JP2017206578A - Thermosetting resin composition, carrier-attached resin film, prepreg, metal-clad laminate, resin substrate, printed wiring board, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that can reduce resin residues while obtaining a low dielectric loss tangent.SOLUTION: A thermosetting resin composition is used for forming an insulating layer in a printed wiring board. The thermosetting resin composition contains (A) polyphenylene ether, (B) a component that contains at least one selected from the group consisting of a cyanate ester resin, a phenolic resin, a maleimide compound, and an epoxy resin and reacts with the (A), and (C) a filler, with the component (A) having a content of 10 pts.wt. or more and 35 pts.wt. or less relative to the resin solid content 100 pts.wt.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermosetting resin composition, a resin film with a carrier, a prepreg, a metal-clad laminate, a resin substrate, a printed wiring board, and a semiconductor device.

  In current electronic devices, higher speed transmission and higher density integration are progressing, and build-up type multilayer printed wiring boards are often used as printed wiring boards used in these electronic devices.

The multilayer printed wiring board is provided with a through hole in the resin layer for interlayer connection, and then subjected to a plating process for conducting the inside of the through hole and the inner layer circuit. If the resin residue due to the resin material forming the resin layer is in the through hole during the plating process, it causes a conduction failure. Therefore, before the plating process, a desmear process that removes the resin residue using a chemical solution is performed.
Here, if the solubility of the resin layer in the chemical solution is too high, the resin layer around the through-hole is also dissolved, which is not preferable. However, if the solubility of the resin layer is low, a resin residue is likely to be generated. Occurs.

  In recent years, electronic devices that operate with high-frequency signals are increasing, and the speed of signal processing is increasing. For this reason, there has been a tendency for transmission loss and delay of electric signals to increase as the necessity of using high frequency increases. Therefore, it is desired to form a resin layer using a resin material having a lower dielectric loss tangent.

  Patent Document 1 discloses a resin composition using polyphenylene ether, an epoxy resin, and an inorganic filler from the viewpoint of obtaining excellent dielectric properties.

JP 2014-240474 A

  However, the technique described in Patent Document 1 is not sufficient in terms of obtaining a low dielectric loss tangent while reducing resin residues.

  As a result of intensive studies by the present inventors, it was found that resin residues can be suppressed while obtaining a low dielectric loss tangent by combining a specific component with polyphenylene ether and controlling the content of polyphenylene ether.

According to the present invention, a thermosetting resin composition used for forming an insulating layer in a printed wiring board,
(A) polyphenylene ether;
(B) a component that includes at least one selected from the group consisting of a cyanate ester resin, a phenol resin, a maleimide compound, and an epoxy resin, and reacts with (A);
(C) a filler;
Including
A thermosetting resin composition is provided in which the content of the component (A) is 10 to 35 parts by weight with respect to 100 parts by weight of the resin solid content.

  Furthermore, according to this invention, the resin film with a carrier provided with a carrier base material and the resin film which consists of said thermosetting resin composition provided on the said carrier base material is provided.

  Furthermore, according to the present invention, there is provided a prepreg in which a fiber base material is impregnated with the thermosetting resin composition.

  Furthermore, according to the present invention, there is provided a metal-clad laminate in which a metal layer is disposed on at least one surface of a cured product of the prepreg.

  Furthermore, according to this invention, a resin substrate provided with the insulating layer comprised with the hardened | cured material of the said thermosetting resin composition is provided.

  Furthermore, according to this invention, the printed wiring board by which the circuit layer was formed in the surface of the said metal-clad laminated board or the said resin substrate is provided.

  Furthermore, according to the present invention, there is provided a semiconductor device comprising the printed wiring board and a semiconductor element mounted on the circuit layer of the printed wiring board or built in the printed wiring board. .

  According to the present invention, a thermosetting resin composition capable of suppressing resin residue while obtaining a low dielectric loss tangent, and a resin film with a carrier, a prepreg, a metal-clad laminate, a resin substrate, a printed wiring board, and a semiconductor using the same A device can be provided.

It is sectional drawing which shows an example of a structure of the resin film with a carrier in this embodiment. It is sectional drawing which shows an example of a structure of the metal-clad laminated board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment.

  Hereinafter, embodiments of the present invention will be described.

  First, a thermosetting resin composition (hereinafter, also referred to as “resin composition (P)”) used for forming an insulating layer in the printed wiring board in the present embodiment will be described.

As an insulating layer in the printed wiring board by the resin composition (P) which concerns on this embodiment, the insulating layer in a buildup layer or a soldering resist layer is mentioned, for example.
In the present embodiment, for example, a thermosetting resin film formed using the resin composition (P) is laminated on the circuit layer, and the insulating layer in the build-up layer or the solder resist layer is obtained by thermosetting the film. Is formed.

Resin composition (P) can be made into the varnish shape containing a solvent, for example.
On the other hand, the resin composition (P) may be in the form of a film. In this case, for example, a film-like resin composition (P) can be obtained by subjecting a resin film obtained by applying the varnish-like resin composition (P) to a solvent removal treatment. In addition, a film-form resin composition (P) can be laminated | stacked on a carrier base material, and can comprise the resin film with a carrier.

  The resin composition (P) includes (A) polyphenylene ether and (B) at least one selected from the group consisting of a cyanate ester resin, a phenol resin, a maleimide compound, and an epoxy resin, and reacts with the (A). A component, and (C) a filler.

<Component (A)>
Component (A) is polyphenylene ether. Component (A) is a material having a low dielectric constant and a low dielectric loss tangent electrical characteristic, whereby a resin layer having excellent high frequency characteristics can be formed. In addition, since component (A) has an ether bond, it is difficult to be thermally decomposed even at a high temperature, and since there is no hydrophilic group, a water absorption is lowered, and a resin layer that is difficult to deteriorate in a humid environment. Can be formed.

  Component (A) is a polymer having a structural unit represented by the following formula (1). The following structural units contained in the polymer may be one kind or plural kinds.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, It represents any one selected from the group consisting of an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, and an optionally substituted alkoxy group.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, for example. Preferably, they are a chlorine atom and a bromine atom.

  The “alkyl group” of the alkyl group which may be substituted is, for example, a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. More specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and the like can be mentioned. More preferably.

  Examples of the “alkenyl group” of the alkenyl group which may be substituted include ethenyl group, 1-propenyl group, 2-propenyl group, 3-butenyl group, pentenyl group, hexenyl group and the like. -More preferred is a propenyl group.

