JP7388482B2 - Thermosetting resin compositions, resin films with carriers, prepregs, printed wiring boards, and semiconductor devices - Google Patents

Description

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

In recent years, with the demand for higher functionality in electronic devices, electronic components have become more densely integrated and even more densely packaged, and the semiconductor devices used in these electronic devices are rapidly becoming smaller. ing. Printed wiring boards used in semiconductor devices are required to be thinner, have higher density, and have finer circuits.

Various developments have been made so far in resin compositions for forming insulating layers used in printed wiring boards. An example of this type of technology is the resin composition described in Patent Document 1, for example. According to the same document, the second silica contains an epoxy resin, an active ester resin, a first silica having an average particle size of 0.1 μm or more and 10 μm or less, and a second silica having an average particle size of 1 nm or more and less than 100 nm. A resin composition is described in which the content of the second silica relative to 100 parts by weight of the first silica is 0.6 parts by weight or more and 30 parts by weight or less.

Japanese Patent Application Publication No. 2011-174035

However, upon investigation by the present inventor, it was found that the resin composition described in the above document has room for improvement in terms of both insulation reliability and semi-additive process (SAP) characteristics. did.

Usually, when the SAP method is used to form fine wiring, a desmear process using a chemical solution is performed. Such desmear treatment is performed by, for example, swelling the surface of the insulating layer with an alkaline swelling solution, roughening the resin surface with an aqueous permanganic acid solution, and then performing a neutralization treatment. . At this time, the adhesion between the surface of the insulating layer and the plated conductor layer is mainly developed by the anchoring effect caused by the fine roughness formed on the surface of the insulating layer. The anchor effect of the roughened surface of the insulating layer is that the greater the roughness, the better the adhesion with the plated conductor layer, but if the roughness is large, the formed plated conductor layer will be partially etched, making it difficult to form fine wiring. It becomes difficult. On the other hand, if the roughness is made small, there is a high possibility that adhesion with the electroless plated conductor layer cannot be sufficiently exhibited. Therefore, it is necessary to achieve both low roughness and adhesion with the plated conductor layer.

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

The present inventor investigated the SAP characteristics of the insulating layer in a printed wiring board when desmear treatment using a chemical solution was used, and found that although the detailed mechanism is not clear, the suppression of swelling of the insulating layer by desmear treatment and the SAP characteristics We found that there was a strong correlation between the improvement of

Focusing on such a correlation, the present inventors conducted intensive studies on curing agents and blended resins used in thermosetting resin compositions, and found that certain resin components constituting the insulating layer were "An active ester compound that has a structural site with an ester group inside the molecular skeleton and a monovalent naphthaleneoxy group at both ends" increases desmear resistance, reduces the surface roughness of the insulating layer, and reduces the surface roughness of the plated conductor layer. It has been found that it is possible to improve the adhesion with.

We have also discovered that it is possible to reduce signal transmission loss in the high frequency range because the surface of the insulating layer can be made to have a fine roughness shape and the dielectric loss tangent can be reduced.

Furthermore, the present inventors have discovered that interlayer connection reliability can be improved by excellent removal of smear generated in blind via holes for interlayer connection using laser, and have completed the present invention.

According to the invention,
A thermosetting resin composition used for forming an insulating layer constituting a build-up layer of a multilayer printed wiring board, the composition comprising:
An epoxy resin (A) with a softening point of 50°C or higher,
An epoxy resin (B) that is liquid at room temperature,
An active ester compound (C) having a structural site represented by the following formula (1),
Inorganic filler (D);
Provided is a thermosetting resin composition comprising:

(In formula (1), l is each independently an integer of 0 or more and 6 or less, m is each independently an integer of 1 or more and 5 or less, and n is an integer of 1 or more and 6 or less.)
Furthermore, according to the present invention,
A thermosetting resin composition is provided that further contains at least one selected from cyanate ester resins, maleimide compounds, benzocyclobutene resins, vinyl resins, and acrylate compounds.

Furthermore, according to the present invention,
A thermosetting resin composition is provided, further comprising a thermoplastic resin.

Furthermore, according to the present invention,
A thermosetting resin composition is provided in which the thermoplastic resin is at least one selected from phenoxy resin, polyimide resin, polyamide resin, polyamideimide resin, and polyphenylene EL resin.

Furthermore, according to the present invention,
A thermosetting resin is provided in which the inorganic filler (D) is at least one selected from talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide.

Furthermore, according to the present invention,
There is provided a thermosetting resin composition in which the content of the inorganic filler (D) is 50% by mass or more and 85% by mass or less based on 100% by mass of the total solid content of the thermosetting resin composition. .

Furthermore, according to the present invention,
A thermosetting resin composition is provided in which the inorganic filler (D) is surface-treated with at least one silane coupling agent selected from the group consisting of amino, epoxy, and thiol.

Furthermore, according to the present invention,
A resin film with a carrier is provided, which includes a carrier base material and a resin film made of the thermosetting resin composition, which is provided on the carrier base material.

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

Furthermore, according to the present invention,
A printed wiring board is provided that includes an insulating layer made of a cured product of the thermosetting resin composition.

Furthermore, according to the present invention,
A semiconductor device is provided that includes the printed wiring board and a semiconductor element mounted on a circuit layer of the printed wiring board or built into the printed wiring board.

According to the present invention, a thermosetting resin that has excellent reduction in surface roughness of an insulating layer and excellent adhesion with a plated conductor layer, and is used to form a build-up layer of a multilayer printed wiring board. A resin film with a carrier, a prepreg, a printed wiring board, and a semiconductor device are provided.

FIG. 2 is a cross-sectional view showing an example of the configuration of a resin film with a carrier in this embodiment. FIG. 3 is a process cross-sectional view showing an example of the manufacturing process of the semiconductor device according to the present embodiment.

Embodiments of the present invention will be described below with reference to the drawings. Note that, in all the drawings, similar constituent elements are given the same reference numerals, and description thereof will be omitted as appropriate. Furthermore, the figure is a schematic diagram and does not correspond to the actual dimensional ratio.

Hereinafter, a thermosetting resin composition, a resin film with a carrier, a prepreg, a printed wiring board, and a semiconductor device will be explained.

First, the thermosetting resin composition (hereinafter sometimes referred to as "resin composition") in this embodiment will be explained.

The resin composition according to this embodiment is used to form an insulating layer that constitutes a build-up layer of a multilayer printed wiring board. In addition, examples of the insulating layer constituting the printed wiring board include insulating layers in prepreg, core base material, solder resist, and the like.

The resin composition can be, for example, in the form of a varnish containing a solvent. On the other hand, the resin composition may be in the form of a film. In this case, for example, a film-like resin composition can be obtained by subjecting a resin film obtained by applying a varnish-like resin composition to a solvent removal treatment. Note that the film-like resin composition can be laminated on a carrier base material to form a carrier-attached resin film, or can be impregnated into a fiber base material to form a prepreg.
[Epoxy resin (A) with a softening point of 50°C or higher]
The epoxy resin (A) having a softening point of 50° C. or higher is a compound having an epoxy group, and any conventionally known resin can be used. Examples include polyfunctional epoxy compounds having two or more epoxy groups in the molecule. Note that a hydrogenated epoxy compound may also be used.

