KR102431012B1 - Resin composition for printed wiring boards, prepregs, resin sheets, laminates, metal foil-clad laminates, printed wiring boards, and multilayer printed wiring boards - Google Patents

Abstract

Resin composition for printed wiring boards, prepregs, resin sheets, laminates, and metal foils that do not have a clear glass transition temperature (Tg-less) and can sufficiently reduce (achieve low warpage) warpage of printed wiring boards, especially multilayer coreless boards In order to provide a clad laminated board, a printed wiring board, and a multilayer printed wiring board, the resin composition by this invention is an allylphenol compound (A), a maleimide compound (B), a cyanate ester compound (C), and/or an epoxy compound (D). Moreover, content of the allylphenol compound (A) with respect to 100 mass parts of resin solid content in the resin composition for printed wiring boards is 10-50 mass parts, The maleimide compound (B) with respect to 100 mass parts of resin solid content in the resin composition for printed wiring boards. The content of is 40 to 80 parts by mass.

Description

Resin composition for printed wiring boards, prepregs, resin sheets, laminates, metal foil-clad laminates, printed wiring boards, and multilayer printed wiring boards

The present invention relates to a resin composition for a printed wiring board, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.

In recent years, as high-functionality and miniaturization of semiconductor packages widely used in electronic devices, communication devices, personal computers, and the like progress, high integration and high-density mounting of each component for semiconductor packages is accelerating in recent years. In connection with this, the various characteristics required for the printed wiring board for semiconductor packages are becoming more and more stringent. As a characteristic required for such a printed wiring board, low water absorption, moisture absorption heat resistance, a flame retardance, a low dielectric constant, a low dielectric loss tangent, a low thermal expansion coefficient, heat resistance, chemical resistance, high metal peel strength, etc. are mentioned, for example. Moreover, in addition to them, suppressing the curvature of a printed wiring board, especially a multilayer coreless board|substrate (achieving low warpage) has become an important subject in recent years, and various countermeasures have been taken.

As one of the countermeasures, low thermal expansion of the insulating layer used for a printed wiring board is mentioned. This is the method of suppressing curvature by making the thermal expansion coefficient of a printed wiring board close to the thermal expansion coefficient of a semiconductor element, and is making an effort actively now (for example, refer patent documents 1 - 3).

As a method of suppressing the warpage of the semiconductor plastic package, in addition to lowering the thermal expansion of the printed wiring board, increasing the rigidity of the laminate (higher rigidity) and increasing the glass transition temperature of the laminate (higher Tg) are being considered ( For example, refer to Patent Documents 4 and 5).

Japanese Patent Laid-Open No. 2013-216884 Japanese Patent No. 3173332 Japanese Patent Laid-Open No. 2009-035728 Japanese Patent Laid-Open No. 2013-001807 Japanese Patent Laid-Open No. 2011-178992

However, according to the detailed examination of the present inventors, even with the said prior art, the curvature of a printed wiring board, especially a multilayer coreless board|substrate cannot yet fully be reduced, and further improvement is desired.

That is, the present invention provides a resin composition for a printed wiring board that does not have a clear glass transition temperature (so-called Tg-less) and can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, particularly a multilayer coreless board, and It aims at providing the prepreg, resin sheet, laminated board, metal foil clad laminated board, printed wiring board, and multilayer printed wiring board using this resin composition for printed wiring boards.

As a result of intensive studies conducted by the present inventors in order to solve the above problems, conventionally, regarding the bending behavior of a printed wiring board for a semiconductor plastic package, in a cured product of a prepreg, a larger thermal storage modulus, and Although it has been thought that the resin composition which can implement|achieve a higher elastic modulus retention rate is effective, it has become clear that it is not necessarily the case. In addition, as a result of intensive research, the present inventors found that the above problems can be solved by using a cyanate ester compound and/or an epoxy compound in addition to an allylphenol compound and a maleimide compound, and to complete the present invention. reached

That is, the present invention is as follows.

[One]

Allylphenol compound (A) and

A maleimide compound (B), and

As a resin composition for printed wiring boards containing a cyanate ester compound (C) and/or an epoxy compound (D),

Content of the said allylphenol compound (A) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 10-50 mass parts,

Content of the said maleimide compound (B) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 40-80 mass parts,

A resin composition for a printed wiring board.

[2]

Total content of the said cyanate ester compound (C) and the said epoxy compound (D) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 5-45 mass parts,

The resin composition for printed wiring boards as described in [1].

[3]

Content of the said cyanate ester compound (C) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 0-25 mass parts,

The resin composition for printed wiring boards as described in [1] or [2].

[4]

Content of the said epoxy compound (D) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 0-25 mass parts,

The resin composition for printed wiring boards as described in [1] or [2].

[5]

Further containing a filler (E),

The resin composition for printed wiring boards in any one of [1]-[4].

[6]

The filler (E) is at least one selected from the group consisting of silica, alumina, and boehmite,

The resin composition for printed wiring boards as described in [5].

[7]

Content of the said filler (E) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 120-250 mass parts,

The resin composition for printed wiring boards as described in [5] or [6].

[8]

The allylphenol compound (A) contains a compound represented by any of the following formulas (I) to (III),

The resin composition for printed wiring boards in any one of [1]-[7].

[Formula 1]

(in formula (I), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, represents a t-butyl group or a phenyl group)

[Formula 2]

[Formula 3]

[9]

Said maleimide compound (B), bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl- At least one selected from the group consisting of 4-maleimidephenyl)methane and a maleimide compound represented by the following formula (1) is included,

The resin composition for printed wiring boards in any one of [1]-[8].

[Formula 4]

(In formula (1), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more)

[10]

The said cyanate ester compound (C) contains the compound represented by following formula (2) and/or (3),

The resin composition for a printed wiring board according to any one of [1] to [9].

[Formula 5]

(In formula (2), R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more)

[Formula 6]

(In formula (3), R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more)

[11]

The hardened|cured material obtained by making the said resin composition for printed wiring boards thermoset the prepreg containing a base material on 230 degreeC and conditions for 100 minutes, following formula (4)-(8);

(In each formula, E' represents the storage elastic modulus of the cured product at the temperature shown in parentheses, and E''max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30°C to 330°C. where E''min represents the minimum value of the loss modulus of the cured product in a temperature range of 30°C to 330°C)

Satisfying the numerical range of the physical property parameters related to the mechanical properties represented by

[1] The resin composition for a printed wiring board according to any one of [10].

[12]

description and

The resin composition for a printed wiring board according to any one of [1] to [11], impregnated or applied to the base material.

A prepreg with

[13]

The base material is at least one fiber selected from the group consisting of E glass fiber, D glass fiber, S glass fiber, T glass fiber, Q glass fiber, L glass fiber, NE glass fiber, HME glass fiber, and organic fiber. which is composed,

The prepreg according to [12].

[14]

support and

The resin composition for a printed wiring board according to any one of [1] to [11], which is laminated on one or both surfaces of the support.

A resin sheet with

[15]

having at least one selected from the group consisting of the prepregs according to [12] and [13], and the resin sheet according to [14], laminated at least one or more sheets,

laminated plate.

[16]

At least one selected from the group consisting of the prepreg according to [12] and [13], and the resin sheet according to [14], in which at least one or more sheets are laminated;

Metal foil disposed on one side or both sides of at least one selected from the group consisting of the prepreg and the resin sheet

A metal foil-clad laminate having a.

[17]

an insulating layer,

A conductor layer formed on the surface of the insulating layer

have,

The said insulating layer contains the resin composition for printed wiring boards in any one of [1]-[11],

printed wiring board.

[18]

A first insulating layer formed of at least one selected from the group consisting of the prepreg according to [12] and [13], and the resin sheet according to [14], which are laminated by at least one sheet, and one side of the first insulating layer A plurality of insulating layers consisting of a second insulating layer formed of at least one selected from the group consisting of the prepreg according to [12] and [13], and the resin sheet according to [14], laminated at least one or more sheets in the direction; ,

A plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers, and a second conductor layer disposed on the surface of the outermost layer of the plurality of insulating layers

A multilayer printed wiring board with

According to the present invention, a resin composition for a printed wiring board that does not have a clear glass transition temperature (Tg-less) and can sufficiently reduce (achieve low warpage) warpage of a printed wiring board, particularly a multilayer coreless board, and a print thereof A prepreg using the resin composition for wiring boards, a resin sheet, a laminated board, a metal foil-clad laminated board, a printed wiring board, and a multilayer printed wiring board can be provided.