  Examples of the “alkynyl group” of the alkynyl group which may be substituted include ethynyl group, 1-propynyl group, 2-propynyl (propargyl) group, 3-butynyl group, pentynyl group, hexynyl group and the like. It is more preferably a group, a 1-propynyl group, or a 2-propynyl (propargyl) group.

  Examples of the “aryl group” of the aryl group which may be substituted include a phenyl group and a naphthyl group, and a phenyl group is more preferable.

  As the “aralkyl group” of the aralkyl group which may be substituted, for example, a benzyl group, a phenethyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, an α-methylbenzyl group, a 2-vinylphenethyl group, 4- A vinyl phenethyl group etc. are mentioned, It is more preferable that it is a benzyl group.

  The “alkoxy group” of the alkoxy group which may be substituted is, for example, a linear or branched alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and the like, and more preferably a methoxy group or an ethoxy group. preferable.

When the alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group, and alkoxy group are substituted, one or more substituents may be included.
Examples of such a substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group). , Isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group), aryl group (for example, phenyl group, naphthyl group), alkenyl group (for example, ethenyl group, 1-propenyl group, 2-propenyl group) ), Alkynyl groups (for example, ethynyl group, 1-propynyl group, 2-propynyl group), aralkyl groups (for example, benzyl group, phenethyl group), alkoxy groups (for example, methoxy group, ethoxy group) and the like.

  Furthermore, the component (A) may have a structural unit represented by the following formula (1a).

（式中、Ｒ_１１，Ｒ_１２，Ｒ_１３，Ｒ_１４，Ｒ_１５，Ｒ_１６，Ｒ_１７，Ｒ_１８は、同一又は異なってもよく、水素原子、炭素数６以下のアルキル基又はフェニル基である。−Ａ−は、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。）

(In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

  Component (A) is a modified polyphenylene ether partially or entirely functionalized with an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxyl group, and a silyl group. It is good.

Moreover, it is preferable that the both ends of a component (A) have a hydroxyl group, an epoxy group, or an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include ethenyl group, allyl group, methacryl group, propenyl group, butenyl group, alkenyl group such as hexenyl group and octenyl group, cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group, vinylbenzyl group And alkenylaryl groups such as a vinylnaphthyl group. In addition, both ends may be the same functional group or different functional groups.
From the viewpoint of highly controlling the balance between low dielectric loss tangent and resin residue reduction, both ends are preferably hydroxy groups or methacrylic groups, and both ends are hydroxy groups or methacrylic groups. More preferably.

  The weight average molecular weight of the component (A) is preferably 500 or more and 4000 or less, and more preferably 1000 or more and 3000 or less. By making the weight average molecular weight of a component (A) more than a lower limit, the flexibility of the resin layer obtained can be made favorable. On the other hand, the solubility with respect to a chemical | medical solution can be made favorable by making the weight average molecular weight of a component (A) below an upper limit.

Content of a component (A) is 10 to 35 weight part with respect to 100 weight part of resin solid content. By setting it as 10 weight part or more with respect to 100 weight part of resin solid content, the low dielectric loss tangent by a component (A) can be obtained, and a resin residue can be suppressed by setting it as 35 weight part or less. The content of the component (A) is preferably 15 parts by weight or more, more preferably 25 parts by weight or more with respect to 100 parts by weight of the resin solid content, and on the other hand, it is 33 parts by weight or less. preferable.
In addition, resin solid content is a resin component except the (C) filler and solvent in a varnish.

<Component (B)>
The component (B) is a component that contains at least one selected from the group consisting of a cyanate ester resin, a phenol resin, a maleimide compound, and an epoxy resin and reacts with the component (A). The component (B) may include at least one selected from the group consisting of a cyanate ester resin, a phenol resin, a maleimide compound, and an epoxy resin, and these may be used in combination. The reaction means that the functional group of the component (A) and the functional group of the component (B) cause a chemical reaction by heating to form a crosslink. Component (B) reacts with component (A) to obtain good dielectric loss tangent characteristics. Further, from the viewpoint of reducing the resin residue, the component (B) preferably has a higher water absorption rate than the component (A).
The combination of the component (A) and the component (B) is not particularly limited. For example, when the component (B) is any one of a cyanate ester resin, a phenol resin, and an epoxy resin, the component (A) has both ends and / or Or it is preferable that it has a hydroxy group in -A-, and if component (B) is a maleimide compound, ethylenically unsaturated groups are present at both ends of component (A) and / or -A-. It is preferable to have it.

  Although cyanate ester resin is not specifically limited, For example, it can obtain by making a halogenated cyanide compound, phenols, and naphthol react, and prepolymerizing by methods, such as a heating, as needed. Moreover, the commercial item prepared in this way can also be used.

  Examples of the cyanate ester resins include novolak-type cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol E-type cyanate ester resins, and tetramethylbisphenol F-type cyanate ester resins; naphthol aralkyl-type phenol resins; Examples thereof include naphthol aralkyl-type cyanate ester resins obtained by reaction with cyanogen halide; dicyclopentadiene-type cyanate ester resins; biphenylalkyl-type cyanate ester resins. Among these, it is preferable to have a bisphenol A skeleton or a novolak skeleton, specifically, a bisphenol A type cyanate ester resin, a novolak type cyanate ester resin, and a naphthol aralkyl type cyanate ester resin are preferable, and a novolak type cyanate ester resin is preferable. More preferred. Of these, good low dielectric loss tangent can be obtained by using bisphenol A type cyanate ester resin. This is because the bisphenol A type cyanate ester resin has few crosslinking points, and therefore, when a triazine ring is formed, an unreacted cyanate group hardly remains and it is easy to maintain good dielectric properties.

  As a novolak-type cyanate ester resin, what is shown by following General formula (2) can be used, for example.

  The average repeating unit n of the novolak-type cyanate ester resin represented by the general formula (2) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is not less than the above lower limit, the heat resistance of the novolak-type cyanate ester resin is improved, and it is possible to suppress desorption and volatilization of the low-mer during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. It can suppress that melt viscosity becomes it high that n is below the said upper limit, and can improve the moldability of a prepreg.

  Further, as the cyanate ester resin, a naphthol aralkyl type cyanate ester resin represented by the following general formula (3) is also preferably used. The naphthol aralkyl type cyanate ester resin represented by the following general formula (3) includes, for example, naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α′-dimethoxy-p-xylene, 1, It is obtained by condensing a naphthol aralkyl type phenolic resin obtained by reaction with 4-di (2-hydroxy-2-propyl) benzene or the like and cyanogen halide. The repeating unit n in the general formula (3) is preferably an integer of 10 or less. When the repeating unit n is 10 or less, a more uniform insulating layer can be obtained. In addition, intramolecular polymerization hardly occurs at the time of synthesis, the liquid separation property at the time of washing with water tends to be improved, and the decrease in yield tends to be prevented.

