JP2015080882A - Metal-clad laminated plate, printed wiring board and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-clad laminated plate capable of improving connection reliability between a semiconductor element and a printed wiring board and to provide a printed wiring board and a semiconductor device using the same.SOLUTION: There is provided a metal-clad laminated plate 100 which has an insulating layer containing an epoxy resin composition (E) and a fiber substrate and comprises a metal foil 103 on both surfaces of the insulating layer 101. The average linear expansion coefficient of the metal-clad laminated plate 100 calculated in the range of 250°C to 260°C in the in-plane direction of the insulating layer 101 is 0.5 ppm/°C or more and 4.0 ppm/°C or less and the glass transition temperature of the insulating layer 101 measured by dynamic viscoelasticity measurement under conditions of a temperature-raising rate of 5°C and a frequency of 1 Hz is 200°C or more and 300°C or less.

Description

  The present invention relates to a metal-clad laminate, a printed wiring board, and a semiconductor device.

  Conventionally, a semiconductor device in which a semiconductor element is mounted on a printed wiring board has been used. For example, Patent Document 1 discloses a semiconductor device that includes a printed wiring board and a semiconductor element, and connects the semiconductor element and the printed wiring board with a wire.

JP-A-8-55867

  Such a semiconductor device is required to have high connection reliability that can withstand various environmental temperature changes between the semiconductor element and the printed wiring board.

  As a result of intensive studies by the present inventors, a semiconductor element is provided by providing an insulating layer having a small average linear expansion coefficient calculated in the range of 250 ° C. to 260 ° C. and a high glass transition temperature on the printed wiring board. As a result, it was found that the reliability of connection between the semiconductor element and the printed wiring board can be improved.

  The present invention has been invented based on such knowledge.

That is, according to the present invention,
A metal-clad laminate having metal foil on both sides of an insulating layer containing an epoxy resin composition and a fiber base material,
The epoxy resin composition includes an epoxy resin, a bismaleimide compound, and an inorganic filler,
After removing the metal foil on both sides of the metal-clad laminate by etching,
The average linear expansion coefficient calculated in the range of 250 ° C. to 260 ° C. in the in-plane direction of the insulating layer is 0.5 ppm / ° C. or more and 4.0 ppm / ° C. or less,
Provided is a metal-clad laminate in which the insulating layer has a glass transition temperature of 200 ° C. or higher and 300 ° C. or lower as measured by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz.

  In this metal-clad laminate, the average linear expansion coefficient calculated in the range of 250 ° C. to 260 ° C. of the insulating layer is smaller than that of the conventional one, and the insulating layer has a high glass transition temperature. Therefore, when this metal-clad laminate is used, the stress generated due to the difference in linear expansion coefficient between the printed wiring board and the semiconductor element when exposed to a high temperature can be reduced. Thereby, even if a big temperature change arises, a deformation | transformation etc. of an insulating layer do not occur easily, and the position shift with respect to the printed wiring board of a semiconductor element can be suppressed. As a result, the connection reliability between the semiconductor element and the printed wiring board can be enhanced for the semiconductor device obtained by the metal-clad laminate.

  Furthermore, according to this invention, the printed wiring board formed by carrying out circuit processing of the said metal-clad laminated board is provided.

  Furthermore, according to the present invention, there is provided a semiconductor device in which a semiconductor element is mounted on the printed wiring board.

  ADVANTAGE OF THE INVENTION According to this invention, the metal-clad laminated board which can improve the connection reliability of a semiconductor element and a printed wiring board, a printed wiring board using this, and a semiconductor device can be provided.

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 the manufacturing method of the prepreg 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.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio.

First, the configuration of the metal-clad laminate in this embodiment will be described. FIG. 1 is a cross-sectional view showing an example of the configuration of the metal-clad laminate 100 in the present embodiment.
The metal-clad laminate 100 includes an insulating layer 101 including an epoxy resin composition (E) and a fiber base material, and includes metal foils 103 on both surfaces of the insulating layer 101. The epoxy resin composition (E) includes an epoxy resin (A), a bismaleimide compound (B), and an inorganic filler (C).
The metal-clad laminate 100 has an average linear expansion coefficient of 0.5 ppm / ° C. or more calculated in the range of 250 ° C. to 260 ° C. in the in-plane direction of the insulating layer 101 after removing the metal foils 103 on both sides by etching. It is 4.0 ppm / ° C. or less, preferably 0.6 ppm / ° C. or more and 3.8 ppm / ° C. or less.
The metal-clad laminate 100 is a glass transition of the insulating layer 101 measured by dynamic viscoelasticity measurement under conditions of a heating rate of 5 ° C./min and a frequency of 1 Hz after removing the metal foils 103 on both sides by etching. The temperature is 200 ° C. or higher and 300 ° C. or lower, preferably 220 ° C. or higher and 280 ° C. or lower.

When the average linear expansion coefficient calculated in the range of 250 ° C. to 260 ° C. of the insulating layer 101 is within the above range, in the semiconductor device using the metal-clad laminate 100, The stress generated due to the difference in linear expansion coefficient with the semiconductor element can be reduced.
In addition, when the glass transition temperature of the insulating layer 101 satisfies the above range, the metal-clad laminate 100 can increase the rigidity of the insulating layer 101 and reduce warping of the insulating layer 101.
From the above, due to these synergistic effects, the semiconductor device obtained by the metal-clad laminate 100 can suppress misalignment of the semiconductor element with respect to the printed wiring board, and as a result, the connection reliability between the semiconductor element and the printed wiring board. Can be increased.
In order to achieve such a linear expansion coefficient and a glass transition temperature, as will be described later, an appropriate epoxy resin composition (E) and fiber base material are selected, and the manufacturing conditions of the metal-clad laminate are appropriate. It is important to set to.

In the metal-clad laminate 100 of this embodiment, the storage elastic modulus E ′ of the insulating layer 101 at 250 ° C. is preferably 15 GPa or more and 25 GPa or less, and more preferably 16 GPa or more and 20 GPa or less.
In the metal-clad laminate 100, when the storage elastic modulus E ′ at 250 ° C. of the insulating layer 101 is equal to or higher than the lower limit, the rigidity of the insulating layer 101 increases and the warpage of the insulating layer 101 can be further reduced. Further, when the storage elastic modulus E ′ at 250 ° C. of the insulating layer 101 is equal to or lower than the upper limit value, the metal-clad laminate 100 is a semiconductor device obtained by the metal-clad laminate 100 and between the semiconductor element and the printed wiring board. The stress generated due to the difference in the linear expansion coefficient with respect to can be further relaxed. Therefore, by setting the storage elastic modulus E ′ at 250 ° C. of the insulating layer 101 within the above range, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection between the semiconductor element and the printed wiring board is possible. Reliability can be further increased.
In order to achieve such a storage elastic modulus E ′, as will be described later, the chemical structure of the epoxy resin, the curing agent, and the bismaleimide compound is appropriately selected, and the crosslinking density of the resin is appropriately adjusted, or inorganic filling is performed. What is necessary is just to adjust the compounding quantity of an agent suitably.

The metal-clad laminate 100 of the present embodiment, the ratio of ₃₀ 'the storage modulus E at 30 ° C. for _250' the storage modulus E at 250 ° C. of the insulating layer 101 (E _'30 / E' ₂₅₀₎ is Preferably, it is 1.2 or more and 2.0 or less, More preferably, it is 1.3 or more and 1.8 or less.
When E ′ ₃₀ / E ′ ₂₅₀ is within the above range, a change in the elastic modulus of the insulating layer 101 with respect to a large temperature change can be suppressed. Thereby, even if a large temperature change occurs, deformation of the insulating layer 101 is less likely to occur, and the displacement of the semiconductor element relative to the printed wiring board can be further suppressed. As a result, the connection reliability between the semiconductor element and the printed wiring board can be further enhanced.
In order to achieve such E ′ ₃₀ / E ′ _250, as will be described later, the chemical structure of the epoxy resin, the curing agent, and the bismaleimide compound is appropriately selected, and the crosslinking density of the resin is appropriately adjusted, What is necessary is just to adjust the compounding quantity of an inorganic filler suitably.

  The thickness of the insulating layer 101 in this embodiment is 0.025 mm or more and 0.1 mm or less, for example. When the thickness of the insulating layer 101 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the metal-clad laminate 100 suitable for a thin printed wiring board can be obtained.