1 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate (however, the method for manufacturing a multilayer coreless substrate is not limited thereto. It is the same as in FIGS. 2 to 8 below. .).
2 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate.
3 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate.
4 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate.
5 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate.
6 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate.
7 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate.
8 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate.
9 is a partial cross-sectional view showing a configuration of an example of a panel of a multilayer coreless substrate.

EMBODIMENT OF THE INVENTION Hereinafter, although the form for implementing this invention (hereinafter referred to as "the present embodiment") is described in detail, the present invention is not limited thereto, and various modifications are possible without departing from the gist thereof. . In addition, in this embodiment, "resin solid content" refers to the component except the solvent and filler in the resin composition for printed wiring boards, unless otherwise indicated, and "resin solid content 100 parts by mass" is for printed wiring boards It shall say that the sum total of the component except the solvent in a resin composition and a filler is 100 mass parts.

[Resin composition for printed wiring boards]

The resin composition for printed wiring boards of this embodiment contains an allylphenol compound (A), a maleimide compound (B), a cyanate ester compound (C), and/or an epoxy resin (D). When the resin composition for a printed wiring board contains such a composition, for example, in a cured product obtained by curing a prepreg, a clear glass transition temperature does not exist (Tg-less), and a printed wiring board, in particular, a multilayer coreless substrate. There is a tendency that warpage can be sufficiently reduced (low warpage is achieved).

[Allylphenol compound (A)]

The allylphenol compound (A) is not particularly limited as long as it is a compound in which at least one or more allyl groups and one or more hydroxyl groups are directly bonded to the aromatic ring, for example, bisphenol in which the hydrogen atom of the aromatic ring is substituted with an allyl group. can Although it does not specifically limit as such a bisphenol, For example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, Bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z are mentioned. Among these, bisphenol A is preferable, as an allylphenol compound (A), diallyl bisphenol A is more preferable, and the compound represented by a following formula (I) or a formula (II) is still more preferable. By using such an allylphenol compound (A), there exists a tendency for bending strength, bending elastic modulus, thermal expansion coefficient, thermal conductivity, and copper foil peeling strength to improve more.

[Formula 7]

Here, in formula (I), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group , a t-butyl group, or a phenyl group.

[Formula 8]

[Formula 9]

Here, in formulas (I) to (III), one allyl group and one hydroxyl group are independently bonded to each other at positions excluding the Bis bonding portion of the benzene ring.

Moreover, the allylphenol compound (A) may further have reactive functional groups other than an allyl group and a hydroxyl group. Moreover, the compound which modified|denatured the hydroxyl group directly couple|bonded with the aromatic ring by reactive functional groups other than an allyl group and a hydroxyl group may be sufficient. Although it does not specifically limit as a reactive functional group other than an allyl group and a hydroxyl group, For example, a cyanate group (cyanate ester group), an epoxy group, an amine group, an isocyanate group, a glycidyl group, and a phosphoric acid group are mentioned. . By having these, there exists a tendency for bending strength, bending elastic modulus, thermal expansion coefficient, and thermal conductivity to improve further. An allylphenol compound (A) may be used individually by 1 type, and may use 2 or more types together. When using two or more types together, reactive functional groups other than an allyl group and a hydroxyl group may be same or different.

The number of allyl groups in one molecule of the allylphenol compound (A) is preferably 1 to 5, more preferably 2 to 4, still more preferably 2. When the number of bases of the allyl group in one molecule of the allylphenol compound (A) falls within the above range, the bending strength, the bending elastic modulus, and the copper foil peeling strength are more improved, the thermal expansion coefficient is low, and the thermal conductivity tends to be excellent.

When the allylphenol compound (A) has a hydroxyl group directly bonded to the aromatic ring, the number of the hydroxyl groups in one molecule of the allylphenol compound (A) is preferably 1 to 5, more preferably 2 to 4, more preferably 2. When the number of the hydroxyl groups in one molecule of the allylphenol compound (A) is within the above range, the bending strength, the bending elastic modulus, and the copper foil peeling strength are more improved, the thermal expansion coefficient is low, and the thermal conductivity tends to be excellent.

When the allylphenol compound (A) has a reactive functional group other than the above-described allyl group and hydroxyl group, the number of reactive functional groups other than the allyl group and hydroxyl group in one molecule of the allylphenol compound (A) is preferably 1 -5, More preferably, it is 2-4, More preferably, it is 2. When the number of reactive functional groups other than the allyl group and the hydroxyl group in one molecule of the allylphenol compound (A) is within the above range, the bending strength, the bending elastic modulus, and the copper foil peeling strength are further improved, the thermal expansion coefficient is low, and the tendency to be excellent in thermal conductivity have.

Content of an allyl phenol compound (A) is 10-50 mass parts with respect to 100 mass parts of resin solid content in the resin composition for printed wiring boards, Preferably it is 10-35 mass parts, More preferably, it is 15-30 mass parts. . When content of an allylphenol compound (A) is in the said range, there exists a tendency for the softness|flexibility of the hardened|cured material obtained, bending strength, bending elastic modulus, thermal expansion coefficient, thermal conductivity, and copper foil peeling strength to improve further.

[Maleimide Compound (B)]

Although it will not specifically limit as a maleimide compound (B), if it is a compound which has one or more maleimide groups in a molecule|numerator, For example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl) Methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4 -maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (1), a prepolymer of these maleimide compounds, or a maleimide compound and an amine compound of prepolymers. Among these, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl) At least one selected from the group consisting of methane and a maleimide compound represented by the following formula (1) is preferable, and a (Tg-less) resin composition having no clear glass transition temperature is easily obtained, and thus the following formula (1) A maleimide compound represented by is particularly preferred. By including the maleimide compound (B) mentioned above, there exists a tendency for the thermal expansion coefficient of the hardened|cured material obtained to fall more and to improve heat resistance and glass transition temperature (Tg) more. A maleimide compound (B) may be used individually by 1 type, and may use 2 or more types together.

[Formula 10]

Here, in Formula (1), R< ₅ > represents a hydrogen atom or a methyl group each independently, Preferably a hydrogen atom is shown. Moreover, in Formula (1), n< ₁ > represents 1 or more integer, Preferably it is an integer of 10 or less, More preferably, it is an integer of 7 or less.

Content of a maleimide compound (B) is 40-80 mass parts with respect to 100 mass parts of resin solid content in the resin composition for printed wiring boards, Preferably it is 40-70 mass parts, More preferably, it is 45-65 mass parts. . When content of a maleimide compound (B) is in the said range, the thermal expansion coefficient of the hardened|cured material obtained falls more and there exists a tendency for heat resistance to improve more.

[Cyanic acid ester compound (C) and/or epoxy compound (D)]

The resin composition for printed wiring boards of this embodiment contains a cyanate ester compound (C) and/or an epoxy compound (D). By using the cyanate ester compound (C) and/or the epoxy compound (D) together with the above-mentioned allylphenol compound (A) and maleimide compound (B), for example, in the cured product obtained by curing the prepreg. Therefore, there is a tendency to become a resin composition that does not have a clear glass transition temperature (Tg-less) and can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, in particular, a multilayer coreless substrate.

(Cyanic acid ester compound (C))

Although it does not specifically limit as a cyanate ester compound (C), For example, naphthol aralkyl type cyanate ester represented by following formula (2), a novolac type cyanate ester represented by following formula (3), biphenyl are Alkyl-type cyanate ester, bis(3,5-dimethyl4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1 ,3,5-Tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicy Anatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl) ) thioether, bis(4-cyanatophenyl)sulfone, and 2,2'-bis(4-cyanatophenyl)propane; The prepolymer of these cyanate esters, etc. are mentioned. You may use these cyanate ester compounds (C) individually by 1 type or in combination of 2 or more type.

