CN110121531B

CN110121531B - Resin composition for printed wiring board, prepreg, resin sheet, laminate, metal foil-clad laminate, and printed wiring board

Info

Publication number: CN110121531B
Application number: CN201780081388.4A
Authority: CN
Inventors: 久保孝史; 滨岛知树; 山口翔平; 伊藤环; 志贺英祐
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2016-12-28
Filing date: 2017-12-27
Publication date: 2021-09-14
Anticipated expiration: 2037-12-27
Also published as: CN110121531A; KR20190095923A; JPWO2018124161A1; KR102431012B1; TWI798194B; WO2018124161A1; JP7025729B2; TW201840675A

Abstract

In order to provide a resin composition for a printed wiring board, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board, which do not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, particularly a multilayer coreless board, the resin composition of the present invention contains an allylphenol compound (A), a maleimide compound (B), and a cyanate ester compound (C) and/or an epoxy compound (D). The content of the allylphenol compound (A) is 10 to 50 parts by mass per 100 parts by mass of the resin solid content in the resin composition for a printed wiring board, and the content of the maleimide compound (B) is 40 to 80 parts by mass per 100 parts by mass of the resin solid content in the resin composition for a printed wiring board.

Description

Resin composition for printed wiring board, prepreg, resin sheet, laminate, metal foil-clad laminate, and printed wiring board

Technical Field

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

Background

In recent years, with the progress of higher functionality and smaller size of semiconductor packages widely used in electronic devices, communicators, personal computers, and the like, high integration and high-density mounting of each component for semiconductor packages have been accelerated in recent years. Along with this, the characteristics required for printed circuit boards for semiconductor packages have become more and more stringent. Examples of the properties required for the printed wiring board include low water absorption, moisture absorption and heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength. In addition to these characteristics, suppression of warpage (achievement of low warpage) of printed wiring boards, particularly multilayer coreless substrates, has become an important issue in recent years, and various countermeasures have been taken.

One of the measures against this problem 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 wiring board close to that of a semiconductor element, and is currently prevalent (for example, see patent documents 1 to 3).

As a method for suppressing warpage of a semiconductor plastic package, in addition to the low thermal expansion of a printed circuit board, improvement of the rigidity of a laminate (high rigidity) and improvement of the glass transition temperature of the laminate (high Tg) have been studied (for example, see patent documents 4 and 5).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2013-216884

Patent document 2: japanese patent No. 3173332

Patent document 3: japanese laid-open patent publication No. 2009-035728

Patent document 4: japanese patent laid-open publication No. 2013-001807

Patent document 5: japanese patent laid-open publication No. 2011-178992

Disclosure of Invention

However, according to the detailed studies of the present inventors, even when the above-described conventional techniques are used, the warpage of the printed wiring board, particularly the multilayer coreless board, cannot be sufficiently reduced, and further improvement is desired.

That is, an object of the present invention is to provide a resin composition for a printed wiring board which does not have a clear glass transition temperature (so-called no Tg) and can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, particularly a multilayer coreless board, and a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board using the resin composition for a printed wiring board.

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition that allows a cured product of a prepreg to achieve a higher storage modulus under heat and a higher retention rate of elastic modulus has been effective for the warpage behavior of a printed circuit board for semiconductor plastic encapsulation, but the present invention is not limited thereto. Further, the present inventors have conducted extensive studies and as a result, have found that the above problems can be solved by using a cyanate ester compound and/or an epoxy compound in addition to an allylphenol compound and a maleimide compound, and have completed the present invention.

Namely, the present invention is as follows.

〔1〕

A resin composition for a printed circuit board, comprising: an allylphenol compound (A),

Maleimide compound (B), and

a cyanate ester compound (C) and/or an epoxy compound (D),

the content of the allylphenol compound (A) is 10 to 50 parts by mass per 100 parts by mass of the resin solid content in the resin composition for a printed wiring board,

the content of the maleimide compound (B) is 40-80 parts by mass relative to 100 parts by mass of resin solid content in the resin composition for printed circuit board.

