JP2019090059A - Thermosetting epoxy resin composition, adhesive film for forming insulating layer and multilayer printed wiring board - Google Patents

Abstract

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

  In the present invention, a thermosetting epoxy resin composition suitable for the formation of an insulating layer having a low dielectric loss tangent and a low roughness and a high peel roughened surface, a cured product thereof, and a 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 peel as an insulating layer.

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

  The anchor effect by the unevenness formed on the surface of the insulating layer is larger as the surface roughness is larger, and the adhesion to the plated conductor layer is enhanced. However, when the roughness of the surface of the insulating layer is large, when partially removing the thin film conductor layer formed on the roughened surface by etching so as to form a predetermined wiring pattern, the surface portion to be removed Since the conductor layer portion which has entered the concave portion is difficult to be removed, the etching process takes a long time, and the wiring pattern portion to be left is eroded by the influence, and the fine wiring is damaged or disconnected. Increase the risk of Therefore, in order to cope with the miniaturization and densification of the wiring, the surface state of the insulating layer is rough as much as possible with sufficient unevenness and adhesion with the thin film conductor layer formed by plating. It is required to be

  In addition, 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 a 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 linear thermal expansion coefficient between the insulating layer and the conductor layer is large, and problems such as generation of cracks between the insulating layer and the conductive layer are likely to occur.

  Heretofore, as a curing agent used for a thermosetting resin composition for forming the insulating layer of the inner layer circuit board of a multilayer printed wiring board as described above, an "active ester compound" is known, and such "active ester compound" As "," an "active ester compound containing a dicyclopentadienyl diphenol structure" has mainly been used. However, in recent years, with the progress in increasing the number of layers and increasing the density of build-up layers of multilayer printed wiring boards, there have been many proposals for epoxy resin compositions capable of forming insulating layers that can be handled.

  Patent Document 1 discloses an insulating layer exhibiting low dielectric properties by using an active ester compound obtained by aryl esterification of 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 can be obtained.

  In Patent Document 2, despite the relatively small roughness of the roughened surface obtained by roughening the surface of the cured product, the roughened surface exhibits high adhesion to the plated conductor, and the linear thermal expansion coefficient (A) epoxy resin, (B) active ester compound, (C) phenol resin having a triazine structure, (D) maleimide compound, and (E) phenoxy resin as an epoxy resin composition capable of forming an insulating layer having a small amount of An epoxy resin composition is described which it contains.

  In addition, Patent Document 3 discloses a polyarylene oxy structure as a thermosetting epoxy resin composition which gives a cured product having both excellent heat resistance and flame retardancy while exhibiting a low dielectric constant and a low dielectric loss tangent. An epoxy resin composition is described which contains an active ester resin having an aryl carbonyl group in the aromatic nucleus of the structure as a main skeleton.

  As described above, many proposals have been made for epoxy resin compositions suitable for the formation of the insulating layer of the inner layer circuit board, but a finely roughened surface having a low dielectric loss tangent and excellent adhesion to the plating layer The demand for an epoxy resin composition capable of forming an insulating layer having well-balanced properties of being able to cope with the increase in the number of layers and increase in density of buildup layers of multilayer printed wiring boards, that can be formed There is.

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

The present invention exhibits a low dielectric loss tangent, and can form a roughened surface having fine asperities excellent in adhesion with a plating layer and etching properties, and increasing the number of layers in a buildup layer of a multilayer printed wiring board A thermosetting epoxy resin composition capable of forming an insulating layer having well-balanced properties corresponding to high density, a printed wiring board having an insulating layer formed of a cured product thereof, and the printed wiring board It is an object of the present invention to provide a multilayer printed wiring board.
Further, according to the present invention, an adhesive film for forming an insulating layer, in which a resin composition layer comprising the above-mentioned thermosetting epoxy resin composition is formed on a supporting film, and the above-mentioned thermosetting epoxy resin composition form a sheet-like reinforcing substrate An object of the present invention is to provide a prepreg for forming an insulating layer, which is impregnated.