Examples of the epoxy resin (A) having a softening point of 50° C. or higher include HP-4700/HP-4710 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC Corporation and HP-6000 (naphthylene ether type epoxy resin) manufactured by DIC Corporation. , naphthalene type epoxy resins such as NC-7000L/NC7300L manufactured by Nippon Kayaku Co., Ltd., ESN-475V/ESN-375/ESN-170/ESN-480 manufactured by Nippon Steel Chemical Co., Ltd. (naphthol type epoxy resin), manufactured by Mitsubishi Chemical Corporation jER1032H60/Trihydroxyphenylmethane type epoxy resin such as EPPN-502H manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene aralkyl type epoxy resin such as Epiclon HP-7200L (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by DIC, Japan Biphenylaralkyl type epoxy resins such as NC-3000/NC-3000L/NC3500 (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Kayaku Co., Ltd., Epiclon N660, Epiclon N690 manufactured by DIC Corporation, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. Novolac type epoxy resin, biphenyl type epoxy resin such as YX-4000HK manufactured by Mitsubishi Chemical Corporation, phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., tris (2,3-epoxypropyl) isocyanate such as TEPIC manufactured by Nissan Chemical Industries, Ltd. Nurate, solid bis A type epoxy resin YL6810 manufactured by Mitsubishi Chemical Corporation, and the like. By using the epoxy resin (A) having a softening point of 50° C. or higher, an insulating layer having a high glass transition temperature (Tg) and excellent crack resistance can be obtained. Aromatic epoxy resins are preferred from the viewpoint of heat resistance. Among these, naphthalene type epoxy compounds and biphenyl type epoxy compounds are more preferred.

As the epoxy resin (A) with a softening point of 50 ° C. or higher, one type of these may be used alone, two or more types may be used in combination, or a prepolymer thereof may be used in combination. .

[Epoxy resin (B) that is liquid at room temperature]
The resin composition of the present invention contains an epoxy resin (B) that is liquid at room temperature. The liquid epoxy resin (B) is an epoxy resin that is liquid at room temperature (for example, 20°C) and has one or two or more epoxy groups, such as liquid bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. Resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, dicyclopentadiene type epoxy resin, hydrogenated type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, Examples include monofunctional reactive dilution type epoxy resins. Commercially available products include jER828EL/jER807/jER152/jER630/jER604/YX8034 manufactured by Mitsubishi Chemical Corporation, HP4032/HP4032D manufactured by DIC Corporation, EP-4088L/EP-4000/ED-523L manufactured by ADEKA Corporation, and monofunctional Sanko Examples include OPP-G manufactured by Seiko. Two or more liquid epoxy resins may be used in combination. By using an epoxy resin (B) that is liquid at room temperature, it has excellent fluidity even when filled with a high amount of inorganic filler, and has excellent crosslinking density adjustment after curing and excellent mechanical strength and elongation at break, making it suitable for use with plated conductor layers. An insulating layer with excellent adhesion can be obtained. From the viewpoint of heat resistance, epoxy resins having two or more functionalities are preferred.

In the resin composition of the present invention, the content of the epoxy resin (B) that is liquid at room temperature is preferably 0.5% by mass or more and 25% by mass or less based on 100% by mass of nonvolatile content in the resin composition. , more preferably 1% by mass or more and 20% by mass or less, and even more preferably 1.5% by mass or more and 12% by mass or less. If the content is too low, the flexibility and fluidity of the resin sheet may decrease, and if the content is too high, the glass transition temperature may decrease and the carrier peelability from the carrier-coated resin film may decrease. Furthermore, the adhesion of the plated conductor layer at low roughness may be reduced. In addition, the content of epoxy resin (B) that is liquid at room temperature is 2% relative to the total amount of 100% by mass (nonvolatile content) of epoxy resin (B) that is liquid at room temperature and epoxy resin (A) with a softening point of 50°C or higher. The range is preferably from 5% by mass to 55% by mass, more preferably from 5% by mass to 45% by mass, and even more preferably from 10% by mass to 35% by mass.

[Active ester compound (C)]
The resin composition of the present invention uses, as a curing agent, an active ester compound ( C). As a result, when the surface of the insulating layer is roughened, it achieves both a reduction in surface roughness and good adhesion with the plated conductor layer, low water absorption and a reduction in dielectric loss tangent, and the formation of blind via holes for interlayer connections using laser. Excellent in removing smear.

(In formula (1), l is each independently an integer of 0 or more and 6 or less, m is each independently an integer of 1 or more and 5 or less, and n is an integer of 1 or more and 6 or less.)
In the above formula (1), l is an integer of 0 or more and 6 or less, preferably an integer of 1 or more and 5 or less, and more preferably an integer of 1 or more and 4 or less. m is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, and more preferably an integer of 1 or more and 3 or less. n is an integer of 1 or more and 6 or less, preferably an integer of 1 or more and 5 or less, and more preferably an integer of 1 or more and 3 or less.

The active ester compound (C) can be obtained by a conventionally known method. The active ester compound (C) can be produced by, for example, a step of reacting a dihydroxynaphthalene compound with benzyl alcohol to obtain a benzyl-modified naphthalene compound, and combining the obtained benzyl-modified naphthalene compound with an aromatic dicarboxylic acid chloride and a monohydric phenol compound. It is an active ester compound obtained through a step of reacting with a compound. The active ester compound (C) is described, for example, in International Publication No. 2016/098488.

Examples of commercially available active ester compounds (C) include "EXB-8100L-65T, EXB-8150L-65T" manufactured by DIC.

The content of the active ester compound (C) is the content of the epoxy resin (A) with a softening point of 50°C or higher, the content of the epoxy resin (B) that is liquid at room temperature, and the content of the active ester compound (C). It is preferably within the range of 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 60% by mass or less, based on the total 100% by mass. preferable. When the content of the active ester compound (C) is 20% by mass or more, the dielectric properties of the cured product of the resin composition can be improved. Particularly preferably, the ratio of the ester equivalents of the active ester compound to the total epoxy equivalents of the epoxy resin is in the range of 0.45:0.55 to 0.65:0.35.

In addition to the active ester compound (C), the resin composition according to the present invention may contain a curing agent other than the active ester compound (C). Only one type of the above-mentioned other curing agents may be used, or two or more types may be used in combination.

Examples of the other curing agents include phenolic compounds, amine compounds, acid anhydrides, dicyandiamide, etc. The resin composition according to the present embodiment contains an inorganic filler (D) as an essential component. Thereby, the storage modulus E' of the cured prepreg and resin substrate obtained can be improved. Furthermore, the coefficient of linear expansion of the resulting insulating layer can be reduced.

[Inorganic filler (D)]
The resin composition of the present invention contains an inorganic filler (D). Thereby, the generation of cracks can be suppressed by reducing the difference in thermal expansion coefficient between the insulating layer and the conductor layer consisting of the wiring pattern. Further, since warping of the semiconductor device can be reduced when the multilayer printed wiring board is made thinner, the connection reliability of the solder connection portion can be improved. Examples of the inorganic filler (D) include silicates such as talc, fired clay, unfired clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; calcium carbonate, and magnesium carbonate. , carbonates such as hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate, barium metaborate, Examples include borates such as aluminum borate, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; and titanates such as strontium titanate and barium titanate. can.

Among these, talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide are preferred, and one type among these may be used alone or two or more types may be used in combination.

In the resin composition of the present invention, the inorganic filler (D) is preferably surface-treated with a coupling agent or the like. Thereby, it is possible to obtain a resin composition for a multilayer printed wiring board that has excellent desmear properties in the surface roughening step of the insulating layer in the multilayer printed wiring board manufacturing process.

The surface treatment method is not particularly limited, but the surface may be pretreated by a wet method or a dry method, or may be treated with a coupling agent contained in the resin composition. In particular, it is preferable that the surface of the inorganic filler (D) has been previously subjected to a surface treatment, since agglomeration of the inorganic filler (D) can be suppressed and the dispersibility is excellent, so even if the filler is highly filled, it has excellent fluidity and can form fine roughness.