[Formula 11]

In Formula (2), R< ⁶ > represents a hydrogen atom or a methyl group each independently, and a hydrogen atom is preferable among these. Moreover, in Formula (2), n< ₂ > represents 1 or more integer. _The upper limit of n2 is normally 10, Preferably it is 6.

[Formula 12]

In Formula (3), R ⁷ each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Moreover, in Formula (3), n< ₃ > represents 1 or more integer. _The upper limit of n3 is normally 10, Preferably it is 7.

Among these, the cyanate ester compound (C) consists of a naphthol aralkyl-type cyanate ester represented by Formula (2), a novolac-type cyanate ester represented by Formula (3), and a biphenyl aralkyl-type cyanate ester. It is preferable to include at least one selected from the group It is more preferable to include By using such a cyanate ester compound (C), it exists in the tendency for the hardened|cured material to be obtained more excellent in a flame retardance, sclerosis|hardenability is higher, and a thermal expansion coefficient lower.

It does not specifically limit as a manufacturing method of these cyanate ester compound (C), A well-known method can be used as a synthesis|combining method of a cyanate ester compound. Although it does not specifically limit as a well-known method, For example, a method of reacting a phenol resin and a cyanide halide in an inert organic solvent in the presence of a basic compound, Formation of a salt of a phenol resin and a basic compound in the solution containing water and a method in which the obtained salt and cyan halide are subjected to a two-phase interface reaction thereafter.

Although it does not specifically limit as a phenol resin used as a raw material of these cyanate ester compound (C), For example, a naphthol aralkyl type phenol resin represented by following formula (9), a novolak type phenol resin, a biphenyl aralkyl A type phenol resin is mentioned.

[Formula 13]

In Formula (9), R< ⁸ > represents a hydrogen atom or a methyl group each independently, and a hydrogen atom is preferable among these. Moreover, in Formula (9), _n4 represents 1 or more integer. The upper limit of _n4 is normally 10, Preferably it is 6.

The naphthol aralkyl type phenol resin represented by Formula (9) can be obtained by condensing a naphthol aralkyl resin and cyanic acid. Although it does not specifically limit as a naphthol aralkyl type phenol resin, For example, Naphthol, such as alpha-naphthol and beta-naphthol, p-xylylene glycol, alpha, alpha'- dimethoxy-p-xylene, and those obtained by reaction of benzenes such as 1,4-di(2-hydroxy-2-propyl)benzene. The naphthol aralkyl-type cyanate ester can be selected from those obtained by condensing cyanic acid with the naphthol aralkyl resin obtained as described above.

To [ content of a cyanate ester compound (C) ] 100 mass parts of resin solid content in the resin composition for printed wiring boards, Preferably it is 0-25 mass parts, More preferably, it is 0-20 mass parts. When content of a cyanate ester compound exists in the said range, there exists a tendency for the heat resistance and chemical-resistance of the hardened|cured material obtained to improve more.

(epoxy compound (D))

Although it will not specifically limit if it is a compound which has two or more epoxy groups in 1 molecule as an epoxy compound (D), For example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin , Phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin Epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, aralkyl novolak type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol A type epoxy resin, an isocyanurate ring containing epoxy resin, or these halides are mentioned. Moreover, as an epoxy compound (D), a non-halogenated epoxy compound (a halogen-containing epoxy compound, a halogen-free epoxy compound) is more preferable. In addition, when an allylphenol compound (A) has an epoxy group, an epoxy compound (D) is things other than the allylphenol compound (A) which has an epoxy group.

To [ content of an epoxy compound (D) ] 100 mass parts of resin solid content in the resin composition for printed wiring boards, Preferably it is 0-25 mass parts, More preferably, it is 0-20 mass parts. When content of an epoxy compound (D) exists in the said range, there exists a tendency for the softness|flexibility of the hardened|cured material obtained, copper foil peeling strength, chemical-resistance, and desmear resistance to improve more.

Moreover, as above-mentioned, since the resin composition for printed wiring boards of this embodiment contains a cyanate ester compound (C) and/or an epoxy compound (D), a cyanate ester compound (C) and an epoxy compound (D) ), the total content of the cyanate ester compound (C) and the epoxy compound (D) with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring boards is preferably 5 to 45 parts by mass, and further Preferably it is 5-40 mass parts, More preferably, it is 10-30 mass parts. When total content of a cyanate ester compound (C) and an epoxy compound (D) exists in the said range, there exists a tendency for the softness|flexibility of the hardened|cured material obtained, copper foil peeling strength, heat resistance, chemical-resistance, and desmear resistance to improve more. Moreover, when the total content of the cyanate ester compound (C) and the epoxy compound (D) is within the above range, for example, in the cured product obtained by curing the prepreg, there is no clear glass transition temperature (Tg lease) Moreover, there exists a tendency to become a resin composition which can further reduce the curvature of a printed wiring board, especially a multilayer coreless board|substrate (achieving low warpage).

[Filling material (E)]

It is preferable that the resin composition for printed wiring boards of this embodiment further contains a filler (E). Although it does not specifically limit as a filler (E), For example, an inorganic filler and an organic filler are mentioned, It is preferable to contain an inorganic filler among both, It is preferable to use an organic filler together with an inorganic filler. Although it does not specifically limit as an inorganic filler, For example, Silicas, such as a natural silica, a fused silica, a synthetic silica, amorphous silica, aerosil, a hollow silica; silicon compounds such as white carbon; metal oxides such as titanium white, zinc oxide, magnesium oxide, and zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride; metal sulfates such as barium sulfate; metal hydrates such as aluminum hydroxide, aluminum hydroxide heat-treated products (things in which aluminum hydroxide is heat-treated to reduce a part of crystal water), boehmite, and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; Alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fiber (including fine glass powders such as E glass, T glass, D glass, S glass and Q glass), hollow glass, spherical glass, and the like. Moreover, although it does not specifically limit as an organic filler, For example, Rubber powder, such as a styrene type powder, a butadiene type powder, and an acryl type powder; core-shell type rubber powder; silicone resin powder; silicone rubber powder; Silicone composite powder, etc. are mentioned. A filler (E) may be used individually by 1 type, and may use 2 or more types together.

Among these, at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride as inorganic fillers is preferably included, silica, alumina It is more preferable to include at least one selected from the group consisting of , and boehmite. By using such a filler (E), there exists a tendency for high rigidity-ization of the hardened|cured material obtained and low warpage-ization to improve more.

Content of the filler (E) (especially inorganic filler) with respect to 100 mass parts of resin solid content in the resin composition for printed wiring boards becomes like this. Preferably it is 120-250 mass parts, More preferably, it is 150-230 mass parts, More preferably is 180 to 220 parts by mass. When content of a filler (E) is in the said range, it exists in the tendency which high-stiffness-ization of the hardened|cured material obtained and low warpage-ization improve further.

[Silane coupling agent and wetting and dispersing agent]

The resin composition for printed wiring boards of this embodiment may further contain a silane coupling agent and a wet dispersing agent. By including a silane coupling agent or a wet dispersing agent, the dispersibility of the said filler (E), the resin component, the filler (E), and the adhesive strength of the base material mentioned later tend to improve more.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances, and for example, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-amino aminosilane-based compounds such as propyltrimethoxysilane; Epoxysilane compounds, such as (gamma)-glycidoxy propyl trimethoxysilane; acrylsilane-based compounds such as γ-acryloxypropyltrimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; A phenylsilane type compound etc. are mentioned. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

Although it will not specifically limit as a wetting and dispersing agent as long as it is a dispersion stabilizer used for paints, For example, DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010 by Big Chemie Japan Co., Ltd. , W903, and the like.

[Other resins, etc.]

The resin composition for printed wiring boards of the present embodiment, if necessary, includes allyl group-containing compounds (hereinafter also referred to as "other allyl group-containing compounds") other than the above-mentioned allylphenol compound (A), phenol resins, jade You may further contain the 1 type(s) or 2 or more types chosen from the group which consists of a cetane resin, a benzoxazine compound, and the compound which has a polymerizable unsaturated group. By including such other resin etc., there exists a tendency for the copper foil peeling strength of the hardened|cured material obtained, bending strength, bending elastic modulus, etc. to improve more.