（式（３）中、Ｒは水素原子またはメチル基を示し、ｎは１以上１０以下の整数を示す。）

(In formula (3), R represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 10 or less.)

Although the weight average molecular weight (Mw) of cyanate ester resin is not specifically limited, Mw500 or more is preferable and Mw600 or more is more preferable. When Mw is equal to or more than the above lower limit, it is possible to suppress the occurrence of tackiness when producing prepregs, and to prevent the prepregs from adhering to each other or the transfer of the prepregs. Mw is not particularly limited, but is preferably Mw 4,500 or less, and more preferably Mw 3,000 or less. When Mw is not more than the above upper limit, it is possible to suppress the cyclization reaction of the cyanate ester resin from being accelerated, and it is possible to suppress the occurrence of defects in the insulating layer and the decrease in peel strength between the insulating layer and the metal layer. can do.
The Mw of the cyanate ester resin can be measured by, for example, GPC (gel permeation chromatography, standard substance: converted to polystyrene).

  Moreover, cyanate ester resin may be used individually by 1 type, may use together 2 or more types which have different Mw, and may use 1 type or 2 types and those prepolymers together. .

  Examples of fail resins include phenol novolac resins, cresol novolac resins, bisphenol A novolak resins, triazine skeleton-containing phenol novolak resins and other novolak type phenol resins; biphenyl aralkyl type phenol resins and the like; Examples include resol type phenol resins such as oil-modified resol phenol resins modified with tung oil, linseed oil, walnut oil, and the like.

  The maleimide group of the maleimide compound has a five-membered planar structure, and since the double bond of the maleimide group is likely to interact between molecules and has high polarity, a maleimide group, a benzene ring, other compounds having a planar structure, etc. It shows strong intermolecular interaction and can suppress molecular motion. Therefore, resin composition (P) can reduce the linear expansion coefficient of the insulating layer obtained by including a maleimide compound, can improve a glass transition temperature, and can improve heat resistance further.

As the maleimide compound, a maleimide compound having at least two maleimide groups in the molecule is preferable.
Examples of maleimide compounds having at least two maleimide groups in the molecule include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis [4- (4-maleimide). Phenoxy) phenyl] propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N'-ethylenedimaleimide, N, N'- Hexamethylene dimaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, etc. Compound with two maleimide groups in the molecule Things, a compound having three or more maleimide groups in the molecule, such as polyphenyl methane maleimide, and the like.
One of these can be used alone, or two or more can be used in combination. Among these maleimide compounds, 4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis- (3-ethyl-), because of its low water absorption. 5-Methyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, and bisphenol A diphenyl ether bismaleimide are preferred.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4 ′-(1,3-phenylenediiso Pridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 ′-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4′-cyclohexyl) Diene bisphenol type epoxy resin), etc .; phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, novolak having condensed ring aromatic hydrocarbon structure Novolak type epoxy resins such as epoxy resins; biphenyl type epoxy resins; aralkyl type epoxy resins such as xylylene type epoxy resins and biphenyl aralkyl type epoxy resins; naphthylene ether type epoxy resins, naphthol type epoxy resins, naphthalenediol type epoxy resins, Naphthalene type epoxy resins such as bifunctional to tetrafunctional naphthalene type epoxy resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins; anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; norbornene type epoxy resins; Type epoxy resin; fluorene type epoxy resin and the like.

  As the epoxy resin, one of these may be used alone, two or more may be used in combination, and one or two or more and those prepolymers may be used in combination.

  Among epoxy resins, bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board One or more selected from the group consisting of anthracene type epoxy resins and dicyclopentadiene type epoxy resins are preferred, and they are selected from aralkyl type epoxy resins, novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure and naphthalene type epoxy resins. One or more selected from the group consisting of

  The component (B) preferably contains any of a cyanate ester resin, a phenol resin, or a maleimide compound, more preferably a cyanate ester resin, from the viewpoint of achieving both low dielectric loss tangent and reduction of resin residue.

  The content of the component (B) is preferably 40 to 90 parts by weight, more preferably 42 to 75 parts by weight, and more preferably 65 to 90 parts by weight with respect to 100 parts by weight of the resin solid content. Is more preferable, and 67 to 75 parts by weight is even more preferable.

  Further, in the component (B), the content of the cyanate ester resin is 40 parts by weight or more and 90 parts by weight with respect to 100 parts by weight of the resin solid content from the viewpoint of further achieving both low dielectric loss tangent and reduction of resin residue. The following is preferable, and 42 parts by weight or more and 75 parts by weight or less are more preferable.

  In addition, in the component (B), the content of the epoxy resin is 25 parts by weight or less with respect to 100 parts by weight of the resin solid content from the viewpoint of further achieving both low dielectric loss tangent and reduction of the resin residue. It is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably no epoxy resin.

<Ingredient (C)>
Component (C) is a filler. Examples of the filler include organic fillers and inorganic fillers, and inorganic fillers are preferable from the viewpoint of obtaining an appropriate elastic modulus and low dielectric loss tangent.

Examples of inorganic fillers include silicates such as talc, calcined clay, unfired clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; calcium carbonate, magnesium carbonate, and hydrotal Carbonates such as sites; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate, barium metaborate, aluminum borate And borate salts such as calcium borate and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride; titanates such as strontium titanate and barium titanate.
Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferable, and silica is more preferable from the viewpoint of achieving both an elastic modulus, a low dielectric loss tangent, and a reduction in resin residue. Among these, one type may be used alone, or two or more types may be used in combination.

  The average particle size of the component (C) is preferably 0.01 μm or more, and more preferably 0.05 μm or more. It can suppress that the viscosity of a varnish becomes high in the average particle diameter of a component (C) being more than the said lower limit, and can improve workability | operativity at the time of insulation layer preparation. Further, the average particle size of the component (C) is preferably 5.0 μm or less, more preferably 2.0 μm or less, and further preferably 1.0 μm or less. When the average particle diameter of the component (C) is not more than the above upper limit, phenomena such as sedimentation of the component (C) in the varnish can be suppressed, and a more uniform resin layer can be obtained. Moreover, when the circuit dimension L / S of the printed wiring board is less than 20 μm / 20 μm, it is possible to suppress the influence on the insulation between the wirings.

The average particle size of the component (C) is measured, for example, by measuring the particle size distribution of the particles on a volume basis with a laser diffraction particle size distribution measuring device (LA-500, manufactured by HORIBA), and the median diameter (D ₅₀ ) is averaged. The particle diameter can be set.

