TW201840675A - 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 board, prepreg, resin sheet, laminated board, metal foil-clad laminated board, printed circuit board, and multilayer printed circuit board

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

In recent years, semiconductor packages that have been widely used in electronic equipment, communication equipment, personal computers, and the like have advanced in function and miniaturization. With this, the high integration and high-density mounting of various components used in semiconductor packages have accelerated in recent years. . Along with this, various characteristics required for a printed circuit board for a semiconductor package have become stricter. For the characteristics required for this printed circuit board, for example: low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric tangent, low thermal expansion coefficient, heat resistance, chemical resistance, high plating peel strength Wait. In addition, suppressing warpage of printed circuit boards, especially suppressing warpage of multilayer multilayer coreless substrates (to achieve low warpage) has recently become an important issue, and various countermeasures have been taken.

One of the countermeasures is to reduce the thermal expansion of the insulating layer used in the printed wiring board. This is a method of suppressing warpage by making the thermal expansion coefficient of a printed circuit board close to the thermal expansion coefficient of a semiconductor device, and has been actively adopted (for example, refer to Patent Documents 1 to 3).

As a method for suppressing the warpage of semiconductor plastic packages, in addition to the low thermal expansion of printed circuit boards, there have been discussions to improve the rigidity (high rigidity) of the laminated board and increase the glass transition temperature (high Tg of the laminated board). (See, for example, Patent Documents 4 and 5). [Prior Art Literature] [Patent Literature]

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

However, according to the detailed research by the inventors of the present case, even the above-mentioned conventional technologies are still unable to sufficiently reduce the warpage of printed circuit boards, especially multilayer non-core substrates, and further improvements are desired.

That is, an object of the present invention is to provide a resin composition for a printed circuit board, and a prepreg, a resin sheet, a laminate, a metal-clad laminate, and a printed circuit using the resin composition for the 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 sufficient reduction of warpage of printed circuit boards, especially multilayer non-core substrates (achieving low warpage) .

The inventors of this case worked hard to solve the above-mentioned problems. As a result of research, it was found that the warpage behavior of printed circuit boards used in conventional semiconductor plastic packages has a greater thermal storage elastic modulus in the hardened material of the prepreg. Resin compositions having a high modulus of elasticity and higher are effective, but they are not necessarily limited to this. In addition, as a result of intensive research by the inventors of the present case, it was found that the use of a cyanate compound and / or an epoxy compound in addition to the allylphenol compound and the maleimide compound can solve the above-mentioned problems. this invention.

That is, the present invention is as follows. [1] a resin composition for a printed circuit board, 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 with respect to 100 parts by mass of the resin solid content in the resin composition for printed circuit boards, and the resin in the resin composition for printed circuit boards The solid content is 100 parts by mass, and the content of the maleimide compound (B) is 40 to 80 parts by mass.

[2] The resin composition for a printed circuit board according to [1], wherein the cyanate ester compound (C) and the epoxy compound are 100 parts by mass of a resin solid content in the resin composition for a printed circuit board. The total content of (D) is 5 to 45 parts by mass.

[3] The resin composition for a printed circuit board according to [1] or [2], wherein the cyanate ester compound (C) is 100 parts by mass of the resin solid content in the resin composition for the printed circuit board. The content is 0 to 25 parts by mass.

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

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

[6] The resin composition for a printed circuit board 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 circuit board according to [5] or [6], wherein the content of the filler (E) is 100 parts by mass based on 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. 120 to 250 parts by mass.

[8] The resin composition for a printed circuit board according to any one of [1] to [7], wherein the allylphenol compound (A) includes any one of the following formulae (I) to (III) Compounds represented:

[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 a printed circuit board according to any one of [1] to [8], wherein the maleimide compound (B) is selected from the group consisting of bis (4-maleimide) Phenyl) methane, 2,2-bis {4- (4-maleimide phenoxy) -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 the 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 a printed circuit board according to any one of [1] to [9], wherein the cyanate ester compound (C) includes a compound represented by the following formulae (2) and / or (3);

[Chemical 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;

[Chemical 6]

In the 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 a printed circuit board according to any one of [1] to [10], wherein the prepreg containing the resin composition for a printed circuit board and a substrate is heated at 230 ° C. for 100 minutes. The hardened material obtained under the condition of thermal hardening conforms to the range of the physical property parameters of the mechanical properties represented by the following formulas (4) to (8); 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) In each formula, E ′ represents the storage elastic modulus of the hardened material at the temperature shown in the brackets, and E ″ max represents the The maximum loss elastic modulus of the hardened material in the temperature range of 30 ° C to 330 ° C, E "min represents the minimum loss elastic modulus of the hardened material 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 substrate is selected from the group consisting of E glass fiber, D glass fiber, S glass fiber, T glass fiber, Q glass fiber, L glass fiber, and NE glass fiber. , HME glass fibers, and organic fibers in a group consisting of one or more 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 laminated board comprising at least one selected from the group consisting of a prepreg such as [12] and [13], and a resin sheet such as [14] in which at least one sheet is laminated.

[16] A metal foil-clad laminate having: at least one sheet laminated on the sheet selected from the group consisting of a prepreg such as [12] and [13], and a resin sheet such as [14] At least one type; and a single-sided or double-sided metal foil arranged in at least one selected from the group consisting of the prepreg and the resin sheet.

[17] A printed circuit board having an insulating layer and a conductor layer formed on a surface of the insulating layer; the insulating layer containing 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 conductor layers, wherein 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 piece or more It is free to form at least one of the group consisting of the prepregs such as [12] and [13], and the resin sheet such as [14], and the second insulating layer is stacked on one side of the first insulating layer. At least one selected from the group consisting of prepregs such as [12] and [13], and resin sheets such as [14], having at least one layer laminated thereon, selected from the group consisting of [12] and [13] The prepreg and at least one of the group consisting of the resin sheet of [14] are formed; and the plurality of conductor layers are composed of a first conductor layer and a second conductor layer, and the first conductor layer is disposed in the majority Between the insulating layers of the insulating layer, the second conductor layer is disposed on the surface of the outermost layer of the plurality of insulating layers. [Effect of the 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 that can sufficiently reduce warpage of printed circuit boards, especially multilayer non-core substrates (to achieve low warpage), and A prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed circuit board, and a multilayer printed circuit board using the resin composition for a printed circuit board are used.

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

[Resin composition for printed wiring board] The resin composition for printed wiring board of this embodiment contains an allylphenol compound (A), a maleimide compound (B), a cyanate compound (C), and / Or epoxy (D). The resin composition for a printed circuit board contains such a composition, for example, a hardened material obtained by hardening a prepreg. There is no clear glass transition temperature (no Tg), and a printed circuit board can be sufficiently reduced. The tendency of the core substrate to warp (to achieve low warpage).