The above coupling agents used for surface treatment include, for example, epoxysilane, styrylsilane, methacryloxysilane, acryloxysilane, mercaptosilane, N-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, -Methylaminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(N-allylamino)propyltrimethoxysilane, (cyclohexylaminomethyl)triethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, N-ethylaminoisobutylmethoxyldiethoxysilane, (phenylaminomethyl)methyldimethoxysilane, N-phenylaminomethyltriethoxysilane, N-methylaminopropylmethyldimethoxysilane, vinylsilane, isocyanatesilane, sulfidesilane, chloropropylsilane, ureido Examples include silane compounds. Among these, aminosilane, epoxysilane, and thiol-based alkoxysilane are preferred, and secondary aminosilane compounds are particularly preferred. Examples of secondary aminosilane compounds include N-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-( N-Alylamino)propyltrimethoxysilane, (cyclohexylaminomethyl)triethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, N-ethylaminoisobutylmethoxyldiethoxysilane, (phenylaminomethyl)methyldimethoxysilane, N-phenylamino Examples include methyltriethoxysilane and N-methylaminopropylmethyldimethoxysilane. Thereby, it is possible to obtain a resin composition for a multilayer printed wiring board that has better desmear properties in the surface roughening step of the insulating layer in the multilayer printed wiring board manufacturing process.

The amount of the surface treatment agent of the coupling agent to the inorganic filler is not particularly limited as it depends on the specific surface area, but is 0.01% by mass or more and 5% by mass or less based on the inorganic filler. It is preferable that More preferably, it is 0.1% by mass or more and 3% by mass or less. If the content of the coupling agent exceeds the above upper limit, cracks may appear in the insulating resin composition for multilayer printed wiring boards, and if it is less than the above lower limit, the adhesion with the resin component may decrease. be. When the content of the coupling agent is at least the above lower limit, the inorganic filler (D) can be sufficiently coated, and the heat resistance of the resulting prepreg cured product and resin substrate can be improved. Moreover, when the content of the coupling agent is below the above upper limit value, it can be suppressed from affecting the reaction, and it is possible to suppress a decrease in the bending strength, etc. of the obtained cured prepreg or resin substrate.

The average particle diameter of the inorganic filler (D) is not particularly limited, but is preferably 0.05 μm or more, more preferably 0.15 μm or more. When the average particle diameter of the inorganic filler (D) is equal to or larger than the above lower limit, the viscosity of the varnish can be suppressed from increasing, and workability during production during application can be improved. Moreover, the average particle diameter of the inorganic filler (D) is not particularly limited, but is preferably 4.0 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.5 μm or less. When the average particle diameter of the inorganic filler (D) is below the above upper limit, phenomena such as sedimentation of the inorganic filler (D) in the varnish can be suppressed, and a more uniform resin layer can be obtained. Moreover, the filling amount can be further improved. Further, when the circuit dimension L/S of the printed wiring board is less than 15/15 μm, it is possible to suppress the influence on the insulation between the wirings. In addition, it is possible to achieve both low roughness and adhesion to the plated conductor layer, which are necessary for forming fine wiring.

The average particle diameter of the inorganic filler (D) can be determined by measuring the particle size distribution of the particles on a volume basis using, for example, a laser diffraction particle size distribution analyzer (manufactured by HORIBA, LA-500), and calculating the median diameter (D ₅₀ ) of the particles. can be taken as the average particle diameter.

Further, the shape and size of the inorganic filler (D) are not particularly limited, but an inorganic filler with a monodisperse average particle size may be used, or an inorganic filler with a polydisperse average particle size may be used. good. Furthermore, one type or two or more types of inorganic fillers having a monodisperse and/or polydisperse average particle size may be used in combination. In addition, from the viewpoint of high filling and high fluidity of the inorganic filler, for example, an inorganic filler with an average particle size of 0.5 μm or more and an inorganic filler with an average particle size of less than 0.5 μm, particularly preferably 0.2 μm or less It is preferred to combine different inorganic fillers.

When the shape of the inorganic filler (D) is anisotropic, such as a scaly shape or a needle shape, it is advantageous for increasing rigidity and lowering CTE. Spherical silica is preferred from the viewpoints of low CTE, filling properties, and fluidity.

The content of the inorganic filler (D) contained in the resin composition is not particularly limited, but is 50.0 mass% when the total solid content of the resin composition (i.e., components excluding the solvent) is 100% by mass. % or more and 85.0% by mass or less, more preferably 50.0% by mass or more and 75.0% by mass or less. When the content of the inorganic filler (D) is within the above range, the resulting insulating layer has excellent strength and adhesion to the plated conductor layer.

The resin composition of the present invention may further contain at least one selected from cyanate ester resins, maleimide compounds, benzocyclobutene resins, vinyl resins, and acrylate compounds. Thereby, the glass transition temperature can be raised and heat resistance can be imparted.

The cyanate ester resin can be obtained by, for example, reacting a halogenated cyanide compound with a phenol, and optionally converting the mixture into a prepolymer by heating or the like. Specifically, bisphenol cyanate ester resins such as novolak cyanate ester resin, bisphenol A cyanate ester resin, bisphenol E cyanate ester resin, and tetramethylbisphenol F cyanate ester resin can be mentioned. Among these, novolac type cyanate ester resins are preferred. This improves heat resistance due to increased crosslinking density, and further improves flame retardancy. This is because the novolac type cyanate ester resin forms a triazine ring after the curing reaction. Furthermore, it is thought that this is because the novolac type cyanate ester resin has a high proportion of benzene rings due to its structure and is easily carbonized.

The above-mentioned maleimide compound is preferably a maleimide compound having, for example, at least two maleimide groups in the molecule.

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'-ethylene dimaleimide, 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. Examples include compounds having two maleimide groups in the molecule, compounds having three or more maleimide groups in the molecule, such as biphenylaralkyl maleimide, and polyphenylmethane maleimide.

One of these can be used alone, or two or more can be used in combination. Among these maleimide compounds, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-4000), biphenylaralkyl maleimide ( Nippon Kayaku Co., Ltd., MIR-3000) is preferable, and from the viewpoint of heat resistance, 4,4'-diphenylmethane bismaleimide (Daiwa Kasei Kogyo Co., Ltd., BMI-1000), bis-(3-ethyl-5-methyl- Preferred are 4-maleimidophenyl)methane (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-5100) and polyphenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300).

Examples of commercially available benzocyclobutene resins include XUS-35077XUS (manufactured by Dow Chemical Co.), and commercially available acrylates include A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The content of at least one resin selected from cyanate ester resins, maleimide compounds, benzocyclobutene resins, vinyl resins, and acrylate compounds is not particularly limited, but is 0.5% of the total insulating resin composition for multilayer printed wiring boards. It is preferably at least 1% by mass and at most 50% by mass, particularly preferably at least 1% by mass and at most 30% by mass. If the content is less than the above lower limit, the effect of increasing the glass transition temperature may not be sufficiently obtained, and if it exceeds the above upper limit, the water absorption rate may deteriorate and the surface smoothness after desmear treatment may deteriorate.

The resin composition of the present invention may contain a thermoplastic resin. Examples of thermoplastic resins include phenoxy resin, acrylic resin, methacrylic resin, polyvinyl acetal resin, polyimide resin, polyamide resin, polyamideimide resin, polyphenylene ether resin, polyether sulfone resin, polyester resin, polyethylene resin, polystyrene resin, and polysulfone. Examples include resin, polybutadiene resin, ABS resin, and the like. As the thermoplastic resin, one type of these may be used alone, two or more types having different weight average molecular weights may be used in combination, or one type or two or more types and their prepolymers may be used together. May be used together.