  It continues and demonstrates the manufacturing method of the metal-clad laminated board 100 in this embodiment. The metal-clad laminate 100 is obtained by heat curing a prepreg (P) containing an epoxy resin composition (E) and a fiber base material.

In order to realize the metal-clad laminate 100 in the present embodiment, it is important to appropriately adjust the following conditions.
(1) Combination of materials constituting epoxy resin composition (E) (2) Tension of fiber base material during prepreg production (3) Pressure and pressure conditions for metal-clad laminate production

More specifically, the following conditions are preferable. However, the present invention is not limited to these.
(1) As a material constituting the metal-clad laminate 100, an epoxy resin (A), a bismaleimide compound (B), and an inorganic filler (C) are selected.
(2) At the time of preparing the prepreg, the tension of the fiber base material is uniformly increased.
(3) The pressure at the time of producing the metal-clad laminate 100 is set to a high pressure. Moreover, pressurization is continued until the end of cooling at the time of heat and pressure molding.

Here, the manufacturing method of a prepreg (P) is demonstrated in detail.
The prepreg (P) of this embodiment is a sheet-like material obtained by laminating a resin layer made of an epoxy resin composition (E) on a fiber base material and then semi-curing it. In the present embodiment, the layer formed by curing the prepreg (P) is the insulating layer 101.

  In this embodiment, the fiber base material is impregnated with the resin layer made of the epoxy resin composition (E) by laminating the fiber base material with the resin layer with the supporting base material from both sides of the fiber base material. In addition, when laminating the resin layer with the supporting substrate, it is more preferable to use a vacuum laminating apparatus or the like.

  The manufacturing process of the prepreg (P) using the method of laminating a fiber base material with the resin layer with a support base material from both surfaces of a fiber base material is demonstrated using FIG.

  First, carrier material 5a, carrier material 5b, and fiber base material 11 are prepared as materials. Further, a vacuum laminating device 60 and a hot air drying device 62 are prepared as devices. The carrier material 5a is composed of a resin layer made of the first epoxy resin composition (P1). The carrier material 5b is composed of a resin layer made of the second epoxy resin composition (P2). The carrier materials 5a and 5b can be obtained by, for example, a method of applying a resin varnish of the first epoxy resin composition (P1) and the second epoxy resin composition (P2) to the carrier film.

  Next, a bonded body is formed by bonding the carrier material 5a, the fiber base material 11, and the carrier material 5b in this order using the vacuum laminating apparatus 60. The vacuum laminating apparatus 60 includes a roll that winds up the carrier material 5a, a roll that winds up the carrier material 5b, a roll that winds up the fiber substrate 11, and a laminating roll 61. Under reduced pressure, the carrier material 5a and the carrier material 5b fed from each roll are superposed on both surfaces of the fiber base material 11. Then, for example, the stacked laminates are joined by the laminate roll 61 in a vacuum at a temperature of 60 ° C. or higher and 150 ° C. or lower. Thereby, the joined body comprised from the carrier material 5a, the fiber base material 11, and the carrier material 5b is obtained.

  In such a joining process, other devices such as a vacuum box device and a vacuum becquerel device can be used.

  Next, heat treatment is performed using a hot air drying device 62 at a temperature equal to or higher than the melting temperature of the epoxy resin composition constituting each of the carrier materials 5a and 5b constituting the joined body. Other methods of heat treatment can be carried out using, for example, an infrared heating device, a heating roll device, a flat platen hot platen pressing device, or the like.

  After laminating the carrier materials 5a and 5b to the fiber substrate 11, the carrier film is peeled off. By this method, the epoxy resin composition (E) is supported on the fiber base material 11, and a prepreg (P) including the epoxy resin composition (E) and the fiber base material 11 is obtained.

In addition, other methods for applying pressure during lamination are not particularly limited, and conventionally known methods that can apply a predetermined pressure, such as a hydraulic method, a pneumatic method, and a gap pressure method, can be employed.
Among these, the method of carrying out without substantially applying pressure to the above-mentioned joined one is preferable. According to this method, since the resin component does not flow excessively, a prepreg (P) having a desired insulating layer thickness and high uniformity in the insulating layer thickness is efficiently manufactured. be able to.
Moreover, since the stress which acts on the fiber base material 11 with the flow of the resin component can be minimized, the internal strain can be made very small. Furthermore, since the pressure is not substantially applied when the resin component is melted, it is possible to substantially eliminate the occurrence of a dent in this step.

  Therefore, the lamination pressure is not particularly limited, but is preferably in the range of 10 KPa or more and 500 KPa or less. Within this range, productivity can be further improved, and the metal-clad laminate 100 can be obtained more efficiently.

  Here, the tension applied to the fiber base material when the resin layer with the support base material is laminated on the fiber base material is preferably in the range of 90 N / m to 500 N / m, and 150 N / m to 400 N / m. More preferably within the following range. By setting the tension within the above range, strain generated in the prepreg is relieved, and as a result, the metal-clad laminate 100 having a small dimensional change can be obtained.

It continues and demonstrates the manufacturing method of the metal-clad laminated board 100 using the prepreg (P) obtained above. A method for producing the metal-clad laminate 100 using the prepreg (P) is, for example, as follows.
Prepreg (P) or two or more prepregs (P) are stacked on top and bottom or both sides of the laminate, and the metal foil 103 is stacked on top and bottom, and these are joined under high vacuum conditions using a laminator or becquerel device. Alternatively, the metal foil 103 is stacked on the upper and lower surfaces or one surface outside the prepreg (P) as it is. When two or more prepregs (P) are laminated, the metal foil 103 is placed on the outermost upper and lower surfaces or one surface of the laminated prepregs (P).
Subsequently, the metal-clad laminate 100 can be obtained by heat-pressing the laminate in which the prepreg (P) and the metal foil 103 are stacked. Here, it is preferable to continue the pressurization until the end of cooling at the time of heat-pressure molding. By continuing the pressurization until the end of cooling, the linear expansion coefficient of the obtained insulating layer 101 can be lowered, and the glass transition temperature can be improved.

The heating temperature at the time of the above-described heating and pressing 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. By setting to a high pressure, the linear expansion coefficient of the obtained insulating layer 101 can be further lowered, and the glass transition temperature can be improved.

  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 this metal-clad laminate 100 as a core substrate.

  Hereinafter, each material used when manufacturing the metal-clad laminate 100 will be described in detail.

Examples of the metal constituting the metal foil 103 include copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and Examples thereof include tin alloys, iron and iron alloys, Kovar (trade name), 42 alloys, Fe-Ni alloys such as Invar and Super Invar, W or Mo, and the like. Among these, the metal constituting the metal foil 103 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 103 is preferably a copper foil.
Further, as the metal foil 103, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil 103 is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

  The epoxy resin composition (E) includes an epoxy resin (A), a bismaleimide compound (B), and an inorganic filler (C).

  Examples of the epoxy resin (A) 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- Phenylenediisopridiene) 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' -Cyclohexiene bisphenol type epoxy resin), etc .; phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol group ethane type novolak type epoxy resin, condensed ring aromatic hydrocarbon structure Novolak-type epoxy resins such as volac-type epoxy resins; biphenyl-type epoxy resins; arylalkylene-type epoxy resins such as xylylene-type epoxy resins and biphenylaralkyl-type epoxy resins; naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy Resin, bifunctional or tetrafunctional epoxy naphthalene resin, binaphthyl epoxy resin, naphthalene aralkyl epoxy resin, etc .; anthracene epoxy resin; phenoxy epoxy resin; dicyclopentadiene epoxy resin; norbornene epoxy resin Adamantane type epoxy resin; fluorene type epoxy resin and the like.

  As the epoxy resin (A), one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, and one or two or more and their prepolymers may be used. May be used in combination.

  Among epoxy resins (A), bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, arylalkylene type epoxy resin, naphthalene from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board 1 type or 2 or more types selected from the group consisting of type epoxy resins, anthracene type epoxy resins, dicyclopentadiene type epoxy resins, arylalkylene type epoxy resins, novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure, and One or more selected from the group consisting of naphthalene type epoxy resins are more preferred.