[Allylphenol compound (A)] The allylphenol compound (A) is not particularly limited as long as it is a compound having at least one allyl group and a hydroxyl group directly bonded to the aromatic ring, for example, hydrogen of the aromatic ring Atomic substituted 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, bis Phenol M, Bisphenol S, Bisphenol P, Bisphenol PH, Bisphenol TMC, Bisphenol Z. Among them, bisphenol A is more preferable, and the allylphenol compound (A) is more preferably diallyl bisphenol A, and the compound represented by the following formula (I) or formula (II) is more preferable. By using such an allylphenol compound (A), the bending strength, the bending elastic modulus, the thermal expansion coefficient, the thermal conductivity, and the copper foil peeling strength tend to be 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 formulae (I) to (III), the allyl group and the hydroxyl group are each independently bonded to a position other than the Bis bonding portion of the benzene ring.

The allylphenol compound (A) may further have a reactive functional group other than an allyl group and a hydroxyl group. Moreover, it may be a compound obtained by modifying a hydroxyl group directly bonded to an aromatic ring with a reactive functional group other than an allyl group and a hydroxyl group. Reactive functional groups other than allyl and hydroxyl are not particularly limited, and examples thereof include a cyanate ester group, an epoxy group, an amine group, an isocyanate group, an epoxy group, and a phosphate group. These bases tend to have better bending strength, bending elastic modulus, thermal expansion coefficient, and thermal conductivity. Allylphenol compound (A) may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, reactive functional groups other than allyl and hydroxyl groups may be the 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, and even more preferably 2. When the number of allyl 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 better, the thermal expansion coefficient is low, and the thermal conductivity is excellent. tendency.

When the allylphenol compound (A) has a hydroxyl group directly bonded to an 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, and More preferably, it is 2. When the number of the hydroxyl groups in the 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 better, 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 allyl group and the hydroxyl group, the number of reactive functional groups other than the allyl group and the hydroxyl group in one molecule of the allylphenol compound (A) is preferably 1 ~ 5, more preferably 2 to 4, and even more preferably 2. The number of reactive functional groups other than the allyl group and the hydroxyl group in the molecule of the allylphenol compound (A) is within the above range, and the flexural strength, flexural modulus of elasticity, and copper foil peel strength are better, and the coefficient of thermal expansion It tends to be low and excellent in thermal conductivity.

The content of the allylphenol compound (A) is 10 to 50 parts by mass, preferably 10 to 35 parts by mass, and more preferably 15 to 30 parts by mass based on 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. Parts by mass. When the content of the allylphenol compound (A) is within the above range, the softness, flexural strength, flexural modulus of elasticity, thermal expansion coefficient, thermal conductivity, and copper foil peeling strength of the obtained cured product tend to be better.

[Maleimide compound (B)] The maleimide compound (B) is not particularly limited as long as it is a compound having at least one maleimide group in the molecule, for example: N-phenyl horse 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), prepolymers of these maleimide compounds , Or a prepolymer of a maleimidine imine compound and an amine compound. Among them, it is selected from the group consisting of bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenyloxy) -phenyl} propane, and bis (3-ethyl At least one of the group consisting of methyl-5-methyl-4-maleimide phenyl) methane and the maleimide imide compound represented by the following formula (1) is preferable, and it is easy to obtain the absence of From the viewpoint of a clear glass transition temperature (no Tg) resin composition, a maleimide compound represented by the following formula (1) is particularly preferred. By containing the said maleimidine imine compound (B), the hardened | cured material obtained will tend to have a lower thermal expansion rate, and heat resistance and a glass transition temperature (Tg) will become better. 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 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In formula (1), n ₁ represents an integer of 1 or more, preferably an integer of 10 or less, and 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, and more preferably 45 to 100 parts by mass based on 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. 65 parts by mass. When the content of the maleimide compound (B) is within the above range, the cured product obtained has a lower thermal expansion coefficient and a higher heat resistance.

[Cyanate Compound (C) and / or Epoxy Compound (D)] The resin composition for a printed wiring board of this embodiment contains a cyanate compound (C) and / or an epoxy compound (D). By using a cyanate compound (C) and / or an epoxy compound (D) together with the allylphenol compound (A) and the maleimide compound (B), it is possible to make a prepreg, for example. There is no tendency for a resin composition having a clear glass transition temperature (no Tg) and a warpage (to achieve low warpage) of a printed circuit board, especially a multilayer non-core substrate, to be sufficiently hardened.

(Cyanate compound (C)) The cyanate compound (C) is not particularly limited, and examples thereof include a naphthol aralkyl type cyanate represented by the following formula (2), and a novolac type cyanide represented by the following formula (3) Acid ester, biphenylaralkyl cyanate, bis (3,5-dimethyl 4-cyanooxyphenyl) methane, bis (4-cyanooxyphenyl) methane, 1,3-dicyanide Oxybenzene, 1,4-dicyanoxybenzene, 1,3,5-tricyanooxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6- Dicyanoxynaphthalene, 1,8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4, 4'-dicyanooxybiphenyl, bis (4-cyanoxyphenyl) ether, bis (4-cyanoxyphenyl) sulfide, bis (4-cyanoxyphenyl) fluorene, and 2, 2'-bis (4-cyanooxyphenyl) propane; prepolymers of these cyanates and the like. These cyanate ester compounds (C) may be used individually by 1 type, and may use 2 or more types together.

[Chemical 11]

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

[Chemical 12]

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

Among them, the cyanate compound (C) preferably contains a naphthol aralkyl type cyanate represented by the formula (2), a novolac type cyanate represented by the formula (3), and a biphenyl aromatic One or more of the group consisting of alkyl cyanate esters are preferred, and they are selected from naphthol aralkyl cyanates represented by formula (2) and novolac cyanates represented by formula (3) One or more members of the group consisting of esters are more preferred. By using such a cyanate ester compound (C), there is a tendency that a cured product having better flame retardancy, higher curability, and a 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 synthesis method of a cyanate ester compound. The known method is not particularly limited, for example, a method in which a phenol resin and a cyanogen halide are reacted in a passive organic solvent in the presence of a basic compound, a salt of the phenol resin and the basic compound is formed in an aqueous solution, and then obtained A method in which a salt and a cyanogen halide undergo a 2-phase interfacial reaction.

The phenol resin used as a raw material of the cyanate compound (C) is not particularly limited, and examples thereof include a naphthol aralkyl phenol resin, a novolac phenol resin, and a biphenylaralkyl phenol resin represented by the following formula (9). Resin.

[Chemical 13]

In the formula (9), each of R ⁸ independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is more preferable. In formula (9), n ₄ represents an integer of 1 or more. The upper limit 値 of n ₄ is usually 10, preferably 6.