Among these, the thermoplastic resin may include one or more selected from the group consisting of phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and polyphenylene ether resin. From the viewpoint of increasing the elongation of the cured product, phenoxy resins and polyimide resins may be used.

The above phenoxy resin is not particularly limited, but includes, for example, phenoxy resin having a bisphenol A skeleton, phenoxy resin having a bisphenol F skeleton, phenoxy resin having a bisphenol S skeleton, bisphenol M (4,4'-(1,3 Phenoxy resin having a bisphenol P (4,4'-(1,4)-phenylene diisopridiene) bisphenol) skeleton, bisphenol Z (4,4' - Phenoxy resins with a bisphenol skeleton, phenoxy resins with a novolak skeleton, phenoxy resins with an anthracene skeleton, phenoxy resins with a fluorene skeleton, phenoxy resins with a dicyclopentadiene skeleton, norbornene Examples include phenoxy resins having a skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton, phenoxy resins having an adamantane skeleton, and the like. Further, as the phenoxy resin, a structure having multiple types of skeletons among these can be used, and phenoxy resins having different ratios of the respective skeletons can be used. Furthermore, it is possible to use a plurality of types of phenoxy resins having different skeletons, a plurality of types of phenoxy resins having different weight average molecular weights, or a combination of prepolymers thereof.

As the above phenoxy resin, one having an ester group in the molecule is sometimes preferable. The phenoxy resin having an ester group in its molecule is represented by the following general formula (2), and is an esterified phenoxy resin having an epoxy group at the end and having a weight average molecular weight Mw of 5,000 or more and 200,000 or less. In this esterified phenoxy resin, some or all of the polar groups such as hydroxyl groups that exhibit water absorption are capped with hydrophobic groups.

(In the above formula (2), A includes the structure represented by the above formula (3), R ¹ and R ² may be different from each other, and are represented by a hydrogen atom or the above formula (4). structure.However, at least one of R ¹ and R ² is a group represented by the above formula (4). 5 mol% or more of ^{R 3} is an aliphatic carbonyl group having 1 to 10 carbon atoms or an aromatic group carbonyl group, the rest are hydrogen atoms, n is the average value of the repeating number, and is an integer of 5 or more and 500 or less.In the above formula (3), X ¹ is a direct bond, carbon number 1 or more, A divalent hydrocarbon group of 13 or less, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - and -CO-, and R ⁴ to R ¹¹ are each Independently, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, (It is a group arbitrarily selected from alkynyl groups having 1 or more and 12 or less carbon atoms.)
The structure represented by the above (3) is a structure represented by the following formula (5) or the following formula (6).

The lower limit of the weight average molecular weight (Mw) of the phenoxy resin is, for example, 10,000 or more, preferably 15,000 or more, and more preferably 20,000 or more. Thereby, compatibility with other resins and solubility in solvents can be improved. On the other hand, the upper limit of the weight average molecular weight (Mw) of the phenoxy resin is, for example, 60,000 or less, preferably 55,000 or less, and more preferably 50,000 or less. This improves film formation properties and can prevent problems from occurring when used for manufacturing printed wiring boards.

Commercial products of the above polyimide resin include PAID series (manufactured by Arakawa Chemical Industry Co., Ltd.) and Ricacoat SN20 (manufactured by Shin Nihon Rika Co., Ltd.), and commercial products of the above polyamide-imide resin include Vylomax HR16NN (manufactured by Toyobo Co., Ltd.), Examples of commercially available polyamide resins include Kayaflex BPAM-155 (manufactured by Nippon Kayaku Co., Ltd.), and examples of commercially available polyphenylene ether resins include NORYL Resin SA90 (manufactured by SABC).

The content of the thermoplastic resin (for example, phenoxy resin) is not particularly limited, but is preferably 0.5% by mass or more and 40% by mass or less, based on the entire thermosetting resin composition excluding the inorganic filler, and 1 It is more preferably at least 20% by mass. When the content is at least the above lower limit, it is possible to suppress a decrease in the mechanical strength of the insulating layer and a decrease in plating adhesion between the insulating layer and the conductor circuit. When it is below the above upper limit, an increase in the coefficient of thermal expansion of the insulating layer can be suppressed, and a decrease in heat resistance can be suppressed.

In addition, a curing accelerator and a coupling agent can be appropriately blended into the resin composition as required.

Although the curing accelerator is not particularly limited, the curing time and curing temperature can be adjusted as appropriate. Examples of the curing accelerator include organic phosphine compounds such as TPP, TPP-K, TPP-S, and TPTP-S (manufactured by Hokko Chemical Industry Co., Ltd.), Curazole 2MZ, 2E4MZ, 2PZ, 1B2PZ, Cl1Z, Cl1Z-CN, and Cl1Z. - Imidazole compounds such as CNS, Cl1Z-A, 2MZ-OK, 2MA-OK, 2PHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), amine adduct compounds such as Novacure (manufactured by Asahi Kasei Kogyo Co., Ltd.), FujiCure (manufactured by Fuji Kasei Kogyo Co., Ltd.), Amine compounds such as 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 4-dimethylaminopyridine, Examples include organometallic complexes or organometallic salts of cobalt, copper, zinc, iron, nickel, manganese, tin, and the like. Two or more types of curing accelerators may be used in combination.

The content of the curing accelerator is preferably 0.01% by mass or more and 5.0% by mass or less, and 0.05% by mass or more, based on 100% by mass of nonvolatile components excluding the inorganic filler (D). , more preferably 3.0% by mass or less, and particularly preferably 0.1% by mass or more and 1.5% by mass or less. By setting the content of the curing accelerator within this range, the heat resistance of the cured product obtained from the resin composition can be improved.

Furthermore, the resin composition may additionally contain a coupling agent. The coupling agent may be added directly at the time of preparing the resin composition, or may be added to the inorganic filler (D) in advance. By using a coupling agent, the wettability of the interface between the fiber base material or inorganic filler (D) and each resin can be further improved. Therefore, it is preferable to use a coupling agent, which can improve the heat resistance of the resulting insulating layer.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and aminosilane coupling agents, titanate coupling agents, and silicone oil type coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination.

Thereby, the wettability of the interface between the fiber base material or inorganic filler (D) and each resin can be increased, and the heat resistance of the resulting cured prepreg or resin substrate can be further improved.

Various types of silane coupling agents can be used, and examples thereof include epoxysilane, aminosilane, alkylsilane, ureidosilane, mercaptosilane, and vinylsilane.

Specific compounds include, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, 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-(3,4epoxycyclohexyl)ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc. Among these, epoxysilane, mercaptosilane, and aminosilane are preferred, and as the aminosilane, primary aminosilane or anilinosilane is more preferred.

Furthermore, the resin composition of the present invention may include curing accelerators, pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, Additives other than the above components such as ion scavengers and rubber particles may be added.

Pigments include inorganic pigments such as kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, synthetic ultramarine blue, polycyclic pigments such as phthalocyanine, and 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.

The resin composition of the present invention includes acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, ethylene glycol, cellosolve type, carbitol type, In an organic solvent such as anisole or N-methylpyrrolidone, using various mixers such as an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation-revolution dispersion method. A resin varnish can be obtained by melting, mixing, and stirring.

The solid content of the resin varnish is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, particularly preferably 50% by mass or more and 70% by mass or less. As a result, when a resin film with a carrier is formed using the resin varnish, the film has excellent uniformity, and the impregnating property into the fiber base material can be further improved.

Next, the resin film of this embodiment will be explained.