  As the bisphenol A type epoxy resin, "Epicoat 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F type epoxy resin, “jER806H” and “YL983U” manufactured by Mitsubishi Chemical Corporation, “EPICLON 830S” manufactured by DIC Corporation, and the like can be used. As the bifunctional naphthalene type epoxy resin, “HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC, and the like can be used. As the tetrafunctional naphthalene type epoxy resin, “HP4700” and “HP4710” manufactured by DIC, etc. can be used. As the naphthol type epoxy resin, “ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd., “NC7000L” manufactured by Nippon Kayaku Co., Ltd. and the like can be used. As the aryl alkylene type epoxy resin, “NC3000”, “NC3000H”, “NC3000L”, “NC3100” and the like manufactured by Nippon Kayaku Co., Ltd. can be used. As the biphenyl type epoxy resin, “YX4000”, “YX4000H”, “YX4000HK”, “YL6121”, etc. manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene type epoxy resin, “YX8800” manufactured by Mitsubishi Chemical Corporation can be used. As the naphthylene ether type epoxy resin, “HP6000”, “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3” and the like manufactured by DIC can be used.

  As the epoxy resin (A), one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, and one or two or more prepolymers thereof. And may be used in combination.

  Among these epoxy resins (A), aryl alkylene type epoxy resins are particularly preferable. Thereby, the moisture absorption solder heat resistance and flame retardance of the insulating layer 101 can be further improved.

  The aryl alkylene type epoxy resin refers to an epoxy resin having one or more aryl alkylene groups in a repeating unit. For example, a xylylene type epoxy resin, a biphenyl dimethylene type epoxy resin, etc. are mentioned. Among these, a biphenyl dimethylene type epoxy resin is preferable. A biphenyl dimethylene type | mold epoxy resin can be shown, for example with the following general formula (IV).

  The average repeating unit n of the biphenyl dimethylene type epoxy resin represented by the general formula (IV) is an arbitrary integer. The lower limit of n is not particularly limited, but is preferably 1 or more, and particularly preferably 2 or more. When n is not less than the above lower limit, crystallization of the biphenyldimethylene type epoxy resin can be suppressed and the solubility in a general-purpose solvent is improved, so that handling becomes easy. The upper limit of n is not particularly limited, but is preferably 10 or less, and particularly preferably 5 or less. When n is less than or equal to the above upper limit, the fluidity of the resin is improved and the occurrence of molding defects and the like can be suppressed.

  The epoxy resin (A) other than the above is preferably a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure. Thereby, heat resistance and low thermal expansibility can further be improved.

  The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is a novolak type epoxy resin having a naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, and tetraphen or other condensed ring aromatic hydrocarbon structure. . The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is excellent in low thermal expansion because a plurality of aromatic rings can be regularly arranged. Moreover, since the glass transition temperature is also high, it is excellent in heat resistance. Furthermore, since the molecular weight of the repeating structure is large, the flame retardancy is excellent as compared with the conventional novolac type epoxy resin.

  The novolak-type epoxy resin having a condensed ring aromatic hydrocarbon structure is obtained by epoxidizing a novolac-type phenol resin synthesized from a phenol compound, an aldehyde compound, and a condensed ring aromatic hydrocarbon compound.

  The phenol compound is not particularly limited, but examples thereof include cresols such as phenol, o-cresol, m-cresol, and p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol, trimethylphenols such as 2,3,5 trimethylphenol, ethyl such as o-ethylphenol, m-ethylphenol, p-ethylphenol Phenols, alkylphenols such as isopropylphenol, butylphenol, t-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,7-naphthalene diols such as dihydroxynaphthalene, resorcinol, catechol, hydroquinone, pyrogallol, polyhydric phenols such as fluoro Guru Singh, alkyl resorcinol, alkyl catechol, alkyl polyhydric phenols such as alkyl hydroquinone. Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.

  The aldehyde compound is not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, Examples include benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxy-3-methoxyaldehyde paraformaldehyde and the like.

  Although the condensed ring aromatic hydrocarbon compound is not particularly limited, for example, naphthalene derivatives such as methoxynaphthalene and butoxynaphthalene, anthracene derivatives such as methoxyanthracene, phenanthrene derivatives such as methoxyphenanthrene, other tetracene derivatives, chrysene derivatives, pyrene derivatives, Derivatives such as triphenylene and tetraphen derivatives are mentioned.

  The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited. For example, methoxynaphthalene-modified ortho-cresol novolak epoxy resin, butoxynaphthalene-modified meta (para) cresol novolak epoxy resin, and methoxynaphthalene-modified novolak epoxy resin Etc. Among these, a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure represented by the following formula (V) is preferable.

(In the formula, Ar is a condensed ring aromatic hydrocarbon group, R may be the same or different from each other, and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen element, a phenyl group, A group selected from an aryl group such as a benzyl group and an organic group containing glycidyl ether, n, p and q are integers of 1 or more, and the values of p and q may be the same or different for each repeating unit. May be.)

(Ar in the formula (V) is a structure represented by (Ar1) to (Ar4) in the formula (VI), and Rs in the formula (VI) may be the same or different from each other. It is often a group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen element, an aryl group such as a phenyl group and a benzyl group, and an organic group including glycidyl ether.)

  Further, as the epoxy resin (A) other than the above, naphthalene type epoxy resins such as naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetrafunctional epoxy type naphthalene resin, naphthylene ether type epoxy resin and the like are preferable. Thereby, the heat resistance and low thermal expansion property of the insulating layer 101 can be further improved. In addition, since the naphthalene ring has a higher π-π stacking effect than a benzene ring, it is particularly excellent in low thermal expansion and low thermal shrinkage. Furthermore, since the polycyclic structure has a high rigidity effect and the glass transition temperature is particularly high, the change in heat shrinkage before and after reflow is small. As a naphthol type epoxy resin, for example, the following general formula (VII-1), as a naphthalene diol type epoxy resin, the following formula (VII-2), as a bifunctional or tetrafunctional epoxy type naphthalene resin, the following formula (VII-3): As (VII-4) (VII-5) and a naphthylene ether type epoxy resin, it can show by the following general formula (VII-6), for example.

（ｎは平均１以上６以下の数を示し、Ｒはグリシジル基または炭素数１以上１０以下の炭化水素基を示す。）

(N represents an average number of 1 to 6, and R represents a glycidyl group or a hydrocarbon group having 1 to 10 carbon atoms.)

（式中、Ｒ^１は水素原子またはメチル基を表し、Ｒ^２はそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、アラルキル基、ナフタレン基、またはグリシジルエーテル基含有ナフタレン基を表し、ｏおよびｍはそれぞれ０〜２の整数であって、かつｏまたはｍの何れか一方は１以上である。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aralkyl group, a naphthalene group, or a glycidyl ether group-containing naphthalene group. , O and m are each an integer of 0 to 2, and either o or m is 1 or more.)

  Although the minimum of the weight average molecular weight (Mw) of an epoxy resin (A) is not specifically limited, Mw500 or more is preferable and especially Mw800 or more is preferable. It can suppress that tackiness arises in a prepreg (P) as Mw is more than the said lower limit. The upper limit of Mw is not particularly limited, but is preferably Mw 20,000 or less, and particularly preferably Mw 15,000 or less. When Mw is not more than the above upper limit value, the impregnation property to the fiber base material is improved when the insulating layer 101 is produced, and a more uniform insulating layer 101 can be obtained. The Mw of the epoxy resin can be measured by GPC, for example.

  The content of the epoxy resin (A) contained in the epoxy resin composition (E) is not particularly limited as long as it is appropriately adjusted depending on the purpose, but the total solid content of the epoxy resin composition (E) (that is, The component excluding the solvent) is 100% by mass, preferably 5.0% by mass to 20.0% by mass, and more preferably 6.0% by mass to 18.0% by mass. When the content of the epoxy resin (A) is not less than the above lower limit value, the handling property is improved and the insulating layer 101 can be easily formed. When the content of the epoxy resin (A) is not more than the above upper limit, the strength and flame retardancy of the insulating layer 101 are improved, the linear expansion coefficient of the insulating layer 101 is reduced, and the warp of the metal-clad laminate 100 is reduced. The effect may be improved.

  The epoxy resin composition (E) according to this embodiment contains a bismaleimide compound (B) as an essential component. The maleimide group of the bismaleimide compound has a five-membered planar structure, and since the double bond of the maleimide group easily interacts between molecules and has high polarity, the compound has a maleimide group, a benzene ring, and other planar structures. It shows strong intermolecular interaction and can suppress molecular motion. Therefore, the epoxy resin composition (E) can contain the bismaleimide compound (B), thereby reducing the linear expansion coefficient of the obtained insulating layer 101, improving the glass transition temperature, and further improving the heat resistance. Can be made.