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

The content of the cyanate ester compound (C) is preferably 0 to 25 parts by mass, and more preferably 0 to 20 parts by mass based on 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. When the content of the cyanate ester 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 is a compound having two or more epoxy groups in one molecule, such as a bisphenol A-type epoxy resin and a bisphenol E-type ring. Oxygen resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, cresol novolac epoxy resin, biphenyl ring Oxygen resin, naphthalene epoxy resin, anthracene epoxy resin, trifunctional phenol epoxy resin, 4-functional phenol epoxy resin, propylene oxide epoxy resin, phenol aralkyl epoxy resin, Benzoaralkyl type epoxy resin, aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyhydric alcohol type epoxy resin, containing isocyanuric acid Ester ring epoxy resins, or these halides. The epoxy compound (D) is more preferably a non-halogenated epoxy compound (non-halogen-containing epoxy compound, halogen-free epoxy compound). When the allylphenol compound (A) contains an epoxy group, the epoxy compound (D) is other than the allylphenol compound (A) having an epoxy group.

The content of the epoxy compound (D) is preferably 0 to 25 parts by mass, and more preferably 0 to 20 parts by mass based on 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. When the content of the epoxy compound (D) is within the above range, the softness of the obtained hardened product, copper foil peeling strength, chemical resistance, and deslagging resistance tend to be better.

As described above, when the resin composition for a printed wiring board of the present embodiment contains a cyanate compound (C) and / or an epoxy compound (D), if the cyanate compound (C) and the epoxy compound are contained (D) In both cases, the total content of the cyanate compound (C) and the epoxy compound (D) in the resin composition for a printed circuit board is preferably from 5 to 45 parts by mass based on 100 parts by mass of the resin solid content. It is more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass. When the total content of the cyanate ester compound (C) and the epoxy compound (D) is within the above range, the softness of the hardened material obtained, the peeling strength of the copper foil, heat resistance, chemical resistance, and resistance to dross removal Sexual orientation. In addition, if the total content of the cyanate compound (C) and the epoxy compound (D) is within the above range, there may be, for example, a hardened material obtained by hardening a prepreg, and there is no clear glass transition temperature (no Tg), and the tendency of the resin composition of printed circuit boards, especially multilayer coreless substrates, to be reduced (to achieve low warpage) can be further reduced.

[Filling Material (E)] The resin composition for a printed circuit board of the present embodiment preferably contains the filler (E) more. The filler (E) is not particularly limited. For example, an inorganic filler and an organic filler are preferred. Among them, an inorganic filler is preferred, and an organic filler is preferably used together with an inorganic filler. The inorganic filler is not particularly limited, for example: natural silicon dioxide, fused silicon dioxide, synthetic silicon dioxide, amorphous silicon dioxide, Aerosil, hollow silicon dioxide and other silicon dioxides; silicon compounds such as white carbon; titanium Metal oxides such as white, zinc oxide, magnesium oxide, and zirconia; metal nitrides such as boron nitride, condensed boron nitride, silicon nitride, and aluminum nitride; metal sulfur oxides such as barium sulfate; aluminum hydroxide and hydroxide Aluminum heat-treated products (those that have undergone heat treatment with aluminum hydroxide minus some crystal water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate and zinc stannate 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 glass micro powders such as E glass, T glass, D glass, S glass, Q glass), hollow glass, spherical glass, etc. In addition, the organic filler is not particularly limited, for example: styrene-based powder, butadiene-based powder, acrylic-based powder, and other rubber powders; core-shell rubber powders; polysiloxane resin powders; polysiloxane rubber powders; and polysiloxanes. Composite powder and so on. The filler (E) may be used individually by 1 type, and may use 2 or more types together.

It also contains a group selected from the group consisting of inorganic fillers, silicon dioxide, aluminum oxide, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride. At least one of them is preferred, and at least one of the groups consisting of silica, alumina, and boehmite is more preferred. By using such a filler (E), the hardened | cured material obtained will tend to become high rigidity and low warpage.

In the resin composition for a printed circuit board, the content of the filler (E) (especially an inorganic filler) is preferably 120 to 250 parts by mass, more preferably 150 to 230 parts by mass, with respect to 100 parts by mass of the resin solid content. It is more preferably 180 to 220 parts by mass. When the content of the filler (E) is within the above range, the obtained hardened product tends to have higher rigidity and lower warpage.

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

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of inorganic substances, for example: γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ- Aminosilane compounds such as aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane; silane-based epoxy compounds; γ-acrylic acid propyltrimethoxysilane; acrylic groups Silane-based compounds; cationic silane-based compounds such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane-based compounds and the like. The silane coupling agent may be used singly or in combination of two or more kinds.

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

[Other resins] The resin composition for a printed circuit board of the present embodiment may further contain an allyl-containing compound (hereinafter also referred to as "others") selected from the allylphenol compound (A) as 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 resins, the copper foil peeling strength, bending strength, and bending elastic modulus of the obtained cured product tend to be better.

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

The content of the other allyl-containing compound is preferably 0 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. 15 to 45 parts by mass, more preferably 20 to 35 parts by mass. When the content of the other allyl-containing compound is within the above range, the flexural strength, flexural modulus, heat resistance, and chemical resistance of the obtained hardened product tend to be better.

[Phenolic resin] The phenolic resin may be a phenolic resin having two or more hydroxyl groups in one molecule, and generally known ones are used, and the type is not particularly limited. Specific examples thereof include bisphenol A-type phenol resin, bisphenol E-type phenol resin, bisphenol F-type phenol resin, bisphenol S-type phenol resin, phenol novolac resin, bisphenol A novolac phenol resin, and propylene oxide Ester-type phenolic resin, aralkyl novolac-type phenolic resin, biphenylaralkyl-type phenolic resin, cresol novolac-type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol Resin, anthracene phenolic resin, naphthalene skeleton modified novolac phenolic resin, phenol aralkyl phenolic resin, naphthol aralkyl phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, grease Cyclic phenolic resins, polyhydric alcohol phenolic resins, phosphorus-containing phenolic resins, and hydroxyl-containing silicone resins are not particularly limited. These phenol resins can be used individually by 1 type or in combination of 2 or more types. By containing such a phenol resin, the obtained cured product tends to have better adhesion, flexibility, and the like.

The content of the phenol resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and even more preferably 3 to 80 parts by mass, with respect to 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. When the content of the phenol resin is within the above range, the adhesiveness and flexibility of the obtained hardened product tend to be more excellent.

[Xetane resin] As the oxetane resin, generally known ones can be used, and the kind is not particularly limited. Specific examples include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyl Alkyloxetane such as oxetane, 3-methyl-3-methoxymethyloxetane, 3,3'-bis (trifluoromethyl) perfluorooxane Butane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toa Synthetic), OXT-121 (trade name of East Asia Synthetic) and the like. These oxetane resins can be used singly or in combination of two or more kinds. By containing such an oxetane resin, there is a tendency that the obtained cured product has better adhesion, flexibility, and the like.