[Other allyl group-containing compounds]

Although it does not specifically limit as another allyl group containing compound, For example, Allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate. , and diallyl maleate.

To [ content of another allyl group containing compound / 100 mass parts of resin solid content in the resin composition for printed wiring boards ], Preferably it is 0-50 mass parts, More preferably, it is 10-45 mass parts, More preferably, it is 15 -45 mass parts, More preferably, it is 20-35 mass parts. When content of another allyl group containing compound is in the said range, there exists a tendency for the bending strength, bending elastic modulus, heat resistance, and chemical-resistance of the hardened|cured material obtained to improve more.

[Phenolic resin]

As a phenol resin, if it is a phenol resin which has two or more hydroxyl groups in 1 molecule, a generally well-known thing can be used, The kind is not specifically limited. Specific examples thereof include bisphenol A phenol resin, bisphenol E phenol resin, bisphenol F phenol resin, bisphenol S phenol resin, phenol novolac resin, bisphenol A novolac phenol resin, and glycidyl ester phenol resin. , Aralkyl novolak type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modification Novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, hydroxyl group Although containing silicone resins etc. are mentioned, It is not restrict|limited in particular. These phenol resins can be used individually by 1 type or in combination of 2 or more type. By including such a phenol resin, there exists a tendency which is more excellent in adhesiveness, flexibility, etc. of the hardened|cured material obtained.

To [ content of a phenol resin / 100 mass parts of resin solid content in the resin composition for printed wiring boards ], Preferably it is 0-99 mass parts, More preferably, it is 1-90 mass parts, More preferably, it is 3-80 mass parts. to be. When content of a phenol resin exists in the said range, there exists a tendency which is further excellent in the adhesiveness, flexibility, etc. of the hardened|cured material obtained.

[Oxetane resin]

As oxetane resin, a generally well-known thing can be used, The kind in particular is not limited. Specific examples thereof include alkyloxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane and 3,3-dimethyloxetane, 3-methyl-3-methoxy Methyloxetane, 3,3'-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (Toa Synthetic product name), OXT-121 (Toa Synthetic product brand name), etc. are mentioned. These oxetane resins can be used 1 type or in combination of 2 or more type. By including such an oxetane resin, there exists a tendency which is more excellent in adhesiveness, flexibility, etc. of the hardened|cured material obtained.

To [ content of oxetane resin / 100 mass parts of resin solid content in the resin composition for printed wiring boards ], Preferably it is 0-99 mass parts, More preferably, it is 1-90 mass parts, More preferably, it is 3-80 mass parts. to be. When content of an oxetane resin exists in the said range, there exists a tendency which is further excellent in the adhesiveness, flexibility, etc. of the hardened|cured material obtained.

[benzoxazine compound]

As a benzoxazine compound, if it is a compound which has two or more dihydrobenzoxazine rings in 1 molecule, a generally well-known thing can be used, The kind is not specifically limited. Specific examples thereof include bisphenol A-type benzoxazine BA-BXZ (trade name manufactured by Konishi Chemicals), bisphenol F-type benzooxazine BF-BXZ (trade name manufactured by Konishi Chemicals), and bisphenol S-type benzooxazine BS-BXZ (manufactured by Konishi Chemicals). brand name) and the like. These benzoxazine compounds can be used 1 type or in mixture of 2 or more types. By including such a benzoxazine compound, there exists a tendency for the flame retardance, heat resistance, low water absorption, low dielectric material, etc. of the hardened|cured material obtained to be more excellent.

To [ content of a benzoxazine compound / 100 mass parts of resin solid content in the resin composition for printed wiring boards ], Preferably it is 0-99 mass parts, More preferably, it is 1-90 mass parts, More preferably, it is 3-80 mass parts. is the mass part. When content of a benzoxazine compound exists in the said range, there exists a tendency for the heat resistance etc. of the hardened|cured material obtained to be further excellent.

[Compound having a polymerizable unsaturated group]

As a compound which has an unsaturated group which can be superposed|polymerized, a generally well-known thing can be used, The kind is not specifically limited. As the specific example, Vinyl compounds, such as ethylene, propylene, styrene, divinylbenzene, and divinyl biphenyl; Methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethyl (meth)acrylates of monohydric or polyhydric alcohols such as allpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy (meth)acrylates such as bisphenol A epoxy (meth)acrylate and bisphenol F epoxy (meth)acrylate; benzocyclobutene resin; (bis) maleimide resin etc. are mentioned. The compound which has these superposition|polymerizable unsaturated groups can be used 1 type or in mixture of 2 or more types. By including a compound having such a polymerizable unsaturated group, the obtained cured product tends to be more excellent in heat resistance, toughness, and the like.

To [ content of the compound which has a superposable|polymerizable unsaturated group / 100 mass parts of resin solid content in the resin composition for printed wiring boards ], Preferably it is 0-99 mass parts, More preferably, it is 1-90 mass parts, More preferably, it is 3 - 80 parts by mass. When the content of the compound having a polymerizable unsaturated group is within the above range, the obtained cured product tends to be further excellent in heat resistance, toughness, and the like.

[curing accelerator]

The resin composition for printed wiring boards of this embodiment may further contain a hardening accelerator. Although it does not specifically limit as a hardening accelerator, For example, Imidazole, such as triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethylpyridine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N - tertiary amines, such as methylmorpholine, a triethanolamine, a triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; What is formed by dissolving these organometallic salts in hydroxyl-containing compounds, such as a phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; Organotin compounds, such as a dioctyl tin oxide, other alkyl tin, and an alkyl tin oxide, etc. are mentioned. Among these, since triphenylimidazole accelerates|stimulates a hardening reaction and there exists a tendency which is excellent in thermal expansion coefficient, it is especially preferable.

[solvent]

The resin composition for printed wiring boards of this embodiment may further contain a solvent. By including a solvent, the viscosity at the time of preparation of the resin composition for printed wiring boards becomes low, while handling property improves more, there exists a tendency for the impregnation property with respect to the base material mentioned later to improve more.

Although it will not specifically limit if it can melt|dissolve some or all of the resin components in the resin composition for printed wiring boards as a solvent, For example, Ketones, such as acetone, methyl ethyl ketone, and a methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; Propylene glycol monomethyl ether, its acetate, etc. are mentioned. A solvent may be used individually by 1 type, and may use 2 or more types together.

[Method for Producing Resin Composition for Printed Wiring Boards]

Although the manufacturing method of the resin composition for printed wiring boards of this embodiment is not specifically limited, For example, each component is mix|blended with a solvent one by one, and the method of fully stirring is mentioned. At this time, in order to melt|dissolve or disperse|distribute each component uniformly, well-known processes, such as stirring, mixing, a kneading|mixing process, can be implemented. The dispersibility of the filler (E) with respect to the resin composition for printed wiring boards can be improved by performing a stirring dispersion process specifically, using the stirring tank which attached the stirrer which has suitable stirring ability. Said stirring, mixing, and kneading|mixing process can be suitably implemented using well-known apparatuses, such as an apparatus for the purpose of mixing, such as a ball mill and a bead mill, or a revolving or autorotation type mixing apparatus, for example.

Moreover, at the time of preparation of the resin composition for printed wiring boards of this embodiment, an organic solvent can be used as needed. The kind of organic solvent will not be specifically limited, if resin in the resin composition for printed wiring boards can be melt|dissolved. The specific example is as above-mentioned.

[Characteristics of the resin composition for printed wiring boards]

In the resin composition for a printed wiring board of the present embodiment, the cured product obtained by thermosetting the prepreg containing it and the base material under the conditions of 230°C and 100 minutes has mechanical properties represented by the following formulas (4) to (8). It is preferable if it satisfies the numerical range of the physical-property parameter related to it, and it is more preferable to satisfy the numerical range of the physical-property parameter regarding the mechanical property shown by following formula (4A) - (8A).