The resin film of this embodiment can be obtained by forming the thermosetting resin composition in the form of a varnish into a film. For example, the resin film of this embodiment can be obtained by removing the solvent from a coating film obtained by applying a varnish-like thermosetting resin composition. In such a resin film, the solvent content can be 5% by mass or less based on the entire resin film. In this embodiment, the step of removing the solvent may be carried out under conditions of, for example, 100° C. or higher and 150° C. or lower, and 1 minute or more and 5 minutes or less. This makes it possible to sufficiently remove the solvent while suppressing the progress of curing of the resin film containing the thermosetting resin.

The resin film of this embodiment can include a fiber base material inside, and may be a prepreg obtained by impregnating the fiber base material with the resin composition.

In this embodiment, the method for impregnating the fiber base material with the resin composition is not particularly limited, but for example, the resin composition is dissolved in a solvent to prepare a resin varnish, and the fiber base material is immersed in the resin varnish. Methods include applying the resin varnish to the fiber base material using various coaters, spraying the resin varnish onto the fiber base material by spraying, laminating both sides of the fiber base material with the resin film made of the resin composition, etc. Can be mentioned.

Examples of the above-mentioned fiber base materials include glass fiber base materials such as glass fibers and glass nonwoven fabrics, inorganic fiber base materials such as woven and nonwoven fabrics containing inorganic compounds other than glass, aromatic polyamide-imide resins, and polyamide resins. Examples include organic fiber base materials made of organic fibers such as resins, aromatic polyester resins, polyester resins, polyimide resins, and fluororesins. Among these base materials, use of a glass fiber base material typified by glass woven fabric in terms of strength allows the printed wiring board to have good mechanical strength and heat resistance.

The thickness of the fiber base material is not particularly limited, but is preferably 5 μm or more and 150 μm or less, more preferably 10 μm or more and 100 μm or less, and still more preferably 12 μm or more and 90 μm or less. By using a fiber base material having such a thickness, handling properties during prepreg production can be further improved.

When the thickness of the fiber base material is less than or equal to the above upper limit value, the impregnation property of the resin composition in the fiber base material is improved, and occurrence of strand voids and a decrease in insulation reliability can be suppressed. In addition, through-holes can be easily formed using lasers such as carbon dioxide, UV, and excimer. Furthermore, when the thickness of the fiber base material is equal to or greater than the above lower limit, the strength of the fiber base material or prepreg can be improved. As a result, handling properties can be improved, prepreg production can be facilitated, and warping of the resin substrate can be suppressed.

The glass fiber base material is, for example, a glass formed from one or more types of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, and quartz glass. A fiber base material is preferably used.
(Resin film with carrier)
Next, the carrier-attached resin film of this embodiment will be explained.

FIG. 1(a) is a cross-sectional view showing an example of the configuration of the carrier-attached resin film 10 in this embodiment.

As shown in FIG. 1(a), the carrier-attached resin film 10 of this embodiment includes a carrier base material 40, a primer layer 30 for plating process provided on the carrier base material 40, and a plating layer. An insulating film 20 serving as a base can be provided. In the carrier-attached resin film 10, at least one of the primer layer 30 and the insulating film 20 is preferably composed of a resin film made of the resin composition described above. Thereby, the handling properties of the resin film can be improved.

Further, the carrier-attached resin film 12 of the present embodiment includes a carrier base material 40 and a resin film made of the above resin composition formed on the carrier base material 40, as shown in FIG. 1(b). be able to. The resin film can be used as an insulating film 20 serving as a base for a plating layer.

The carrier-attached resin films 10 and 12 may have a roll shape that can be rolled up, or a sheet shape such as a rectangular shape. The surfaces of the carrier-attached resin films 10 and 12 may be exposed, for example, or may be covered with a protective film (cover film). As the protective film, a film having a known protective function can be used, and for example, a PET film may be used.

In this embodiment, as the carrier base material 40, for example, a polymer film, metal foil, or the like can be used. The polymer film is not particularly limited, but includes, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, release papers such as silicone sheets, and heat-resistant materials such as fluorine resins and polyimide resins. Examples include thermoplastic resin sheets having the following properties. The metal foil is not particularly limited, but includes, for example, copper and/or copper-based alloys, aluminum and/or aluminum-based alloys, iron and/or iron-based alloys, silver and/or silver-based alloys, gold and gold-based alloys. , zinc and zinc-based alloys, nickel and nickel-based alloys, tin and tin-based alloys, and the like. Among these, a sheet made of polyethylene terephthalate is most preferred because it is inexpensive and its peel strength can be easily adjusted. This makes it easy to peel off from the carrier-attached resin film 10 with appropriate strength.

The lower limit of the thickness of the resin film is not particularly limited, but may be, for example, 1 μm or more, 3 μm or more, or 5 μm or more. Thereby, the mechanical strength of the resin film 10 can be increased. On the other hand, the upper limit of the thickness of the resin film 10 is not particularly limited, but may be, for example, 500 μm or less, 300 μm or less, or 100 μm or less. This allows the semiconductor device to be made thinner. The thickness of the resin film may be the thickness of the insulating film 20 or the total thickness of the insulating film 20 and the primer layer 30.

The lower limit of the film thickness of the primer layer 30 is, for example, 1 μm or more, preferably 2 μm or more. Thereby, insulation reliability can be improved. On the other hand, the upper limit of the film thickness of the primer layer 30 is, for example, 10 μm or less, preferably 8 μm or less. This makes it possible to make the printed wiring board thinner. Further, by setting the film thickness of the primer layer 30 within the above range, a printed wiring board that can be made thinner can be obtained without losing the properties of the insulating layer in the buildup layer.

The lower limit of the thickness of the insulating film 20 is, for example, 5 μm or more, preferably 10 μm or more. Thereby, insulation reliability can be improved. On the other hand, the upper limit of the thickness of the insulating film 20 is, for example, 50 μm or less, preferably 40 μm or less. This makes it possible to make the printed wiring board thinner. Furthermore, by setting the thickness of the insulating film 20 within the above range, when manufacturing a printed wiring board, it is possible to fill in the unevenness of the inner layer circuit and form the insulating resin layer of a suitable build-up layer. Thickness can be ensured.

The thickness of the carrier base material 40 is not particularly limited, but may be, for example, 10 μm or more and 100 μm or less, or 10 μm or more and 70 μm or less. This is preferable because the handleability when manufacturing the carrier-attached resin film 10 is improved.

The resin film of the carrier-attached resin film 10 of this embodiment may be a single layer or a multilayer, and may be composed of one type or two or more types of films. When the resin sheet is multilayered, it may be composed of the same kind or different kinds. Further, the carrier-attached resin film 10 may have a protective film on the outermost layer side on the resin film 10.

The resin film of this embodiment is a resin film made of the above thermosetting resin composition. The cured resin film is composed of a cured product of the thermosetting resin composition. A cured film, which is a cured product of the thermosetting resin composition, can be used as an insulating layer constituting a build-up layer of a printed wiring board.
(Printed wiring board)
The printed wiring board of this embodiment includes an insulating layer made of a cured product of the above-mentioned resin film (cured product of a thermosetting resin composition).

In this embodiment, the cured resin film is, for example, a build-up layer of a normal printed wiring board, a build-up layer of a printed wiring board without a core base material, a build-up layer of a coreless board used for PLP, or an MIS. It can be used as a build-up layer of a substrate, etc. The insulating layer constituting such a build-up layer is also suitably used as the build-up layer constituting the printed wiring board in a large-area printed wiring board that is used to create multiple semiconductor packages at once. be able to.

Furthermore, in this embodiment, a resin film made of a thermosetting resin composition for forming an insulating film may be impregnated with glass fibers. Even in a semiconductor package using such a resin film as a build-up layer, the coefficient of linear expansion of the cured resin film can be lowered, so that package warpage can be sufficiently suppressed.
(semiconductor package)
FIG. 2 is a process cross-sectional view showing an example of the manufacturing process of the semiconductor package 200 of this embodiment.