The content of the oxetane resin is preferably from 0 to 99 parts by mass, more preferably from 1 to 90 parts by mass, and even more preferably 3 to 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. ~ 80 parts by mass. When the content of the oxetane resin is within the above range, the adhesiveness and flexibility of the obtained cured product tend to be more excellent.

[Benzo Compound] benzo As long as the compound is two or more dihydrobenzo in one molecule A ring compound is sufficient, and generally known ones 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 of Konishi Chemical Co., Ltd.) and the like. Benzo The compounds may be used singly or in combination of two or more. By containing such benzo The compound tends to be more excellent in flame retardancy, heat resistance, low water absorption, and low dielectric properties of the obtained cured product.

Benzo The content of the compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. Benzo When the content of the compound is within the above range, the heat resistance of the obtained hardened product tends to be more excellent.

[Compound Having Polymerizable Unsaturated Group] The compound having polymerizable unsaturated group can be generally known, and its kind 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, and (meth) 2-hydroxypropyl acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentaerythritol tetra (methyl) (Meth) acrylates, mono- or polyhydric alcohols (meth) acrylates, such as bis (pentaerythritol) hexa (meth) acrylate; bisphenol A epoxy (meth) acrylate, bisphenol F epoxy Epoxy (meth) acrylates such as (meth) acrylates; benzocyclobutene resins; (bis) maleimide resins and the like. These polymerizable unsaturated compounds may be used singly or in combination of two or more kinds. By containing such a polymerizable unsaturated group-containing compound, there is a tendency that the obtained cured product is more excellent in heat resistance and alkali resistance.

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 more preferably 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. It is 3 to 80 parts by mass. When the content of the compound having a polymerizable unsaturated group is within the above range, the heat resistance and heat resistance of the obtained hardened product tend to be more excellent.

[Hardening Accelerator] The resin composition for a printed wiring board of this embodiment may further contain a hardening accelerator. The hardening accelerator is not particularly limited, for example: imidazoles such as triphenylimidazole; benzamidine peroxide, laurel oxide, acetamidine peroxide, benzamidine peroxychloride, and diperoxyphthalate Organic peroxides such as tributyl ester; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N -Dimethylpyridine, 2-N-ethylaniline ethanol, tri-n-butylamine, pyridine, quinoline, N-methyl Tertiary amines such as phosphine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; Organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron ethylacetonate; etc. Metal salts dissolved in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; dioctyl tin oxide, other alkyl tin, and alkyl tin oxide Organotin compounds, etc. Among these, triphenylimidazole is particularly preferable because it promotes a curing reaction and tends to have an excellent thermal expansion rate.

[Solvent] The resin composition for a printed wiring board 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 will fall, workability will become better, and the impregnation property with respect to the base material mentioned later tends to become better.

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 cyperidine; aromatic hydrocarbons such as toluene and xylene Amines such as dimethylformamide; propylene glycol monomethyl ether and its acetate. The solvents may be used singly or in combination of two or more kinds.

[Manufacturing method of the resin composition for printed wiring boards] The manufacturing method of the resin composition for printed wiring boards in this embodiment is not particularly limited, and for example, a method in which each component is sequentially mixed with a solvent and sufficiently stirred. In this case, in order to dissolve or disperse each component uniformly, a known treatment such as stirring, mixing, and kneading may be performed. Specifically, the dispersibility of the filler (E) with respect to the resin composition for a printed circuit board can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading processes can be appropriately performed using, for example, a device for mixing such as a ball mill and a bead mill, or a known device such as a revolving or self-converting mixing device.

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

[Characteristics of the resin composition for a printed circuit board] The resin composition for a printed circuit board according to this embodiment is a cured product obtained by thermally curing a prepreg containing the composition and a substrate at 230 ° C and 100 minutes. It should be in accordance with the range of the physical property parameters related to the mechanical characteristics represented by the following formulae (4) to (8), and more preferably in the range of the physical property parameters related to the mechanical properties represented by the following formulae (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 hardened material at the temperature shown in the brackets, and E ″ max represents the maximum loss elastic modulus of the hardened material in the temperature range of 30 ° C to 330 ° C, E ” min represents the minimum loss modulus of the hardened material in the temperature range of 30 ° C to 330 ° C (E "represents the loss modulus of the hardened material.).

In the past, with regard to the warping behavior of printed circuit boards, it is believed that a cured composition of a prepreg can achieve a large thermal storage modulus of elasticity and a resin composition having a high modulus of elasticity retention, but this is not necessarily the case , The number of physical property parameters of mechanical properties of the hardened material obtained by thermally curing the prepreg at 230 ° C and 100 minutes is in the range of the above formulas (4) to (8), and is preferably the formula In the range of (4A) to (8A), the glass transition temperature (Tg) can be sufficiently increased, and the warpage amount of the laminated board, metal foil-clad laminated board, and printed circuit board, especially the multilayer coreless substrate itself can be sufficiently increased. Decrease.

In other words, the number of physical property parameters of mechanical properties of the hardened material obtained by thermally hardening the prepreg at 230 ° C and 100 minutes is in the range of the above formulas (4) to (8), and more preferably In the range of formulas (4A) to (8A), it is desirable that a clear glass transition temperature (without Tg) does not exist, and the warpage of printed circuit boards (especially multilayered coreless substrates) can be sufficiently reduced (achieving low warpage) song). That is, if the formulas (7) and (8) related to the loss elastic modulus are met, and if the formulas (7A) and (8A) are better matched, it can be said that there is no clear glass transition temperature (Tg) (no Tg) as Synonymously, if the hardened product only conforms to the formulae (7) and (8), it preferably conforms to the formulae (7A) and (8A) and does not conform to the formulae (4) to (6), and preferably does not conform to the formulae (4A) to (6A). ), The loss of elastic modulus itself is small and it is not easy to elongate, but when it is made into a printed circuit board, this elongation difficulty will cause it to be difficult to achieve low warpage. In contrast, if the hardened material not only conforms to the formulae (7) and (8), preferably the formulae (7A) and (8A), but also conforms to the formulae (4) to (8), and preferably the formulae (4A) and (8A), then Since it does not have Tg, it is not easy to stretch and the printed circuit board tends to achieve low warpage.