  Among the various resins known as resin components to be compounded in the epoxy resin composition, the present inventors have intensively studied the curing agent and the compounding resins used in the thermosetting epoxy resin composition, It has been found that "an active ester compound containing a naphthalene structure" is a resin component which can be a means for solving the above problems when the specific amount thereof is blended in the resin composition, and the following invention has been made. .

[1] Active ester compound (B) containing naphthalene structure when the non-volatile component in the resin composition containing at least epoxy resin (A) and active ester compound (B) containing naphthalene structure is 100% by mass The thermosetting epoxy resin composition whose content of 0.1-30 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 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], 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 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 substrate.
[10] An insulator for a printed wiring board, comprising the resin composition layer of the adhesive film for forming an insulating layer according to [8] and the cured product of any of 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 consisting of the insulator for a printed wiring board according to [10].
[12] A surface roughness Ra of the insulating layer is 10 to 200 nm, Rq is 15 to 250 nm, and peel strengths of the insulating layer and the conductor layer are 0.35 kgf / cm or more. The insulator for printed wiring boards as described in [10] or [11].
[13] A multilayer printed wiring board, which is formed by laminating multiple layers of 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, can form a roughened surface excellent in adhesion to the plating layer, and can increase the number of build-up layers of a multilayer printed wiring board, and increase the height. It is a thermosetting epoxy resin composition capable of forming a cured material layer to be an insulating layer having well-balanced properties capable of coping with density formation.
In addition, a cured product obtained by curing the above-mentioned thermosetting epoxy resin composition has a surface roughness Ra, when it has a surface roughness Ra of 10 to 200 nm and Rq of 15 to 250 nm. Since it also becomes a roughened surface excellent in adhesiveness with a 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 printed wiring board, and the multilayer printed wiring board of the present invention will be described in more detail.

  The thermosetting epoxy resin composition of the present invention contains, as essential components, an epoxy resin (A) and an active ester compound (B) containing a naphthalene structure, and in addition, for inorganic fillers, thermoplastic resins and epoxy resins The curing agent, the curing accelerator, and the additive used for the resin composition which forms the insulating layer in a multilayer printed wiring board can be contained as needed.

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

  For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthol epoxy resin, naphthalene epoxy resin Naphthylene ether type epoxy resin, glycidyl amine 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, Alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogen Epoxy resins.

The epoxy resin (A) may be used in combination of two or more. When the nonvolatile component of the epoxy resin (A) is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Furthermore, an embodiment is preferable in which an aromatic epoxy resin (liquid epoxy resin) having two or more epoxy groups in one molecule and which is liquid at a temperature of 20 ° C. is contained. It is more preferable to use an embodiment containing an aromatic epoxy resin (solid epoxy resin) which has at least 20 epoxy groups and is solid at a temperature of 20 ° C.
In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in its molecule. Moreover, an epoxy equivalent (g / eq) is a molecular weight per epoxy group. By using a liquid epoxy resin and a solid epoxy resin as the epoxy resin, when using the epoxy resin composition in the form of an adhesive film, it can exhibit sufficient flexibility and form a film excellent in handleability. 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 blending ratio (liquid: solid) is preferably in the range of 1: 0.1 to 1: 2 in mass ratio. By using a liquid epoxy resin in such a range, sufficient flexibility can be obtained when used in the form of an adhesive film, and the handleability can be improved, and sufficient fluidity can be obtained in the case of lamination. It 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 reduced, and when used in the form of an adhesive film, the degassing property at the time of vacuum lamination can be improved. Moreover, the peelability of a protective film or a support film can be made favorable at the time of vacuum lamination, and the heat resistance after hardening can also 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) in this range, the curability of the epoxy resin composition tends to be improved.

