TWI798194B - Resin composition for printed wiring board, prepreg, resin sheet, laminate, metal foil-clad laminate, printed wiring board, and multi-layered printed wiring board - Google Patents

Abstract

This invention aims to provide a resin composition for printed wiring board, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board and a multi-layered printed wiring board without clear glass-transition temperature (Tg-less), and capable of sufficiently reducing the warpage of printed wiring board and, particularly, the warpage of multi-layered coreless substrate (achieving the object of low warpage). To this end, the resin composition according to this invention includes an allylphenol compound (A), a maleimide compound (B), a cyanate ester compound (C) and/or an epoxy compound (D). Besides, the content of allylphenol compound (A) is 10 to 50 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring board, and the content of maleimide compound (B) is 40 to 80 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring board.

Description

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

The present invention relates to a resin composition for printed wiring boards, 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, the high-function and miniaturization of semiconductor packages widely used in electronic equipment, communication equipment, and personal computers have progressed. Accompanied by this, the high integration and high-density mounting of various components used in semiconductor packages has been accelerating in recent years. . Along with this, various characteristics required for printed circuit boards for semiconductor packages have become more stringent. For the characteristics required for the printed circuit board, such as: low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric tangent, low thermal expansion rate, heat resistance, chemical resistance, high plating peel strength wait. In addition, suppressing warpage of printed wiring boards, especially multilayer coreless substrates (achievement of low warpage), has recently become an important issue, and various countermeasures have been taken.

One of the countermeasures is to reduce thermal expansion of insulating layers used in printed circuit boards. It is a method of suppressing warpage by making the thermal expansion coefficient of a printed circuit board close to that of a semiconductor element, and it has been actively used at present (for example, refer to Patent Documents 1 to 3).

As a method of suppressing the warpage of the semiconductor plastic package, in addition to reducing the thermal expansion of the printed circuit board, there are still people who have explored improving the rigidity (high rigidity) of the laminated board and increasing the glass transition temperature of the laminated board (high Tg B) (for example, refer to Patent Documents 4 and 5). [Prior Art Document] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2013-216884 Patent Document 2: Japanese Patent No. 3173332 Patent Document 3: Japanese Patent Laid-Open No. 2009-035728 Patent Document 4: Japanese Patent Laid-Open No. 2013-001807 Patent Document 5: Japanese Patent Laid-Open No. 2011-178992

However, according to the detailed research of the inventors of the present application, even the above-mentioned conventional technology still cannot sufficiently reduce the warpage of the printed circuit board, especially the multi-layer coreless substrate, and further improvement is desired.

That is, the object of the present invention is to provide a resin composition for printed circuit boards, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed circuit board, and a resin composition using the resin composition for a printed circuit board. Boards, and multilayer printed circuit boards, which do not have a clear glass transition temperature (Tg) (that is, no Tg), and can achieve a sufficient reduction in the warpage of printed circuit boards, especially multilayer coreless substrates (achieve low warpage) .

The inventors of this case worked hard to solve the above problems. As a result of their research, they found that the warpage behavior of the printed circuit boards used in the conventional semiconductor plastic packages, although it is thought that the cured product of the prepreg can achieve a greater heat storage elastic modulus. , and higher elastic modulus retention rate of the resin composition is effective, but not necessarily limited to this. Furthermore, as a result of diligent research by the inventors of the present case, it was found that by using a cyanate compound and/or an epoxy compound in addition to the use of an allylphenol compound and a maleimide compound, the above-mentioned problems can be solved. this invention.

That is, the present invention is as follows. [1] A resin composition for printed circuit boards, comprising an allylphenol compound (A), a maleimide compound (B), and a cyanate compound (C) and/or an epoxy compound (D), The content of the allylphenol compound (A) is 10 to 50 parts by mass relative to 100 parts by mass of resin solid content in the resin composition for printed wiring boards, The content of the maleimide compound (B) is 40 to 80 parts by mass per 100 parts by mass of solid content.

[2] The resin composition for printed wiring boards according to [1], wherein the cyanate compound (C) and the epoxy compound are The total content of (D) is 5-45 mass parts.

[3] The resin composition for printed wiring boards according to [1] or [2], wherein the cyanate compound (C) is The content is 0 to 25 parts by mass.

[4] The resin composition for a printed wiring board according to [1] or [2], wherein the content of the epoxy compound (D) is 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. It is 0-25 mass parts.

[5] The resin composition for a printed wiring board according to any one of [1] to [4], further comprising a filler (E).

[6] The resin composition for printed wiring boards according to [5], wherein the filler (E) is at least one selected from the group consisting of silica, alumina, and boehmite.

[7] The resin composition for a printed wiring board according to [5] or [6], wherein the content of the filler (E) is: 120 to 250 parts by mass.

[8] The resin composition for printed wiring boards according to any one of [1] to [7], wherein the allylphenol compound (A) includes any one of the following formulas (I) to (III) Represented compound:

【Chemical 1】

In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, or phenyl;

【Chemical 2】

【Chemical 3】

[9] The resin composition for printed circuit boards according to any one of [1] to [8], wherein the maleimide compound (B) is selected from bis(4-maleimide Phenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimide At least one compound in the group consisting of phenyl)methane and a maleimide compound represented by the following formula (1);

【Chemical 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 resin composition for printed circuit boards according to any one of [1] to [9], wherein the cyanate compound (C) includes compounds represented by the following formulas (2) and/or (3);

【Chemical 5】

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

【Chemical 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 resin composition for printed wiring boards according to any one of [1] to [10], wherein the prepreg containing the resin composition for printed wiring boards and the substrate is heated at 230° C. for 100 minutes. The hardened product obtained by conditional thermal curing conforms to the numerical range of the physical parameters of the mechanical properties represented by the following formulas (4) to (8); E'(200°C)/E'(30°C)≦0.90...(4) E'(260℃)/E'(30℃)≦0.85...(5) E'(330℃)/E'(30℃)≦0.80...(6) E”max/E'(30℃)≦3.0 %...(7) E"min/E'(30℃)≧0.5%...(8) In each formula, E' represents the storage elastic modulus of the cured product at the temperature shown in the brackets, and E"max represents the The maximum value of the loss elastic modulus of the hardened product in the temperature range of 30°C to 330°C, and E"min represents the minimum value of the loss elastic modulus of the hardened product in the temperature range of 30°C to 330°C.

[12] A prepreg comprising: a substrate; and the resin composition for a printed circuit board according to any one of [1] to [11] impregnated or coated on the substrate.

[13] The prepreg according to [12], wherein the base material is selected from 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 one or more types of fibers in the group consisting of organic fibers.

[14] A resin sheet comprising: a support; and the resin composition for a printed circuit board according to any one of [1] to [11] laminated on one or both sides of the support.

[15] A laminate comprising at least one laminated sheet of at least one selected from the group consisting of the prepregs of [12] and [13] and the resin sheet of [14].

[16] A metal foil-clad laminate comprising: at least one sheet selected from the group consisting of the prepregs of [12] and [13] and the resin sheet of [14] laminated At least one type; and metal foil arranged on one side or both sides of at least one type selected from the group consisting of the prepreg and the resin sheet.

[17] A printed circuit board having an insulating layer, and a conductive layer formed on the surface of the insulating layer; the insulating layer contains the resin composition for a printed circuit board according to any one of [1] to [11].

[18] A multilayer printed circuit board having a plurality of insulating layers and a plurality of conductive layers, the plurality of insulating layers are composed of a first insulating layer and a second insulating layer, and the first insulating layer is selected by laminating at least one sheet At least one of the group consisting of the prepregs of [12] and [13] and the resin sheet of [14] is formed, and the second insulating layer is stacked on one side of the first insulating layer. At least one kind selected from the group consisting of the prepregs such as [12] and [13] and the resin sheet such as [14] layered with at least one sheet is selected from the group consisting of such as [12] and [13] Prepreg, and at least one of the group consisting of resin sheets as in [14]; and the plurality of conductor layers are composed of a first conductor layer and a second conductor layer, and the first conductor layer is arranged on the plurality of Between each insulating layer of the insulating layer, the second conductor layer is arranged on the surface of the outermost layer of the plurality of insulating layers. [Effect of Invention]

According to the present invention, it is possible to provide a resin composition for a printed circuit board that does not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage of a printed circuit board, especially a multilayer coreless substrate (achieves low warpage), and Prepregs, resin sheets, laminates, metal foil-clad laminates, printed wiring boards, and multilayer printed wiring boards using the resin composition for printed wiring boards.