As the bismaleimide compound (B), a bismaleimide compound (B-1) having at least two maleimide groups in the molecule is preferable.
Examples of the bismaleimide compound (B-1) include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, and 2,2-bis [4- (4-maleimidophenoxy) phenyl]. Propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N′-ethylenedimaleimide, N, N′-hexamethylenedimaleimide , Compounds having two maleimide groups in the molecule, such as bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide , Compounds having three or more maleimide groups in the molecule, such as polyphenylmethanemaleimide Etc. The.
One of these can be used alone, or two or more can be used in combination. Among these bismaleimide compounds (B), 4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis- ( 3-Ethyl-5-methyl-4-maleimidophenyl) methane and polyphenylmethanemaleimide are preferred.

  As the bismaleimide compound (B), a reaction product of a bismaleimide compound (B-1) and an amine compound can also be used. As the amine compound, at least one selected from an aromatic diamine compound and a monoamine compound can be used.

  Examples of the aromatic diamine compound include o-dianisidine, o-tolidine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, and 2,2 ′. -Dimethyl-4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2- [4- (4 -Aminophenoxy) phenyl] propane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, Bis (4- (4-aminophenoxy) phenyl) sulfone and the like can be mentioned.

  Examples of monoamine compounds include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-amino. Benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, o-aniline, m-aniline, p-aniline, o-methylaniline, m-methylaniline, p- Examples include methylaniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinylaniline, p-vinylaniline, o-allylaniline, m-allylaniline, p-allylaniline, etc. It is done.

  Reaction of a bismaleimide compound (B-1) and an amine compound can be made to react in an organic solvent. The reaction temperature is, for example, 70 to 200 ° C., and the reaction time is, for example, 0.1 to 10 hours.

  The content of the bismaleimide compound (B) is not particularly limited. When the total solid content of the epoxy resin composition (E) (that is, the component excluding the solvent) is 100% by mass, 8.0% by mass or more and 30%. 0.0 mass% or less is preferable, and 9.0 mass% or more and 25.0 mass% or less is more preferable. When the content of the bismaleimide compound (B) is not less than the above lower limit, the elastic modulus is improved. When the content of the bismaleimide compound (B) is not more than the above upper limit value, the peel strength is improved.

The epoxy resin composition (E) according to this embodiment contains an inorganic filler (C) as an essential component. Thereby, the storage elastic modulus E ′ of the insulating layer 101 can be improved. Further, the linear expansion coefficient of the obtained insulating layer 101 can be reduced.
Examples of the inorganic filler (C) 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 and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite; zinc borate, barium metaborate, Borates such as aluminum borate, 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 it can.
Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferable. As the inorganic filler (C), one of these may be used alone, or two or more may be used in combination.

The average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.05 μm or more. When the average particle diameter of the inorganic filler (C) is not less than the above lower limit value, it is possible to suppress the viscosity of the varnish from being increased, and workability at the time of manufacturing the insulating layer 101 can be improved. The average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and even more preferably 1.0 μm or less. When the average particle diameter of the inorganic filler (C) is not more than the above upper limit, phenomena such as sedimentation of the inorganic filler (C) in the varnish can be suppressed, and a more uniform insulating layer 101 can be obtained. Further, when the circuit dimension L / S of the printed wiring board 100 is less than 20/20 μm, it is possible to suppress the influence on the insulation between the wirings.
The average particle size of the inorganic filler (C) is measured, for example, by measuring the particle size distribution on a volume basis using a laser diffraction particle size distribution measuring device (LA-500, manufactured by HORIBA), and the median diameter (D ₅₀ ). Can be the average particle size.

  The inorganic filler (C) is not particularly limited, but an inorganic filler having a monodispersed average particle diameter may be used, or an inorganic filler having a polydispersed average particle diameter may be used. Furthermore, one type or two or more types of inorganic fillers having an average particle size of monodispersed and / or polydispersed may be used in combination.

  The inorganic filler (C) is preferably silica particles having an average particle size of 5.0 μm or less, more preferably silica particles having an average particle size of 0.01 μm to 2.0 μm, and silica particles of 0.05 μm to 1.0 μm. Is particularly preferred. Thereby, the filling property of an inorganic filler (C) can further be improved.

  The content of the inorganic filler (C) is not particularly limited, but is 30.0% by mass or more and 79% by mass when the total solid content of the epoxy resin composition (E) (that is, the component excluding the solvent) is 100% by mass. It is preferably 9% by mass or less, and more preferably 50.0% by mass or more and 75.0% by mass or less. When the content of the inorganic filler (C) is within the above range, the resulting insulating layer 101 can have particularly low thermal expansion and low water absorption.

The inorganic filler (C) preferably further contains silica nanoparticles.
The average particle diameter of the silica nanoparticles is preferably 1 nm to 100 nm, more preferably 10 nm to 100 nm, and particularly preferably 10 nm to 70 nm.
In particular, it is preferably used in combination with silica particles having an average particle size of 0.1 μm or more and 5.0 μm or less. Thereby, silica can be uniformly contained in the epoxy resin composition (E) at a high concentration.
The average particle diameter of the silica nanoparticles can be measured by, for example, a dynamic light scattering method. Particles are dispersed in water with ultrasonic waves, and the particle size distribution of the particles is measured on a volume basis using a dynamic light scattering particle size distribution analyzer (manufactured by HORIBA, LB-550). The median diameter (D ₅₀ ) is the average particle diameter. And

Commercially available products such as NSS-5N (manufactured by Tokuyama) and Sicastar 43-00-501 (manufactured by Micromod) can also be used as the silica nanoparticles.
Moreover, 1.0 mass% or more and 20.0 mass% or less are preferable with respect to 100 mass% of inorganic fillers (C), and content of the said silica nanoparticle is 5.0 mass% or more and 18.0 mass% or less. More preferred.

  In addition, a hardening | curing agent and a coupling agent can be suitably mix | blended with an epoxy resin composition (E) as needed.

Examples of the curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4-methylimidazole (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ), 1-benzyl-2-phenylimidazole (1B2PZ) ) And the like; and catalyst-type curing agents such as Lewis acids such as BF ₃ complexes.
In addition, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4′- (P-phenylenediisopropylidene) dianiline, 2,2- [4- (4-aminophenoxy) phenyl] propane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3 , 3′-diethyl-5,5′-dimethyldiphenylmethane, 3 In addition to aromatic polyamines such as 3′-diethyl-4,4′-diaminodiphenylmethane, polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, etc .; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides including aromatic acid anhydrides such as alicyclic acid anhydrides such as, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); polysulfide, thioester, Polymercaptan compounds such as thioethers; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; polyaddition type curing agents such as organic acids such as carboxylic acid-containing polyester resins; 2,2′-methylenebis (4-ethyl-6- t ert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3- Methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, 1,3,5-tris (3,5-di-tert) Phenolic compounds such as -butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione can also be used.

Furthermore, for example, phenolic resin-based curing agents such as novolak-type phenolic resins and resol-type phenolic resins; urea resins such as methylol group-containing urea resins; and condensation-type curing agents such as melamine resins such as methylol group-containing melamine resins It may be used.
The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak Resin, novolak type phenolic resin such as naphthol novolak resin; polyfunctional phenolic resin such as triphenolmethane type phenolic resin; modified phenolic resin such as terpene modified phenolic resin and dicyclopentadiene modified phenolic resin; phenylene skeleton and / or biphenylene skeleton Aralkyl-type resins such as phenol aralkyl resins having phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F Gerare, these may be used in combination of two or more be used one kind alone. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.
The weight average molecular weight of the phenol resin is not particularly limited, but is preferably 4 × 10 ^{2 to} 1.8 × 10 ^{3 and} more preferably 5 × 10 ^{2 to} 1.5 × 10 ³ . By making the weight average molecular weight equal to or higher than the above lower limit value, problems such as tackiness occur in the prepreg, and by making the above upper limit value or less, the impregnation property to the fiber base material is improved at the time of prepreg production, A more uniform product can be obtained.