<Active Ester Compound Containing Naphthalene Structure (B)>
When 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 an epoxy resin, the surface of the cured resin is roughened. In addition, it is thought that it also 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 is preferably an active ester compound having a polynaphthylene oxide structure and an arylcarbonyloxy group, More preferred is an active ester compound in which an arylcarbonyloxy group is bonded to the naphthalene nucleus of the naphthylene oxide structure. The polynaphthylene oxide structure may be a polynaphthylene oxide structure substituted with an alkyl group having 1 to 4 carbon atoms, and may further have a polyphenylene oxide structure. The active ester compound as described above can be produced by the condensation reaction of a compound having a naphthalene structure having a nucleus-substituted hydroxyl group and a carboxylic acid compound having a carboxyl group at a naphthalene nucleus or a benzene nucleus. Such an active ester compound is, for example, a compound which is included in "an active ester compound having a polyarylene oxy-based structure as a main skeleton and being esterified with an arylcarboxylic acid" described in Patent Document 3.

  Specifically, the thing of 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. Each R 2 independently represents a hydrogen atom or the following general formula (2). X is each independently hydrogen, benzoyl group or naphthylcarbonyl group, preferably benzoyl group. n and m are each an integer of 0 to 5, 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。〕

[Wherein, R 1 is as defined above. X is the same as above. p is an integer of 1 or 2. In addition, at least one of X in the above 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 having fine asperities excellent in adhesion with the plating layer and in etching property as well as exhibiting a low dielectric loss tangent. A more preferable range is 3 to 30% by mass, and a further preferable range is 5 to 28% by mass.

<Inorganic filler>
The epoxy resin composition of the present invention can reduce the linear thermal expansion coefficient and the dielectric loss tangent by further containing an inorganic filler. As the inorganic filler, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium oxide, boron nitride, aluminum borate, barium titanate, Strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like can be mentioned. Among them, silicas such as amorphous silica, crushed silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica and the like are preferable, and fused silica and spherical silica are more preferable in that they reduce the surface roughness of the insulating layer. Preferably, spherical fused silica is more preferred. 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 Admatechs Co., Ltd.

  The average particle size of the inorganic filler is not particularly limited, but it 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 has low roughness and enables fine wiring formation. Is more preferably 1 μm or less, particularly 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, in the case where the resin composition is a resin varnish, the viscosity 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 the handling property being reduced. The thickness is more preferably 05 μm or more, still more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle size 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 type particle size distribution measuring device, and the median diameter can be measured as an average particle size. As a measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 or the like manufactured by Horiba, Ltd. can be used. The inorganic filler includes aminosilane type coupling agent, ureido silane type coupling agent, epoxy silane type coupling agent, mercaptosilane type coupling agent, silane type coupling agent, vinyl silane type coupling agent, styrylsilane type coupling agent 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 their moisture resistance and dispersibility. Are preferred. These may be used alone or in combination of two or more.

  When an inorganic filler is blended, it varies depending 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 preferable that 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, and if the content is too large, film formation becomes difficult when preparing the adhesive film, or the cured product becomes brittle. Tend to

<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 moldability when used in the form of an adhesive film. . Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide imide resin, polyether imide resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone 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 1,200 to 100,000. The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (in terms of polystyrene). 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. It can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and calculated using a calibration curve of standard polystyrene.

  In the case of blending a thermoplastic resin, when the non-volatile component in the epoxy resin composition is 100% by mass, 0.1 to 10% by mass is preferable, and 0.5 to 5% by mass is more preferable. Within this range, the effect of improving the film moldability and mechanical strength is exhibited, and the increase in the melt viscosity and the roughness of the surface of the insulating layer after the wet roughening step can be further reduced.

<Hardener for epoxy resin>
The epoxy resin composition of the present invention can also use a general epoxy resin curing agent. As curing agents for epoxy resin which can be used, TD 2090, TD 2131 (trade names of DIC Corporation), MEH-7600, MEH-7851, MEH-8000 H (trade names of Meiwa Kasei Co., Ltd.), NHN, CBN, GPH -65, GPH-103 (Nippon Kayaku Co., Ltd., trade name), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (trade name of Nippon Steel Chemical Co., Ltd.), LA7052, LA7054, Phenolic curing agents such as LA3018, LA1356 (DIC, Inc., trade names), Fa, Pd (Shikoku Kasei, trade names), HFB 2006 M (Showa Highpolymer, trade names), etc. Benzoxazine-based curing agent, methyl hexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadiz 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.