  As the component (C), those having an average particle size of monodisperse may be used, and those having an average particle size of polydispersion may be used. Furthermore, monodisperse and / or polydispersion of the average particle diameter may be used alone or in combination of two or more.

  As the component (C), silica particles are preferable, silica particles having an average particle diameter of 5.0 μm or less are preferable, silica particles having an average particle diameter of 0.1 μm to 4.0 μm are more preferable, and 0.2 μm to 2.0 μm. The following silica particles are more preferable. Thereby, the filling property of a component (C) can further be improved.

  Content of a component (C) is 150 to 300 weight part with respect to 100 weight part of resin solid content of a resin composition (P). By setting it to 150 parts by weight or more, a favorable elastic modulus can be obtained while obtaining a low dielectric loss tangent. On the other hand, by setting it to 300 parts by weight or less, a good elastic modulus can be obtained while reducing the resin residue. The content of the component (C) is preferably 155 parts by weight or more and 250 parts by weight or less, more preferably 160 parts by weight or more and 230 parts by weight or less with respect to 100 parts by weight of the resin solid content of the resin composition (P). It is. Moreover, it is preferable that content of a component (C) is 170 weight part or more from a viewpoint of obtaining a high elasticity modulus.

Here, the effect by a resin composition (P) is explained in full detail.
The resin composition (P) can realize low dielectric loss tangent and reduction of resin residue only by combining the components (A) to (C) and blending the component (A) with a specific content. That is, the component (A) is known as a resin capable of obtaining a low dielectric loss tangent, but has a tendency to cause a resin residue because it has a low water absorption rate and is not easily removed by chemical treatment. For this reason, it has been difficult to increase the content of the component (A) from the viewpoint of suppressing resin residues. On the other hand, the resin composition (P) combines the component (B) with a relatively high water absorption rate with respect to the component (A), and controls the content of the component (A), thereby improving the resin residue removability. As a result of the first discovery that the dielectric characteristics can be improved while improving, the present invention has been completed. That is, the resin composition (P) is the first to realize both the low dielectric loss tangent and the reduction of the resin residue, which could not be achieved conventionally, by combining the components and controlling the content.

  In addition, a curing accelerator and a coupling agent can be appropriately blended in the resin composition (P) as necessary.

  Resin composition (P) can contain a hardening accelerator, for example. Thereby, the sclerosis | hardenability of a resin composition (P) can be improved. As a hardening accelerator, what accelerates | stimulates hardening reaction of a thermosetting resin (A) can be used, The kind is not specifically limited. In this embodiment, as a hardening accelerator, for example, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) Organic metal salts such as triethylamine, tributylamine, tertiary amines such as diazabicyclo [2,2,2] octane, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, Imidazoles such as 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxyimidazole , Phenol, bisphe Lumpur A, phenolic compounds nonylphenol, acetic, benzoic acid, salicylic, organic acids such as p-toluenesulfonic acid, and one or more selected from an onium salt compound. Among these, it is more preferable to include an onium salt compound from the viewpoint of more effectively improving curability.

  Although the onium salt compound used as a hardening accelerator is not specifically limited, For example, the compound represented by following General formula (5) can be used.

（式（５）中、Ｐはリン原子、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を示し、互いに同一であっても異なっていてもよい。Ａ⁻は分子外に放出しうるプロトンを少なくとも１個以上分子内に有するｎ（ｎ≧１）価のプロトン供与体のアニオン、またはその錯アニオンを示す。）

(In Formula (5), P is a phosphorus atom, R ₇ , R ₈ , R ₉ and R ₁₀ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. Each of which may be the same as or different from each other, and A ⁻ represents an anion of an n-valent proton donor having at least one proton that can be released to the outside of the molecule in the molecule, or The complex anion is shown.)

  For example, when the resin solid content of the resin composition (P) is 100 parts by weight, the content of the curing accelerator is preferably 0.01 parts by weight or more and preferably 0.1 parts by weight or more. More preferred. By making content of a hardening accelerator more than the said lower limit, sclerosis | hardenability of a resin composition (P) can be improved more effectively. On the other hand, the content of the curing accelerator is, for example, preferably 5 parts by weight or less, more preferably 1 part by weight or less, when the resin solid content of the resin composition (P) is 100 parts by weight. preferable. By making content of a hardening accelerator below the said upper limit, the preservability of a thermosetting resin composition (P) can be improved.

  Furthermore, the resin composition (P) may contain a coupling agent. The coupling agent may be added directly at the time of preparing the resin composition (P), or may be added in advance to the (C) filler. The use of the coupling agent can improve the wettability of the interface between (C) the filler and each resin. Therefore, it is preferable to use a coupling agent, and the heat resistance of the obtained insulating layer can be improved.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and amino silane coupling agents, titanate coupling agents, and silicone oil type coupling agents. A coupling agent may be used individually by 1 type, and may use 2 or more types together.
Thereby, the wettability of the interface of (C) a filler and each resin can be made high, and the heat resistance of the insulating layer obtained can be improved more.

  Various types of silane coupling agents can be used, and examples thereof include epoxy silane, amino silane, alkyl silane, ureido silane, mercapto silane, and vinyl silane.

  Specific examples of the compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-amino. Propylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, β- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc., and a combination of one or more of these. Of these, epoxy silane, mercapto silane, and amino silane are preferable, and the amino silane is more preferably primary amino silane or anilino silane.

The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the filler (C), but 0.01 parts by weight or more when the resin solid content of the resin composition (P) is 100 parts by weight. Part by weight or less is preferable, and 0.05 part by weight or more and 1 part by weight or less is more preferable.
When the content of the coupling agent is not less than the above lower limit, the filler (C) can be sufficiently covered, and the heat resistance of the obtained insulating layer can be improved. Moreover, when content of a coupling agent is below the said upper limit, it can suppress affecting a reaction and can suppress the fall of the bending strength etc. of the insulating layer obtained.

  Furthermore, in the resin composition (P), a thermoplastic resin, a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, as long as the object of the present invention is not impaired. Additives other than the above components such as an ion scavenger may be added.

  The thermoplastic resin can be used for further low dielectric constant and low dielectric loss tangent. Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polybutadiene, and a styrene-butadiene copolymer. These may have a specific functional group at the terminal or in the molecular chain, and examples of the functional group include an epoxy group, a hydroxy group, and an acrylic group. Among these, polybutadiene modified with a hydroxy group or an acrylic group is preferable.

  Examples of pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, synthetic ultramarine blue, etc., polycyclic pigments such as phthalocyanine, azo pigments Etc.

  Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, azomethine and the like.

Resin composition (P) is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, In organic solvents such as anisole and N-methylpyrrolidone, using various mixing machines such as ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, rotation and revolution dispersion method, etc. The resin varnish (I) can be obtained by dissolving, mixing and stirring.
40 mass% or more and 80 mass% or less are preferable, and, as for solid content of resin varnish (I), 50 mass% or more and 70 mass% or less are more preferable. Thereby, workability | operativity and film-forming property of resin varnish (I) can further be improved.

  In addition, the resin composition (P) according to the present embodiment may not include a fiber substrate such as a glass fiber substrate or a paper substrate. Thereby, the resin composition (P) suitable for forming a buildup layer or a solder resist layer can be realized.

-Cured product The cured product obtained by heat-treating the resin composition (P) at 230 ° C for 2 hours preferably has a dielectric loss tangent at 1 GHz of 0.005 or less, preferably 0.0045 or less. More preferred.

  The water absorption rate of the cured product is 0.10% or more and 0.40% or less when moisture is absorbed in distilled water at 23 ± 0.5 ° C. for 24 hours by a method according to JIS C 6481. It is preferably 0.12% or more and 0.30% or less. By setting the lower limit value or more, it is possible to suppress the generation of resin residues. By setting the upper limit value or less, a printed wiring board having characteristics of a low dielectric constant and a low dielectric loss tangent can be obtained. .

  The elastic modulus at 25 ° C. of the cured product obtained by heat-treating the resin composition (P) at 230 ° C. for 2 hours is preferably 5 GPa or more from the viewpoint of reducing the warpage of the substrate and obtaining low dielectric loss tangent characteristics. More preferably, it is 8 GPa or more. On the other hand, from the viewpoint of relieving the stress of the obtained insulating layer and improving the adhesion to other members such as a circuit layer, it is preferably 21 Gpa or less, more preferably 15 Gpa or less, and still more preferably 13 GPa or less.

  In order to achieve such an elastic modulus, it is important to appropriately control the contents of components (A) to (C), the type and blending amount of additives such as a curing accelerator, and the like.

Next, the resin film with carrier 100 will be described.
FIG. 1 is a cross-sectional view showing an example of the configuration of the resin film with carrier 100 in the present embodiment. The resin film with carrier 100 is used to form an insulating layer in a build-up layer or a solder resist layer of a printed wiring board. As shown in FIG. 1, the resin film with carrier 100 includes, for example, a carrier substrate 12 and a resin film 10 provided on the carrier substrate 12. The resin film 10 is comprised by the resin composition (P) which concerns on this embodiment. For this reason, as described above, the reliability of the semiconductor device including the insulating layer formed using the resin film with carrier 100 can be improved.

  For example, the resin film with carrier 100 is formed by applying a varnish-like resin composition (P) on the carrier substrate 12 to form a coating film, and then performing a solvent removal process on the coating film. 10 can be produced. Although the carrier base material 12 is not specifically limited, For example, it is comprised by PET (Polyethylene terephthalate) and copper foil. Moreover, the film thickness of the resin film 10 is not particularly limited, but may be, for example, 5 μm or more and 300 μm or less. Thereby, the resin film 10 suitable for formation of the insulating layer in a buildup layer or a soldering resist layer is realizable.

  In the present embodiment, for example, an insulating layer in the buildup layer or the solder resist layer can be formed using the resin film with carrier 100 as follows. First, the resin film with carrier 100 is stuck on the surface of the circuit board on which the conductor circuit pattern is provided so that the resin film 10 faces the circuit board. The application of the resin film with carrier 100 can be performed, for example, by laminating the resin film with carrier 100 on a circuit board and then vacuum-pressing it. Next, the carrier substrate 12 is peeled from the resin film 10. Next, the resin film 10 remaining on the circuit board is thermally cured. Thus, an insulating layer made of a cured film obtained by curing the resin film 10 is formed on the circuit board so as to cover the conductor circuit pattern.

Next, the prepreg and the resin substrate will be described.
A prepreg is used to form an insulating layer in a build-up layer and an insulating layer in a core layer in a printed wiring board. When the prepreg is used to form an insulating layer in the core layer of the printed wiring board, for example, two or more prepregs are stacked, and the obtained laminate is heat-cured to form an insulating layer for the core layer. You can also.
The prepreg is a sheet-like material obtained by impregnating a fiber base material with the thermosetting resin composition (P) (hereinafter also referred to as a resin composition (P)) in the present embodiment and then semi-curing the fiber base material. Material.
The resin substrate is used for forming an insulating layer of a printed wiring board. The resin substrate contains a cured product of prepreg, and can be obtained, for example, by heat curing the prepreg.

  The thickness of the prepreg is, for example, 20 μm or more and 220 μm or less. When the thickness of the prepreg is within the above range, the balance between mechanical strength and productivity is particularly excellent, and a resin substrate suitable for a thin printed wiring board can be obtained.

It continues and the manufacturing method of a prepreg is demonstrated.
The prepreg is, for example, a sheet-like material obtained by impregnating the fiber base material with the resin composition (P) in the present embodiment and then semi-curing it. The sheet-like material having such a structure is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing an insulating layer of a printed wiring board.

  The method for impregnating the fiber base material with the resin composition (P) is not particularly limited. For example, the resin composition (P) is dissolved in a solvent to prepare a resin varnish, and the fiber base material is immersed in the resin varnish. A method of applying the resin varnish to the fiber base material with various coaters, a method of spraying the resin varnish onto the fiber base material by spraying, a resin layer (P) comprising the resin composition (P) from both sides of the fiber base material And a method of laminating the fiber base material.

  FIG. 2 is a cross-sectional view showing an example of the configuration of the metal-clad laminate 200 in the present embodiment. The metal-clad laminate 200 is provided with a metal foil 105 on one side or both sides of a cured product of prepreg (insulating layer 301) or a cured product of laminated body (insulating layer 301) in which two or more prepregs are stacked. The metal-clad laminate 200 can be used for forming an insulating layer of a printed wiring board.

Next, a method for manufacturing the metal-clad laminate 200 using the prepreg obtained above will be described. A method for producing the metal-clad laminate 200 using prepreg is, for example, as follows.
Two or more prepregs or a laminate of two or more prepregs stacked on top and bottom or one side of the laminate are laminated with metal foil 105 and bonded together under high vacuum conditions using a laminator or becquerel device, or directly outside the prepreg. The metal foil 105 is stacked on both upper and lower surfaces or one surface. When two or more prepregs are stacked, the metal foil 105 is stacked on the outermost upper and lower surfaces or one surface of the stacked prepregs.
Subsequently, the metal-clad laminate 200 can be obtained by heat-pressing the laminate in which the prepreg and the metal foil 105 are stacked. Here, it is preferable to continue the pressurization until the end of cooling at the time of heat-pressure molding.