  Although content of the said hardening | curing agent is not specifically limited, When the total solid content (namely, component except a solvent) of an epoxy resin composition (E) is 100 mass%, 0.01 mass% or more and 15 mass% or less Is preferable, and 0.1 mass% or more and 10 mass% or less are more preferable. When the content of the curing agent is not less than the above lower limit, the effect of promoting curing can be sufficiently exhibited. The preservability of a prepreg can be improved more as content of a hardening | curing agent is below the said upper limit.

  Furthermore, the epoxy resin composition (E) may contain a coupling agent. By using the coupling agent, the wettability of the interface between the inorganic filler (C) and each resin can be improved. Therefore, it is preferable to use a coupling agent, and the heat resistance of the insulating layer 101 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 with the interface of a textile material and an epoxy resin composition (E) can be made high, and, thereby, the heat resistance of the insulating layer 101 can be improved more.

The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the inorganic filler (C), but the total solid content of the epoxy resin composition (E) (that is, the component excluding the solvent) is 100% by mass. When it is, 0.01 mass% or more and 1 mass% or less are preferable, and 0.05 mass% or more and 0.5 mass% or less are more preferable.
When the content of the coupling agent is not less than the above lower limit, the epoxy resin composition (E) can be sufficiently covered, and the heat resistance of the insulating layer 101 can be improved. Further, when the content of the coupling agent is equal to or less than the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress a decrease in the bending strength or the like of the insulating layer 101.

  Furthermore, the epoxy resin composition (E) includes pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, as long as the object of the present invention is not impaired. You may add additives other than the said components, such as.

  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 and other inorganic pigments, phthalocyanine polycyclic pigments, azo pigments, etc. 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 epoxy resin composition (E) 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 various organic solvents such as anisole and N-methylpyrrolidone, 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, and rotation and revolution dispersion method The resin varnish (I) can be obtained by dissolving, mixing, and stirring.
The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, and particularly preferably 50% by mass or more and 70% by mass or less. Thereby, the impregnation property to the fiber base material of resin varnish (I) can further be improved.

In the above epoxy resin composition (E), the ratio of each component is as follows, for example.
When the total solid content of the epoxy resin composition (E) (that is, the component excluding the solvent) is 100% by mass, the proportion of the epoxy resin (A) is preferably 5.0% by mass or more and 20.0% by mass or less. The ratio of the bismaleimide compound (B) is 8.0 to 30.0% by mass, and the ratio of the inorganic filler (C) is 30.0 to 79.9% by mass. .
More preferably, the proportion of the epoxy resin (A) is 6.0% by mass or more and 18.0% by mass or less, and the proportion of the bismaleimide compound (B) is 9.0% by mass or more and 25.0% by mass or less. The ratio of the inorganic filler (C) is 50.0 mass% or more and 75.0 mass% or less.

  The fiber substrate is not particularly limited, but glass fiber substrates such as glass cloth and glass nonwoven fabric, polyamide resin fibers, aromatic polyamide resin fibers, polyamide resin fibers such as wholly aromatic polyamide resin fibers, polyester resin fibers, Synthetic fiber substrate, kraft paper, composed of woven or non-woven fabric mainly composed of aromatic polyester resin fiber, polyester resin fiber such as wholly aromatic polyester resin fiber, polyimide resin fiber, fluororesin fiber, Examples thereof include organic fiber substrates such as cotton linter paper or a paper substrate 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, the insulating layer 101 having 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 60 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 epoxy resin composition (E) in the fiber base material is improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. In addition, it is possible to easily form 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 warpage of the metal-clad laminate 100 can be suppressed.

The fiber base material used in the present embodiment, the basis weight is preferably (1m weight of the fiber base material per ²⁾ is 150 g / ^{m 2} or less 4g / ^{m 2} or more, 8 g / ^{m 2} or more 110g / ^{m 2} Or less, more preferably 12 g / m ² or more and 60 g / m ² or less, further preferably 12 g / m ² or more and 30 g / m ² or less, more preferably 12 g / m ² or more and 24 g / m ² or less. It is particularly preferred that it is ² or less.

  When the basis weight is not more than the above upper limit value, the impregnation property of the epoxy resin composition (E) in the fiber base material is improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. In addition, it is possible to easily form 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 basic weight is more than the said lower limit. As a result, handling properties can be improved, production of a prepreg can be facilitated, and warpage of the metal-clad laminate 100 can be suppressed.

  In addition, the content of the fiber base material included in the insulating layer 101 in the present embodiment is preferably 20% by mass or more and 70% by mass or less, and more preferably 30% when the total amount of the insulating layer 101 is 100% by mass. It is 0.0 mass% or more and 60.0 mass% or less. When the content of the fiber base material satisfies the above range, the rigidity of the metal-clad laminate 100 is increased while balancing the resin impregnation property and moldability into the fiber base material. Warpage can be further reduced.

  As the glass fiber substrate, for example, a glass fiber substrate made of E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, quartz glass, or the like 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 according to the embodiment of the present invention.

  The printed wiring board 300 includes at least an insulating layer 301 provided with a via hole 307 and a metal layer 303 provided on at least one surface of the insulating layer 301. 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.

As shown in FIG. 3, 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 print in which two or more metal layers 303 are stacked on an insulating layer 301 via an interlayer insulating layer (also referred to as a build-up layer) by a plated through hole method, a build-up method, or the like. It is a wiring board.
Here, the printed wiring board 300 according to the present embodiment is obtained by curing the prepreg (P) according to the present embodiment, and the insulating layer 301 corresponds to the insulating layer 101 of the metal-clad laminate 100. .

  The metal layer 303 is, for example, a circuit layer, and includes an electroless metal plating film 308 and an electrolytic metal plating layer 309.

  The metal layer 303 is a circuit layer, for example. 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 insulating layer 301 that has been subjected to chemical treatment or plasma treatment. After the electroless plating film 308 is applied on 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, and the electroless metal plating is removed by removing the plating resist and flash etching. The metal layer 303 is formed over the insulating layer 301 by removing the film 308.

  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 adhesiveness decreases and 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.

  The thickness of the metal layer 303 is not particularly limited, but is usually 5 μm or more and 25 μm or less.

The insulating layer 305 in the buildup layer 317 is not particularly limited as long as it is made of an insulating material. For example, the insulating layer 305 can be made of either a resin film or a prepreg. Among these, the prepreg is a sheet-like material and has excellent dielectric properties, various properties such as mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing a build-up layer 317 for a printed wiring board. preferable.
As the prepreg, the prepreg (P) described above is particularly preferable.

  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 0.1 mm or less. When the thickness of the insulating layer 301 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 301 suitable for a thin printed wiring board can be obtained.

  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. However, the method for manufacturing the printed wiring board 300 according to the present embodiment is not limited to the following example.

First, the metal-clad laminate 100 is prepared.
Next, the metal foil 103 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 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 103 is removed by the etching treatment.

Next, a chemical treatment or a plasma treatment is performed on the surface of the insulating layer 301.
The chemical treatment is not particularly limited, and examples thereof include a method using an oxidant solution having an organic substance decomposing action. Examples of the plasma treatment include a method of directly irradiating a target object with active species (plasma, radical, etc.) having a strong oxidizing action to remove organic residue.

  Next, the metal layer 303 is formed. The metal layer 303 can be formed by, for example, a semi-additive process. This will be specifically described below.

  First, an electroless metal plating film 308 is formed on the surface of the insulating layer 301 and the via hole 307 by using an electroless plating method. Conduction of both sides of the printed wiring board 300 is attempted. 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 insulating layer 301. 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 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 electroless metal plating film 308. Although it does not specifically limit as an electroplating process, The well-known method used with a normal printed wiring board can be used, For example, in the state immersed in plating solutions, such as copper sulfate, an electric current is supplied to a plating solution. A method such as flowing can be used. The electrolytic metal plating layer 309 may be a single layer or may have a multilayer structure. The material of the electrolytic metal plating layer 309 is not particularly limited, and for example, any 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 electroless metal plating film 308 other than the region where the electrolytic metal plating layer 309 is formed is removed. For example, 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 composed of an electroless metal plating film 308 and an electrolytic metal plating layer 309.

  Furthermore, a build-up layer can be stacked on the printed wiring board 300 as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process can be repeated to form a multilayer.