<Hardening accelerator>
The epoxy resin composition of the present invention can efficiently adjust the curing time and curing temperature by further incorporating a curing accelerator. As the curing accelerator, for example, organic phosphine compounds such as TPP, TPP-K, TPP-S, TPTP-S (trade name of Hokuko Chemical Industry Co., Ltd.), Cuazole 2MZ, 2E4MZ, Cl1Z, Cl1Z-CN, Cl1Z -Imidazole compounds such as CNS, Cl1Z-A, 2MZ-OK, 2MA-OK, 2PHZ (trade names of Shikoku Kasei Kogyo Co., Ltd., etc.), Novacua (Asahi Kasei Kogyo Co., Ltd., trade names), Fujicure (Fuji Kasei Kogyo Co., Ltd. Etc., brand names], 1,8-diazabicyclo [5,4,0] undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) Phenol, amine compounds such as 4-dimethylaminopyridine, cobalt, copper, zinc, iron, nickel, manganese, tin, etc. Machine metal complex or organic metal salt, and the like. The curing accelerator may be used in combination of two or more. When mix | blending a hardening accelerator, when the total amount of the epoxy resin contained in an epoxy resin composition shall be 100 mass% (non-volatile component), it is preferable to use in 0.05-1 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 resin additives include organic fillers such as silicone powder, nylon powder, fluorine powder and rubber particles, thickeners such as olben and benton, silicone based, fluorine based, polymeric based antifoaming agents or leveling agents, Adhesion-imparting agents such as imidazole, thiazole, triazole, and silane coupling agents, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, colorants such as carbon black, metal hydroxides, phosphorus-containing compounds, etc. Flame retardants and the like can be mentioned.

  The epoxy resin composition of the present invention can be suitably mixed by the above components, and if necessary, by mixing means such as a triple roll, ball mill, bead mill, sand mill or stirring means such as a super mixer or planetary mixer. It can be adjusted by mixing. Moreover, it can also be adjusted as a resin varnish by adding an organic solvent.

  The epoxy resin composition of the present invention exhibits a low dielectric loss tangent and can form a roughened surface excellent in adhesion to the plating layer, so that a resin composition for forming a conductor layer by plating (plating (plating) It can be used suitably as resin composition for insulating layers of the multilayer printed wiring board which forms a conductor layer by this, and is further suitable as a resin composition for buildup layers of a multilayer printed wiring board.

  The resin composition of the present invention is a composition particularly suitable as an insulating layer forming material of a multilayer printed wiring board, but solder resist, underfill material, die bonding material, semiconductor sealing material, hole filling resin, component embedding resin, etc. It can be used in a wide range of applications where resin compositions are 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 laminate materials such as adhesive films and prepregs, and circuit boards (laminate board applications, multilayer printed wiring board applications, etc.). The resin composition of the present invention can be applied to a circuit board in the form of a varnish to form an insulating layer, but generally, industrially, the insulating layer is formed as a sheet-like laminate material such as an adhesive film or a prepreg. Used.

<Sheet-like laminated material>
(Adhesive film for insulating layer formation)
The adhesive film for forming an insulating layer of the present invention is characterized by having a resin composition layer comprising a thermosetting epoxy resin composition on a support film. A method known to those skilled in the art, for example, a resin varnish prepared by dissolving a resin composition in an organic solvent is prepared, this resin varnish is applied to a support using a die coater or the like, and further heating or hot air blowing etc. It can manufacture by drying an organic solvent by this, and forming a resin composition layer.

  Examples of organic solvents include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, acetates such as propylene glycol monomethyl ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol And aromatic hydrocarbons such as toluene and xylene; and 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 varnish containing 30 to 60% by mass of the organic solvent is dried at 50 to 150 ° C. for about 3 to 10 minutes to form a resin composition layer. 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.

  As the support, films of polyolefins such as polyethylene, polypropylene and polyvinyl chloride, films of polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), films of polyesters such as polyethylene naphthalate, polycarbonate films, polyimide films, etc. Various plastic films are mentioned. Further, release paper, copper foil, metal foil such as aluminum foil, or the like may be used. Among them, plastic films are preferable and polyethylene terephthalate films are more preferable from the viewpoint of versatility. The support and a protective film to be described later may be subjected to surface treatment such as mud treatment and corona treatment. Further, the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluorine resin release agent.