The measurement method of the mechanical properties (storage elastic modulus E 'and loss elastic modulus E ") of the hardened body of the prepreg is not particularly limited, and it can be measured, for example, by the following method. That is, on the top and bottom sides of one prepreg A copper foil (3EC-VLP, made by Mitsui Metals Mining Co., Ltd., thickness 12 μm) is arranged, and laminated molding (thermosetting) is performed at a pressure of 30 kgf / cm ² and a temperature of 230 ° C. for 100 minutes to obtain a coating with a predetermined insulation layer thickness. Copper foil laminate. The obtained copper-clad laminate was cut with a saw to a size of 5.0 mm × 20 mm, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this sample for measurement, conform to JIS C6481 Using a dynamic viscoelasticity analyzer (manufactured by TA Instruments), the mechanical properties (storage elastic modulus E 'and loss elastic modulus E ") can be measured by the DMA method. At this time, an average 値 of n = 3 can also be obtained.

[Application] The resin composition for a printed circuit board of this embodiment is suitable for use as a prepreg, a resin sheet, an insulating layer, a laminated board, a metal foil-clad laminated board, a printed circuit board, or a multilayer printed circuit board. The following is a description of prepregs, resin sheets, laminated boards, metal foil-clad laminated boards, and printed circuit boards (including multilayer printed circuit boards).

[Prepreg] The prepreg according to this embodiment includes a substrate and a resin composition for a printed circuit board impregnated or coated on the substrate. The manufacturing method of the prepreg can be carried out according to a conventional method, and there is no particular limitation. For example, after impregnating or coating the resin composition for a printed circuit board in this embodiment with a substrate, heating it in a dryer at 100 to 200 ° C for 1 to 30 minutes, etc. to make it semi-hardened (B-staged) ) To produce a prepreg according to this embodiment.

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

The substrate is not particularly limited, and various known substrates used in printed circuit board materials can be appropriately selected depending on the purpose and performance of the purpose. The substrate is, for example, a glass substrate, an inorganic substrate other than glass, an organic substrate, and the like. Among them, a glass substrate is particularly preferable from the viewpoints of high rigidity and stability of heating dimensions. Specific examples of the fibers constituting these substrates are not particularly limited. For example, the glass substrate may be selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Fiber of more than one kind of glass. Examples of the inorganic substrate other than glass include inorganic fibers other than glass such as quartz. Examples of the organic substrate include poly-paraphenylene terephthalamide (KEVLAR (registered trademark), manufactured by DuPont), and copolymerized para-phenylene terephthalamide. Fully aromatic polyfluorene such as copoly- (paraphenlene / 3,4-oxydiphenylene terephthalamide) (Technora (registered trademark), TEIJIN TECHNO PRODUCTS (shares) company) Amine; Polyesters such as 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid (Vectran (registered trademark), Kuraray Co., Ltd.), Zxion (registered trademark, manufactured by KB Seiren); polyparaphenylene benzo double Organic fibers such as poly (p-phenylene-2,6-benzobisoxazole) (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide, etc. These substrates can be used alone or in combination. 2 More than that.

The shape of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, cut felts, and surface felts. The weaving method of the weaving cloth is not particularly limited. For example, plain weaving, basket weave, twill weave, etc. are known, and these publicly known laws can be appropriately selected according to the purpose and performance of the purpose. In addition, a glass woven fabric which has been subjected to a fiber opening treatment or a surface treatment with a silane coupling agent can be preferably used. The thickness and quality of the base material are not particularly limited, but usually about 0.01 to 0.3 mm is suitable. Especially considering the viewpoint of strength and water absorption, it is preferable that the substrate is a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m 2 or less, and a glass woven fabric composed of glass fibers of E glass, S glass, and T glass is more preferable.

As described above, the prepreg of this embodiment is preferably a formula (4) to (8) if the cured product obtained by thermally curing the prepreg at 230 ° C and 100 minutes meets the formulae (4) to (8). (8A) The range of the physical parameter about the mechanical characteristics indicated, 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 there is It can reduce warpage sufficiently (to achieve low warpage), so it is ideal.

[Resin sheet] The resin sheet according to this embodiment includes a sheet-like substrate (support) and the above-mentioned resin composition for a printed circuit board laminated on one or both sides of the sheet-like substrate. The resin sheet is used as a method of thinning, and can be produced, for example, 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 it.

The sheet-like substrate is not particularly limited, and known materials that can be used as various printed circuit board materials can be used. For example, polyimide film, polyimide 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.

The coating method is, for example, a method in which the resin composition for a printed circuit board of the present embodiment is dissolved in a solvent to obtain a solution, and then coated on a sheet-shaped substrate by a coating rod, a die coater, a doctor blade, a Baker applicator, or the like. .

The resin sheet is preferably one obtained by applying the resin composition for a printed circuit board to a sheet-like substrate and then semi-hardening (B-stage). Specifically, for example, the resin composition for a printed circuit board is coated on a sheet-like substrate such as copper foil, and then semi-hardened by heating in a dryer at 100 to 200 ° C for 1 to 60 minutes. Method for manufacturing resin sheet and the like. The adhesion amount of the resin composition for a printed circuit board to a sheet-like substrate is preferably in the range of 1 to 300 μm based on the resin thickness of the resin sheet.

[Laminated Sheet and Metal-Foil Laminated Sheet] The laminated sheet according to this embodiment includes at least one sheet of the prepreg of the present embodiment and / or the resin sheet of the present embodiment. The metal foil-clad laminate according to this embodiment includes the laminate according to this embodiment (that is, at least one sheet of the prepreg according to this embodiment and / or the above-mentioned prepreg according to this embodiment are laminated. Resin sheet), and metal foil (conductor layer) disposed on one or both sides of the laminated board.

The conductor layer may be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is a user in a printed circuit board material, and is preferably a known copper foil such as a rolled copper foil or an electrolytic copper foil. The thickness of the conductive layer is not particularly limited, but is preferably 1 to 70 μm, and more preferably 1.5 to 35 μm.

The method for forming a laminated board or a metal foil-clad laminated board and the forming conditions thereof are not particularly limited, and methods and conditions for a general laminated board for a printed circuit board and a multilayer board 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 plates or metal-clad laminated plates. In addition, in forming a laminated plate or a metal-clad laminated plate (laminate forming), generally, the temperature is 100 to 300 ° C., the pressure is 2 to 100 kgf / cm ² , and the heating time is 0.05 to 5 hours. Range. Further, if necessary, post-curing may be performed at a temperature of 150 to 300 ° C. Especially when using a multi-stage press, consider the viewpoint of fully promoting the hardening of the prepreg and / or resin sheet. The temperature is 200 ° C to 250 ° C, the pressure is 10 to 40kgf / cm ² , and the heating time is 80 minutes to 130 minutes. The temperature is 215 ° C. It is more preferable to be -235 ° C, a pressure of 25 to 35 kgf / cm ² , and a heating time of 90 minutes to 120 minutes. Furthermore, a multilayer board can also be produced by combining the prepreg and / or resin sheet and a wiring board for an inner layer that is separately produced, and forming a multilayer board.