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

In the printed wiring board 300 according to this embodiment, the average linear expansion coefficient calculated in the range of 250 ° C. to 260 ° C. of the insulating layer 301 is smaller than the conventional one, and the insulating layer 301 has a high glass transition temperature. ing.
Thereby, even if a big temperature change arises, generation | occurrence | production of malfunctions, such as the printed wiring board 300 deform | transforming, can be suppressed. As a result, the semiconductor device obtained from the printed wiring board 300 can suppress a positional shift of the semiconductor element with respect to the printed wiring board 300, and can improve the connection reliability between the semiconductor element and the printed wiring board 300.

  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 according to the embodiment of the present invention. 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 methods.

  First, a build-up layer is laminated on the metal layer 303 as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process are repeated. And the soldering resist layer 401 is laminated | stacked on the both surfaces or single side | surface of the printed wiring board 300 as needed.

  The method of forming the solder resist layer 401 is not particularly limited. For example, a method of forming by laminating, exposing and developing a dry film type solder resist, or exposing and developing a liquid resist printed This is done by the forming method.

  Subsequently, by performing a reflow process, the semiconductor element 407 is fixed onto the connection terminal which is a part of the wiring pattern 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.

In the semiconductor device 400 according to the present embodiment, the average linear expansion coefficient calculated in the range of 250 ° C. to 260 ° C. of the insulating layer 301 is smaller than the conventional one, and the insulating layer 301 has a high glass transition temperature. Yes.
Thereby, even if a big temperature change arises, generation | occurrence | production of malfunctions, such as the printed wiring board 300 deform | transforming, can be suppressed. As a result, with respect to the semiconductor device 400 obtained by the printed wiring board 300, the positional deviation of the semiconductor element 407 with respect to the printed wiring board 300 can be suppressed, and the connection reliability between the semiconductor element 407 and the printed wiring board 300 can be improved. it can.

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. For example, in this embodiment, although the case where the prepreg is one layer was shown, you may produce the metal-clad laminated board 100 using what laminated | stacked two or more layers of prepregs.
Moreover, in the said embodiment, although the semiconductor element 407 and 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 printed wiring board 300 may be connected by a bonding wire.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In addition, in an Example, unless otherwise specified, a part represents a mass part. Moreover, each thickness is represented by the average film thickness.

(Example 1)
(1) Preparation of resin varnish Resin varnish (A)
2,1-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285, manufactured by Keisei Kasei Co., Ltd.), 13.1 parts by mass, naphthol-modified novolac epoxy resin (NC, manufactured by Nippon Kayaku Co., Ltd.) -7000 L, epoxy equivalent 230, epoxy resin represented by the above formula (VII-1), n = 1.7, R is glycidyl group) 10.6 parts by mass, 3,3′-diethyl-4,4′-diamino Diphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 5.8 parts by mass, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Ouchi Shinsei Chemical Nocrack NS-30) 0.3 part by mass, epoxy silane coupling agent (Momentive Performance Materials, A187) 0.2 part by mass, silica particles (Admatete SOX, SO25R, average particle size 0.5 μm) 60.0 parts by mass, silica nanoparticles (Tokuyama, NSS-5N, average particle size 70 nm) 10.0 parts by mass, N-methylpyrrolidone is added and nonvolatile content 65 %, The resin varnish (A) was prepared by stirring using a high-speed stirring device.

(2) Production of film with resin layer The resin varnish (A) obtained in (1) is applied to one side of a polyethylene terephthalate (PET) film (Mitsubishi Chemical Polyester, SFB-38, thickness 38 μm, width 480 m). Using a comma coater device, the resin layer after drying (after semi-curing) was coated so that the thickness of the resin layer was 15 μm. Subsequently, this was dried with a 120 degreeC drying apparatus for 10 minutes, and the film (B) with a resin layer was produced.

(3) Production of prepreg Using a glass cloth (cross type # 1015, width 360 mm, thickness 15 μm, T glass, basis weight 17 g / m ² ) as a fiber base material, a prepreg was produced by a vacuum laminating apparatus and a hot air drying apparatus. .
Specifically, the film with the resin layer (B) is overlapped on both surfaces of the glass cloth so as to be positioned at the center in the width direction of the glass cloth, respectively, and using a laminate roll at 80 ° C. under a reduced pressure of 1330 Pa. Joined. The tension applied to the glass cloth was 200 N / m.
Here, in the inner region of the width direction dimension of the glass cloth, the resin layer of the film with resin layer (B) is bonded to both sides of the glass cloth, and in the outer region of the width direction dimension of the glass cloth, the resin The resin layers of the layered film (B) were joined together.
Next, the above-mentioned joined piece was heat-treated without applying pressure by passing it through a horizontal conveyance type hot-air drying apparatus set at 120 ° C. for 2 minutes to obtain a thickness of 35 μm (however, the thickness of the PET film was Excluding) (resin layer: 10 μm, fiber substrate: 15 μm, resin layer: 10 μm) A prepreg with a double-sided PET film was obtained.

(4) Production of metal-clad laminate The PET films on both sides of the prepreg with the double-sided PET film obtained in (3) were peeled off. Next, two prepregs were overlaid, and 2 μm copper foil (NSAP-2B, manufactured by Nippon Electrolytic Co., Ltd.) was overlaid on both sides. Next, the laminate was sandwiched between smooth metal plates and subjected to heat and pressure molding under conditions of a temperature of 220 ° C. and a pressure of 4 MPa for 2 hours. Next, while maintaining the pressure of 4 MPa, the metal-clad laminate was obtained by cooling to 30 ° C. at a rate of temperature decrease of 5 ° C./min. The thickness of the insulating layer (part excluding the copper foil) of the obtained metal-clad laminate was 0.07 mm.

(5) Fabrication of multilayer laminate board A circuit pattern is formed on both sides of the metal-clad laminate obtained in (4) by a semi-additive method (residual copper ratio 70%, L / S = 25/25 μm). Obtained.
Next, the prepreg with one side of the prepreg with the double-sided PET film obtained in (3) was peeled off and the both sides of the printed wiring board were overlapped with the side of the prepreg from which the PET film was peeled inward. Subsequently, using a vacuum pressurization type laminator apparatus, vacuum heating and press molding was performed at a temperature of 130 ° C., a pressure of 0.2 MPa, and a time of 20 seconds to obtain a multilayer laminate.

  The outer PET film was peeled from the obtained multilayer laminate, and copper foil (“MT18SD-H”, 3 μm thick (with 18 μm carrier), manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on both sides of the multilayer laminate. Next, the laminate was sandwiched between smooth metal plates and subjected to heat and pressure molding under conditions of a temperature of 220 ° C. and a pressure of 4 MPa for 2 hours. Next, while maintaining the pressure of 4 MPa, it was cooled to 30 ° C. at a rate of 5 ° C./min to obtain a metal-clad multilayer laminate having a carrier-attached copper foil on both sides.

(6) Production of printed wiring board The carrier copper foil of the metal-clad multilayer laminate of (5) was peeled off, and the copper foil was further etched away. Next, a through hole (through hole) was formed by a carbonic acid laser. Next, the inside of the through hole and the surface of the insulating layer were immersed for 10 minutes in an 80 ° C. swelling liquid (Atotech Japan Co., Swelling Dip Securigant P), and further an 80 ° C. potassium permanganate aqueous solution (Atotech Japan Co., Ltd., After immersion for 5 minutes in Concentrate Compact CP), neutralization and roughening treatment were performed.
After passing through the steps of degreasing, applying a catalyst, and activating this, electroless copper plating film is about 1 μm, plating resist formation, electroless copper plating film is used as a power feeding layer, and pattern electroplating copper is formed to form 12 μm L / S = 12 / 12 μm fine circuit processing was performed. Next, an annealing process was performed at 200 ° C. for 60 minutes with a hot air drying apparatus, and then the power feeding layer was removed by flash etching.
Next, a solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR-4000 AUS703) is printed, exposed with a predetermined mask so that the semiconductor element mounting pads and the like are exposed, developed and cured, and the solder resist on the circuit The layer thickness was 12 μm.
Finally, on the circuit layer exposed from the solder resist layer, an electroless nickel plating layer of 3 μm and a plating layer of 0.1 μm of the electroless gold plating layer were further formed to obtain a printed wiring board. .

(7) Manufacture of Semiconductor Device A semiconductor device is a semiconductor device (TEG chip, size 8 mm × 8 mm, thickness 0.1 mm) having solder bumps on the printed wiring board obtained in (6), using a flip chip bonder device. It was mounted by thermocompression bonding. Next, after solder bumps were melt bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4160G) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes. As the solder bumps of the semiconductor element, those formed of eutectic of Sn / Pb composition were used. Finally, it was separated into pieces of 14 mm × 14 mm with a router to obtain a semiconductor device.