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

  The protective film according to the support can be further laminated on the surface of the resin composition layer to which the support is not adhered. 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 adhesion of dust and the like to the surface of the resin composition layer and scratches. The adhesive film can also be wound and stored in a roll.

(Pre-preg for insulating layer formation)
The prepreg for insulating layer formation of the present invention is characterized in that a thermosetting epoxy resin composition is impregnated into a sheet-like fiber substrate. That is, it can be manufactured by impregnating a sheet-like reinforcing substrate with the resin composition of the present invention by a hot melt method or a solvent method, heating and semi-curing it. As a sheet-like reinforcement base material, what consists of fibers usually used as fibers for prepregs, such as glass cloth and an aramid fiber, can be used, for example. And it is preferable that a prepreg is formed on a support.

  In the hot melt method, the resin composition is once coated on a support without dissolving it in an organic solvent, and then it is laminated on a sheet-like reinforcing substrate, or directly coated on a sheet-like reinforcing substrate by a die coater. And so on, to produce a prepreg. In the solvent method, the resin is dissolved in an organic solvent to prepare a resin varnish in the same manner as in the adhesive film, and the sheet-like reinforcing substrate is immersed in the varnish to impregnate the resin varnish into the sheet-like reinforcing substrate. It is a method of drying. The adhesive film can also be prepared by continuously heat laminating from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support, a protective film and the like can also be used in the same manner as the adhesive film.

  As described above, an insulator for a printed wiring board comprising the resin composition layer of the adhesive film for forming an insulating layer and the cured product of any of the prepregs for forming the insulating layer is suitable as an insulating layer for a multilayer printed wiring board It is. Further, 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 laminate material produced as described above will be described.

  First, a sheet-like laminate 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 that by which the conductor layer (circuit) by which pattern processing was carried out was carried out on the single side | surface or both surfaces of the above board | substrates here. In addition, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately stacked, a conductor layer (circuit) in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned is also used here. Included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, 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 if necessary, and the sheet-like laminate material is pressurized and Laminate on a circuit board while heating. In the sheet-like laminate material of the present invention, a method of laminating on a circuit board under reduced pressure by vacuum lamination is suitably used. The conditions of the laminate are not particularly limited, but, for example, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressing pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × It is preferable to use 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), a pressure bonding time (lamination time) of preferably 5 to 180 seconds, and laminating under a reduced pressure of 20 mm Hg (26.7 hPa) or less. In addition, the method of laminating may be a batch system or a continuous system with a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, Vacuum Applicator manufactured by Nichigo Morton Co., Ltd., vacuum pressure type laminator manufactured by Meiki Co., Ltd., roll type dry coater manufactured by Hitachi Industries, Ltd., Hitachi AC Co., Ltd. A vacuum laminator etc. can be mentioned.

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

The sheet-like laminate material can also be laminated on one side or both sides of the circuit board using a vacuum press. The lamination process of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press. For example, it can be carried out 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 reduced pressure 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 in order to control the bleeding of the resin. For example, the temperature of the first stage press is 70 to 150 ° C., the pressure is 1 to 15 kgf / cm 2, and the second stage press is 150 to 200 ° C., the pressure is 1 to 40 kgf / cm 2 It is preferred to do. The time of each step is preferably 30 to 120 minutes. By thermally curing the resin composition layer in this manner, an insulating layer can be formed on the circuit board. As a vacuum hot press marketed commercially, MNPC-V-750-5-200 (made by Meiki Seisakusho KK), VH1-1603 (made by Kitagawa Seiki Co., Ltd.) etc. are mentioned, for example.

  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. There is no lower limit, but it is 0.001 or more, 0.003 or more.