[Printed Circuit Board] The printed circuit board of this embodiment includes an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition for a printed circuit board described above. For example, by forming a predetermined wiring pattern on the metal foil-clad laminate, it can be ideally used as a printed circuit board. As described above, the metal foil-clad laminate using the resin composition for a printed circuit board of the present embodiment has no clear glass transition temperature (no Tg) and can sufficiently reduce warpage (to achieve low warpage). Tends to be particularly effective as a printed wiring board requiring such performance.

Specifically, the printed wiring board of this embodiment can be manufactured by the following method, for example. First, the above-mentioned metal-clad laminate (copper-clad laminate, 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 layer circuit surface of this inner layer substrate is optionally subjected to a surface treatment to improve the adhesive strength, and then the above-mentioned prepreg and / or resin sheet of the required number are laminated on the inner circuit surface, and then laminated on the outer side thereof The metal foil for the outer layer circuit is heated and pressurized and formed integrally (laminated). In this manner, a multilayer laminated board having a base material and an insulating layer made of a cured product of a thermosetting resin composition between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. The method of lamination forming and the forming conditions thereof are the same as those of the above-mentioned laminated plate or metal foil-clad laminated plate. Then, after applying through-hole processing for the through-holes and interlayer holes to this multilayer laminated board, in order to remove the slag, which is a residue from the resin component resin contained in the hardened material layer, a slag removal treatment is performed. After that, a plating metal film is formed on the wall surface of the hole to allow the inner layer circuit and the outer layer metal foil to be conducted, and then the metal foil for the outer layer circuit is etched to form an outer layer circuit to manufacture a printed circuit board.

For example: the prepreg (the substrate and the resin composition for a printed circuit board attached to the substrate), and a resin composition layer (a layer composed of the resin composition for a printed circuit board) of a metal foil-clad laminate To form the insulating layer containing the resin composition for a printed circuit board.

When a metal foil-clad laminate is not used, a conductor layer to be a circuit may be formed on the prepreg or the resin composition for a printed wiring board, and a printed wiring board may be produced. In this case, the formation of the conductive layer may also be performed by an electroless plating method.

In addition, as shown in FIG. 9, the printed circuit board of this embodiment 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 piece 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 piece or more of at least one selected from the group consisting of the above-mentioned prepreg and resin sheet on one side of the insulating layer (the direction below the figure); the majority of the conductor layers are formed by The first conductor layer (3) and the second conductor layer (3) are configured. The first conductor layer (3) is disposed between the insulating layers of the plurality of insulating layers (1,2). The second conductor layer (3) ) Is disposed on the outermost layer of most of these insulating layers (1,2).

According to the knowledge and knowledge of the inventors of the present case, a general laminated board 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. At least one of the group consisting of a immersion body and a resin sheet is used to form a multilayer printed circuit board, but it has been confirmed that at least one of the groups selected from the group consisting of a prepreg and a resin sheet is used in this embodiment. At least one of the first insulating layer (1) selected from the group consisting of a prepreg and a resin sheet is laminated on one side to form a second insulating layer (2). The other is selected from a prepreg and a resin. A coreless multilayer printed circuit board (multilayer coreless substrate) manufactured by using at least one of the group consisting of sheets is particularly effective.

In other words, when the prepreg, the resin sheet, and the resin composition for a printed circuit board of this embodiment are used in a printed circuit board, the amount of warpage can be effectively reduced. Multi-layer coreless substrates are particularly effective. That is, the general printed circuit board generally adopts a symmetrical structure on both sides, which tends to be difficult to warp, and the multilayer non-core substrate is prone to become asymmetrical on both sides. Therefore, it is more likely to warp than a normal printed circuit board Propensity. Therefore, by using the prepreg, the resin sheet, and the resin composition for a printed circuit board of this embodiment, the amount of warpage of a multilayer coreless substrate that has tended to tend to warp in the past can be particularly effectively reduced.

9 shows a structure in which two pieces of the second insulating layer (2) are laminated on one piece of the first insulating layer (1) (that is, a structure in which most of the 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 described above, the printed circuit board of the present embodiment having the above-mentioned structure can be subjected to the thermal storage elastic modulus and loss of the hardened material obtained by hardening the prepreg, for example, by using the resin composition for a printed circuit board of the present embodiment. Mechanical properties such as elastic modulus are controlled in a specific range suitable for low warpage. Thereby, there is no clear glass transition temperature (no Tg), and the warpage of printed circuit boards, especially multilayer coreless substrates can be sufficiently reduced (achieving low Warpage), so it can be effectively used as printed circuit boards for semiconductor packages and multilayer coreless substrates. [Example]

Hereinafter, the present invention will be described more specifically using examples and comparative examples. However, the present invention is not limited to the following examples.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl cyanate compound (SN495VCN) in a reactor, and α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Nissin Made by ferrochemical (stock): those containing naphthol aralkyl repeating units n is 1 to 5.) 0.47 mole (in terms of OH group) is dissolved in 500 ml of chloroform, and 0.7 mole of triethylamine is added to this solution. While maintaining the temperature at -10 ° C, 300 g of a 0.93 mole of cyanogen chloride chloroform solution was added dropwise in the reactor over 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 to the reactor, and the reaction was completed by stirring for 30 minutes. After the by-product triethylamine hydrochloride was separated and filtered from the reaction solution, the obtained filtrate was washed with 500 ml of 0.1 N hydrochloric acid, and then washed repeatedly with 500 ml of water four times. This was dried over sodium sulfate, evaporated at 75 ° C, and degassed at 90 ° C under reduced pressure to obtain an α-naphthol aralkyl cyanate compound represented by the above formula (2) (wherein R ⁶ Are all hydrogen atoms). The obtained α-naphthol aralkyl type cyanate compound was analyzed by infrared absorption spectrum, and absorption of a cyanate group was confirmed in the vicinity of 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.), Allyl phenol compound (A) 60.9 parts by mass of amine compound (B) (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd., maleimide equivalent: 186 g / eq.), Α-naphthalene of (C) Synthesis Example 1 of a cyanate compound 5.0 parts by mass of a phenol aralkyl cyanate compound (SN495VCN, cyanate equivalent: 261 g / eq.), Epoxy compound (D) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent: 328 g / eq.) 10.0 parts by mass, 200 parts by mass of silica dioxide slurry (SC-2050MB, manufactured by Admatechs), and filler material (E), and polysilicone composite powder (KMP-605M, Shin-Etsu Chemical Industry Co., Ltd. ) 25 parts by mass, 5 parts by mass of a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.5 parts by mass of triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) as a hardening accelerator. Mix and dilute with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E glass woven fabric, and heated and dried at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73% by volume for a printed circuit board.