The heating temperature at the time of the above-described heat and pressure molding is preferably 120 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 240 ° C. or lower.
Moreover, the pressure at the time of the above-described heat and pressure molding is preferably 0.5 MPa or more and 5 MPa or less, and more preferably a high pressure of 2.5 MPa or more and 5 MPa or less.

  Further, after the heat and pressure molding, if necessary, post-curing may be performed in a thermostatic bath or the like. The post-curing temperature is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 250 ° C. or higher and 300 ° C. or lower.

  Moreover, a printed wiring board can be obtained using the metal-clad laminate 200 or the resin substrate as a core substrate.

  Hereinafter, each material used when manufacturing the prepreg, the metal-clad laminate 200, and the resin substrate will be described in detail.

Examples of the metal constituting the metal foil 105 include copper, a copper alloy, aluminum, an aluminum alloy, silver, a silver alloy, gold, a gold alloy, zinc, a zinc alloy, nickel, a nickel alloy, tin, Examples thereof include tin-based alloys, iron, iron-based alloys, Kovar (trade name), 42-alloy, invar, super-invar and other Fe—Ni-based alloys, W, Mo, and the like. Among these, the metal constituting the metal foil 105 is preferably copper or a copper alloy because of its excellent conductivity, easy circuit formation by etching, and low cost. That is, the metal foil 105 is preferably a copper foil.
Further, as the metal foil 105, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil 105 is preferably 0.5 μm or more and 40 μm or less, and more preferably 1.5 μm or more and 35 μm or less.

Subsequently, the fiber base material used for a prepreg is demonstrated.
Although it does not specifically limit as a fiber base material, Glass fiber base materials, such as a glass woven fabric and a glass nonwoven fabric; Polyamide-type resin fibers, such as a polyamide resin fiber, an aromatic polyamide resin fiber, and a wholly aromatic polyamide resin fiber; Polyester resin fiber Polyester resin fibers such as aromatic polyester resin fibers and wholly aromatic polyester resin fibers; synthetic fiber base materials composed of woven or non-woven fabrics mainly composed of either polyimide resin fibers or fluororesin fibers; kraft paper , Cotton linter paper, or a paper base material mainly composed of linter and kraft pulp mixed paper. Any of these can be used. Among these, a glass fiber base material is preferable. Thereby, a resin substrate with low water absorption, high strength, and low thermal expansion can be obtained.

Although the thickness of a fiber base material is not specifically limited, Preferably it is 5 micrometers or more and 150 micrometers or less, More preferably, they are 10 micrometers or more and 100 micrometers or less, More preferably, they are 12 micrometers or more and 90 micrometers or less. By using the fiber base material having such a thickness, the handling property at the time of producing the prepreg can be further improved.
When the thickness of the fiber base material is not more than the above upper limit, the impregnation property of the resin composition (P) in the fiber base material can be improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. Further, it is possible to facilitate formation of a through hole by a laser such as carbon dioxide, UV, or excimer. Moreover, the intensity | strength of a fiber base material or a prepreg can be improved as the thickness of a fiber base material is more than the said lower limit. As a result, handling properties can be improved, production of a prepreg can be facilitated, and warping of the resin substrate can be suppressed.

  As a glass fiber substrate, for example, glass fiber formed of one or more kinds of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass A substrate is preferably used.

  Next, the printed wiring board 300 according to the present embodiment will be described. 3 and 4 are cross-sectional views showing an example of the configuration of the printed wiring board 300 in the present embodiment.

The printed wiring board 300 includes, for example, a core layer 311 and a solder resist layer 401 as shown in FIG. Moreover, the printed wiring board 300 may include a core layer 311, a buildup layer 317, and a solder resist layer 401 as shown in FIG. 4, for example.
In the present embodiment, the via hole 307 is a hole for electrically connecting the layers, and may be either a through hole or a non-through hole.

The printed wiring board 300 according to the present embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multilayer printed wiring board. A double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both sides of an insulating layer 301. The multilayer printed wiring board is a printed wiring board in which two or more buildup layers 317 are stacked on the core layer 311 by a plated through hole method, a buildup method, or the like.
Here, in the printed wiring board 300 according to the present embodiment, at least one layer selected from the insulating layer 305 and the solder resist layer 401 in the build-up layer 317 is configured by a cured product of the resin composition (P) according to the present embodiment. In addition, it is preferable that all layers selected from the insulating layer 305 and the solder resist layer 401 in the build-up layer 317 are made of a cured product of the resin composition (P) according to this embodiment.

  The metal layer 303 is a circuit layer, for example, and includes the metal foil 105 and / or the electroless metal plating film 308 and the electrolytic metal plating layer 309.

  When the printed wiring board 300 is a multilayer printed wiring board as shown in FIG. 4, the metal layer 303 is a circuit layer in the core layer 311 or the buildup layer 317.

  The metal layer 303 is formed by, for example, the SAP (semi-additive process) method on the surface of the metal foil 105 or the insulating layer 301 that has been subjected to chemical treatment or plasma treatment. After the electroless metal plating film 308 is applied on the metal foil 105 or the insulating layer 301, the non-circuit forming portion is protected by a plating resist, the electrolytic metal plating layer 309 is applied by electrolytic plating, the plating resist is removed, and flash etching is performed. The metal layer 303 is formed on the metal foil 105 or the insulating layer 301 by removing the electroless metal plating film 308 by the above.

  The circuit dimension of the metal layer 303 can be 25 μm / 25 μm or less, particularly 15 μm / 15 μm or less, when expressed in line and space (L / S). If the circuit dimensions are reduced and the wiring is made fine, the insulation reliability between the wirings decreases. However, the printed wiring board 300 according to the present embodiment is capable of fine wiring with a line and space (L / S) of 15 μm / 15 μm or less, and the line and space (L / S) can be refined to about 10 μm / 10 μm. Can be achieved.

  Although the thickness of the metal layer 303 is not specifically limited, Usually, it is preferable that they are 0.5 micrometer or more and 40 micrometers or less.

  The thickness of the insulating layer 301 in the core layer 311 (including the insulating layer 301 in the printed wiring board 300 not including the build-up layer 317) is preferably 0.025 mm or more and 0.3 mm or less. When the thickness of the insulating layer 301 is within the above range, it is possible to obtain an insulating layer 301 that is excellent in balance between mechanical strength and productivity and suitable for a thin printed wiring board.