Here, in each formula, E' represents the storage elastic modulus of the cured product at the temperature shown in parentheses, and E''max represents the maximum value of the loss elastic modulus of the cured product in the temperature range of 30°C to 330°C, , E''min represents the minimum value of the loss elastic modulus of the cured product in a temperature range of 30°C to 330°C (E'' represents the loss elastic modulus of the cured product).

Conventionally, regarding the bending behavior of a printed wiring board, in the cured product of a prepreg, a resin composition capable of realizing a larger thermal storage elastic modulus and a higher elastic modulus retention rate has been considered effective, but this is not necessarily the case, The numerical value of the physical property parameter relating to the mechanical properties of the cured product obtained by thermosetting the prepreg under the conditions of 230°C and 100 minutes is preferably within the range of the above formulas (4) to (8), and preferably the formulas (4A) to (8A). , it becomes possible to sufficiently increase the glass transition temperature (Tg), and to sufficiently reduce the amount of warpage of laminates, metal foil-clad laminates, printed wiring boards, and especially multilayer coreless substrates themselves.

In other words, the numerical value of the physical property parameter relating to the mechanical properties of the cured product obtained by thermosetting the prepreg under the conditions of 230°C and 100 minutes is the formulas (4) to (8), preferably the formulas (4A) to (8A) By being in the range, it becomes possible to reduce the warpage of a printed wiring board (especially multilayer coreless board|substrate) sufficiently (achieving low warpage) preferably without a clear glass transition temperature (Tgless). That is, it can be said that the expression (7) and (8) related to the loss modulus, preferably satisfying the formulas (7A) and (8A), has the same meaning as the absence of a clear glass transition temperature (Tg-less). , the cured product preferably satisfies only formulas (7) and (8), preferably formulas (7A) and (8A), and preferably does not satisfy formulas (4) to (6), preferably formulas (4A) to (6A) The thing is, the loss elastic modulus itself is small and does not extend easily, but when it is set as a printed wiring board, the elongation difficulty is a cause, and it becomes difficult to achieve low warpage. On the other hand, the cured product preferably satisfies not only the formulas (7) and (8) but also the formulas (7A) and (8A), but also the formulas (4) to (8), preferably the formulas (4A) and (8A). It tends to become difficult to extend|stretch by a Tg lease, and to become easy to achieve low warpage of a printed wiring board.

The measuring method of the mechanical properties (storage elastic modulus E' and loss elastic modulus E'') of the hardened|cured material of a prepreg is not specifically limited, For example, it can measure with the following method. That is, copper foil (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd., thickness 12 µm) is placed on the upper and lower surfaces of one prepreg sheet, and lamination molding (heat) at a pressure of 30 kgf/cm 2 and a temperature of 230° C. for 100 minutes hardening) to obtain a copper-clad clad laminate having a predetermined insulating layer thickness. Next, after cut|disconnecting the obtained copper foil clad laminated board to size 5.0 mm x 20 mm with a dicing saw, the copper foil on the surface is removed by an etching, and the sample for a measurement is obtained. Using this sample for measurement, mechanical properties (storage elastic modulus E' and loss elastic modulus E'') can be measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481. At this time, you may obtain|require the average value of n=3.

[purpose]

The resin composition for printed wiring boards of this embodiment can be used suitably as a prepreg, a resin sheet, an insulating layer, a laminated board, a metal foil clad laminated board, a printed wiring board, or a multilayer printed wiring board. Hereinafter, a prepreg, a resin sheet, a laminated board, a metal foil clad laminated board, and a printed wiring board (multilayer printed wiring board are included) are demonstrated.

[Prepreg]

The prepreg of this embodiment contains a base material and the resin composition for printed wiring boards impregnated or apply|coated to the base material. The manufacturing method of a prepreg can be implemented according to a conventional method, and is not specifically limited. For example, after impregnating or apply|coating the resin composition for printed wiring boards in this embodiment to a base material, it heats for 1-30 minutes in a 100-200 degreeC dryer, etc., and semi-hardening (B-staging), The prepreg of an embodiment can be manufactured.

To [ content of the resin composition for printed wiring boards (a filler (E) is included) in the prepreg of this embodiment) with respect to the total amount of a prepreg, Preferably it is 30-90 volume%, More preferably, it is 35- It is 85 volume%, More preferably, it is 40-80 volume%. When content of a resin composition exists in the said range, there exists a tendency for a moldability to improve more.

It does not specifically limit as a base material, According to the target use and performance, the well-known thing used for various printed wiring board materials can be selected and used suitably. As a base material, a glass base material, inorganic base materials other than glass, organic base materials etc. are mentioned, for example, Among these, a glass base material is especially preferable from a viewpoint of high rigidity and heating dimensional stability. It does not specifically limit as a specific example of the fiber which comprises these base materials, In a glass base material, it consists of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass, for example. and at least one glass fiber selected from the group. Moreover, in inorganic base materials other than glass, inorganic fibers other than glass, such as quartz, are mentioned. In addition, in organic substrates, polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin) wholly aromatic polyamides such as Techno Products Co., Ltd.); polyesters such as 2,6-hydroxynaphthoic acid/parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.) and Xexion (registered trademark, manufactured by KB Siren); Organic fibers, such as polyparaphenylene benzoxazole (Zyron (trademark), Toyo Spinning Co., Ltd. make) and polyimide, are mentioned. These base materials may be used individually by 1 type, and may use 2 or more types together.

Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, a surfacing mat, etc. are mentioned. Although it does not specifically limit as a weaving method of a woven fabric, For example, plain weave, a lion type, a twill weave, etc. are known, From these well-known things, it can select suitably according to the intended use and performance, and can use it. Moreover, what carried out the fiber opening process, the glass woven fabric surface-treated with the silane coupling agent etc. are used preferably. Although the thickness and mass of a base material are not specifically limited, Usually, the thing of about 0.01-0.3 mm is used preferably. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g/m 2 or less, and more preferably a glass woven fabric made of glass fibers of E glass, S glass, and T glass. .

Moreover, as above-mentioned, the hardened|cured material obtained by making the prepreg of this embodiment thermoset it on the conditions of 230 degreeC and 100 minutes is said Formula (4)-(8) Preferably Formula (4A)- If it satisfies the numerical range of the physical property parameters related to the mechanical properties represented by (8A), the laminated board, the metal foil-clad laminate, the printed wiring board, or the multilayer printed wiring board does not have a clear glass transition temperature (Tg-less), and the warpage is sufficiently suppressed. Since there exists a tendency which can make it reduce (achieving low warpage), it is preferable.

[resin sheet]

The resin sheet of this embodiment has a sheet base material (support body), and the said resin composition for printed wiring boards laminated|stacked on the single side|surface or both surfaces of this sheet base material. A resin sheet is used as one means of thinning, and for example, a thermosetting resin (including a filler (E)) used for a prepreg or the like is applied directly to a support such as a metal foil or a film and dried. can be manufactured by

Although it does not specifically limit as a sheet|seat base material, Well-known thing used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, aluminum foil, copper foil , gold leaf, and the like. Especially, an electrolytic copper foil and a PET film are preferable.

As a coating method, for example, the method of apply|coating the solution which melt|dissolved the resin composition for printed wiring boards of this embodiment in the solvent on the sheet|seat base material with a bar coater, a die coater, a doctor blade, a baker applicator etc. is mentioned. .

After apply|coating the said resin composition for printed wiring boards to a sheet|seat base material, as for a resin sheet, it is preferable that semi-hardening (B-staging) was carried out. Specifically, for example, after apply|coating the said resin composition for printed wiring boards to sheet base materials, such as copper foil, it is made semi-hardened by the method of heating 1 to 60 minutes in a 100-200 degreeC dryer, etc., and a resin sheet is manufactured how to do it, etc. As for the adhesion amount of the resin composition for printed wiring boards with respect to a sheet|seat base material, the range of 1-300 micrometers is preferable in resin thickness of a resin sheet.

[Laminated sheet and metal foil-clad laminate]

The laminated board of this embodiment has the said prepreg of this embodiment and/or the said resin sheet of this embodiment laminated|stacked at least 1 or more sheets. In addition, the metal foil-clad laminate of this embodiment includes the laminate of this embodiment (that is, the prepreg of this embodiment and/or the resin sheet of this embodiment laminated on at least one or more sheets), and one side of the laminate, or It has the metal foil (conductor layer) arrange|positioned on both surfaces.