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

[Example 3] A printed circuit was obtained in the same manner as in Example 1 except that the cyanate compound (C) (SN495VCN) was not used, and the epoxy compound (D) (NC-3000FH) was changed to 15.0 parts by mass. A prepreg with a resin composition content of 73% by volume.

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

[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 epoxy compound (D) (NC-3000FH) was not used, and a prepreg having a resin composition content of 73 vol% for a printed circuit board was obtained in the same manner as in Example 1.

[Comparative Example 2] The allylphenol compound (A) (DABPA) was changed to 60.0 parts by mass, the maleimide compound (B) (BMI-2300) was changed to 32.1 parts by mass, and the cyanate compound (C) ( SN495VCN) was changed to 2.6 parts by mass, and the epoxy compound (D) (NC-3000FH) was changed to 5.3 parts by mass. In the same manner as in Example 1, the resin composition content of the printed circuit board was 73% by volume. Prepreg.

[Comparative Example 3] The allylphenol compound (A) (DABPA) was changed to 12.7 parts by mass, the maleimide compound (B) (BMI-2300) was changed to 32.1 parts by mass, and the 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 the same manner as in Example 1, the content of the resin composition for a printed circuit board was 73% by volume. 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, and 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 the same manner as in Example 1, the content of the resin composition for a printed circuit board was 73% by volume. Prepreg.

[Physical property measurement evaluation] Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 4, a sample for physical property measurement evaluation was prepared according to the procedure shown in each of the following items, and the mechanical properties (storage elastic modulus, storage elastic modulus, And loss modulus of elasticity), physical property parameters related to mechanical properties in formulas (4) to (8) and formulas (4A) to (8A), glass transition temperature (Tg), and warpage amount (three types). 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, Mitsui Metals 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 / Lamination (thermal curing) was performed for 100 minutes under conditions of cm ² and a temperature of 230 ° C. to obtain a copper-clad laminate with an insulation layer thickness of 0.1 mm. The obtained copper-clad laminate was cut with a dicing saw to a size of 20 mm × 5 mm, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this sample for measurement, the mechanical properties (storage elastic modulus E 'and loss elastic modulus E ") were measured by a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481 according to the DMA method (n = 3 average 値).

[Glass transition temperature (Tg)] Copper foils (3EC-VLP, made by Mitsui Metals Mining Co., Ltd., thickness 12 μm) are arranged on the upper and lower sides of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, Lamination (thermal curing) was performed for 100 minutes under conditions of a pressure of 30 kgf / cm ² and a temperature of 230 ° C. to obtain a copper-clad laminated board having an insulation layer thickness of 0.1 mm. The obtained copper-clad laminate was cut with a dicing saw to a size of 12.7 × 2.5 mm, and then 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) (n = 3 average 値) was measured by a DMA method using a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JISC6481.

[Warpage: Bimetal Method] First, copper foil (3EC-VLP, made by Mitsui Metals Mining Co., Ltd.) was placed on the upper and lower sides of one of the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the thickness 12 μm), lamination was performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a copper-clad laminate. The copper foil was then removed from the obtained copper-clad laminate. Next, one sheet of the prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was further arranged on one side of the laminated board from which copper foil was removed, and the above-mentioned copper foil (3EC-VLP, Mitsui It was made by metal mining (stock) (thickness: 12 μm), and laminated for 120 minutes at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. to obtain a copper-clad laminate. Furthermore, the copper foil was removed from the obtained copper-clad laminated sheet to obtain a laminated sheet. Then, a strip-shaped 20 mm × 200 mm plate was cut out from the obtained laminated plate, and the surface of the second prepreg was laminated upward, and the maximum amount of warpage at both ends in the longitudinal direction was measured with a metal ruler.値, this average 値 is defined as the "warpage amount" measured by the bimetal method.

[Warpage: Multi-layer coreless substrate] First, as shown in FIG. 1, ultra-thin copper foil (b1) (MT18Ex, Mitsui Metals Mining Co., Ltd.) with a carrier will be attached to both sides of the prepreg that becomes the support (a). ), The thickness of the carrier copper foil is 5). The copper foil surface of the carrier 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 thereon, and copper is further arranged thereon. Foil (d) (3EC-VLP, manufactured by Mitsui Metals Mining Co., Ltd., thickness 12 μm), laminated for 120 minutes at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. to obtain a copper-clad foil as shown in FIG. 2 Laminated boards.

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, as shown in FIG. 4, the prepreg (c2) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was arranged on the laminated board shown in FIG. 3 where the conductor layer (d ′) was formed. An ultra-thin copper foil (b2) with a carrier (MT18Ex, manufactured by Mitsui Metals Mining Co., Ltd., 5 μm thick) was further disposed thereon, and laminated for 120 minutes under a condition of a pressure of 30 kgf / cm ² and a temperature of 230 ° C. A copper-clad laminate shown in FIG. 5 was obtained.

Next, in the copper-clad laminate shown in FIG. 5, the carrier copper foil and the electrode of the ultra-thin copper foil (b1) with a carrier arrange | positioned on the support body (a) (prepreg for hardened support body) are arrange | positioned. The thin copper foil was peeled to peel off the two laminates from the support (a) as shown in FIG. 6, and the carrier was further removed from the ultra-thin copper foil (b2) with a carrier in the upper part of each of these laminates. The copper foil was peeled. Then, the obtained ultra-thin copper foils on each of the obtained laminates were processed by a laser processing machine, and as shown in FIG. 7, predetermined through holes (v) were formed by electroless copper plating. Then, for example, as shown in FIG. 8, a predetermined wiring pattern is etched to form a conductor layer to obtain a multilayer coreless panel (size: 500 mm × 400 mm). Then, the total amount of warpage at the four corners of the panel and the center of the four sides was measured with a metal ruler, and the average value was defined as the "warpage" of the multi-layer, non-core substrate panel.

[Substrate shrinkage ratio before and after the reflow step] Copper foils (3EC-VLP, made by Mitsui Metals Mining Co., Ltd., thickness 12 μm) are arranged on the upper and lower sides of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, Lamination was performed under conditions of a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a copper-clad laminate. Then, the obtained copper-clad laminate was uniformly drilled at 9 o'clock in a grid pattern using a drill, and then the copper foil was removed.

Then, first, the distance (distance I) between the holes of the laminated plate from which the copper foil was removed was measured. Then, this laminated board was subjected to a reflow treatment using a SALAMANDER reflow device at a maximum temperature of 260 ° C. After that, the distance (distance II) between the holes in the laminated plate was measured again. Then, the measured distance I and distance II are substituted into the following formula (I), and the dimensional change rate of the substrate subjected to the reflow process is determined. This is defined as the shrinkage rate of the substrate before and after the reflow step. ((Distance I)-(distance II)) / distance I × 100 ... Formula (I)

【Table 1】

【Table 2】 [Industrial availability]

The resin composition for a printed circuit board of this embodiment has industrial applicability as a material of a prepreg, a resin sheet, a laminated board, a metal-clad laminated board, a printed circuit board, or a multilayer printed circuit board. The present application is based on Japanese Patent Application No. 2016-255272 filed on December 28, 2016, and the contents thereof are incorporated herein by reference.