〔2〕

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

〔3〕

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

〔4〕

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

〔5〕

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

〔6〕

The resin composition for a printed wiring board according to [ 5 ], wherein the filler (E) is at least 1 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 relative to 100 parts by mass of a resin solid content in the resin composition for a printed wiring board.

〔8〕

The resin composition for a printed wiring board according to any one of [ 1] to [ 7 ], wherein the allylphenol compound (A) comprises a compound represented by any one of the following formulas (I) to (III).

(in the formula (I), R₁And R₂Each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group. )

〔9〕

The resin composition for a printed wiring board according to any one of [ 1] to [ 8 ], wherein the maleimide compound (B) comprises at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and a maleimide compound represented by the following formula (1).

(in the formula (1), R₅Each independently represents a hydrogen atom or a methyl group, n₁Represents an integer of 1 or more. )

〔10〕

The resin composition for a printed wiring board according to any one of [ 1] to [ 9 ], wherein the cyanate ester compound (C) comprises a compound represented by the following formula (2) and/or (3).

(in the formula (2), R₆Each independently represents a hydrogen atom or a methyl group, n₂Represents an integer of 1 or more. )

(in the formula (3), R₇Each independently represents a hydrogen atom or a methyl group, n₃Represents an integer of 1 or more. )

〔11〕

The resin composition for a printed wiring board according to any one of [ 1] to [ 10 ], wherein a cured product obtained by thermally curing a prepreg comprising the resin composition for a printed wiring board and a substrate at 230 ℃ for 100 minutes satisfies a numerical range of physical property parameters relating to 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)

(wherein E ' represents the storage modulus of the cured product at the temperature shown in parentheses, E ' max represents the maximum value of the loss modulus of the cured product in the temperature range of 30-330 ℃, and E ' min represents the minimum value of the loss modulus of the cured product in the temperature range of 30-330 ℃)

〔12〕

A prepreg, having:

a base material, and

the resin composition for a printed wiring board according to any one of [ 1] to [ 11 ] which is impregnated or coated on the base material.

〔13〕

The prepreg according to [ 12 ], wherein the base material comprises 1 or more kinds of fibers selected from the group consisting of E glass fibers, D glass fibers, S glass fibers, T glass fibers, Q glass fibers, L glass fibers, NE glass fibers, HME glass fibers, and organic fibers.

〔14〕

A resin tablet having:

a support body, and

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

〔15〕

A laminated sheet comprising at least 1 or more sheets of at least 1 selected from the group consisting of the prepregs [ 12 ] and [ 13 ] and the resin sheet [ 14 ].

〔16〕

A metal-clad laminate comprising: stacking at least 1 or more sheets of at least 1 selected from the group consisting of the prepregs [ 12 ] and [ 13 ] and the resin sheet [ 14 ]; and

and a metal foil disposed on one or both surfaces of at least 1 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 the surface of the insulating layer,

the insulating layer comprises the resin composition for a printed wiring 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,

the plurality of insulating layers includes: stacking at least 1 or more 1 insulating layers of at least 1 selected from the group consisting of the prepregs [ 12 ] and [ 13 ] and the resin sheets [ 14 ]; and at least 1 or more second insulating layers of at least 1 selected from the group consisting of the prepregs [ 12 ] and [ 13 ] and the resin sheets [ 14 ] are laminated in the direction of one surface of the first insulating layer [ 1 ];

the plurality of conductor layers include a 1 st conductor layer disposed between the plurality of insulating layers, and a 2 nd conductor layer disposed on an outermost surface of the plurality of insulating layers.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a resin composition for a printed wiring board which does not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, particularly a multilayer coreless board, and a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board using the resin composition for a printed wiring board.

Drawings

Fig. 1 is a process flow diagram showing an example of a process for manufacturing a panel of a multilayer coreless substrate (however, the method for manufacturing a multilayer coreless substrate is not limited thereto, and the same is applied to fig. 2 to 8 below).

Figure 2 is a process flow diagram illustrating one example of a process for fabricating a panel of a multi-layer coreless substrate.