(8) 250-260 degreeC average linear expansion coefficient The metal foil of the metal-clad laminated board obtained by (4) was removed by etching, and the test piece of 4 mm x 20 mm was produced from the insulating layer from which the metal foil was removed. About this test piece, TMA was measured on the conditions of a temperature range of 30-300 degreeC, 10 degree-C / min, and a load of 5 g using the TMA (thermomechanical analysis) apparatus (the TA instrument company make, Q400). As the linear expansion coefficient, the average linear expansion coefficient (CTE) in the plane direction (XY direction) at 250 to 260 ° C. in the second cycle was measured.

(9) Glass transition temperature, storage elastic modulus at 250 ° C. and 30 ° C. The metal foil of the metal-clad laminate obtained by (4) was removed by etching, and a test of 6 mm × 25 mm from the insulating layer from which the metal foil was removed. A piece was made. About this test piece, it heated up at 5 degree-C / min (frequency 1Hz) using the DMA apparatus (The TA instrument company dynamic viscoelasticity measuring apparatus DMA983), and the storage elastic modulus E 'in 250 degreeC and 30 degreeC. Was measured respectively. The peak position of tan δ was defined as the glass transition temperature.

(10) Peel strength The copper foil is removed by etching from the metal-clad laminate obtained in (4), and immersed in a swelling liquid at 60 ° C. (Swelling Dip Securigant P, manufactured by Atotech Japan) for 10 minutes, and further 80 After immersion for 5 minutes in an aqueous potassium permanganate solution (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP), the solution was neutralized and roughened. After passing through the steps of degreasing, applying a catalyst, and activating this, an electroless copper plating film was formed to have a thickness of about 1 μm and electroplated copper was formed to 30 μm, and annealed at 200 ° C. for 60 minutes in a hot air drying apparatus. A 100 mm × 20 mm test piece was prepared based on JIS-C-6481, and the peel strength at 23 ° C. was measured.

(11) Fine wire workability evaluation In (6), the printed wiring board after forming a fine circuit pattern of L / S = 12/12 μm was evaluated by a thin wire appearance inspection and a continuity check with a laser microscope. The evaluation criteria are as follows.
◎: No problem in both shape and continuity ○: No short circuit or wire breakage, no problem ×: Short circuit, wire breakage

(12) Insulation reliability evaluation On the fine circuit pattern of L / S = 12/12 μm of the printed wiring board obtained in (6), a build-up material (BLA-3700GS manufactured by Sumitomo Bakelite Co., Ltd.) is used instead of the solder resist. A test sample was prepared by laminating and curing. Using this test sample, the continuous humidity insulation resistance was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 3.3 V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
◎: No failure for 300 hours or more ○: Failure for 150 hours or more and less than 300 hours ×: Failure for less than 150 hours

(13) Warpage evaluation of semiconductor device Warpage of the semiconductor device obtained in (7) at room temperature (23 ° C.) and 260 ° C. is measured using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Technology and Service, model LS220-MT100MT50). Was used to evaluate. The semiconductor element surface was placed in the sample chamber of the measuring machine, the displacement in the height direction was measured, and the largest value of the displacement difference was taken as the amount of warpage. The evaluation criteria are as follows.
Normal temperature (23 ℃)
A: Warpage amount is less than 150 μm B: Warpage amount is 150 μm or more and less than 200 μm ×: Warpage amount is 200 μm or more and 260 ° C.
A: Warpage amount is less than 100 μm B: Warpage amount is 100 μm or more and less than 150 μm ×: Warpage amount is 150 μm or more

(14) Heat cycle test Four semiconductor devices obtained in (7) were treated under conditions of 60 ° C. and 60% for 40 hours, and then treated three times in an IR reflow furnace (peak temperature: 260 ° C.). And 500 cycles at −55 ° C. (15 minutes) and 125 ° C. (15 minutes). Next, using an ultrasonic imaging apparatus (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., FS300), the semiconductor element and the solder bump were observed for abnormalities.
◎: No abnormalities in both semiconductor element and solder bumps ○: Cracks are found in some of the semiconductor elements and / or solder bumps, but there are no practical problems △: Cracks are found in some of the semiconductor elements and / or solder bumps There is a problem ×: Cracks are seen in both the semiconductor element and the solder bump, and cannot be used

(Example 2)
1,7.7 parts by weight of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285 manufactured by Keisei Kasei Co., Ltd.), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 6.1 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 5.6 parts by mass Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a metal-clad laminate, a multilayer laminate, a printed wiring board, and a semiconductor device.

(Example 3)
10.7 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by Keisei Kasei Co., Ltd., double bond equivalent 285), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 12.9 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 5.9 parts by mass Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a metal-clad laminate, a multilayer laminate, a printed wiring board, and a semiconductor device.

Example 4
12.2 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285, manufactured by Keisei Kasei Co., Ltd.), biphenylaralkyl epoxy resin (NC, manufactured by Nippon Kayaku Co., Ltd.) -3000H, epoxy equivalent 285) is 12.1 parts by mass, and 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) is 5.4 parts by mass. A resin varnish was prepared in the same manner as in Example 1 except that naphthol-modified novolac epoxy resin (NC-7000L, Nippon Kayaku Co., Ltd., epoxy equivalent 230) was not used. A prepreg, a metal-clad laminate, a multilayer laminate, A printed wiring board and a semiconductor device were obtained.

(Example 5)
13.3 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (KMI Kasei Co., Ltd. BMI-80, double bond equivalent 285), cresol novolac epoxy resin (DIC Corporation N-690) , Epoxy equivalent 220) 10.3 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 5.9 parts by mass, and naphthol A resin varnish was prepared in the same manner as in Example 1 except that a modified novolak epoxy resin (NC-7000L, Nippon Kayaku Co., Ltd., epoxy equivalent 230) was not used, and a prepreg, a metal-clad laminate, a multilayer laminate, and a printed wiring. A substrate and a semiconductor device were obtained.

(Example 6)
12.1 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (KMI Kasei Co., Ltd. BMI-80, double bond equivalent 285), naphthylene ether type epoxy resin (DIC Corporation HP) -6000, epoxy equivalent 285) 12.1 parts by mass, 3,3'-diethyl-4,4'-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 5.4 parts by mass A resin varnish was prepared in the same manner as in Example 1 except that naphthol-modified novolac epoxy resin (NC-7000L, Nippon Kayaku Co., Ltd., epoxy equivalent 230) was not used. A prepreg, a metal-clad laminate, a multilayer laminate, A printed wiring board and a semiconductor device were obtained.

(Example 7)
12.8 parts by weight of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285, manufactured by Keisei Kasei Co., Ltd.), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 10.3 parts by mass, 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane (Cure Hard MED amine equivalent 70.5, manufactured by Ihara Chemical) Was 6.3 parts by mass, and 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) was used in the same manner as in Example 1. A resin varnish was prepared to obtain a prepreg, a metal-clad laminate, a multilayer laminate, a printed wiring board, and a semiconductor device.

(Example 8)
13.7 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by Keisei Kasei Co., Ltd., double bond equivalent 285), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) was 11.1 parts by mass, 4,4′-diaminodiphenylmethane (Tokyo Kasei Co., Ltd., amine equivalent 49.5) was 4.8 parts by mass, and 3,3′-diethyl-4 , 4'-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) is used except that a resin varnish is prepared in the same manner as in Example 1, and a prepreg, a metal-clad laminate, and a multilayer laminate are prepared. A printed wiring board and a semiconductor device were obtained.