  The thickness of the insulating layer 305 in the buildup layer 317 is preferably 0.015 mm or more and 0.05 mm or less. When the thickness of the insulating layer 305 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 305 suitable for a thin printed wiring board can be obtained.

  Next, an example of a method for manufacturing the printed wiring board 300 will be described.

First, the above-described metal-clad laminate is prepared.
Next, part or all of the metal foil 105 is removed by etching.

Next, a via hole 307 is formed in the insulating layer 301. The via hole 307 can be formed using, for example, a drilling machine or laser irradiation. Examples of the laser used for laser irradiation include an excimer laser, a UV laser, and a carbon dioxide gas laser. Resin residues and the like after forming the via hole 307 may be removed by an oxidizing agent such as permanganate or dichromate.
Note that the via hole 307 may be formed in the insulating layer 301 before the metal foil 105 is removed by the etching treatment.

Next, chemical treatment or plasma treatment is performed on the surface of the metal foil 105 or the insulating layer 301 in the via hole 307.
The chemical treatment is not particularly limited, and examples thereof include a method using an oxidizing agent solution having an organic substance decomposing action. Examples of the plasma treatment include a method of removing a resin residue by irradiating a target object with active species (plasma, radical, etc.) having a strong oxidizing action directly.

  Next, a metal layer 303 is formed in the via hole 307. The metal layer 303 can be formed by, for example, a semi-additive process (SAP) or a modified semi-additive process (MSAP). This will be specifically described below.

  First, an electroless metal plating film 308 is formed on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307 by using an electroless plating method, and conduction between both surfaces of the printed wiring board 300 is achieved. The via hole 307 can be appropriately filled with a conductor paste or a resin paste. An example of the electroless plating method will be described. For example, first, catalyst nuclei are provided on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307. The catalyst nucleus is not particularly limited. For example, a noble metal ion or palladium colloid can be used. Subsequently, an electroless metal plating film 308 is formed by electroless plating using the catalyst nucleus as a nucleus. For the electroless plating treatment, for example, a material containing copper sulfate, formalin, complexing agent, sodium hydroxide or the like can be used. In addition, it is preferable to heat-process 100-250 degreeC after electroless plating, and to stabilize a plating film. A heat treatment at 120 to 180 ° C. is particularly preferable in that a film capable of suppressing oxidation can be formed. Moreover, the average thickness of the electroless metal plating film 308 is, for example, about 0.1 to 2 μm.

  Next, a plating resist having a predetermined opening pattern is formed on the metal foil 105 and / or the electroless metal plating film 308. This opening pattern corresponds to, for example, a circuit pattern. The plating resist is not particularly limited, and known materials can be used, but liquid and dry films can be used. In the case of forming fine wiring, it is preferable to use a photosensitive dry film or the like as the plating resist. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 308, the non-circuit formation region is exposed and photocured, and the unexposed portion is dissolved and removed with a developer. A plating resist is formed by leaving the cured photosensitive dry film.

  Next, an electrolytic metal plating layer 309 is formed by electroplating at least inside the opening pattern of the plating resist and on the metal foil 105 and / or the electroless metal plating film 308. As the electroplating treatment, a known method used in a normal printed wiring board can be used. For example, a method of passing a current through the plating solution while being immersed in a plating solution such as copper sulfate. Can be used. The electrolytic metal plating layer 309 may be a single layer or may have a multilayer structure. As the material of the electrolytic metal plating layer 309, for example, one or more of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

  Next, the plating resist is removed using an alkaline stripping solution, sulfuric acid, a commercially available resist stripping solution, or the like.

  Next, the metal foil 105 and / or the electroless metal plating film 308 other than the region where the electrolytic metal plating layer 309 is formed are removed. For example, the metal foil 105 and / or the electroless metal plating film 308 can be removed by using soft etching (flash etching) or the like. Here, the soft etching treatment can be performed, for example, by etching using an etchant containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 303 can be formed. The metal layer 303 is constituted by the metal foil 105 and / or the electroless metal plating film 308 and the electrolytic metal plating layer 309.

  Furthermore, a build-up layer 317 can be laminated on the metal layer 303 as necessary, and a multilayer can be formed by repeating the steps of interlayer connection and circuit formation by a semi-additive process. Then, a solder resist layer 401 is laminated on the metal layer 303.

  The printed wiring board 300 of this embodiment is obtained by the above.

  Next, the semiconductor device 400 according to the present embodiment will be described. 5 and 6 are cross-sectional views showing an example of the configuration of the semiconductor device 400 in the present embodiment. The printed wiring board 300 can be used in a semiconductor device 400 as shown in FIGS. A method for manufacturing the semiconductor device 400 is not particularly limited, and examples thereof include the following method.

  First, by performing a reflow process, the semiconductor element 407 is fixed to the connection terminal which is a part of the circuit layer via the solder bump 410. Thereafter, the semiconductor device 400 as shown in FIGS. 5 and 6 is obtained by sealing the semiconductor element 407, the solder bump 410, and the like with the sealing material 413.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Moreover, in the said embodiment, although the semiconductor element 407 and the circuit layer of the printed wiring board 300 were connected by the solder bump 410, it is not restricted to this. For example, the semiconductor element 407 and the circuit layer of the printed wiring board 300 may be connected by a bonding wire.

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In the examples, parts represent parts by weight unless otherwise specified. Moreover, each thickness is represented by the average film thickness.

Examples and Comparative Examples The components (A) to (C) are dissolved or dispersed at a solid content ratio shown in Table 1, and adjusted so as to have a nonvolatile content of 70% by mass with methyl ethyl ketone, and stirred using a high-speed stirring device. Resin varnish 1 was prepared.
As the components (A) to (C), the following materials were used: (A) Polyphenylene ether 1 (manufactured by SABIC Innovative Plastics Japan GK, product name SA-90-100, unmodified polyphenylene ether resin, weight average molecular weight Mw = 1,700)
Polyphenylene ether 2 (manufactured by SABIC Innovative Plastics Japan LLC, product name SA-9000-100, terminal methacrylic group-modified polyphenylene ether resin, weight average molecular weight Mw = 1,700)
(B) Cyanate ester resin 1 (manufactured by Lonza, product name BA-230S, bisphenol A type cyanate resin: solid content 75% by weight, methyl ethyl ketone 25% by weight)
Cyanate ester resin 2 (manufactured by Lonza, product name PT-30S, novolac-type cyanate resin, solid content 80% by weight, methyl ethyl ketone 20% by weight)
Maleimide compound (manufactured by Daiwa Kasei Co., Ltd., product name BMI-2300, polyphenylmethane maleimide)
Epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name NC-3000H, biphenyl aralkyl type epoxy resin)
Phenol resin (product name GPH-103, manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type phenol resin)
(C) Silica particles (manufactured by Admatechs, product name SC2050, average particle size 0.5 μm)