Figure 3 is a process flow diagram illustrating one example of a process for fabricating a panel of a multi-layer coreless substrate.

Figure 4 is a process flow diagram illustrating one example of a process for fabricating a panel of a multi-layer coreless substrate.

Figure 5 is a process flow diagram illustrating one example of a process for fabricating a panel of a multi-layer coreless substrate.

Figure 6 is a process flow diagram illustrating one example of a process for fabricating a panel of a multi-layer coreless substrate.

Figure 7 is a process flow diagram illustrating one example of a process for fabricating a panel of a multi-layer coreless substrate.

Figure 8 is a process flow diagram illustrating one example of a process for fabricating a panel of a multi-layer coreless substrate.

Fig. 9 is a partial cross-sectional view showing a configuration of an example of a panel of a multilayer coreless substrate.

Detailed Description

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

[ resin composition for printed Circuit Board ]

The resin composition for a printed wiring board of the present embodiment contains: an allylphenol compound (A), a maleimide compound (B), and a cyanate ester compound (C) and/or an epoxy resin (D). By containing such a composition in the resin composition for a printed wiring board, for example, a cured product obtained by curing a prepreg does not have a clear glass transition temperature (no Tg), and warpage of a printed wiring board, particularly a multilayer coreless board, tends to be sufficiently reduced (low warpage is achieved).

[ allylphenol compound (A) ]

The allylphenol compound (a) is not particularly limited as long as it is a compound in which at least 1 or more each of an allyl group and a hydroxyl group is directly bonded to an aromatic ring, and examples thereof include bisphenols in which a hydrogen atom of an aromatic ring is substituted with an allyl group. The bisphenol is not particularly limited, and examples thereof include bisphenol a, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. Among these, bisphenol a is preferred, and as the allylphenol compound (a), diallyl bisphenol a is more preferred, and compounds represented by the following formula (I) or formula (II) are further preferred. By using such an allylphenol compound (a), the flexural strength, flexural modulus, thermal expansion coefficient, thermal conductivity, and copper foil peel strength tend to be further improved.

Here, in the formula (I), R₁And R₂Each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group.

In the formulae (I) to (III), each of the allyl group and the hydroxyl group is independently bonded to a position other than the Bis bonding portion of the benzene ring.

The allylphenol compound (a) may have a reactive functional group other than an allyl group and a hydroxyl group. The hydroxyl group directly bonded to the aromatic ring may be modified with a reactive functional group other than allyl and hydroxyl groups. The reactive functional group other than the allyl group and the hydroxyl group is not particularly limited, and examples thereof include an isocyanate group (Cyanate group), an epoxy group, an amine group, an isocyanate group, a glycidyl group, and a phosphoric acid group. By providing these elements, the bending strength, the bending modulus, the thermal expansion coefficient, and the thermal conductivity tend to be further improved. The allylphenol compound (a) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more kinds are used in combination, the reactive functional groups other than allyl and hydroxyl groups may be the same or different.

The number of allyl groups in the molecule of the allylphenol compound (A)1 is preferably 1 to 5, more preferably 2 to 4, and still more preferably 2. When the number of allyl groups in the molecule of the allylphenol compound (a)1 is in the above range, the flexural strength, flexural modulus, and copper foil peel strength tend to be further improved, the thermal expansion coefficient tends to be low, and the thermal conductivity tends to be excellent.

When the allylphenol compound (a) has a hydroxyl group directly bonded to an aromatic ring, the number of the hydroxyl groups in the molecule of the allylphenol compound (a)1 is preferably 1 to 5, more preferably 2 to 4, and still more preferably 2. When the number of the hydroxyl groups in the molecule of the allylphenol compound (a)1 is in the above range, the flexural strength, flexural modulus, and copper foil peel strength tend to be further improved, the thermal expansion coefficient tends to be low, and the thermal conductivity tends to be excellent.