Hereinafter, this embodiment (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof. In addition, in this embodiment, "resin solid content" refers to components other than the solvent and filler in the resin composition for printed circuit boards unless otherwise specified, and "resin solid content 100 parts by mass" refers to the printed circuit board resin composition. The total of the components other than the solvent and the filler in the resin composition for wiring boards is 100 parts by mass.

[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), and a cyanate compound (C) and/or or epoxy resin (D). The resin composition for printed circuit boards contains such a composition that, for example, in the cured product obtained by curing a prepreg, there is no clear glass transition temperature (no Tg) and it is possible to sufficiently reduce the thickness of printed circuit boards, especially multilayer Tendency to warp the core substrate (achieve low warpage).

[Allylphenol compound (A)] The allylphenol compound (A) is not particularly limited as long as at least one allyl group and hydroxyl group are directly bonded to the aromatic ring, for example: the hydrogen of the aromatic ring Atoms substituted with allyl groups of bisphenols. The bisphenol is not particularly limited, for example: bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol Phenol M, Bisphenol S, Bisphenol P, Bisphenol PH, Bisphenol TMC, Bisphenol Z. Among them, bisphenol A is more preferable, and the allyl phenol compound (A) is more preferably diallyl bisphenol A, and the compound represented by the following formula (I) or formula (II) is more ideal. By using such an allylphenol compound (A), there exists a tendency for a flexural strength, a flexural modulus, thermal expansion coefficient, thermal conductivity, and copper foil peeling strength to become better.

【Chemical 7】

Here, in formula (I), R ₁ and R ₂ each independently represent a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third Butyl, or phenyl.

【chemical 8】

【Chemical 9】

Here, in the formulas (I) to (III), each of the allyl group and the hydroxyl group is independently bonded one by one to a position other than the Bis bonding portion of the benzene ring.

Moreover, the allylphenol compound (A) may have reactive functional groups other than an allyl group and a hydroxyl group further. Also, a compound obtained by modifying the hydroxyl group directly bonded to the aromatic ring with an allyl group and a reactive functional group other than the hydroxyl group may be used. The reactive functional groups other than allyl group and hydroxyl group are not particularly limited, for example: cyanate ester group, epoxy group, amine group, isocyanate group, glycidyl group, and phosphoric acid group. By having these groups, there is a tendency that the flexural strength, flexural modulus, thermal expansion rate, and thermal conductivity are better. The allylphenol compound (A) may be used alone or in combination of two or more. When using two or more kinds together, the reactive functional groups other than the allyl group and the hydroxyl group may be the same or different.

The number of allyl groups in 1 molecule of the allylphenol compound (A) is preferably 1-5, more preferably 2-4, still more preferably 2. The allyl phenol compound (A) has better flexural strength, flexural elastic modulus, and copper foil peel strength, lower coefficient of thermal expansion, and excellent thermal conductivity when the number of allyl groups in the molecule of the allylphenol compound (A) is within the above range. tendency.

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 1-5, more preferably 2-4, and More preferably 2. When the number of hydroxyl groups in the molecule of the allylphenol compound (A) is within the above range, the flexural strength, flexural modulus, and copper foil peel strength tend to be better, the coefficient of thermal expansion is low, and the thermal conductivity tends to be excellent .

When the allylphenol compound (A) has a reactive functional group other than the above-mentioned 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 2~4, and more preferably 2. When the number of reactive functional groups other than the allyl group and hydroxyl group in the molecule of the allylphenol compound (A) is within the above range, the flexural strength, flexural elastic modulus, and copper foil peel strength will be better, and the coefficient of thermal expansion will be better. Low, excellent thermal conductivity tendency.

The content of the allylphenol compound (A) is 10 to 50 parts by mass, preferably 10 to 35 parts by mass, more preferably 15 to 30 parts by mass relative to 100 parts by mass of resin solids in the resin composition for printed circuit boards. parts by mass. When the content of the allylphenol compound (A) is within the above range, the obtained cured product tends to have better flexibility, flexural strength, flexural modulus, thermal expansion coefficient, thermal conductivity, and copper foil peel strength.

[Maleimide compound (B)] The maleimide compound (B) is not particularly limited as long as it has one or more maleimide groups in the molecule, for example: N-phenylmaleimide Laimide, 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, maleimide compounds represented by the following formula (1), and prepolymers of these maleimide compounds , or a prepolymer of a maleimide compound and an amine compound. Among them, selected from bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethane Base-5-methyl-4-maleimide phenyl) methane, and at least one of the group consisting of maleimide compounds represented by the following formula (1) is more ideal, considering that it is easy to obtain and does not exist From the viewpoint of a resin composition having a clear glass transition temperature (no Tg), a maleimide compound represented by the following formula (1) is particularly preferable. By containing the above-mentioned maleimide compound (B), the obtained cured product tends to have a lower coefficient of thermal expansion and better heat resistance and glass transition temperature (Tg). The maleimide compound (B) may be used alone or in combination of two or more.

【chemical 10】

Here, in formula (1), R ₅ each independently represent a hydrogen atom or a methyl group, preferably a hydrogen atom. Also, in formula (1), n ₁ represents an integer of 1 or more, preferably an integer of 10 or less, more preferably an integer of 7 or less.

The content of the maleimide compound (B) is 40 to 80 parts by mass, preferably 40 to 70 parts by mass, more preferably 45 to 100 parts by mass of the resin solid content in the resin composition for printed circuit boards 65 parts by mass. When the content of the maleimide compound (B) is within the above range, the thermal expansion coefficient of the obtained cured product tends to be lower and the heat resistance tends to be better.

[Cyanate compound (C) and/or epoxy compound (D)] The resin composition for printed wiring boards of this embodiment contains a cyanate compound (C) and/or epoxy compound (D). By using the cyanate compound (C) and/or the epoxy compound (D) together with the above-mentioned allylphenol compound (A) and the maleimide compound (B), it is possible to make, for example, a prepreg In the cured product obtained by curing, there is no clear glass transition temperature (no Tg) and resin composition that can sufficiently reduce warpage of printed circuit boards, especially multilayer coreless substrates (achieve low warpage).

(Cyanate compound (C)) The cyanate compound (C) is not particularly limited, for example: naphthol aralkyl type cyanate represented by the following formula (2), novolac type cyanide represented by the following formula (3) Ester, biphenyl aralkyl cyanate, bis(3,5-dimethyl 4-cyanophenyl)methane, bis(4-cyanophenyl)methane, 1,3-dicyano Oxybenzene, 1,4-dicyanoxybenzene, 1,3,5-tricyanoxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6- Dicyanoxynaphthalene, 1,8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4, 4'-dicyanoxybiphenyl, bis(4-cyanoxyphenyl)ether, bis(4-cyanoxyphenyl)sulfide, bis(4-cyanoxyphenyl)sulfide, and 2, 2'-bis(4-cyanooxyphenyl)propane; prepolymers of these cyanate esters, etc. These cyanate compounds (C) can be used individually by 1 type or in combination of 2 or more types.

【chemical 11】

In formula (2), R ⁶ each independently represent a hydrogen atom or a methyl group, among which a hydrogen atom is preferred. In addition, in formula (2), n ₂ represents an integer of 1 or more. The upper limit of n ₂ is usually 10, preferably 6.

【Chemical 12】

In formula (3), R ⁷ each independently represent a hydrogen atom or a methyl group, among which a hydrogen atom is preferred. In addition, in formula (3), n ₃ represents an integer of 1 or more. The upper limit of n ₃ is usually 10, preferably 7.

Among them, the cyanate compound (C) preferably contains a naphthol aralkyl type cyanate selected from the formula (2), a novolac type cyanate represented by the formula (3), and a biphenyl aryl Preferably, one or more of the group consisting of alkyl-type cyanate is selected from naphthol aralkyl-type cyanate represented by formula (2) and novolak-type cyanate represented by formula (3) One or more of the group consisting of esters is more preferable. By using such a cyanate compound (C), there is a tendency that a cured product having better flame retardancy, higher curability, and lower thermal expansion coefficient can be obtained.