1‧‧‧The first insulation layer

2‧‧‧ 2nd insulating layer

3‧‧‧conductor layer

a‧‧‧ support

b1‧‧‧ ultra-thin copper foil

b2‧‧‧thin copper foil

c1‧‧‧prepreg

c2‧‧‧prepreg

d‧‧‧copper foil

d’ ‧‧‧conductor layer

V‧‧‧through hole

FIG. 1 shows a processing flowchart of an example of a process for manufacturing a multi-layer coreless substrate panel (however, the manufacturing method of a multi-layer coreless substrate is not limited to this. The same is shown in FIGS. 2 to 8 below). FIG. 2 shows a processing flowchart of an example of a process for manufacturing a multi-layer panel without a core substrate. FIG. 3 shows a processing flowchart of an example of a procedure for manufacturing a multi-layer coreless panel. FIG. 4 shows a processing flowchart of an example of a procedure for manufacturing a multi-layered coreless panel. FIG. 5 shows a processing flowchart of an example of a process for manufacturing a multi-layer panel without a core substrate. FIG. 6 shows a processing flowchart of an example of a procedure for manufacturing a multi-layered coreless panel. FIG. 7 shows a processing flowchart of an example of a process for manufacturing a multi-layer panel without a core substrate. FIG. 8 shows a processing flowchart of an example of a procedure for manufacturing a multi-layer coreless panel. FIG. 9 is a partial cross-sectional view showing the structure of an example of a multi-layer coreless panel.

Claims (21)

A resin composition for a printed circuit board comprising an allylphenol compound (A), a maleimide compound (B), and a cyanate compound (C) and / or an epoxy compound (D). 100 parts by mass of the resin solid content in the resin composition for a printed circuit board, and the content of the allylphenol compound (A) is 10 to 50 parts by mass, relative to 100 parts of the resin solid content in the resin composition for the printed circuit board The content of the maleimidine imine compound (B) is 40 to 80 parts by mass. For example, the resin composition for a printed circuit board according to item 1 of the patent application, wherein the cyanate ester compound (C) and the epoxy compound are 100 parts by mass of the resin solid content in the resin composition for the printed circuit board. The total content of (D) is 5 to 45 parts by mass. For example, if the resin composition for a printed circuit board according to item 1 or 2 of the patent application scope is, the content of the cyanate ester compound (C) is 100 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for the printed circuit board. 0 to 25 parts by mass. For example, the resin composition for a printed circuit board according to item 1 or 2 of the patent application scope, wherein the content of the epoxy compound (D) is 0 with respect to 100 parts by mass of the resin solid content in the resin composition for the printed circuit board. ～ 25 parts by mass. For example, the resin composition for a printed circuit board in the scope of the patent application No. 1 or 2 further contains a filler (E). For example, the resin composition for a printed circuit board according to item 5 of the patent application, wherein the filler (E) is at least one selected from the group consisting of silica, alumina, and boehmite. For example, the resin composition for a printed circuit board according to the scope of application for a patent No. 5 wherein the content of the filler (E) is 120 to 250 masses with respect to 100 parts by mass of the resin solid content in the resin composition for the printed circuit board. Serving. For example, the resin composition for a printed circuit board of claim 1 or 2, wherein the allylphenol compound (A) includes a compound represented by any one of the following formulae (I) to (III): [化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 3] . For example, the resin composition for a printed circuit board according to item 1 or 2 of the patent application scope, wherein the maleimide compound (B) includes a compound selected from 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 a maleimidine imine compound represented by formula (1); In the formula (1), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more. For example, the resin composition for a printed circuit board according to item 1 or 2 of the patent application scope, wherein the cyanate ester compound (C) includes a compound represented by the 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 the formula (3), R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more. For example, the resin composition for a printed circuit board for which the scope of the patent application is item 1 or 2 is obtained by thermally curing a prepreg containing the resin composition for a printed circuit board and a substrate at 230 ° C and 100 minutes. The hardened material conforms to the range of the physical property parameters related to the mechanical characteristics expressed by the following formulae (4) to (8); 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) In each formula, E ′ represents the storage elastic modulus of the hardened material at the temperature shown in parentheses, and E” max represents the hardened material at 30 ℃ to The maximum loss modulus of the elastic modulus in the temperature range of 330 ° C, E ”min represents the minimum loss modulus of the cured product in the temperature range of 30 ° C to 330 ° C. A prepreg comprising: a substrate; and the resin composition for a printed circuit board according to any one of claims 1 to 11 impregnated or coated on the substrate. For example, the prepreg according to item 12 of the application, wherein the substrate is selected from the group consisting of E glass fiber, D glass fiber, S glass fiber, T glass fiber, Q glass fiber, L glass fiber, and NE glass fiber. , HME glass fibers, and organic fibers in a group consisting of one or more fibers. A resin sheet comprising: a support; and a resin composition for a printed circuit board according to any one of claims 1 to 11 laminated on one or both sides of the support. A laminated board having at least one piece of prepreg according to item 12 of the patent application scope. A laminated board has at least one resin sheet laminated as described in claim 14 of the patent application scope. A metal foil-clad laminated board includes: at least one piece of prepreg as described in item 12 of the scope of patent application; and a metal foil disposed on one or both sides of the prepreg. A metal foil-clad laminated board includes: at least one resin sheet laminated as described in the scope of claim 14 in the patent application; and a metal foil disposed on one or both sides of the resin sheet. A printed circuit board has an insulating layer and a conductor layer formed on a surface of the insulating layer; the insulating layer contains the resin composition for a printed circuit board according to any one of claims 1 to 11 of the scope of patent application. A multi-layer printed circuit board having 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. The prepreg of item 12, wherein the second insulating layer is formed by laminating at least one piece of the prepreg on one side of the first insulating layer; and the majority of the conductor layers are composed of the first conductor layer And a second conductor layer, the first conductor layer is disposed between the insulating layers of the plurality of insulating layers, and the second conductor layer is disposed on the surface of the outermost layer of the plurality of insulating layers. A multi-layer printed circuit board having 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. The resin sheet according to item 14, wherein the second insulating layer is formed by laminating at least one resin sheet on one side of the first insulating layer; and the plurality of conductor layers are composed of the first conductor layer and the first conductor layer. It has a two-conductor layer. The first conductor layer is disposed between the insulating layers of the plurality of insulating layers, and the second conductor layer is disposed on the surface of the outermost layer of the plurality of insulating layers.