The conductor layer can be made of metal foil such as copper or aluminum. Although it will not specifically limit if the metal foil used here is used for a printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. Moreover, although the thickness of a conductor layer is although it does not specifically limit, 1-70 micrometers is preferable, More preferably, it is 1.5-35 micrometers.

The forming method and the forming conditions for a laminated board or a metal foil-clad laminated board are not specifically limited, The method and conditions of the general laminated board for printed wiring boards and a multilayer board are applicable. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of shaping|molding a laminated board or a metal foil-clad laminated board. Moreover, in the shaping|molding (laminated molding) of a laminated board or a metal foil clad laminated board, the temperature is 100-300 degreeC, the pressure is 2-100 kgf/cm<2> of surface pressure, and the range of 0.05-5 hours is common for a heating time. Moreover, post-curing can also be performed at the temperature of 150-300 degreeC as needed. In particular, when a multi-stage press machine is used, from the viewpoint of sufficiently accelerating curing of the prepreg and/or resin sheet, a temperature of 200 ° C. to 250 ° C., a pressure of 10 to 40 kgf/cm 2 , and a heating time of 80 minutes to 130 minutes are preferable, A temperature of 215°C to 235°C, a pressure of 25 to 35 kgf/cm 2 , and a heating time of 90 minutes to 120 minutes are more preferable. Moreover, it can also be set as a multilayer board by combining and laminating|stacking the prepreg and/or resin sheet mentioned above and the wiring board for inner layers manufactured separately.

[Printed wiring board]

The printed wiring board of this embodiment is a printed wiring board which has an insulating layer and the conductor layer formed in the surface of the insulating layer, The insulating layer contains the said resin composition for printed wiring boards. For example, it can be used suitably as a printed wiring board by forming a predetermined|prescribed wiring pattern in the metal foil clad laminated board mentioned above. In addition, since the metal foil-clad laminate using the resin composition for a printed wiring board of this embodiment does not have a clear glass transition temperature (Tg-less) and tends to sufficiently reduce warpage (achieve low warpage), such performance is It can be used especially effectively as a requested|required printed wiring board.

The printed wiring board of this embodiment can be manufactured with the following method specifically, for example. First, the above-mentioned metal foil clad laminated board (copper clad laminated board etc.) is prepared. The surface of the metal foil-clad laminate is etched to form an inner-layer circuit, and an inner-layer substrate is produced. The inner circuit surface of this inner layer substrate is subjected to surface treatment for increasing adhesive strength if necessary, and then the above-mentioned prepreg and/or resin sheet is laminated on the inner circuit surface for a necessary number of sheets, and further on the outside Metal foils for external circuits are laminated, heated and pressed, and integrally formed (laminated molding). In this way, the multilayer laminated board in which the insulating layer which consists of a base material and hardened|cured material of a thermosetting resin composition was formed between the metal foil for inner-layer circuits and outer-layer circuits is manufactured. The method of lamination molding and its molding conditions are the same as those of the above-described laminate or metal foil-clad laminate. Next, after drilling for through-holes or via-holes is performed on this multilayer laminated board, desmear processing is performed in order to remove the smear which is a residue of the resin derived from the resin component contained in the hardened|cured material layer. Thereafter, a plated metal film is formed on the wall surface of the hole to conduct the metal foil for the inner circuit and the outer circuit, and the metal foil for the outer circuit is etched to form an outer circuit, and a printed wiring board is manufactured.

For example, the above-mentioned prepreg (a base material and the above-mentioned resin composition for a printed wiring board attached thereto), a resin composition layer of a metal foil-clad laminate (a layer made of the above-mentioned resin composition for a printed wiring board) , which constitutes the insulating layer containing the resin composition for printed wiring boards mentioned above.

Moreover, when not using a metal foil clad laminated board, you may form the conductor layer used as a circuit in what consists of the said prepreg or the said resin composition for printed wiring boards, and may manufacture a printed wiring board. At this time, the method of electroless plating can also be used for formation of a conductor layer.

Further, as shown in Fig. 9, the printed wiring board of the present embodiment includes a first insulating layer (1) formed of at least one selected from the group consisting of the above-described prepreg and resin sheet laminated at least one or more, and a second insulating layer (2) formed of at least one selected from the group consisting of the above-mentioned prepreg and resin sheet laminated at least one or more sheets in the direction of one side (lower surface direction as shown) of the first insulating layer (1) a plurality of insulating layers formed therein, a first conductor layer 3 disposed between each of the plurality of insulating layers 1 and 2, and a first conductor layer 3 disposed on the outermost layer of the plurality of insulating layers 1 and 2 It is preferable to have a some conductor layer which consists of two conductor layers (3).

According to the knowledge of the present inventors, in a conventional laminate, for example, at least one selected from the group consisting of a prepreg and a resin sheet serving as a single core substrate is selected from the group consisting of prepregs and resin sheets that differ in both directions. Although forming a multilayer printed wiring board is performed by laminating|stacking at least 1 type, at least 1 type selected from the group which consists of the prepreg and resin sheet of this embodiment is one prepreg which forms the 1st insulating layer 1 and a coreless type manufactured by laminating at least one selected from the group consisting of a resin sheet and another prepreg forming the second insulating layer 2 only in the single-sided direction of at least one selected from the group consisting of a resin sheet. It was confirmed that it is especially effective for the multilayer printed wiring board (multilayer coreless board|substrate) of.

In other words, when the prepreg of this embodiment, a resin sheet, and the resin composition for printed wiring boards are used for a printed wiring board, the curvature amount can be reduced effectively, Although it is not specifically limited, Multilayer coreless among a printed wiring board It is especially effective in a board|substrate. In other words, a typical printed wiring board generally has a double-sided symmetrical configuration, so it tends not to bend easily, whereas a multilayer coreless board tends to have a double-sidedly asymmetrical configuration, so it is more warped than a conventional printed wiring board. tends to be easy. Therefore, by using the prepreg of this embodiment, a resin sheet, and the resin composition for printed wiring boards, the curvature amount of the multilayer coreless board|substrate which conventionally tends to warp easily can be reduced especially effectively.

9 shows a configuration in which two second insulating layers 2 are laminated on one first insulating layer 1 (that is, a configuration in which a plurality of insulating layers are three layers), but the second insulating The number of layers (2) may be one or two or more sheets may be sufficient as them. Therefore, the number of 1st conductor layers 3 may also be one, and two or more layers may be sufficient as them.

Thus, as for the printed wiring board of this embodiment which has the structure mentioned above, the resin composition for printed wiring boards of this embodiment mentioned above is the hardened|cured material which hardened the prepreg, for example. WHEREIN: Storage elastic modulus and loss at the time of heat By being able to control mechanical properties such as elastic modulus in a specific range desirable for low warpage, there is no clear glass transition temperature (Tgless), and the warpage of printed wiring boards, especially multilayer coreless boards, is sufficiently reduced (low warpage is achieved) Therefore, it can be used particularly effectively as a printed wiring board for semiconductor packages and a multilayer coreless board.

Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the present invention is not limited at all by the following examples.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl type cyanate ester compound (SN495VCN)

In the reactor, 0.47 mol of α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Shin-Nitetsu Chemical Co., Ltd.: naphthol aralkyl having a repeating unit number n of 1 to 5) (OH group conversion) was dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine was added to this solution. While maintaining the temperature at -10°C, 300 g of a 0.93 mol cyanogen chloride solution in chloroform was added dropwise into the reactor over 1.5 hours, and after completion of the dropping, the mixture was stirred for 30 minutes. After that, the mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was further dripped in a reactor, and it stirred for 30 minutes, and completed reaction. After the hydrochloric acid salt of triethylamine by-produced was separated by filtration from the reaction solution, the resulting filtrate was washed with 500 ml of 0.1 N hydrochloric acid, followed by washing with 500 ml of water 4 times. After drying this with sodium sulfate, evaporating at 75 degreeC, and also degassing under reduced pressure at 90 degreeC, the alpha-naphthol aralkyl type cyanate ester compound represented by the said Formula (2) as a brown solid (R ⁶ in the formula) are all hydrogen atoms). As a result of analyzing the obtained α-naphthol aralkyl-type cyanate ester compound by an infrared absorption spectrum, absorption of a cyanate ester group was confirmed in the vicinity of 2264 cm ^-1 .