The manufacturing method of these cyanate ester compounds (C) is not specifically limited, A well-known method can be used as a synthetic method of a cyanate ester compound. Known methods are not particularly limited, for example, a method of reacting a phenolic resin and a cyanogen halide in a passive organic solvent in the presence of a basic compound, forming a salt of a phenolic resin and a basic compound in an aqueous solution, and then obtaining A method of two-phase interfacial reaction between the salt of cyanide and cyanogen halide.

The phenol resin used as the raw material of the cyanate compound (C) is not particularly limited, for example: naphthol aralkyl type phenol resin, novolak type phenol resin, biphenyl aralkyl type phenol resin represented by the following formula (9) resin.

【chemical 13】

In formula (9), R ⁸ each independently represent a hydrogen atom or a methyl group, among which a hydrogen atom is preferred. In addition, in formula (9), n ₄ represents an integer of 1 or more. The upper limit of _n4 is usually 10, preferably 6.

The naphthol aralkyl type phenolic resin represented by formula (9) can be obtained by condensing a naphthol aralkyl resin and cyanic acid. The naphthol aralkyl-type phenolic resin is not particularly limited, for example, naphthols such as α-naphthol and β-naphthol are mixed with p-xylylene glycol, α,α'-dimethoxy-p-xylene , And 1,4-two (2-hydroxy-2-propyl) benzene and other benzene reaction to get. The naphthol aralkyl type cyanate can be selected from those obtained by condensing a naphthol aralkyl resin with cyanic acid as described above.

The content of the cyanate compound (C) is preferably from 0 to 25 parts by mass, more preferably from 0 to 20 parts by mass, based on 100 parts by mass of resin solid content in the resin composition for printed wiring boards. When the content of the cyanate compound is within the above range, the heat resistance and chemical resistance of the obtained cured product tend to be better.

(Epoxy compound (D)) The epoxy compound (D) is not particularly limited as long as it has two or more epoxy groups in one molecule, for example: bisphenol A type epoxy resin, bisphenol E type epoxy resin Oxygen resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolak type epoxy resin, biphenyl type ring Oxygen resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, 3-functional phenol-type epoxy resin, 4-functional phenol-type epoxy resin, glycidyl ester-type epoxy resin, phenol aralkyl-type epoxy resin, Benzene aralkyl type epoxy resin, aralkyl novolak type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, containing isocyanurate Epoxy resins with ester rings, or their halides. Also, the epoxy compound (D) is more preferably a non-halogenated epoxy compound (non-halogen-containing epoxy compound, halogen-free epoxy compound). Moreover, when an allylphenol compound (A) contains an epoxy group, an epoxy compound (D) is a thing other than the allylphenol compound (A) which has an epoxy group.

The content of the epoxy compound (D) is preferably 0 to 25 parts by mass, more preferably 0 to 20 parts by mass, based on 100 parts by mass of resin solid content in the resin composition for printed wiring boards. When content of an epoxy compound (D) exists in the said range, there exists a tendency for the flexibility of the hardened|cured material obtained, copper foil peeling strength, chemical resistance, and desmear resistance to become better.

Also, as described above, when the resin composition for printed wiring boards of this embodiment contains the cyanate compound (C) and/or the epoxy compound (D), if the cyanate compound (C) and the epoxy compound are contained (D) Both, in the resin composition for printed circuit boards, the total content of the cyanate compound (C) and the epoxy compound (D) is preferably 5 to 45 parts by mass relative to 100 parts by mass of resin solid content, More preferably, it is 5-40 mass parts, More preferably, it is 10-30 mass parts. When the total content of the cyanate compound (C) and the epoxy compound (D) is within the above range, the obtained hardened product has flexibility, copper foil peel strength, heat resistance, chemical resistance, and desmear resistance. Sexually better tendencies. In addition, when the total content of the cyanate compound (C) and the epoxy compound (D) is within the above range, for example, there is no clear glass transition temperature (no clear glass transition temperature) in the cured product obtained by curing the prepreg. Tg) and can reduce the tendency of the resin composition of the warpage of the printed circuit board, especially the multilayer non-core substrate (to achieve low warpage).

[Filler (E)] The resin composition for printed circuit boards of this embodiment preferably further contains a filler (E). The filler (E) is not particularly limited, for example: an inorganic filler and an organic filler. Of the two, it is better to contain the inorganic filler, and it is better to use the organic filler together with the inorganic filler. Inorganic fillers are not particularly limited, for example: silicon dioxide such as natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, hollow silica; silicon compounds such as white carbon; titanium White, zinc oxide, magnesium oxide, zirconia and other metal oxides; boron nitride, condensed boron nitride, silicon nitride, aluminum nitride and other metal nitrides; metal sulfur oxides such as barium sulfate; aluminum hydroxide, hydroxide Aluminum heat-treated products (heat-treated aluminum hydroxide and subtracted part of the crystal water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate, zinc stannate, etc. Zinc compounds; 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, glass short fiber (including E glass, T glass, D glass, S glass, Q glass and other glass powders), insulating glass, spherical glass, etc. Also, the organic filler is not particularly limited, for example: rubber powder such as styrene type powder, butadiene type powder, acrylic type powder; core-shell type rubber powder; polysiloxane resin powder; polysiloxane rubber powder; Composite powder, etc. The filler (E) may be used alone or in combination of two or more.

Among them, it is selected from the group consisting of inorganic fillers, silicon dioxide, aluminum oxide, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, condensed boron nitride, silicon nitride, and aluminum nitride. At least one of them is preferred, and at least one of the group consisting of silica, alumina, and boehmite is more preferred. By using such a filler (E), there exists a tendency for the high rigidity and low warpage of the obtained hardened|cured material to become more favorable.

In the resin composition for printed circuit boards, the content of the filler (E) (especially the inorganic filler) is preferably 120 to 250 parts by mass, more preferably 150 to 230 parts by mass, based on 100 parts by mass of the solid content of the resin, and More preferably, it is 180-220 mass parts. When the content of the filler (E) is within the above range, the obtained cured product tends to have higher rigidity and lower warpage.

[Silane Coupling Agent and Wetting and Dispersing Agent] The resin composition for printed circuit boards of this embodiment may further contain a silane coupling agent and a wetting and dispersing agent. By containing the silane coupling agent and the wetting and dispersing agent, the dispersibility of the filler (E), the resin component, the filler (E), and the adhesive strength of the substrate described below tend to be better.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used in the surface treatment of inorganic substances, such as: γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ- Amino silane compounds such as aminopropyl trimethoxysilane; epoxy silane compounds such as γ-glycidoxypropyl trimethoxysilane; acrylic compounds such as γ-acryloxypropyl trimethoxysilane Silane-based compounds; cationic silane-based compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane-based compounds, etc. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

The wetting and dispersing agent is not particularly limited as long as it is a dispersing and stabilizing agent used in coating applications, for example: DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, W903 manufactured by BYK Chemie Japan Co., Ltd.

化合物、及具可聚合之不飽和基之化合物構成之群組中之1種或2種以上。藉由含有如此的其他樹脂等，有獲得之硬化物之銅箔剝離強度、彎曲強度、及彎曲彈性模數等更好的傾向。[Other Resins, etc.] The resin composition for printed circuit boards of this embodiment may further contain allyl group-containing compounds (hereinafter also referred to as "other resins") other than the above-mentioned allylphenol compound (A) if necessary. Allyl-containing compounds"), phenolic resins, oxetane resins, benzo

One or two or more of the group consisting of a compound and a compound having a polymerizable unsaturated group. By containing such other resin etc., there exists a tendency for the copper foil peeling strength, bending strength, and bending elastic modulus of the obtained hardened|cured product to become better.

[Other allyl group-containing compounds] Other allyl group-containing compounds are not particularly limited, for example: allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triene isocyanurate Propyl ester, diallyl phthalate, diallyl isophthalate, diallyl maleate, etc.

The content of other allyl group-containing compounds is preferably 0 to 50 parts by mass, more preferably 10 to 45 parts by mass, and still more preferably 100 parts by mass of resin solids in the resin composition for printed circuit boards. 15 to 45 parts by mass, more preferably 20 to 35 parts by mass. When the content of other allyl group-containing compounds is within the above range, the obtained cured product tends to have better flexural strength, flexural modulus, heat resistance, and chemical resistance.