When the allylphenol compound (a) has the reactive functional groups other than allyl and hydroxyl groups, the number of reactive functional groups other than allyl and hydroxyl groups in the molecule of the allylphenol compound (a)1 is preferably 1 to 5, more preferably 2 to 4, and still more preferably 2. When the number of reactive functional groups other than allyl and hydroxyl groups in the molecule of the allylphenol compound (a)1 is in the above range, the flexural strength, flexural modulus, and copper foil peel strength tend to be further improved, the thermal expansion coefficient tends to be low, and the thermal conductivity tends to be excellent.

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 per 100 parts by mass of the resin solid content in the resin composition for a printed circuit board. When the content of the allylphenol compound (a) is in the above range, flexibility, flexural strength, flexural modulus, thermal expansion coefficient, thermal conductivity, and copper foil peel strength of the obtained cured product tend to be further improved.

[ Maleimide Compound (B) ]

The maleimide compound (B) is not particularly limited as long as it is a compound having 1 or more maleimide groups in the molecule, examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, maleimide compounds represented by the following formula (1), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. Among them, at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and a maleimide compound represented by the following formula (1) is preferable, and the maleimide compound represented by the following formula (1) is particularly preferable in terms of easily obtaining a resin composition having no clear glass transition temperature (no Tg). By containing the maleimide compound (B), the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance and the glass transition temperature (Tg) tend to be further improved. The maleimide compound (B) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Here, in the formula (1), R₅Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula (1), n₁Represents 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, and more preferably 45 to 65 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. When the content of the maleimide compound (B) is in the above range, the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

[ cyanate ester compound (C) and/or epoxy compound (D) ], a process for producing the same, and a process for producing a semiconductor device using the same

The resin composition for a printed wiring board of the present embodiment contains a cyanate ester compound (C) and/or an epoxy compound (D). By using the cyanate ester compound (C) and/or the epoxy compound (D) together with the allyl phenol compound (a) and the maleimide compound (B), for example, a cured product obtained by curing a prepreg tends to be a resin composition which does not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieve low warpage) of a printed wiring board, particularly a multilayer coreless board.

(cyanate ester Compound (C))

The cyanate ester compound (C) is not particularly limited, and examples thereof include naphthol aralkyl type cyanate ester represented by the following formula (2), novolak type cyanate ester represented by the following formula (3), biphenyl aralkyl type cyanate ester, bis (3, 5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1,3, 5-tricyanobenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 6-dicyanobenzene, 1, 8-dicyanobenzene, 2, 6-dicyanobenzene, 2, 7-dicyanobenzene, 1,3, 6-tricyanobenzene, 4' -dicyanobenzene, bis (4-cyanatophenyl) ether, and the like, Bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, and 2, 2' -bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters, and the like. These cyanate ester compounds (C) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In the formula (2), R⁶Each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In the formula (2), n₂Represents an integer of 1 or more. n is₂The upper limit value of (b) is usually 10, preferably 6.

In the formula (3), R⁷Each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In the formula (3), n₃Represents 1 or moreAn integer number. n is₃The upper limit value of (b) is usually 10, preferably 7.

Among these, the cyanate ester compound (C) preferably contains 1 or more selected from the group consisting of naphthol aralkyl type cyanate ester represented by formula (2), novolac type cyanate ester represented by formula (3), and biphenyl aralkyl type cyanate ester, and more preferably contains 1 or more selected from the group consisting of naphthol aralkyl type cyanate ester represented by formula (2) and novolac type cyanate ester represented by formula (3). By using such a cyanate ester compound (C), a cured product having more excellent flame retardancy, higher curability, and a lower thermal expansion coefficient tends to be obtained.

The method for producing the cyanate ester compound (C) is not particularly limited, and a known method for synthesizing the cyanate ester compound can be used. The known methods are not particularly limited, and examples thereof include: a method of reacting a phenol resin with a cyanogen halide in an inactive organic solvent in the presence of a basic compound; a method comprising forming a salt of a phenol resin and an alkaline compound in a solution containing water, and then subjecting the resulting salt to a 2-phase interfacial reaction with a cyanogen halide.