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

  Next, the surface of the insulating layer is roughened. In the case of dry roughening treatment, plasma treatment etc. may be mentioned, and in the case of wet roughening treatment, swelling treatment by swelling liquid, roughening treatment by oxidizing agent and neutralization treatment by neutralization solution may be mentioned in this order Be The wet roughening treatment is preferable in that the 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 solution is performed by immersing the insulating layer in the swelling solution at 50 to 80 ° C. for 5 to 20 minutes (preferably 8 to 15 minutes at 55 to 70 ° C.). The swelling solution includes an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and examples of the alkaline solution include sodium hydroxide solution, potassium hydroxide solution and the like. Examples of commercially available swelling solutions include Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd., Swelling Dip Securiganth SBU, and the like. be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer at 60 to 80 ° C. for 10 to 30 minutes (preferably, at 70 to 80 ° C. for 15 to 25 minutes) in an oxidizing agent solution. As the oxidizing agent, for example, alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. may be mentioned. 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 manufactured by Atotech Japan Co., Ltd. and dosing solution Security G. The neutralization treatment with the neutralization solution is carried out by immersing in the neutralization solution for 3 to 10 minutes at 30 to 50 ° C. (preferably 3 to 8 minutes at 35 to 45 ° C.). As the neutralization solution, an acidic aqueous solution is preferable, and as a commercial product, reduction solution thin security G made by Atotech Japan Co., Ltd. can be mentioned.

  The roughness of the roughened surface obtained by roughening the surface of the insulating layer is preferably 200 nm or less in Ra value, more preferably 150 nm or less, and still more preferably 100 nm or less, in order to form 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 surface roughness, and is called arithmetic average roughness, and specifically, from the surface which is an average line, the absolute value of the height changing in the measurement area Measured and arithmetically averaged. For example, using WYKONT 3300 manufactured by Becoin Instruments, it can be determined by numerical values obtained with a measurement range of 121 μm × 92 μm with a VSI contact mode, 50 × lens.

    Further, since the root mean square roughness (Rq value) reflects the local state of the surface of the insulating layer, it is possible to confirm that the insulating layer surface is dense and smooth by grasping the Rq value, and the peel strength is I found it to stabilize. The Rq value is preferably 250 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and still more preferably 100 nm or less, in order to obtain a dense and smooth insulating layer surface. 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 surface roughness, and is called root mean square roughness, and more specifically, a surface whose average line is the absolute value of the height changing in the measurement area. And the root mean square is represented.

  Then, a conductor layer is formed on the insulating layer by dry plating or wet plating. As dry plating, known methods such as vapor deposition, sputtering, ion plating and the like can be used. As wet plating, a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a pattern reverse to that of the conductor layer, and forming a conductor layer only by electroless plating, etc. may be mentioned. Be As a subsequent pattern formation method, for example, a subtractive method, a semi-additive method or the like known to those skilled in the art can be used, and a multilayer formed by stacking buildup layers in multiple stages by repeating the above-described series of steps multiple times 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, 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 upper limit of the peel strength is preferably as high as possible, and is not particularly limited, but 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, and the like. In the present invention, since it has low roughness and high peel, it can be suitably used as a buildup 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 the conduction part of the multilayer printed wiring board of the present invention. The "conductive location" is a "location for transmitting an electrical signal 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 in the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, the wire bonding mounting method, flip chip mounting method, no bump A mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like can be given.

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

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

(1) Underlayer treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminated board with inner layer circuit formed (copper foil thickness 18 μm, residual copper rate 60%, substrate thickness 0.3 mm, Matsushita Electric Works Co., Ltd.) Both surfaces of R5715 ES) manufactured by Meck Co., Ltd. were immersed in CZ 8100 manufactured by Mec Co., Ltd. to roughen the copper surface.

(2) Lamination of adhesive film The adhesive film prepared in each Example and each Comparative Example was used as a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meishin Machinery Co., Ltd.) to make a double-sided laminate. Laminated to Lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then press-bonding at 100 ° C. under 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 the curing conditions of 170 ° C. for 30 minutes.