[Phenolic resin] As long as the phenolic resin has two or more hydroxyl groups in one molecule, generally known ones can be used, and the type is not particularly limited. Specific examples thereof include bisphenol A phenolic resins, bisphenol E phenolic resins, bisphenol F phenolic resins, bisphenol S phenolic resins, phenol novolak resins, bisphenol A novolac phenolic resins, glycidyl phenolic resins, Ester type phenolic resin, aralkyl novolak type phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolak type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol Resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, grease Cyclic phenolic resins, polyol-type phenolic resins, phosphorus-containing phenolic resins, hydroxyl-containing polysiloxane resins, etc., but not particularly limited. These phenolic resins can be used individually by 1 type or in combination of 2 or more types. By containing such a phenolic resin, the obtained cured product tends to be more excellent in adhesiveness, flexibility, and the like.

The content of the phenolic resin is preferably from 0 to 99 parts by mass, more preferably from 1 to 90 parts by mass, and still more preferably from 3 to 80 parts by mass, based on 100 parts by mass of resin solids in the resin composition for printed wiring boards. When the content of the phenolic resin is within the above range, the obtained cured product tends to be more excellent in adhesiveness, flexibility, and the like.

[Oxetane Resin] As the oxetane resin, generally known ones can be used, and the type is not particularly limited. Specific examples thereof include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyl Alkyl oxetane such as oxetane, 3-methyl-3-methoxymethyl oxetane, 3,3'-bis(trifluoromethyl)perfluorooxetane Butane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name manufactured by Toagosei), OXT-121 (trade name manufactured by Toa Gosei Co., Ltd.) and the like. These oxetane resins may be used alone or in combination of two or more. By containing such an oxetane resin, the obtained cured product tends to be more excellent in adhesiveness, flexibility, and the like.

The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 parts by mass relative to 100 parts by mass of resin solids in the resin composition for printed circuit boards. ~80 parts by mass. When content of an oxetane resin exists in the said range, the adhesiveness, flexibility, etc. of the obtained hardened|cured material tend to be more excellent.

化合物] 苯并

化合物只要是在1分子中有2個以上之二氫苯并

環之化合物即可，可使用一般公知者，種類無特殊限制。其具體例可列舉雙酚A型苯并

BA-BXZ(小西化學製商品名)雙酚F型苯并

BF-BXZ(小西化學製商品名)、雙酚S型苯并

BS-BXZ(小西化學製商品名)等。該等苯并

化合物可使用1種或混用2種以上。藉由含有如此的苯并

化合物，有獲得之硬化物之阻燃性、耐熱性、低吸水性、低介電等更優良的傾向。[Benzo

compound] benzo

As long as the compound has two or more dihydrobenzos in one molecule

A ring compound is sufficient, and generally known compounds can be used, and the type is not particularly limited. Specific examples thereof include bisphenol A benzo

BA-BXZ (trade name manufactured by Konishi Chemical) bisphenol F type benzo

BF-BXZ (trade name manufactured by Konishi Chemical), bisphenol S-type benzo

BS-BXZ (trade name manufactured by Konishi Chemical), etc. The benzos

These compounds may be used alone or in combination of two or more. By containing such benzos

Compounds tend to have better flame retardancy, heat resistance, low water absorption, and low dielectric properties of the obtained hardened product.

化合物之含量，相對於印刷電路板用樹脂組成物中之樹脂固體成分100質量份較佳為0～99質量份，更佳為1～90質量份，又更佳為3～80質量份。苯并

化合物之含量藉由為上述範圍內，有獲得之硬化物之耐熱性等更優良的傾向。Benzo

The content of the compound is preferably from 0 to 99 parts by mass, more preferably from 1 to 90 parts by mass, and still more preferably from 3 to 80 parts by mass, based on 100 parts by mass of resin solids in the resin composition for printed wiring boards. Benzo

When the content of the compound is within the above range, the obtained cured product tends to be more excellent in heat resistance and the like.

[Compound having a polymerizable unsaturated group] As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the type thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) 2-Hydroxypropyl Acrylate, Polypropylene Glycol Di(meth)acrylate, Trimethylolpropane Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Neopentylthritol Tetra(meth)acrylate (meth)acrylates of monohydric or polyhydric alcohols such as di-neopentylthritol hexa(meth)acrylate; bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy Epoxy (meth)acrylates such as (meth)acrylates; benzocyclobutene resins; (bis)maleimide resins, etc. These compounds having a polymerizable unsaturated group can be used alone or in combination of two or more. By containing such a compound having a polymerizable unsaturated group, the obtained cured product tends to be more excellent in heat resistance, corrosion resistance, and the like.

The content of the compound having a polymerizable unsaturated group is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 100 parts by mass of resin solids in the resin composition for printed circuit boards. It is 3-80 mass parts. When the content of the compound having a polymerizable unsaturated group is within the above range, the obtained cured product tends to be more excellent in heat resistance, corrosion resistance, and the like.

啉、三乙醇胺、三乙二胺、四甲基丁二胺、N-甲基哌啶等三級胺類；苯酚、二甲酚、甲酚、間苯二酚、兒茶酚等苯酚類；環烷酸鉛、硬脂酸鉛、環烷酸鋅、辛酸鋅、油酸錫、蘋果酸二丁基錫、環烷酸錳、環烷酸鈷、乙醯基丙酮鐵等有機金屬鹽；此等有機金屬鹽溶於苯酚、雙酚等含羥基之化合物而成者；氯化錫、氯化鋅、氯化鋁等無機金屬鹽；二辛基氧化錫、其他之烷基錫、烷基氧化錫等有機錫化合物等。該等之中，三苯基咪唑會促進硬化反應且有熱膨脹率優良的傾向，故特別理想。[Hardening Accelerator] The resin composition for a printed wiring board according to this embodiment may further contain a curing accelerator. The hardening accelerator is not particularly limited, for example: imidazoles such as triphenylimidazole; Organic peroxides such as tributyl ester; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N -lutidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methyl

Tertiary amines such as morphine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, etc.; phenols such as phenol, xylenol, cresol, resorcinol, catechol, etc.; Lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate and other organic metal salts; these organic Metal salts dissolved in hydroxyl-containing compounds such as phenol and bisphenol; tin chloride, zinc chloride, aluminum chloride and other inorganic metal salts; dioctyl tin oxide, other alkyl tin, alkyl tin oxide, etc. Organotin compounds, etc. Among them, triphenylimidazole is particularly preferable since it tends to accelerate the hardening reaction and has an excellent thermal expansion coefficient.

[Solvent] The resin composition for printed wiring boards of this embodiment may further contain a solvent. By containing a solvent, the viscosity at the time of preparation of the resin composition for printed wiring boards falls, and it tends to improve handleability and the impregnation property to the base material mentioned later.

The solvent is not particularly limited as long as it can dissolve part or all of the resin components in the resin composition for printed circuit boards, for example: ketones such as acetone, methyl ethyl ketone, and methyl cellulosulfone; aromatic hydrocarbons such as toluene and xylene Classes; Amides such as dimethylformamide; Propylene glycol monomethyl ether and its acetate, etc. A solvent may be used individually by 1 type, and may use 2 or more types together.

[Manufacturing Method of Resin Composition for Printed Wiring Board] The manufacturing method of the resin composition for printed wiring board of this embodiment is not particularly limited, for example, a method of sequentially blending each component in a solvent and stirring thoroughly. At this time, well-known treatments such as stirring, mixing, and kneading can be performed in order to dissolve or disperse each component uniformly. Specifically, the dispersibility of the filler (E) with respect to the resin composition for printed wiring boards can be made better by carrying out the stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity. The aforementioned stirring, mixing, and kneading treatments can be appropriately carried out using known devices such as ball mills, bead mills, etc. for the purpose of mixing, or orbital or self-rotating mixing devices, for example.

Moreover, when preparing the resin composition for printed wiring boards of this embodiment, an organic solvent can be used as needed. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition for printed wiring boards. Specific examples thereof are as described above.

[Characteristics of the resin composition for printed wiring boards] The resin composition for printed wiring boards of this embodiment is a cured product obtained by thermosetting a prepreg containing the composition and a base material at 230°C for 100 minutes. It is preferable to meet the numerical value ranges of the physical parameters of the mechanical properties represented by the following formulas (4) to (8), and more ideally to meet the numerical ranges of the physical parameters of the mechanical properties represented by the following formulas (4A) to (8A).