<Evaluation>
Resin residue, shape of through hole The obtained resin varnish 1 was impregnated into a glass woven fabric (cross type # 1078, E glass, basis weight 48 g / m ² ) with a coating apparatus, and 10 with a hot air drying apparatus at 140 ° C. The prepreg 1 having a thickness of 70 μm was obtained by drying for a minute.
Super thin copper foil (Mitsui Metal Mining Co., Ltd., Micro Thin Ex, 2.0 μm) is placed on both sides of prepreg 1 and heated and pressed at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours to form a resin substrate with a metal foil. Got. The thickness of the core layer (part consisting of the resin substrate) of the obtained resin substrate with metal foil was 0.070 mm.
The ultrathin copper foil layer on the surface of the resulting resin substrate with metal foil was subjected to a roughening treatment of about 1 μm, and then a through hole of φ80 μm for interlayer connection was formed with a carbon dioxide gas laser. Next, it is immersed in a 60 ° C. swelling liquid (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further immersed in an 80 ° C. aqueous potassium permanganate solution (Atotech Japan, Concentrate Compact CP) for 2 minutes. Then, it neutralized and the desmear process in a through hole was performed. Subsequently, the resin residue in the through hole was observed from the top surface of the through hole using a scanning electron microscope, JSM-6501 series (manufactured by JEOL Ltd.), evaluated according to the following criteria, and the results are shown in Table 1. .
○: There was no resin residue.
X: Resin residue was present.
Further, the shape of the through hole was confirmed in the same manner, evaluated according to the following criteria, and the results are shown in Table 1.
○: No abnormal shape ×: Excessive desmearing and irregular shape

-Dielectric loss tangent After applying the resin varnish 1 on a polyethylene terephthalate (PET) film as a carrier substrate, the solvent was removed at 140 ° C. for 3 minutes to form a resin film having a thickness of 25 μm. Next, the two resin films obtained were laminated so that the resin films were inside, and the process of peeling the outer PET film was repeated twice to obtain a resin plate with a total thickness of 100 μm, and then at 230 ° C. It was cured by heating for 2 hours. With respect to the obtained resin plate, the dielectric loss tangent at a frequency of 1 GHz was measured according to JIS C 6481. The measurement was performed 3 times, and the average value was calculated.

-Elastic modulus After apply | coating the said resin varnish 1 on PET film which is a carrier base material, the solvent was removed on 140 degreeC and the conditions for 3 minutes, and the 25-micrometer-thick resin film was formed. Next, the two resin films obtained were laminated so that the resin films were inside, and the process of peeling the outer PET film was repeated twice to obtain a resin plate with a total thickness of 100 μm, and then at 230 ° C. It was cured by heating for 2 hours. About the obtained resin board, the elastic modulus (GPa) in frequency 1GHz and temperature 25 degreeC was measured using the viscoelasticity measuring apparatus (DMA-7e, product made by PERKIN ELMER).

-Water absorption rate After apply | coating the said resin varnish 1 on PET film which is a carrier base material, the solvent was removed on 140 degreeC and the conditions for 3 minutes, and the 25-micrometer-thick resin film was formed. Next, the process of laminating the two obtained resin films so that the resin films are inside each other and peeling the outer PET film is repeated twice to obtain a resin plate having a total thickness of 100 μm. Cured by heating for hours. The water absorption (%) of the obtained resin plate was measured after absorbing moisture in distilled water at 23 ± 0.5 ° C. for 24 hours by a method according to JIS C 6481.

10 resin film 12 carrier substrate 100 resin film with carrier 105 metal foil 200 metal-clad laminate 300 printed wiring board 301 insulating layer 303 metal layer 305 insulating layer 307 via hole 308 electroless metal plating film 309 electrolytic metal plating layer 311 core layer 317 Build-up layer 400 Semiconductor device 401 Solder resist layer 407 Semiconductor element 410 Solder bump 413 Sealant

Claims (16)

A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
(A) polyphenylene ether;
(B) a component that includes at least one selected from the group consisting of a cyanate ester resin, a phenol resin, a maleimide compound, and an epoxy resin, and reacts with (A);
(C) a filler;
Including
The thermosetting resin composition whose content of a component (A) is 10 to 35 weight part with respect to 100 weight part of resin solid content.   The thermosetting resin composition of Claim 1 whose dielectric loss tangent in 1 GHz of the hardened | cured material of the said thermosetting resin composition is 0.005 or less.   The thermosetting resin composition according to claim 1 or 2, wherein the cured product of the thermosetting resin composition has a water absorption rate (based on JIS C 6481) of 0.10% or more and 0.40% or less.   The thermosetting resin composition according to any one of claims 1 to 3, wherein the component (C) has an average particle size of 0.01 µm or more and 5.0 µm or less.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the content of the component (C) is 150 to 300 parts by weight with respect to 100 parts by weight of the resin solid content.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the component (C) contains silica particles.   The thermosetting resin composition according to any one of claims 1 to 6, wherein the cyanate ester resin of the component (B) has a bisphenol A skeleton or a novolak skeleton.   The thermosetting resin composition according to any one of claims 1 to 7, wherein both ends of the component (A) have a hydroxy group or a methacryl group.   The thermosetting resin composition according to any one of claims 1 to 8, wherein the component (A) has a weight average molecular weight of 500 or more and 4,000 or less.   The thermosetting resin composition according to any one of claims 1 to 9, wherein the content of the epoxy resin as the component (B) is 25 parts by weight or less with respect to 100 parts by weight of the resin solid content. A carrier substrate;
The resin film with a carrier provided with the resin film which consists of the thermosetting resin composition of any one of Claims 1 thru | or 10 provided on the said carrier base material.   A prepreg in which a fiber base material is impregnated with the thermosetting resin composition according to any one of claims 1 to 10.   A metal-clad laminate in which a metal layer is disposed on at least one surface of a cured product of the prepreg according to claim 12.   A resin substrate provided with the insulating layer comprised with the hardened | cured material of the thermosetting resin composition of any one of Claims 1 thru | or 10.   A printed wiring board in which a circuit layer is formed on the surface of the metal-clad laminate according to claim 13 or the resin substrate according to claim 14. The printed wiring board according to claim 15;
A semiconductor device comprising: a semiconductor element mounted on the circuit layer of the printed wiring board or built in the printed wiring board.

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