 kgf / cm (3.43 N / cm). 14) The printed wiring board insulator according to claim 12 or 13, characterized in that it is above.   The multilayer printed wiring board formed by laminating | stacking the insulator for printed wiring boards of Claim 13 or 14 in multiple layers.   A semiconductor device comprising the multilayer printed wiring board according to claim 15.