(4) Coarsening treatment The laminate is immersed in a swelling solution, a swelling dip-cure ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 10 minutes at 60 ° C., and then as a roughening solution, Atotech Japan Co., Ltd. Immersed in Concentrated compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) for 20 minutes at 80 ° C., and finally, as a neutralization solution, reduction choleucine of Atotech Japan Co., Ltd. Immersed in Security G at 5O 0 C for 5 minutes. The laminated board after this roughening treatment was taken 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 a solution for electroless plating containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing for heating at 150 ° C. for 30 minutes, an etching resist was formed, and after forming a pattern 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 laminated board was used as sample B.

(6) Measurement of Arithmetic Average Roughness (Ra Value) and Root-Mean-Square Roughness (Rq Value) For sample A, VSI contact mode, using a non-contact surface roughness meter (WYKO NT3300 manufactured by Becoin Instruments, Inc.) Ra and Rq values were determined by numerical values obtained with a 50 × lens as a measurement range of 121 μm × 92 μm. And it was set as the measured value by calculating | requiring the average value of 10 points | pieces, respectively.

(7) Measurement of peel strength (peel strength) of the plated conductor layer The conductor layer of sample B was cut into a portion with a width of 10 mm and a length of 100 mm, and one end of this was peeled off to hold E. Grasp with an autocom type tester AC-50C-SL) and measure the load (kgf / cm) when 35 mm was peeled off vertically at a speed of 50 mm / min in room temperature.

<Measurement of dielectric loss tangent>
The adhesive film obtained in each Example and each Comparative Example was thermally cured at 190 ° C. for 90 minutes to peel off the PET film to obtain a sheet-like cured product. The cured product is cut into test pieces of 2 mm in width and 80 mm in length, and using a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362 B manufactured by Agilent Technologies Co., Ltd. The dielectric loss tangent (tan δ) was measured at a measurement frequency of 5.8 GHz by the cavity resonance method. The measurement was performed on two test pieces, and the average value was calculated.

Example 1
15 parts of liquid bisphenol A-type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Co., Ltd. “828US”) and 15 parts of biphenyl type epoxy resin (epoxy equivalent 291; Nippon Kayaku Co., Ltd. “NC3000H”) and methyl ethyl ketone The solution was heated and dissolved in 15 parts of cyclohexanone and 15 parts of cyclohexanone while stirring. Thereto, 43 parts of a naphthalene type active ester compound ("EXB 9411-65BK" manufactured by DIC Corporation, active ester equivalent weight 272, 65% solid content in toluene), curing accelerator (manufactured by Hiroei Kagaku Kogyo Co., Ltd., "4 -Dimethylaminopyridine]] 0.15 parts, spherical silica [average particle size 0.5 μm, with phenylaminosilane treatment "SO-C2", manufactured by Admatechs Co., Ltd., carbon amount per unit mass: 0.18%] 100 A resin varnish was prepared by mixing 15 parts of phenoxy resin (YL 6954 BH30, MEK solution with a solid content of 30% by mass, weight average molecular weight 40000) and dispersing uniformly using a high-speed rotary mixer. Next, the resin varnish is applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) by a die coater so that the thickness of the resin after drying is 40 μm, and the temperature is 80 to 120 ° C. (average The film was dried at 100 ° C. for 6 minutes to obtain a sheet-like adhesive film.

Example 2
Example 1 except that the naphthalene type active ester compound [EXB 9411-65BK made by DIC Corporation, active ester equivalent 272, toluene solution with a solid content of 65%] of Example 1 was changed to 80 parts A resin varnish was prepared in exactly the same manner as in. Next, in the same manner as in Example 1, an adhesive film was obtained.

Example 3
Example 1 except that the naphthalene type active ester compound [EXB 9411-65BK made by DIC Corporation, active ester equivalent 272, toluene solution with 65% solid content] of Example 1 was changed to 20 parts A resin varnish was prepared in exactly the same manner as in. Next, in the same manner as in Example 1, an adhesive film was obtained.

Example 4
15 parts of the biphenyl type epoxy resin [epoxy equivalent 291 manufactured by Nippon Kayaku Co., Ltd. "NC3000H"] of Example 1 and naphthol type epoxy resin [epoxy equivalent 332 manufactured by Nippon Steel Chemical Co., Ltd. "ESN 475V"] 15 Change to part and 15 parts of cyanate ester resin ("BA230S75" manufactured by Lonza, 75% solid content in methyl ethyl ketone solution) and curing catalyst (3% cyclohexanone diluted solution of zinc naphthenate mineral spirit solution (metal content 8%)) A resin varnish was produced in exactly the same manner as in Example 3 except that 0.03 part was added. Next, in the same manner as in Example 1, an adhesive film was obtained.