E'(200℃)/E'(30℃)≦0.90...(4) E'(260℃)/E'(30℃)≦0.85...(5) E'(330℃)/E'(30℃ )≦0.80...(6) E"max/E'(30℃)≦3.0%...(7) E"min/E'(30℃)≧0.5%...(8) 0.40≦E'(200℃)/ E'(30℃)≦0.90...(4A) 0.40≦E'(260℃)/E'(30℃)≦0.85...(5A) 0.40≦E'(330℃)/E'(30℃)≦0.80 …(6A) 0.5%≦E”max/E'(30℃)≦3.0%…(7A) 3.0%≧E”min/E’(30℃)≧0.5%…(8A)

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

In the past, regarding the warping behavior of printed circuit boards, it was considered that the hardened prepreg can achieve a large thermal storage elastic modulus and a resin composition with a high elastic modulus retention rate, but this is not necessarily the case. , the values of the physical parameters of the hardened product obtained by thermally curing the prepreg at 230°C and 100 minutes for mechanical properties are within the range of the above formulas (4) to (8), preferably the formula Within the range of (4A) to (8A), the glass transition temperature (Tg) can be sufficiently increased, and the warpage of laminated boards, metal foil-clad laminated boards, printed circuit boards, especially multilayer coreless substrates can be sufficiently increased. decrease.

In other words, the numerical values of the physical parameters of the mechanical properties of the cured product obtained by thermally curing the prepreg at 230°C and 100% are within the range of the above formulas (4) to (8), preferably Within the range of formulas (4A) to (8A), ideally there is no clear glass transition temperature (no Tg), and the warpage of printed circuit boards (especially multilayer coreless substrates) can be sufficiently reduced (to achieve low warpage song). That is, if the formulas (7) and (8) related to the loss elastic modulus are satisfied, and if the formulas (7A) and (8A) are better satisfied, it can be said that there is no clear glass transition temperature (Tg) (no Tg) as Synonymous, if the cured product only conforms to formulas (7) and (8), it is better to conform to formulas (7A) and (8A) and not to conform to formulas (4)～(6), preferably not to conform to formulas (4A)～(6A) ), the loss elastic modulus itself is small and not easy to elongate, but when it is made into a printed circuit board, the difficulty of elongation will make it difficult to achieve low warpage. On the other hand, if the cured product not only conforms to formulas (7) and (8), it is preferably formulas (7A) and (8A), and it also conforms to formulas (4) to (8), preferably formulas (4A) and (8A), then Since there is no Tg, it is difficult to elongate and there is a tendency to achieve low warpage of printed circuit boards.

The method for measuring the mechanical properties (storage elastic modulus E' and loss elastic modulus E") of the cured product of the prepreg is not particularly limited, for example, the following methods can be used. That is, on the upper and lower sides of a prepreg sheet Configure copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12μm), and perform lamination forming (thermal curing) at a pressure of 30kgf/cm ² and a temperature of 230°C for 100 minutes to obtain a predetermined insulating layer thickness. Copper-clad laminated board. Then cut the obtained copper-clad laminated board into a size of 5.0mm×20mm with a dicing saw, and remove the copper foil on the surface by etching to obtain a sample for measurement. Use this sample for measurement according to JIS C6481 Using a dynamic viscoelasticity analyzer (manufactured by TA Instruments), mechanical properties (storage elastic modulus E' and loss elastic modulus E") can be measured by the DMA method. At this time, the average value of n=3 can also be obtained.

[Applications] The resin composition for printed wiring boards of this embodiment is suitable for use as prepregs, resin sheets, insulating layers, laminates, metal foil-clad laminates, printed wiring boards, or multilayer printed wiring boards. Prepregs, resin sheets, laminates, metal foil-clad laminates, and printed circuit boards (including multilayer printed circuit boards) will be described below.

[Prepreg] The prepreg of the present embodiment includes a base material and a resin composition for a printed wiring board impregnated or coated on the base material. The manufacturing method of the prepreg can be carried out according to the usual method, without special restrictions. For example, after impregnating or coating the resin composition for printed circuit boards in this embodiment on the substrate, heating it in a dryer at 100-200°C for 1-30 minutes to make it semi-hardened (B-staged) ), the prepreg of this embodiment can be produced.

In the prepreg of this embodiment, the content of the resin composition for printed circuit boards (including the filler (E)) is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, relative to the total amount of the prepreg. % by volume, and more preferably 40 to 80% by volume. When the content of the resin composition is within the above range, the formability tends to be better.

唑(poly(p-phenylene-2,6-benzobisoxazole)(Zylon(註冊商標)、東洋紡(股)公司製)、聚醯亞胺等有機纖維。此等基材可單獨使用1種也可併用2種以上。The substrate is not particularly limited, and various known substrates used in printed circuit board materials can be appropriately selected according to the intended use and performance. Substrates include, for example, glass substrates, inorganic substrates other than glass, organic substrates, etc. Among them, glass substrates are particularly preferable in view of high rigidity and thermal dimensional stability. Specific examples of fibers constituting these substrates are not particularly limited, and glass substrates, for example, can be selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. One or more types of glass fibers. In addition, examples of inorganic substrates other than glass include inorganic fibers other than glass such as quartz. In addition, examples of the organic base material include poly-paraphenylene terephthalamide (KEVLAR (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene terephthalamide, Wholly aromatic polyamides such as copoly-(paraphenlene/3,4-oxydiphenylene terephthalamide) (manufactured by Technora (registered trademark), TEIJIN TECHNO PRODUCTS Co., Ltd.) Amines; polyesters such as 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zxion (registered trademark, manufactured by KB seiren); polyparaphenylenebenzoic acid pair

Poly(p-phenylene-2,6-benzobisoxazole) (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide and other organic fibers. These substrates can be used alone or in combination. more than one species.

The shape of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, cut mats, surface mats, and the like. The weaving method of the weaving fabric is not particularly limited. For example, plain weave, basket weave, twill weave, etc. are known, and these known methods can be appropriately selected according to the intended use and performance. In addition, glass woven fabrics that have been subjected to fiber opening treatment or surface-treated with silane coupling agents can be ideally used. The thickness and mass of the base material are not particularly limited, and generally about 0.01 to 0.3 mm is suitable. Especially from the viewpoint of strength and water absorption, the base material is ideally a glass fabric with a thickness of less than 200 μm and a mass of less than 250 g/m2, and a glass fabric made of glass fibers of E glass, S glass, and T glass is more ideal.

Also, as mentioned above, the prepreg of this embodiment, if the hardened product obtained by thermal curing at 230°C and 100% of the conditions satisfies the above formulas (4) to (8), it is preferably the formula (4A) to (8A) represents the numerical value range of physical parameters related to mechanical properties, then the laminated board, metal foil clad laminated board, printed circuit board, or multilayer printed circuit board does not have a clear glass transition temperature (no Tg) and has It is preferable because it can sufficiently reduce warpage (achieve low warpage).

[Resin Sheet] The resin sheet according to this embodiment has a sheet-like base material (support body), and the above-mentioned resin composition for printed wiring boards laminated on one or both sides of the sheet-like base material. The resin sheet can be produced by directly coating a thermosetting resin (including a filler (E)) used in a prepreg or the like on a support such as a metal foil or a film, and drying the resin sheet.

The sheet base material is not particularly limited, and known ones that can be used as various printed circuit board materials can be used. Such as 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 foil, etc. Among them, electrolytic copper foil and PET film are preferred.

Coating method, for example: the method of dissolving the resin composition for printed circuit boards of this embodiment in a solvent to obtain a solution, and then coating it on a sheet-shaped substrate with a coating rod, die coater, doctor blade, Baker applicator, etc. .

The resin sheet is preferably obtained by applying the above-mentioned resin composition for a printed wiring board to a sheet-shaped base material, and then semi-curing (B-staging). Specifically, for example, after coating the above-mentioned resin composition for printed circuit boards on a sheet-like base material such as copper foil, heating it in a dryer at 100 to 200°C for 1 to 60 minutes is used to semi-cure and dry it. A method of manufacturing a resin sheet, etc. The adhesion amount of the resin composition for printed circuit boards to the sheet-like substrate is preferably in the range of 1 to 300 μm based on the resin thickness of the resin sheet.