The semiconductor device (semiconductor package 200) of this embodiment can include a printed wiring board and a semiconductor element 240 mounted on a circuit layer of the printed wiring board or built into the printed wiring board.

Hereinafter, an outline of the manufacturing process of the semiconductor package 200 of this embodiment will be explained.

First, as shown in FIG. 2(a), a core base material 100 including an insulating layer 102, a via hole 104, and a metal layer 108 is prepared. A via hole 104 is formed in the insulating layer 102. A metal layer (via) is buried in the via hole 104 . The metal layer may be covered with an electroless metal plating film 106. A metal layer 108 (a circuit layer having a predetermined circuit pattern) formed on the surface of the insulating layer 102 is electrically connected to a via formed in the via hole 104. In FIG. 2A, the metal layer 108 is formed on one surface of the core base material 100, but it may be formed on both surfaces.

Subsequently, a resin film made of the thermosetting resin composition is formed on one surface of the core base material 100 so as to embed the metal layer 108 therein. As the resin film, a plurality of layers including the insulating film 20 and the primer layer 30 can be used. Furthermore, a single layer of only the insulating film 20 may be used as the resin film.

Subsequently, an opening (not shown) is formed in the resin film. The opening can be formed to expose the metal layer 108. The method for forming the opening is not particularly limited, and for example, a method such as a laser processing method, an exposure and development method, or a blasting method can be used.

In this embodiment, after forming such an opening, the resin film (insulating film 20, primer layer 30) may be thermally cured. Thereby, the resin film can be composed of a cured product of the thermosetting resin composition of this embodiment.

Further, desmear processing can be performed as necessary. In the desmear treatment, the smear generated inside the opening can be removed and the surface of the resin film can be roughened.

The desmear process described above can be performed, for example, as follows, although it is not particularly limited. First, the core base material 100 on which resin films are laminated is immersed in a swelling liquid containing an organic solvent, and then immersed in an aqueous alkaline permanganate solution for neutralization and roughening treatment. As the organic solvent, diethylene glycol monobutyl ether, ethylene glycol, etc. can be used. An example of such a swelling liquid is "Swelling Dip Securigant P" manufactured by Atotech Japan. As the permanganate, for example, potassium permanganate, sodium permanganate, etc. can be used. The temperature of the swelling liquid or permanganate aqueous solution may be, for example, 50°C or higher, or 100°C or lower. Further, the immersion time in the swelling liquid or permanganate aqueous solution may be, for example, 1 minute or more and 30 minutes or less.

In the step of desmearing, only the above wet desmearing process can be performed, but plasma irradiation may be performed in addition to the desmearing process.

Subsequently, an electroless metal plating film 202 is formed on the primer layer 30. An example of electroless plating method will be explained. For example, catalyst nuclei are provided on the surface of the primer layer 30 as the base layer. The catalyst nucleus is not particularly limited, but for example, noble metal ions or palladium colloid can be used. Subsequently, an electroless metal plating film 202 is formed by electroless plating using this catalyst nucleus as a nucleus. For electroless plating, for example, a material containing copper sulfate, formalin, a complexing agent, sodium hydroxide, etc. can be used. Note that after electroless plating, a heat treatment at 100° C. or more and 250° C. or less can be performed to stabilize the plating film.

Subsequently, as shown in FIG. 2(b), a resist 204 having a predetermined opening pattern (openings 206) is formed on the electroless metal plating film 202. This opening pattern corresponds to, for example, a circuit pattern. The resist 204 is not particularly limited, and any known material can be used, and liquid or dry films can be used. In the case of forming fine wiring, a photosensitive dry film or the like can be used as the resist 204. An example using a photosensitive dry film will be explained. For example, a photosensitive dry film is laminated on the electroless metal plating film 202, the non-circuit forming area is exposed to light and photocured, and the unexposed area is dissolved and removed with a developer. A resist 204 is formed by leaving the cured photosensitive dry film.

Subsequently, as shown in FIG. 2C, an electrolytic metal plating layer 208 is formed at least inside the opening pattern of the resist 204 and on the electroless metal plating film 202 by electroplating. Electroplating is not particularly limited, but it is possible to use a known method used for ordinary printed wiring boards, such as passing an electric current through the plating solution while the board is immersed in a plating solution such as copper sulfate. Methods such as the following can be used. The electrolytic metal plating layer 208 may be a single layer or may have a multilayer structure. The material for the electrolytic metal plating layer 208 is not particularly limited, and for example, one or more of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

Subsequently, as shown in FIG. 2(d), the resist 204 is removed using an alkaline stripper, sulfuric acid, a commercially available resist stripper, or the like.

Subsequently, as shown in FIG. 2E, the electroless metal plating film 202 in the area (opening 210) other than the area where the electrolytic metal plating layer 208 is formed is removed. That is, using the electrolytic metal plating layer 208 as a mask, the underlying electroless metal plating film 202 is selectively removed. For example, the electroless metal plating film 202 can be removed by using soft etching (flash etching) or the like. Here, the soft etching process can be performed, for example, by etching using an etching solution containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 220 having a predetermined pattern can be formed. In this way, the metal layer 220 made up of the electroless metal plating film 202 and the electrolytic metal plating layer 208 is formed on the insulating layer made of the cured resin film of this embodiment by a semi-additive process (SAP). be able to.

Furthermore, by repeating the process of laminating buildup layers as necessary on the printed wiring board composed of the core base material 100 and the buildup layer described above, and forming interlayer connections and circuits by a semi-additive process, multilayer It can be done.

Through the above steps, the printed wiring board of this embodiment is obtained.

Subsequently, as shown in FIG. 2(f), build-up layers are laminated as necessary on the obtained printed wiring board, and the steps of forming interlayer connections and circuits by a semi-additive process are repeated. Then, if necessary, a solder resist layer 230 is laminated on both sides or one side of the printed wiring board.

The method of forming the solder resist layer 230 is not particularly limited, but for example, a dry film type solder resist may be laminated, exposed and developed, or a printed liquid resist may be exposed and developed. This is done by a method of forming.

Subsequently, by performing a reflow process, the semiconductor element 240 is fixed onto the connection terminal, which is a part of the wiring pattern, via the solder bump 250. Thereafter, the semiconductor element 240, the solder bumps 250, and the like are covered and sealed with a sealing material layer 260.

Through the above steps, a semiconductor package 200 shown in FIG. 2(f) is obtained.

Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than those described above may also be adopted.
Examples of reference embodiments of the present invention will be described below.
[1]
A thermosetting resin composition used for forming an insulating layer constituting a build-up layer of a multilayer printed wiring board, the composition comprising:
An epoxy resin (A) with a softening point of 50°C or higher,
An epoxy resin (B) that is liquid at room temperature,
An active ester compound (C) having a structural site represented by the above formula (1),
Inorganic filler (D);
A thermosetting resin composition comprising:
(In formula (1), l is each independently an integer of 0 or more and 6 or less, m is each independently an integer of 1 or more and 5 or less, and n is an integer of 1 or more and 6 or less.)
[2]
The thermosetting resin composition according to [1],
A thermosetting resin composition further comprising at least one selected from a cyanate ester resin, a maleimide compound, a benzocyclobutene resin, a vinyl resin, and an acrylate compound.
[3]
The thermosetting resin composition according to [1] or [2],
A thermosetting resin composition further comprising a thermoplastic resin.
[4]
The thermosetting resin composition according to [3],
A thermosetting resin composition in which the thermoplastic resin is at least one selected from phenoxy resin, polyimide resin, polyamide resin, polyamideimide resin, and polyphenylene EL resin.
[5]
The thermosetting resin composition according to any one of [1] to [4],
A thermosetting resin in which the inorganic filler (D) is at least one selected from talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide.
[6]
The thermosetting resin composition according to any one of [1] to [5],
A thermosetting resin composition in which the content of the inorganic filler (D) is 50% by mass or more and 85% by mass or less based on 100% by mass of the total solid content of the thermosetting resin composition.
[7]
The thermosetting resin composition according to any one of [1] to [6],
A thermosetting resin composition in which the inorganic filler (D) is surface-treated with at least one silane coupling agent selected from the group consisting of amino, epoxy, and thiol.
[8]
a carrier base material;
A resin film with a carrier, comprising: a resin film made of the thermosetting resin composition according to any one of [1] to [7], which is provided on the carrier base material.
[9]
A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of [1] to [7].
[10]
A printed wiring board comprising an insulating layer made of a cured product of the thermosetting resin composition according to any one of [1] to [7].
[11]
The printed wiring board according to [10],
A semiconductor device comprising: a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.
(Preparation of thermosetting resin composition)
A varnish-like thermosetting resin composition (resin varnish P) was prepared for each Example and each Comparative Example.