Comparative Example 1
43 parts of a naphthalene type active ester compound ("EXB9411-65BK" manufactured by DIC Corporation, active ester equivalent weight 272, a solid content of 65% solid content), an active ester compound [HPC8000-65T manufactured by DIC Corporation] "Active ester equivalent 223, toluene solution with solid content 65%" Change to spherical silica [average particle size 0.5 μm, with phenylaminosilane treatment "SO-C2", manufactured by Admatex Co., Ltd., unit mass The amount of carbon per 0.18%] was changed to 90 parts of 100 parts, and 0.15 parts of a hardening accelerator ("4-dimethylaminopyridine" manufactured by Koei Chemical Industry Co., Ltd.) was changed to 0.1 parts A resin varnish was produced in exactly the same manner as in Example 1 except for the above. Next, in the same manner as in Example 1, an adhesive film was obtained.

Comparative example 2
Example 1 except that the naphthalene type active ester compound [EXB 9411-65BK made by DIC Corporation, active ester equivalent 272, toluene solution of 65% solid content] of Example 1 was changed to 95 parts A resin varnish was prepared in exactly the same manner as in. Next, in the same manner as in Example 1, an adhesive film was obtained.

  The peel strength of the plating conductor layer of the evaluation sample using the adhesive film manufactured in the example and the comparative example, the surface roughness (Ra value) and (Rq value) after the roughening treatment, and the measurement results of the dielectric loss tangent of the evaluation sample The evaluation results of flexibility are shown in Table 1.

As shown in Table 1, a 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 Also, the numerical values of Ra and Rq after the roughening treatment are far greater than the numerical 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 (peel strength) with the plating layer is smaller than that of Example 1, and the value of the dielectric loss tangent is larger.
In addition, in the epoxy resin composition of Comparative Example 2, the compounding amount of the active ester compound containing a naphthalene structure is larger than the range of the present invention, so the adhesion (peel strength) with the plating layer is an example. It is smaller than one.
As is clear from the results of the above-described Examples and Comparative Examples, the epoxy resin composition of the present invention has well-balanced characteristics capable of coping with the formation of a multilayer and the increase in density of buildup layers of multilayer printed wiring boards. It is the epoxy resin composition which can form the insulating layer which consists of hardened | cured material.

Claims (14)

  Content of 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 a naphthalene structure is 100% by mass The thermosetting epoxy resin composition whose is 0.1-30 mass%.   The thermosetting epoxy resin composition according to claim 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.   The thermosetting epoxy resin composition according to claim 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 of a polynaphthylene oxide structure. .   The thermosetting epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin (A) contains a liquid epoxy resin.   The thermosetting epoxy resin composition according to any one of claims 1 to 4, further comprising an inorganic filler.   The thermosetting epoxy resin composition according to any one of claims 1 to 5, further comprising a thermoplastic resin.   The thermosetting epoxy resin composition according to any one of claims 1 to 6, which is a resin composition for an insulating layer of a multilayer printed wiring board which forms a conductor layer 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 7 on a support film.   The prepreg for insulating layer formation characterized by the sheet-like fiber base material being impregnated with the thermosetting epoxy resin composition of any one of Claims 1-7.   The insulator for printed wiring boards which consists of hardened | cured material of the resin composition layer of the adhesive film for insulating layer formation of Claim 8, and the prepreg for insulating layer formation of Claim 9.   The insulator for printed wiring boards which has a conductor layer circuit patterned on the insulating layer which consists of an insulator for printed wiring boards of Claim 10.   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. Or the insulator for printed wiring boards as described in 11.   A multilayer printed wiring board formed by multilayer-stacking the printed wiring board insulator according to claim 11 or 12.   A semiconductor device comprising the multilayer printed wiring board according to claim 13.