[Laminate and Metal Foil-Clad Laminate] The laminate of this embodiment has at least one prepreg of this embodiment and/or the resin sheet of this embodiment laminated. Also, the metal foil-clad laminate of this embodiment has: the laminate of this embodiment (that is, at least one sheet or more of the above-mentioned prepreg of this embodiment and/or the above-mentioned prepreg of this embodiment are laminated. resin sheet), and the metal foil (conductor layer) arranged on one or both sides of the laminated board.

The conductor layer can be metal foils such as copper and aluminum. The metal foil used here is not particularly limited as long as it is used in printed circuit board materials, and known copper foils such as rolled copper foil and electrolytic copper foil are preferred. Also, the thickness of the conductive layer is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

The forming method and forming conditions of the laminated board or the metal foil-clad laminated board are not particularly limited, and methods and conditions for general laminated boards and multilayer boards for printed circuit boards can be used. For example, multi-stage presses, multi-stage vacuum presses, continuous forming machines, autoclave forming machines, etc. can be used for forming laminated boards or metal foil-clad laminated boards. In addition, in forming laminates or metal foil-clad laminates (lamination molding), generally, the temperature is 100-300°C, the pressure is 2-100kgf/cm ² , and the heating time is 0.05-5 hours. range. Furthermore, post-curing may be performed at a temperature of 150 to 300° C. if necessary. Especially when using a multi-stage pressing machine, consider the viewpoint of fully accelerating the hardening of the prepreg/or resin sheet. The temperature is 200°C-250°C, the pressure is 10-40kgf/cm ² , and the heating time is 80-130 minutes. The temperature is 215°C. ～235℃, pressure 25～35kgf/cm ² , and heating time 90 minutes～120 minutes are more ideal. In addition, a multilayer board can also be obtained by combining the above-mentioned prepreg and/or resin sheet with a wiring board for an inner layer separately and laminating them.

[Printed Wiring Board] A printed wiring board according to this embodiment has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the above-mentioned resin composition for a printed wiring board. For example, by forming a predetermined wiring pattern on the above-mentioned metal foil-clad laminate, it can be ideally used as a printed circuit board. As described above, there are metal foil-clad laminates using the resin composition for printed wiring boards of this embodiment that do not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieve low warpage) Tendency, so it is particularly effective as a printed circuit board that requires such performance.

The printed circuit board of this embodiment can be manufactured specifically, for example by the following method. First, the above-mentioned metal foil-clad laminate (copper-clad laminate, etc.) is prepared. Etching is performed on the surface of the metal foil-clad laminate to form an inner layer circuit and make an inner layer substrate. For the surface of the inner layer circuit of the inner layer substrate, if necessary, perform surface treatment in order to improve the adhesion strength, and then laminate the required number of the above-mentioned prepreg and/or resin sheet on the surface of the inner layer circuit, and then laminate it on the outside The metal foil for the outer circuit is integrally formed by heating and pressing (lamination forming). In this manner, a multilayer laminate in which a base material and an insulating layer made of a cured product of a thermosetting resin composition are formed between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. The method of lamination forming and its forming conditions are the same as those of the above-mentioned laminate or metal foil-clad laminate. Then, after perforating the through-holes and vias to this multilayer laminate, a desmearing process is performed to remove the smear which is the residue of the resin derived from the resin component contained in the cured product layer. Afterwards, a plated metal film is formed on the wall of the hole to conduct the inner circuit and the metal foil for the outer circuit, and then the metal foil for the outer circuit is etched to form an outer circuit to manufacture a printed circuit board.

For example: the above-mentioned prepreg (base material and the above-mentioned resin composition for printed wiring board attached to the base material), resin composition layer of metal foil-clad laminate (layer composed of the above-mentioned resin composition for printed wiring board) , constituting the above-mentioned insulating layer containing the resin composition for a printed circuit board.

Also, when the metal foil-clad laminate is not used, a conductor layer serving as a circuit may be formed on the above-mentioned prepreg or the above-mentioned resin composition for a printed wiring board, and a printed wiring board may be produced. In this case, electroless plating may also be used for the formation of the conductor layer.

Furthermore, the printed circuit board of the present embodiment, as shown in FIG. 9, preferably has a plurality of insulating layers and a plurality of conductor layers, and the plurality of insulating layers are composed of a first insulating layer (1) and a second insulating layer (2). The first insulating layer (1) is formed by laminating at least one sheet or more of at least one selected from the group consisting of the above-mentioned prepreg and resin sheet, and the second insulating layer (2) is formed on the first The insulating layer (1) is formed by laminating at least one sheet of at least one selected from the group consisting of the above-mentioned prepreg and resin sheet in the single-sided direction (the direction below the figure); the plurality of conductor layers are formed by the second 1 conductor layer (3) and a 2nd conductor layer (3), the 1st conductor layer (3) is arranged between each insulation layer of these many insulation layers (1, 2), and the 2nd conductor layer (3 ) is configured on the outermost layer of most of these insulating layers (1,2).

According to the knowledge of the inventors of the present application, a general laminate is, for example, laminated on both sides of at least one selected from the group consisting of a core substrate, that is, a prepreg and a resin sheet, and the other selected from the prepreg. At least one of the group consisting of a prepreg and a resin sheet is used to form a multilayer printed circuit board. The first insulating layer (1) is selected from the group consisting of a prepreg and a resin sheet, and at least one of the group consisting of a prepreg and a resin sheet is laminated on one side to form another second insulating layer (2). The other is selected from a prepreg and a resin It is especially effective for coreless multilayer printed circuit boards (multilayer coreless substrates) manufactured by at least one of the group consisting of chips.

In other words, when the prepreg, the resin sheet, and the resin composition for printed circuit boards of this embodiment are used in printed circuit boards, the amount of warpage can be effectively reduced. Although there is no particular limitation, among printed circuit boards, Multilayer coreless substrates are especially effective. That is to say, ordinary printed circuit boards generally have a symmetrical structure on both sides, which tends not to warp easily, while multi-layer coreless substrates tend to have an asymmetric structure on both sides, so they are easier to warp than ordinary printed circuit boards. Propensity. Therefore, by using the prepreg, the resin sheet, and the resin composition for a printed circuit board of this embodiment, it is possible to effectively reduce the amount of warping of a multilayer coreless substrate that has a tendency to warp conventionally.

9 shows a structure in which two second insulating layers (2) are stacked on one first insulating layer (1) (that is, a structure in which most insulating layers are three layers), but the second insulating layer (2 ) may be 1 piece or 2 or more pieces. Therefore, the first conductor layer (3) may be one layer or two or more layers.

As above, in the printed wiring board of the present embodiment having the above-mentioned structure, the thermal storage modulus of elasticity, loss The mechanical properties such as modulus of elasticity are controlled in a specific range suitable for low warpage, so that there is no clear glass transition temperature (no Tg), and the warpage of printed circuit boards, especially multilayer coreless substrates, can be sufficiently reduced (to achieve low Warpage), so it can be effectively used as a printed circuit board for semiconductor packages and a multilayer coreless substrate. [Example]

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

[Synthesis Example 1] Synthesis of α-naphthol aralkyl type cyanate compound (SN495VCN) In the reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236g/eq., Xinri Manufactured by Tie Chemical Co., Ltd.: the number of repeating units containing naphthol aralkyl groups n is 1-5.) 0.47 mol (OH group conversion) is dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine is added to this solution. While maintaining the temperature at -10°C, 300 g of a 0.93 mole cyanogen chloride solution in chloroform was added dropwise to the reactor over a period of 1.5 hours, and stirred for 30 minutes after the dropwise addition was completed. Then, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise into the reactor, and stirred for 30 minutes to complete the reaction. After the by-produced triethylamine hydrochloride was filtered off from the reaction liquid fraction, the obtained filtrate was washed with 500 ml of 0.1N hydrochloric acid, and then washed with 500 ml of water four times. After it is dried with sodium sulfate, evaporate at 75 DEG C, carry out vacuum degassing at 90 DEG C again, obtain the α-naphthol aralkyl type cyanate compound represented by above formula (2) (the ^R in the formula are all hydrogen atoms). The obtained α-naphthol aralkyl type cyanate compound was analyzed by infrared absorption spectrum, and the absorption of cyanate group was confirmed around 2264 cm ^-1 .