First, each component was dissolved or dispersed at the solid content ratio shown in Table 1, the nonvolatile content was adjusted to 70% by mass with methyl ethyl ketone, and the resin varnish P was prepared by stirring using a high-speed stirring device.

Details of the raw materials for each component in Table 1 are as follows.
(thermosetting resin)
Epoxy resin A1: Biphenylaralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 276 g/eq)
Epoxy resin A2: Biphenylaralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3500, epoxy equivalent weight 205 g/eq)
Epoxy resin A3: trihydroxyphenylmethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1032H60, epoxy equivalent 169 g/eq)
Epoxy resin A4: naphthylene ether type epoxy resin (manufactured by DIC, HP-6000, epoxy equivalent 250 g/eq)
Epoxy resin A5: 4-functional naphthalene type epoxy resin (manufactured by DIC, HP-4710, epoxy equivalent: 171 g/eq)
Epoxy resin B1: Bisphenol F type epoxy resin (manufactured by DIC, EPICLON, 830S, epoxy equivalent: 170 g/eq, liquid at room temperature)
Epoxy resin B2: Bifunctional dicyclopentadiene type epoxy resin (manufactured by ADEKA, EP-4088L, epoxy equivalent 170 g/eq, liquid at room temperature)
Epoxy resin B3: triglycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER630, epoxy equivalent: 96 g/eq, liquid at room temperature)
Epoxy resin B4: Bifunctional naphthalene type epoxy resin (manufactured by DIC, HP-4032D, epoxy equivalent: 142 g/eq, liquid at room temperature)
Cyanate ester resin: Phenol novolac type cyanate ester resin (manufactured by Lonza, PT-30)
Maleimide compound: biphenylaralkyl maleimide (manufactured by Nippon Kayaku Co., Ltd., MIR-3000)
Acrylate compound: Ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300)
Benzocyclobutene resin: Divinyltetramethylsiloxane benzocyclobutene resin (manufactured by Dow Chemical Company, XUS-35077XUS)
(hardening agent)
Active ester curing agent 1: Active ester resin having a structural moiety represented by formula (1) (manufactured by DIC, EXB-8100L-65T, active ester equivalent weight 245 g/eq)
Active ester curing agent 2: dicyclopentadiene type active ester resin (manufactured by DIC, HPC-8000-65T, active ester equivalent weight 223 g/eq)
(Thermoplastic resin)
Phenoxy resin 1: Esterified phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YL7899)
Phenoxy resin 2: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YX6900)
Polyphenylene ether resin: terminal OH-containing polyphenylene ether resin (manufactured by SABI, SA90, number average molecular weight 1670)
Polyimide resin: Silicone modified polyimide resin (4,4'-bisphenol A dianhydride and 4,4'-oxydiphthalic anhydride as acid anhydrides, 2,2'-bis(trifluoromethyl)benzidine and α as diamines) , ω-bis(3-aminopropyl)polydimethylsiloxane (average molecular weight 836), molar ratio of acid anhydride 50/50 mol%, diamine 80/20 mol%, weight average molecular weight 49000)
(Inorganic filler)
Inorganic filler: Spherical silica particles (manufactured by Admatex, SC4050 treated with aminophenylpropyltrimethoxysilane, average particle size 1.1 μm)
(coupling agent)
Coupling agent: Aminophenylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)
(hardening accelerator)
Amine compound: N,N-dimethylaminopyridine (resin membrane with carrier: manufacture of resin sheet)
The obtained resin varnish P was coated on one side of a PET film with a thickness of 38 μm using a comma coater device so that the total thickness of the resin layer after drying was 30 μm, and this was dried in a drying device at 160 ° C. It was dried for 3 minutes to obtain a resin sheet (resin film with carrier) in which an insulating film was laminated on a PET film.
(Printed wiring board)
A laminate was manufactured from a 30 μm thick resin sheet (resin film with carrier 1) using a two-stage build-up laminator (CVP300 manufactured by Nichigo Morton). Specifically, using ELC-4785TH-G (manufactured by Sumitomo Bakelite Co., Ltd., copper foil 12 μm) with a thickness of 100 μm, holes were drilled at predetermined locations with a drill machine, electrical conductivity was achieved by electroless plating, and the copper foil was A core layer having a circuit forming surface and having a residual copper content of 60% was prepared by etching. Further, the resin film of the carrier-attached resin film was cut into sheets, set in the CVP 300, temporarily attached to the core layer, and vacuum laminated at 110° C., 0.8 MPa, and 30 seconds in a vacuum laminator.

Thereafter, it was smoothed by hot pressing at 110° C., 0.6 MPa, and 60 seconds using a hot press device included in Nichigo Morton's CPV300.

Thereafter, the obtained laminate was placed in a hot air dryer at 160° C. for 60 minutes, the PET film was peeled off, and the thermosetting resin of the resin film was subjected to a curing reaction.

Next, via holes were formed in the obtained laminate using a carbon dioxide laser. The inside of the via and the surface of the resin layer were immersed in a 60°C swelling solution (Swelling Dip Securigant P, manufactured by Atotech Japan) for 5 minutes, and then immersed in a potassium permanganate aqueous solution (manufactured by Atotech Japan, Concentrate) at 80°C. Compact CP: After 45 minutes of immersion in sodium permanganate concentration 60 g/l, NaOH concentration 45 g/l), it was neutralized and roughened.

After going through the steps of degreasing, catalyst application, and activation, an electroless copper plating film of about 0.5 μm is formed, a resist is formed, and a pattern of electroplated copper of 20 μm is formed using the electroless copper plating film as a power supply layer. The circuit has been processed. Next, annealing treatment was performed at 200° C. for 60 minutes using a hot air dryer, and then the power supply layer was removed by flash etching. The same process was repeated one more time, including the inner layer circuit, to produce a 6-layer board. Next, a solder resist layer was formed, and openings were formed to expose semiconductor element mounting pads and the like. Finally, a plating layer consisting of a 3 μm electroless nickel plating layer and a 0.1 μm electroless gold plating layer is formed on the circuit layer exposed from the solder resist layer, and the resulting board is 50 mm thick. It was cut into a size of 50 mm to obtain a printed wiring board.
(Production of semiconductor package)
For the semiconductor package, a semiconductor element (TEG chip, size 10 mm x 10 mm, thickness 0.1 mm) having solder bumps was mounted on the obtained printed wiring board by heat compression bonding using a flip chip bonder device. Next, after melting and bonding the solder bumps in an IR reflow oven, a liquid sealing resin (CRP-4152S, manufactured by Sumitomo Bakelite Co., Ltd.) was filled, and then the liquid sealing resin was cured to obtain a semiconductor package. The liquid sealing resin was cured at a temperature of 150° C. for 120 minutes. The solder bumps of the semiconductor element were formed from eutectic having a Sn/Pb composition. Finally, it was cut into pieces of 14 mm x 14 mm using a router to obtain semiconductor packages.