[Example 1]

Allylphenol compound (A) diallylbisphenol A (DABPA, manufactured by Daiwa Chemical Industries, Ltd., hydroxyl group equivalent: 154 g/eq.) 24.1 parts by mass, maleimide compound (B) (BMI-2300, Daiwa Chemicals) Manufactured by Kogyo Co., Ltd., maleimide equivalent: 186 g/eq.) 60.9 parts by mass, α-naphthol aralkyl-type cyanate ester compound of Synthesis Example 1, which is cyanate ester compound (C) (SN495VCN, cyanate equivalent: 261) g/eq.) 5.0 parts by mass, epoxy compound (D) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 328 g/eq.) 10.0 parts by mass, filler (E) phosphorus slurry silica (SC-2050MB) , Adomatex Co., Ltd.) 200 parts by mass and copper silicone composite powder (KMP-605M, manufactured by Shin-Etsu Chemical Co., Ltd.) 25 parts by mass, silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) A varnish was obtained by mixing 5 mass parts and 0.5 mass parts of triphenylimidazole (Tokyo Chemical Industry Co., Ltd. product) which is a hardening accelerator, and diluting with methyl ethyl ketone. This varnish was impregnated and apply|coated to E-glass woven fabric, it heat-dried at 160 degreeC for 3 minute(s), and the prepreg with the resin composition content for printed wiring boards 73 volume% was obtained.

[Example 2]

Allylphenol compound (A) (DABPA) in 19.9 parts by mass, maleimide compound (B) (BMI-2300) in 50.1 parts by mass, and cyanate ester compound (C) (SN495VCN) in 10.0 parts by mass And the prepreg of 73 volume% of resin composition content for printed wiring boards was obtained by the method similar to Example 1 except having made the epoxy compound (D) (NC-3000FH) 20.0 mass parts.

[Example 3]

Resin composition content for printed wiring boards by the method similar to Example 1 except having not used the cyanate ester compound (C) (SN495VCN), and having made the epoxy compound (D) (NC-3000FH) 15.0 mass parts. A prepreg of 73% by volume was obtained.

[Example 4]

Resin composition content for printed wiring boards by the method similar to Example 1 except having made cyanate ester compound (C) (SN495VCN) 15.0 mass parts, and having not used epoxy compound (D) (NC-3000FH) A prepreg of 73% by volume was obtained.

[Comparative Example 1]

Allylphenol compound (A) (DABPA) was 28.4 parts by mass, maleimide compound (B) (BMI-2300) was 71.6 parts by mass, cyanate ester compound (C) (SN495VCN) was not used; And the prepreg of 73 volume% of resin composition content for printed wiring boards was obtained by the method similar to Example 1 except not having used the epoxy compound (D) (NC-3000FH).

[Comparative Example 2]

Allylphenol compound (A) (DABPA) in 60.0 parts by mass, maleimide compound (B) (BMI-2300) in 32.1 parts by mass, and cyanate ester compound (C) (SN495VCN) in 2.6 parts by mass And the prepreg of 73 volume% of resin composition content for printed wiring boards was obtained by the method similar to Example 1 except having made the epoxy compound (D) (NC-3000FH) 5.3 mass parts.

[Comparative Example 3]

Allylphenol compound (A) (DABPA) in 12.7 parts by mass, maleimide compound (B) (BMI-2300) in 32.1 parts by mass, and cyanate ester compound (C) (SN495VCN) in 50.0 parts by mass And the prepreg of 73 volume% of resin composition content for printed wiring boards was obtained by the method similar to Example 1 except having made the epoxy compound (D) (NC-3000FH) 5.2 mass parts.

[Comparative Example 4]

Allylphenol compound (A) (DABPA) in 5.0 parts by mass, maleimide compound (B) (BMI-2300) in 85.0 parts by mass, and cyanate ester compound (C) (SN495VCN) in 5.0 parts by mass And the prepreg of 73 volume% of resin composition content for printed wiring boards was obtained by the method similar to Example 1 except having made the epoxy compound (D) (NC-3000FH) 5.0 mass parts.

[Evaluation of physical properties]

Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 4, samples for measurement evaluation of physical properties were prepared according to the procedure shown in each of the following items, and mechanical properties (storage elastic modulus, and loss elastic modulus), the formula (4) to (8) and the physical property parameters regarding the mechanical properties in the formulas (4A) to (8A), the glass transition temperature (Tg), and the amount of warpage (three types) were measured and evaluated. The results of Examples are summarized in Table 1, and the results of Comparative Examples are summarized in Table 2.

[Machine Characteristics]

Copper foil (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd., thickness 12 µm) was placed on both upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf/cm 2 , Lamination molding (thermosetting) for 100 minutes was performed at the temperature of 230 degreeC, and the copper-clad laminated board with an insulating layer thickness of 0.1 mm was obtained. After cut|disconnecting the obtained copper foil clad laminated board to size 20 mm x 5 mm with a dicing saw, the copper foil on the surface was removed by etching, and the sample for a measurement was obtained. Using this measurement sample, mechanical properties (storage elastic modulus E' and loss elastic modulus E'') were measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481 (n = 3). medium).

[Glass Transition Temperature (Tg)]

Copper foil (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd., thickness 12 µm) was placed on both upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf/cm 2 , Lamination molding for 100 minutes was performed at the temperature of 230 degreeC, and the copper-clad laminated board with an insulating layer thickness of 0.1 mm was obtained. After cut|disconnecting the obtained copper foil clad laminated board to size 12.7*2.5mm with a dicing saw, the copper foil on the surface was removed by etching, and the sample for a measurement was obtained. Using this sample for measurement, the glass transition temperature (Tg) was measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481 (average value of n=3).

[Bending amount: bimetal method]

First, copper foil (3EC-VLP, Mitsui Metals Mining Co., Ltd. make, thickness 12 micrometers) is arrange|positioned on the upper and lower surfaces of 1 sheet of prepreg obtained in Examples 1-4 and Comparative Examples 1-4, pressure 30 kgf/ The laminate molding die for 120 minutes was implemented at cm<2> and the temperature of 220 degreeC, and the copper-clad laminated board was obtained. Next, the said copper foil was removed from the obtained copper foil clad laminated board. Next, on one side of the laminate from which the copper foil has been removed, one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4 is further placed, and on both upper and lower sides thereof, the copper foil (3EC-VLP, Mitsui Metals Mining Co., Ltd.) ) manufacture, thickness 12 micrometers) was arrange|positioned, the pressure of 30 kgf/cm<2>, and the temperature of 220 degreeC were laminated|mold for 120 minutes, and the copper foil clad laminated board was obtained again. Furthermore, the said copper foil was removed from the obtained copper-clad laminated board, and the laminated board was obtained. Then, a 20 mm × 200 mm strip plate is cut out from the obtained laminate, the surface of the prepreg laminated on the second sheet is turned up, and the maximum value of the amount of warpage at both ends in the long direction is measured with a multiplier, and the The average value was made into "the amount of warpage" by the bimetal method.

[Amount of warpage: multi-layer coreless substrate]

First, as shown in FIG. 1, the carrier copper foil surface of the ultra-thin copper foil b1 with a carrier (MT18Ex, Mitsui Metals Mining Co., Ltd. product, thickness 5 micrometers) is prepreg on both surfaces of the prepreg used as the support body (a). side, the prepregs (c1) obtained in Examples 1-4 and Comparative Examples 1-4 are further disposed thereon, and copper foil (d) (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd.) thereon; 12 micrometers in thickness), the pressure of 30 kgf/cm<2>, and the temperature of 220 degreeC were laminated|mold for 120 minutes, and the copper-clad laminated board shown in FIG. 2 was obtained.