Example 9
13.2 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285 manufactured by Keisei Kasei Co., Ltd.), naphthol-modified novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) is 10.6 parts by mass, 4,4′-diaminodiphenylsulfone (4,4′-DAS amine equivalent 62 manufactured by Mitsui Chemicals Fine) is 5.7 parts by mass, -Resin varnish was prepared in the same manner as in Example 1 except that diethyl-4,4'-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) was not used, and a prepreg, metal-clad laminate A multilayer laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 10)
12.2 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (KMI Kasei Co., Ltd. BMI-80, double bond equivalent 285), naphthol-modified novolak epoxy resin (Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) is 9.9 parts by mass, 4,4 ′-(p-phenylenediisopropylidene) dianiline (BISAILLINE-P amine equivalent 86 manufactured by Mitsui Chemicals Fine) is 7.4 parts by mass, 3 , 3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) was used except that a resin varnish was prepared in the same manner as in Example 1 to prepare a prepreg, metal A tension laminate, a multilayer laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 11)
1,1.7 parts by mass of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285, manufactured by Keisei Kasei Co., Ltd.), naphthol-modified novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) is 9.4 parts by mass, 2,2- [4- (4-aminophenoxy) phenyl] propane (BAPP amine equivalent 103 manufactured by Wakayama Seika) is 8.4 parts by mass, , 3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) was used except that a resin varnish was prepared in the same manner as in Example 1 to prepare a prepreg, metal A tension laminate, a multilayer laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 12)
11.3 parts by mass of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70, double bond equivalent 221 manufactured by Keisei Kasei), naphthol-modified novolac epoxy resin (NC manufactured by Nippon Kayaku Co., Ltd.) -7000L, epoxy equivalent 230) 11.7 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 6.5 parts by mass Resin varnish was prepared in the same manner as in Example 1 except that 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by Keisei Kasei Co., Ltd., double bond equivalent 285) was not used. Thus, a prepreg, a metal-clad laminate, a multilayer laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 13)
9.9 parts by mass of 4,4′-diphenylmethane bismaleimide (KMI Kasei BMI-H, double bond equivalent 179), naphthol-modified novolak epoxy resin (Nippon Kayaku NC-7000L, epoxy equivalent 230) 12 .6 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) in 7.0 parts by mass, 2,2-bis [4- A resin varnish was prepared in the same manner as in Example 1 except that (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by Keisei Kasei Co., Ltd., double bond equivalent 285) was not used. A prepreg, a metal-clad laminate, A multilayer laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 14)
9.9 parts by mass of polyphenylmethane maleimide (BMI-2300, manufactured by Daiwa Kasei Co., Ltd., double bond equivalent 179), 12.6 parts by mass of naphthol-modified novolac epoxy resin (NC-7000L, Nippon Kayaku Co., Ltd., epoxy equivalent 230) , 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) in 7.0 parts by mass, 2,2-bis [4- (4-maleimide) A resin varnish was prepared in the same manner as in Example 1 except that phenoxy) phenyl] propane (BMI-80 manufactured by Keisei Kasei Co., Ltd., double bond equivalent 285) was not used. A prepreg, a metal-clad laminate, a multilayer laminate, A printed wiring board and a semiconductor device were obtained.

(Example 15)
Instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol (Nouchi 200 manufactured by Ouchi Shinsei) was 0.3 parts by mass. Except for the above, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a laminate, a printed wiring board, and a semiconductor device.

(Example 16)
Silica particles (manufactured by Admatechs, SO25R, average particle size 0.5 μm) 55.0 parts by mass, talc (manufactured by Fuji Talc, LMS-300, average particle size 4.8 μm) 5.0 parts by mass, silica nanoparticles ( A resin varnish was prepared in the same manner as in Example 1 except that 10.0 parts by mass (Tokuyama Corporation, NSS-5N, average particle diameter 70 nm) was obtained, and a prepreg, a laminate, a printed wiring board, and a semiconductor device were obtained. It was.

(Comparative Example 1)
30.9 parts by weight of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285, manufactured by Keisei Kasei Co., Ltd.), naphthol-modified novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) NC-7000L, epoxy equivalent 230) 24.9 parts by mass, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent 63.5) 13.8 parts by mass Example 1 except that 30.0 parts by mass of silica particles (manufactured by Admatechs, SO25R, average particle size 0.5 μm) and silica nanoparticles (manufactured by Tokuyama, NSS-5N, average particle size 70 nm) are not used. A resin varnish was prepared in the same manner as above to obtain a prepreg, a metal-clad laminate, a multilayer laminate, a printed wiring board, and a semiconductor device.

(Comparative Example 2)
23.1 parts by mass of naphthol-modified novolak epoxy resin (NC-7000L, Nippon Kayaku Co., Ltd., epoxy equivalent 230), 3,3′-diethyl-4,4′-diaminodiphenylmethane (Kayahard AA amine, manufactured by Nippon Kayaku Co., Ltd.) Equivalent 63.5) is 6.4 parts by mass, and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285 manufactured by Keisei Kasei Co., Ltd.) is not used. A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a metal-clad laminate, a multilayer laminate, a printed wiring board, and a semiconductor device.

(Comparative Example 3)
24.1 parts by weight of biphenylaralkyl epoxy resin (Nippon Kayaku Co., Ltd. NC-3000H, epoxy equivalent 285), 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA amine equivalent) 63.5) is 5.4 parts by mass, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80, double bond equivalent 285 manufactured by Keiai Kasei Co., Ltd.) and naphthol-modified novolac epoxy resin A resin varnish is prepared in the same manner as in Example 1 except that (Nippon Kayaku NC-7000L, epoxy equivalent 230) is not used, and a prepreg, a metal-clad laminate, a multilayer laminate, a printed wiring board, and a semiconductor are prepared. Got the device.

  The results are shown in Table 1.

5a Carrier material 5b Carrier material 100 Metal-clad laminate 101 Insulating layer 103 Metal foil 11 Fiber substrate 60 Vacuum laminating device 61 Laminating roll 62 Hot air drying device 300 Printed wiring board 301 Insulating layer 302 Metal foil 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 Sealing material

Claims (12)

A metal-clad laminate having metal foil on both sides of an insulating layer containing an epoxy resin composition and a fiber base material,
The epoxy resin composition includes an epoxy resin, a bismaleimide compound, and an inorganic filler,
After removing the metal foil on both sides of the metal-clad laminate by etching,
The average linear expansion coefficient calculated in the range of 250 ° C. to 260 ° C. in the in-plane direction of the insulating layer is 0.5 ppm / ° C. or more and 4.0 ppm / ° C. or less,
A metal-clad laminate in which the glass transition temperature of the insulating layer is 200 ° C. or higher and 300 ° C. or lower as measured by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz. The metal-clad laminate according to claim 1,
The metal-clad laminate in which the storage elastic modulus E ′ ₂₅₀ at 250 ° C. of the insulating layer is 15 GPa or more and 25 GPa or less. In the metal-clad laminate according to claim 2,
Metal whose ratio of storage elastic modulus E ′ ₃₀ at 30 ° C. to storage elastic modulus E ′ ₂₅₀ at 250 ° C. of the insulating layer (E ′ ₃₀ / E ′ ₂₅₀ ) is 1.2 or more and 2.0 or less. Tension laminate. In the metal tension laminate sheet according to any one of claims 1 to 3,
The bismaleimide compound is 4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, And a metal-clad laminate which is at least one selected from the group consisting of polyphenylmethanemaleimide. The metal-clad laminate according to any one of claims 1 to 4,
The epoxy resin is at least one selected from the group consisting of bisphenol-type epoxy resins, novolak-type epoxy resins, biphenyl-type epoxy resins, arylalkylene-type epoxy resins, naphthalene-type epoxy resins, anthracene-type epoxy resins, and dicyclopentadiene-type epoxy resins. A metal-clad laminate. In the metal tension laminate sheet according to any one of claims 1 to 5,
A metal-clad laminate, wherein the inorganic filler is at least one selected from the group consisting of talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide. In the metal tension laminate sheet according to any one of claims 1 to 6,
Metal, wherein the fiber substrate is a glass fiber substrate made of at least one selected from the group consisting of E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, and quartz glass Tension laminate. In the metal tension laminate sheet according to any one of claims 1 to 7,
The metal-clad laminate in which the content of the inorganic filler is 30% by mass or more and 79.9% by mass or less with respect to 100% by mass of the total solid content of the epoxy resin composition. In the metal tension laminate sheet according to any one of claims 1 to 8,
The metal-clad laminate in which the content of the fiber base material is 20% by mass or more and 70% by mass or less with respect to 100% by mass of the insulating layer. The metal-clad laminate according to any one of claims 1 to 9,
A metal-clad laminate, wherein the insulating layer has a thickness of 0.1 mm or less.   The printed wiring board formed by carrying out circuit processing of the metal-clad laminated board as described in any one of Claims 1 thru | or 10.   A semiconductor device in which a semiconductor element is mounted on the printed wiring board according to claim 11.

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