As described above, a resin film with a carrier, a printed wiring board, and a semiconductor package were created using the resin varnish P (thermosetting resin composition) obtained in each Example and each Comparative Example. Regarding these, the following evaluation was performed. The evaluation results are shown in Table 1.
(cured product)
Four 30 μm thick resin films of the carrier-attached resin film described above were stacked and heated and pressed using a hot press using copper foil at 200° C. and 1 kgf/mm ² for 2 hours to harden the resin film. . Next, the copper foil of the obtained cured product was removed by etching to produce a cured product as a sample.
(dielectric loss tangent)
The dielectric loss tangent of the obtained cured product at 1 GHz was measured using a cavity resonator method.
(Surface roughness Ra, peel strength)
Using the obtained printed wiring board, the peel strength at 23° C. after the above-mentioned roughening treatment was measured in accordance with JIS C-6481:1996.

Here, the surface roughness Ra after the roughening treatment was evaluated by measuring with a non-contact three-dimensional optical interference type surface roughness meter (WYKO NT1100, manufactured by Biko Corporation). The surface roughness Ra was measured at 10 points, and the average value of the 10 points was taken as the average value.
(Moisture absorption heat resistance test)
The obtained semiconductor package was pretreated in accordance with JEDEC (Level 1) at a temperature of 85°C and a humidity of 85% for 168 hours, and then passed through a reflow oven that reached 260°C three times for ultrasonic flaw detection. The plating inside the via and the plating formed on the wiring were evaluated using the equipment. Each code is as follows.
○: No plating blistering △: Up to 2 reflows, no plating blistering ×: Plating blistering after 1 reflow or less (smear removability)
The area around the bottom of the blind via hole was observed using a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image. The samples used were the inside of the via during the manufacturing process of the printed wiring board and the sample after the surface of the resin layer had been roughened. Regarding the smear removability, each code is as follows.
◎: Maximum smear length is less than 2 μm ○: Maximum smear length is 2 μm or more and less than 3.5 μm ×: Maximum smear length is 3.5 μm or more (insulation test)
The insulation reliability of the fine circuit pattern of L/S=15/15 μm of the obtained printed wiring board was evaluated. Continuous humidity insulation resistance was evaluated under the conditions of a temperature of 130° C., a humidity of 98%, and an applied voltage of 5.0 V. Note that a resistance value of 10 ⁶ Ω or less was considered a failure. The evaluation criteria are as follows.
○: No failure for 200 hours or more △: Failure for 100 or more but less than 200 hours ×: Failure for less than 100 hours

It is thought that when the thermosetting resin compositions of Comparative Examples 1 and 2 are used, the dielectric loss tangent becomes high and therefore the transmission loss becomes large. When the thermosetting resin composition of Comparative Example 1 was used, the smear removability was poor. It was found that when the thermosetting resin composition of Comparative Example 2 was used, the peel strength of the plating was low and the Ra was also high, resulting in a decrease in SAP properties. Furthermore, when the thermosetting resin compositions of Comparative Examples 1 and 2 were used, it was found that the moisture absorption and heat resistance and insulation properties were poor.

On the other hand, it was found that by using the thermosetting resin compositions of Examples 1 to 15, it was possible to realize an insulating layer that had a low dielectric loss tangent and improved SAP characteristics due to a low surface roughness. . It also has excellent smear removal properties at the bottom of blind vias. This insulating layer was found to be suitable as a build-up layer for printed wiring boards. Furthermore, it was found that by using the thermosetting resin compositions of Examples 1 to 15, a build-up substrate with excellent insulation properties and a semiconductor device with excellent reflow heat resistance could be obtained.

Although the present invention has been described in more detail based on the embodiments above, these are merely illustrative of the present invention, and various configurations other than those described above may be adopted.

10 Resin film with carrier 12 Resin film with carrier 20 Insulating film 30 Primer layer 40 Carrier base material 100 Core layer 102 Insulating layer 104 Via hole 106 Electroless metal plating film 108 Metal layer 200 Semiconductor package 202 Electroless metal plating film 204 Resist 206 Opening Section 208 Electrolytic metal plating layer 210 Opening 220 Metal layer 230 Solder resist layer 240 Semiconductor element 250 Solder bump 260 Encapsulant layer

Claims (11)

A thermosetting resin composition used for forming an insulating layer constituting a build-up layer of a multilayer printed wiring board, the composition comprising:
An epoxy resin (A) with a softening point of 50°C or higher,
An epoxy resin (B) that is liquid at room temperature,
An active ester compound (C) having a structural site represented by the following formula (1),
Inorganic filler (D);
including;
The epoxy resin (A) is at least one selected from the group consisting of a biphenylaralkyl epoxy resin, a trihydroxyphenylmethane epoxy resin, a naphthylene ether epoxy resin, and a tetrafunctional naphthalene epoxy resin,
The epoxy resin (B) is at least one selected from the group consisting of bisphenol F-type epoxy resin, bifunctional dicyclopentadiene-type epoxy resin, triglycidylamine-type epoxy resin, and difunctional naphthalene-type epoxy resin,
The content of the epoxy resin (B) that is liquid at room temperature relative to the total amount of 100% by mass (nonvolatile content) of the epoxy resin (A) with a softening point of 50 ° C. or higher and the epoxy resin (B) that is liquid at room temperature. is in the range of 560/23 mass% or more and 35 mass% or less,
Based on the total of 100% by mass of the content of the epoxy resin (A) having a softening point of 50 ° C. or higher, the content of the epoxy resin (B) that is liquid at room temperature, and the content of the active ester compound (C), A thermosetting resin composition characterized in that the content of the active ester compound (C) is in the range of 40% by mass or more and 70% by mass or less.
(In formula (1), l is each independently an integer of 0 or more and 6 or less, m is each independently an integer of 1 or more and 5 or less, and n is an integer of 1 or more and 6 or less.) The thermosetting resin composition according to claim 1,
A thermosetting resin composition further comprising at least one selected from a cyanate ester resin, a maleimide compound, a benzocyclobutene resin, a vinyl resin, and an acrylate compound. The thermosetting resin composition according to claim 1 or 2,
A thermosetting resin composition further comprising a thermoplastic resin. The thermosetting resin composition according to claim 3,
A thermosetting resin composition in which the thermoplastic resin is at least one selected from phenoxy resin, polyimide resin, polyamide resin, polyamideimide resin, and polyphenylene EL resin. The thermosetting resin composition according to any one of claims 1 to 4,
A thermosetting resin in which the inorganic filler (D) is at least one selected from talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide. The thermosetting resin composition according to any one of claims 1 to 5,
A thermosetting resin composition in which the content of the inorganic filler (D) is 50% by mass or more and 85% by mass or less based on 100% by mass of the total solid content of the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 6,
A thermosetting resin composition in which the inorganic filler (D) is surface-treated with at least one silane coupling agent selected from the group consisting of amino, epoxy, and thiol. a carrier base material;
A resin film with a carrier, comprising a resin film made of the thermosetting resin composition according to any one of claims 1 to 7, provided on the carrier base material. A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of claims 1 to 7. A printed wiring board comprising an insulating layer made of a cured product of the thermosetting resin composition according to any one of claims 1 to 7. The printed wiring board according to claim 10,
A semiconductor device comprising: a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.