Next, as shown in FIG. 3, the said copper foil (d) of the obtained copper-clad laminated board shown in FIG. 2 was etched by predetermined wiring pattern, for example, and the conductor layer (d') was formed. Next, on the laminated board shown in FIG. 3 on which the conductor layer (d') was formed, as shown in FIG. 4, the prepreg (c2) obtained in Examples 1-4 and Comparative Examples 1-4 is arrange|positioned, and on it, Furthermore, ultra-thin copper foil (b2) with a carrier (MT18Ex, manufactured by Mitsui Metals Mining Co., Ltd., thickness 5 µm) is placed, and lamination molding is performed at a pressure of 30 kgf/cm 2 and a temperature of 220° C. for 120 minutes, FIG. 5 . The copper-clad laminated board shown in was obtained.

Next, in the copper foil clad laminate shown in FIG. 5, as shown in FIG. 6 by peeling the carrier copper foil and ultra-thin copper foil of the ultra-thin copper foil (b1) with a carrier arrange|positioned on the support body (a) (hardened|cured prepreg for support bodies) , The laminated boards of 2 sheets were peeled from the support body (a), and also carrier copper foil was peeled from the ultra-thin copper foil with a carrier (b2) in the upper part in these laminated boards. Next, the processing by a laser processing machine was performed on the ultra-thin copper foil of the upper and lower sides of each obtained laminated board, and, as shown in FIG. 7, the predetermined|prescribed via (v) was formed by chemical copper plating. And, as shown in FIG. 8, for example, it etched by a predetermined wiring pattern, the conductor layer was formed, and the panel (size: 500 mm x 400 mm) of a multilayer coreless board|substrate was obtained. Then, the amount of warpage at 8 points in total of the four corners and the center portion of the four sides of the obtained panel was measured with a multiplier, and the average value was taken as the “deflection amount” of the panel of the multilayer coreless substrate.

[Substrate shrinkage before and after reflow process]

Copper foil (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd., thickness 12 µm) was placed on both upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf/cm 2 , Lamination molding for 120 minutes was performed at the temperature of 220 degreeC, and the copper-clad laminated board was obtained. Next, after drilling 9 points|pieces equally in grid shape to the obtained copper foil clad laminated board with a drill, the said copper foil was removed.

And first, the distance between holes in the laminated board from which the copper foil was removed was measured (distance A). Next, with respect to the laminated board, the reflow process was performed by making 260 degreeC the maximum temperature with the Salamander reflow apparatus. Thereafter, the distance between the holes in the laminate was measured again (distance B). And the measured distance k and distance i were substituted into the following formula (I), the dimensional change rate of the board|substrate in a reflow process was calculated|required, and the value was made into the board|substrate shrinkage rate before and behind a reflow process.

((Distance A) - (Distance B))/Distance A × 100 … Formula (I)

The resin composition for printed wiring boards of this embodiment has industrial applicability as a material of a prepreg, a resin sheet, a laminated board, a metal foil clad laminated board, a printed wiring board, or a multilayer printed wiring board. In addition, this application is based on the Japanese Patent Application No. 2016-255272 for which it applied on December 28, 2016, The description is used here.

Claims (18)

Allylphenol compound (A) and
a maleimide compound (B);
As a resin composition for printed wiring boards containing a cyanate ester compound (C) and/or an epoxy compound (D),
Content of the said allylphenol compound (A) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 10-50 mass parts,
Content of the said maleimide compound (B) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 45-80 mass parts,
In the cured product of the resin composition for a printed wiring board, there is no clear glass transition temperature, and the glass transition temperature is measured by the DMA method with a dynamic viscoelasticity analyzer in accordance with JIS C6481, the resin for a printed wiring board composition. The method of claim 1,
The resin composition for printed wiring boards whose total content of the said cyanate ester compound (C) and the said epoxy compound (D) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 5-45 mass parts. The method of claim 1,
The resin composition for printed wiring boards whose content of the said cyanate ester compound (C) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 0-25 mass parts. The method of claim 1,
The resin composition for printed wiring boards whose content of the said epoxy compound (D) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 0-25 mass parts. The method of claim 1,
The resin composition for printed wiring boards which further contains a filler (E). 6. The method of claim 5,
The resin composition for printed wiring boards whose said filler (E) is at least 1 sort(s) chosen from the group which consists of silica, alumina, and a boehmite. 6. The method of claim 5,
The resin composition for printed wiring boards whose content of the said filler (E) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 120-250 mass parts. The method of claim 1,
The resin composition for printed wiring boards in which the said allylphenol compound (A) contains the compound represented by any one of following formula (I)-(III).

(in formula (I), R ₁ and R ₂ are each independently a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, represents a t-butyl group or a phenyl group)

The method of claim 1,
Said maleimide compound (B) is bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl- The resin composition for printed wiring boards containing at least 1 sort(s) chosen from the group which consists of 4-maleimidephenyl) methane and the maleimide compound represented by following formula (1).

(In formula (1), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more) The method of claim 1,
The resin composition for printed wiring boards in which the said cyanate ester compound (C) contains the compound represented by following formula (2) and/or (3).

(In formula (2), R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more)

(In formula (3), R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more) The method of claim 1,
The hardened|cured material obtained by making the said resin composition for printed wiring boards thermoset the prepreg containing a base material on 230 degreeC and conditions for 100 minutes, following formula (4)-(8);

(In each formula, E' represents the storage elastic modulus of the cured product at the temperature shown in parentheses, and E''max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30°C to 330°C. where E''min represents the minimum value of the loss modulus of the cured product in the temperature range of 30°C to 330°C)
The resin composition for printed wiring boards which satisfy|fills the numerical range of the physical-property parameter regarding the mechanical characteristic represented by. description and,
The prepreg which has the resin composition for printed wiring boards in any one of Claims 1-11 impregnated or apply|coated to the base material. 13. The method of claim 12,
The base material is at least one fiber selected from the group consisting of E glass fiber, D glass fiber, S glass fiber, T glass fiber, Q glass fiber, L glass fiber, NE glass fiber, HME glass fiber, and organic fiber. A prepreg, which is composed. support and
The resin sheet which has the resin composition for printed wiring boards in any one of Claims 1-11 laminated|stacked on the single side|surface or both surfaces of this support body. at least one stacked
A prepreg comprising a substrate and the resin composition for a printed wiring board according to any one of claims 1 to 11 impregnated or applied to the substrate, and
The resin sheet which has a support body and the resin composition for printed wiring boards in any one of Claims 1-11 laminated|stacked on the single side|surface or both surfaces of the support body.
A laminate having at least one selected from the group consisting of. at least one stacked
A prepreg comprising a substrate and the resin composition for a printed wiring board according to any one of claims 1 to 11 impregnated or applied to the substrate, and
The resin sheet which has a support body and the resin composition for printed wiring boards in any one of Claims 1-11 laminated|stacked on the single side|surface or both surfaces of the support body.
At least one selected from the group consisting of,
A metal foil-clad laminate having a metal foil disposed on one or both surfaces of at least one selected from the group consisting of the prepreg and the resin sheet. an insulating layer,
It has a conductor layer formed on the surface of the insulating layer,
The printed wiring board in which the said insulating layer contains the resin composition for printed wiring boards in any one of Claims 1-11. at least one stacked
A prepreg comprising a substrate and the resin composition for a printed wiring board according to any one of claims 1 to 11 impregnated or applied to the substrate, and
The resin sheet which has a support body and the resin composition for printed wiring boards in any one of Claims 1-11 laminated|stacked on the single side|surface or both surfaces of the support body.
A first insulating layer formed of at least one selected from the group consisting of
A prepreg comprising a substrate and the resin composition for a printed wiring board according to any one of claims 1 to 11 impregnated or applied to the substrate, and
The resin sheet which has a support body and the resin composition for printed wiring boards in any one of Claims 1-11 laminated|stacked on the single side|surface or both surfaces of the support body.
A plurality of insulating layers consisting of a second insulating layer formed of at least one selected from the group consisting of;
A multilayer printed wiring board having a plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers, and a second conductor layer disposed on the surface of an outermost layer of the plurality of insulating layers.

Images