[Example 1] 24.1 parts by mass of diallyl bisphenol A (DABPA, manufactured by Daiwa Chemical Industry Co., Ltd., hydroxyl equivalent: 154 g/eq.), which is an allyl phenol compound (A), maleyl Amine compound (B) (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide equivalent: 186 g/eq.) 60.9 parts by mass, α-naphthalene in Synthesis Example 1 of (C) cyanate compound Phenol aralkyl type cyanate compound (SN495VCN, cyanate ester equivalent: 261g/eq.) 5.0 parts by mass, epoxy compound (D) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 328g /eq.) 10.0 parts by mass, 200 parts by mass of silicon dioxide slurry (SC-2050MB, manufactured by Admatechs Co., Ltd.) as a filler (E), and homopolysiloxane composite powder (KMP-605M, manufactured by Shin-Etsu Chemical Co., Ltd. )) 25 parts by mass, silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) 5 parts by mass, and triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) 0.5 parts by mass as a hardening accelerator Mix and dilute with methyl ethyl ketone to obtain a varnish. This varnish was dip-coated on E-glass woven fabric, and heated and dried at 160° C. for 3 minutes to obtain a prepreg with a resin composition content of 73% by volume for printed circuit boards.

[Example 2] Change the allylphenol compound (A) (DABPA) to 19.9 parts by mass, the maleimide compound (B) (BMI-2300) to 50.1 parts by mass, the cyanate compound (C) (SN495VCN) was changed to 10.0 parts by mass, and epoxy compound (D) (NC-3000FH) was changed to 20.0 parts by mass. In addition, according to the same method as in Example 1, the content of the resin composition for printed circuit boards was 73 volumes. % of prepreg.

[Example 3] Instead of using the cyanate compound (C) (SN495VCN), the epoxy compound (D) (NC-3000FH) was changed to 15.0 parts by mass, and the printed circuit was obtained in the same manner as in Example 1 except that A prepreg with a resin composition content of 73% by volume for panels.

[Example 4] The cyanate compound (C) (SN495VCN) was changed to 15.0 parts by mass, and the epoxy compound (D) (NC-3000FH) was not used. In addition, the printed circuit was obtained in the same way as in Example 1 A prepreg with a resin composition content of 73% by volume for panels.

[Comparative Example 1] The allylphenol compound (A) (DABPA) was changed to 28.4 parts by mass, the maleimide compound (B) (BMI-2300) was changed to 71.6 parts by mass, and the cyanate compound (C ) (SN495VCN), except that the epoxy compound (D) (NC-3000FH) was not used, and in the same manner as in Example 1, a prepreg with a resin composition content of 73% by volume for printed circuit boards was obtained.

[Comparative Example 2] Allylphenol compound (A) (DABPA) was changed to 60.0 parts by mass, maleimide compound (B) (BMI-2300) was changed to 32.1 parts by mass, cyanate compound (C) ( SN495VCN) was changed to 2.6 parts by mass, and epoxy compound (D) (NC-3000FH) was changed to 5.3 parts by mass. In addition, according to the same method as in Example 1, a resin composition content of 73% by volume for printed circuit boards was obtained. prepreg.

[Comparative Example 3] Allylphenol compound (A) (DABPA) was changed to 12.7 parts by mass, maleimide compound (B) (BMI-2300) was changed to 32.1 parts by mass, cyanate compound (C) ( SN495VCN) was changed to 50.0 parts by mass, and the epoxy compound (D) (NC-3000FH) was changed to 5.2 parts by mass. In addition, according to the same method as in Example 1, the content of the resin composition for printed circuit boards was 73% by volume. The prepreg.

[Comparative Example 4] The allylphenol compound (A) (DABPA) was changed to 5.0 parts by mass, the maleimide compound (B) (BMI-2300) was changed to 85.0 parts by mass, the cyanate compound (C) ( SN495VCN) was changed to 5.0 parts by mass, and the epoxy compound (D) (NC-3000FH) was changed to 5.0 parts by mass. In addition, according to the same method as in Example 1, the content of the resin composition for printed circuit boards was 73% by volume. The prepreg.

[Measurement and evaluation of physical properties] Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 4, samples for measurement and evaluation of physical properties were prepared according to the procedures shown in the following items, and the mechanical properties (storage elastic modulus, and loss elastic modulus), physical parameters of mechanical properties, glass transition temperature (Tg), and warpage (three types) in formulas (4)-(8) and formulas (4A)-(8A). The results of the examples are summarized in Table 1, and the results of the comparative examples are summarized in Table 2.

[Mechanical properties] Copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) was placed on the upper and lower sides of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf/ cm ² and a temperature of 230°C for 100 minutes of lamination forming (thermosetting) to obtain a copper-clad laminate with an insulating layer thickness of 0.1mm. The obtained copper-clad laminate was cut into a size of 20 mm×5 mm with a dicing saw, and the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the 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) according to JISC6481 (average value of n=3).

[Glass transition temperature (Tg)] Copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) was placed on the upper and lower sides of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, Lamination forming (thermosetting) was performed for 100 minutes at a pressure of 30kgf/cm ² and a temperature of 230°C to obtain a copper-clad laminate with an insulating layer thickness of 0.1mm. The obtained copper-clad laminate was cut into a size of 12.7×2.5 mm with a dicing saw, and the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the glass transition temperature (Tg) (average value of n=3) was measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) according to JISC6481.

[Warpage amount: bimetallic method] First, copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm), lamination forming was performed at a pressure of 30kgf/cm ² and a temperature of 220°C for 120 minutes to obtain a copper-clad laminate. Then, the above copper foil was removed from the obtained copper clad laminate. Next, one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was further arranged on one side of the laminate from which the copper foil was removed, and the above-mentioned copper foil (3EC-VLP, Mitsui Manufactured by Metal Mining Co., Ltd., thickness 12 μm), lamination molding was carried out at a pressure of 30 kgf/cm ² and a temperature of 220° C. for 120 minutes to obtain a copper-clad laminate. Furthermore, the said copper foil was removed from the obtained copper-clad laminated board, and the laminated board was obtained. And, cut out a strip-shaped 20mm×200mm sheet from the obtained laminated sheet, make the surface of the prepreg laminated on the second sheet face up, and measure the maximum amount of warpage at both ends in the longitudinal direction with a metal ruler. Value, define this average value as the "warpage" measured by the bimetallic method.

[Warpage amount: multi-layer coreless substrate] First, as shown in Figure 1, an ultra-thin copper foil (b1) with a carrier (MT18Ex, Mitsui Metal Mining Co., Ltd. ) made of carrier copper foil with a thickness of 5 μm) is arranged facing the prepreg side, and the prepregs (c1) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 are further arranged on it, and copper is further arranged thereon. Foil (d) (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12μm) was laminated at a pressure of 30kgf/cm ² and a temperature of 220°C for 120 minutes to obtain a copper-clad foil as shown in Figure 2 Laminates.

Next, the copper foil (d) of the obtained copper-clad laminate shown in FIG. 2 is etched into a predetermined wiring pattern as shown in FIG. 3 to form a conductor layer (d'). Then, on the laminate shown in FIG. 3 with the conductor layer (d') formed, as shown in FIG. 4, the prepregs (c2) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were placed, An ultra-thin copper foil (b2) with a carrier (MT18Ex, manufactured by Mitsui Metal Mining Co., Ltd., thickness 5 μm) is further placed on it, and laminated at a pressure of 30kgf/cm ² and a temperature of 230°C for 120 minutes. A copper clad laminate as shown in FIG. 5 was obtained.

Next, the carrier copper foil of the ultra-thin copper foil with carrier (b1) arranged on the support (a) (hardened prepreg for support) in the copper-clad laminate shown in FIG. The thin copper foil is peeled off, as shown in Figure 6, the two laminated boards are peeled off from the support (a), and the carrier is further removed from the ultra-thin copper foil (b2) attached to the carrier on the upper part of each laminated board. Copper foil peeled off. Then, the ultra-thin copper foils above and below each of the obtained laminates were processed by a laser processing machine, and predetermined through holes (v) were formed by electroless copper plating as shown in FIG. 7 . Then, for example, as shown in FIG. 8, a predetermined wiring pattern is etched to form a conductor layer to obtain a multilayer coreless substrate panel (size: 500mm×400mm). Then, the amount of warping at 8 points in total at the 4 corners and the central part of the 4 sides of the obtained panel was measured with a metal ruler, and the average value was defined as the "warping amount" of the panel of the multilayer coreless substrate.

[Substrate shrinkage before and after the reflow step] Copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) was placed on the upper and lower sides of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, Lamination molding was performed for 120 minutes under conditions of a pressure of 30 kgf/cm ² and a temperature of 220° C. to obtain a copper-clad laminate. Then, the obtained copper-clad laminated board was uniformly subjected to 9 points of drilling processing in a grid form with a drill, and then the above-mentioned copper foil was removed.

Then, first, the distance (distance I) between the holes of the laminated board from which the copper foil was removed was measured. Then, for this laminated board, a SALAMANDER reflow device was used to set 260°C as the highest temperature to perform reflow treatment. After that, the distance between the holes in the laminate (distance II) was measured again. Then, substitute the measured distance I and distance II into the following formula (I) to obtain the dimensional change rate of the reflowed substrate, and define this value as the shrinkage rate of the substrate before and after the reflow step. ((distance I)-(distance II))/distance I×100...Formula (I)

【Table 1】

[產業利用性]【Table 2】

[Industrial Utilization]

The resin composition for printed wiring boards of this embodiment is industrially applicable as a material for prepregs, resin sheets, laminates, metal foil-clad laminates, printed wiring boards, or multilayer printed wiring boards. In addition, this application is based on Japanese Patent Application No. 2016-255272 filed on December 28, 2016, and its description is incorporated herein.

1‧‧‧First insulating layer 2‧‧‧Second insulating layer 3‧‧‧conductor layera‧‧‧support b1‧‧‧ultra-thin copper foil b2‧‧‧ultra-thin copper foil c1‧‧‧prepreg Body c2‧‧‧prepreg d‧‧‧copper foil d'‧‧‧conductor layer V‧‧‧through hole

FIG. 1 shows a processing flow chart of an example of a procedure for manufacturing a panel of a multilayer coreless substrate (however, the method of manufacturing a multilayer coreless substrate is not limited to this. The same applies to FIGS. 2 to 8 below.). FIG. 2 shows a process flow diagram of an example of a procedure for fabricating a multilayer coreless substrate panel. Fig. 3 shows a process flowchart of an example of a procedure for fabricating a multilayer coreless substrate panel. FIG. 4 shows a process flowchart of an example of a procedure for fabricating a multilayer coreless substrate panel. Fig. 5 shows a process flowchart of an example of a procedure for fabricating a multilayer coreless substrate panel. Fig. 6 shows a process flowchart of an example of a procedure for fabricating a multilayer coreless substrate panel. Fig. 7 shows a process flowchart of an example of a procedure for fabricating a multilayer coreless substrate panel. Fig. 8 shows a process flowchart of an example of a procedure for fabricating a multilayer coreless substrate panel. Fig. 9 is a partial cross-sectional view showing the structure of an example of a multilayer coreless substrate panel.

Claims (21)

A resin composition for printed circuit boards, containing an allylphenol compound (A), a maleimide compound (B), and a cyanate compound (C) and/or an epoxy compound (D), relative to the The content of the allylphenol compound (A) is 10 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition for printed circuit boards relative to 100 parts by mass of the resin solid content in the resin composition for printed circuit boards. parts by mass, the content of the maleimide compound (B) is 45 to 80 parts by mass, and the cured product of the resin composition for printed circuit boards does not have a clear glass transition temperature, and the glass transition temperature is based on JIS C6481 and above The dynamic viscoelasticity analyzer is measured by the DMA method. The resin composition for printed circuit boards as claimed in claim 1, wherein, relative to 100 parts by mass of resin solids in the resin composition for printed circuit boards, the cyanate compound (C) and the epoxy compound The total content of (D) is 5-45 mass parts. Such as the resin composition for printed circuit boards of claim 1 or 2 of the patent scope, wherein, relative to 100 parts by mass of resin solids in the resin composition for printed circuit boards, the content of the cyanate compound (C) is 0~25 parts by mass. Such as the resin composition for printed circuit boards in claim 1 or 2 of the scope of the patent application, wherein, Content of this epoxy compound (D) is 0-25 mass parts with respect to 100 mass parts of resin solid content in this resin composition for printed wiring boards. If the resin composition for printed circuit boards in claim 1 or 2 of the scope of the patent application, it further contains a filler (E). The resin composition for printed circuit boards as claimed in claim 5, wherein the filler (E) is at least one selected from the group consisting of silica, alumina, and boehmite. For example, the resin composition for printed circuit boards of claim 5, wherein the content of the filler (E) is 120 to 250 parts by mass relative to 100 parts by mass of resin solids in the resin composition for printed circuit boards share. The resin composition for printed circuit boards as claimed in claim 1 or 2 of the patent scope, wherein the allylphenol compound (A) includes a compound represented by any one of the following formulas (I) to (III):

In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, or phenyl; [chemical 2]

Such as the resin composition for printed circuit boards of item 1 or 2 of the scope of the patent application, wherein the maleimide compound (B) comprises bis(4-maleimidephenyl)methane, 2 , 2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane and the following At least one compound in the group consisting of maleimide compounds represented by 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 resin composition for printed circuit boards as claimed in claim 1 or 2 of the patent claims, wherein the cyanate compound (C) includes compounds represented by the following formulas (2) and/or (3);

In formula (2), R ₆ each independently represents a hydrogen atom or a methyl group, 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 resin composition for printed circuit boards as claimed in Claim 1 or 2 of the patent application, wherein the prepreg containing the resin composition for printed circuit boards and the substrate is thermally cured at 230°C for 100 minutes The hardened product conforms to the numerical range of the physical parameters of the mechanical properties represented by the following formulas (4)~(8); E'(200°C)/E'(30°C)≦0.90...(4) E'(260°C )/E'(30℃)≦0.85...(5) E'(330℃)/E'(30℃)≦0.80...(6) E"max/E'(30℃)≦3.0%...(7) E"min/E'(30℃)≧0.5%...(8) In each formula, E' means that the cured product is in brackets The storage elastic modulus at the temperature shown in the table, E"max indicates the maximum value of the loss elastic modulus of the hardened product at a temperature range of 30°C to 330°C, and E"min indicates the hardened product at a temperature range of 30°C to 330°C The minimum value of the loss elastic modulus in the temperature range. A prepreg, comprising: a base material; and the resin composition for printed circuit boards impregnated or coated on the base material according to any one of items 1 to 11 of the scope of the patent application. Such as the prepreg of item 12 of the scope of the patent application, wherein the base material is selected from 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 one or more types of fibers in the group consisting of organic fibers. A resin sheet comprising: a support; and the resin composition for printed circuit boards according to any one of items 1 to 11 of the patent application scope laminated on one or both sides of the support. A laminated board having at least one prepreg as claimed in claim 12 of the scope of the patent application. A laminated board having at least one laminated resin sheet according to claim 14 of the scope of the patent application. A metal foil-clad laminate, comprising: a prepreg as described in claim 12 of the patent application on which at least one sheet is laminated; and metal foils arranged on one or both sides of the prepreg. A metal foil-clad laminate, comprising: at least one resin sheet as claimed in claim 14 of the patent application; and metal foils arranged on one or both sides of the resin sheet. A printed circuit board has an insulating layer and a conductor layer formed on the surface of the insulating layer; the insulating layer contains the resin composition for printed circuit board according to any one of items 1 to 11 of the scope of the patent application. A multi-layer printed circuit board, which has a plurality of insulating layers and a plurality of conductor layers, the plurality of insulating layers are composed of a first insulating layer and a second insulating layer, and the first insulating layer is laminated with at least one piece as in the scope of the patent application Formation of a prepreg according to item 12, the second insulating layer is formed by laminating at least one sheet of the prepreg in the direction of one side of the first insulating layer; and the plurality of conductor layers are formed by the first conductor layer and a second conductor layer, the first conductor layer is arranged between the insulation layers of the plurality of insulation layers, and the second conductor layer is arranged on the surface of the outermost layer of the plurality of insulation layers. A multi-layer printed circuit board, which has a plurality of insulating layers and a plurality of conductor layers, the plurality of insulating layers are composed of a first insulating layer and a second insulating layer, and the first insulating layer is laminated with at least one piece as in the scope of the patent application Formation of resin sheets according to item 14, the second insulating layer is formed by laminating at least one or more resin sheets in the direction of one side of the first insulating layer; The first conductive layer is arranged between each insulating layer of the plurality of insulating layers, and the second conductive layer is arranged on the surface of the outermost layer of the plurality of insulating layers.

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