The phenolic resin to be a raw material of the cyanate ester compound (C) is not particularly limited, and examples thereof include naphthol aralkyl type phenolic resins, novolac type phenolic resins, and biphenyl aralkyl type phenolic resins represented by the following formula (9).

In the formula (9), R⁸Each independently represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In the formula (9), n₄Represents an integer of 1 or more. n is₄The upper limit value of (b) 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 with cyanic acid. The naphthol aralkyl type phenol resin is not particularly limited, and examples thereof include those obtained by the reaction of a naphthol such as α -naphthol or β -naphthol with a benzene such as p-xylylene glycol, α' -dimethoxyp-xylene, or 1, 4-bis (2-hydroxy-2-propyl) benzene. The naphthol aralkyl type cyanate ester may be selected from those obtained by condensing the naphthol aralkyl resin obtained as described above with cyanic acid.

The content of the cyanate ester compound (C) is preferably 0 to 25 parts by mass, more preferably 0 to 20 parts by mass, per 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 in the above range, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.

(epoxy Compound (D))

The epoxy compound (D) is not particularly limited as long as it is a compound having 2 or more epoxy groups in 1 molecule, and for example, examples thereof include bisphenol a type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol a novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy 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, biphenyl aralkyl type epoxy resin, aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyhydric alcohol type epoxy resin, isocyanurate ring-containing epoxy resin, and halides thereof. Further, as the epoxy compound (D), a non-halogenated epoxy compound (a non-halogen-containing epoxy compound, a halogen-free epoxy compound) is more preferable. When the allylphenol compound (a) has an epoxy group, the epoxy compound (D) is a compound 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, more preferably 0 to 20 parts by mass, per 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 in the above range, flexibility, copper foil peel strength, chemical resistance, and smear removal resistance of the obtained cured product tend to be further improved.

As described above, when the resin composition for a printed wiring board of the present embodiment contains the cyanate ester compound (C) and/or the epoxy compound (D), and both the cyanate ester compound (C) and the epoxy compound (D) are contained, the total content of the cyanate ester compound (C) and the epoxy compound (D) is preferably 5 to 45 parts by mass, more preferably 5 to 40 parts by mass, and still more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. When the total content of the cyanate ester compound (C) and the epoxy compound (D) is within the above range, flexibility, copper foil peel strength, heat resistance, chemical resistance, and smear removal resistance of the obtained cured product tend to be further improved. Further, when the total content of the cyanate ester compound (C) and the epoxy compound (D) is in the above range, for example, a cured product obtained by curing a prepreg tends to be a resin composition which does not have a clear glass transition temperature (no Tg) and can further reduce warpage (achieve low warpage) of a printed circuit board, particularly a multilayer coreless substrate.

[ filling Material (E) ]

The resin composition for a printed wiring board of the present embodiment preferably further contains a filler (E). The filler (E) is not particularly limited, and examples thereof include an inorganic filler and an organic filler, and preferably include both of them, and the organic filler is preferably used together with the inorganic filler. The inorganic filler is not particularly limited, and examples thereof include silicas such as natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL, and hollow silica; silicon compounds such as white carbon black; metal oxides such as titanium white, zinc oxide, magnesium oxide, and zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride; metal sulfates such as barium sulfate; metal hydrates such as aluminum hydroxide, aluminum hydroxide heat-treated products (products obtained by heat-treating aluminum hydroxide to reduce a part of crystal water), boehmite, and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass fine powders such as E glass, T glass, D glass, S glass, Q glass), hollow glass, spherical glass, and the like. The organic filler is not particularly limited, and examples thereof include rubber powders such as styrene-based powder, butadiene-based powder, and acrylic-based powder; core-shell rubber powder; a silicone resin powder; a silicone rubber powder; silicone composite powder, and the like. The filler (E) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among them, at least 1 selected from the group consisting of silica, aluminum oxide, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride is preferably contained as the inorganic filler, and more preferably at least 1 selected from the group consisting of silica, alumina, and boehmite is contained. By using such a filler (E), the cured product obtained tends to have higher rigidity and lower warpage.

The content of the filler (E) (particularly, an inorganic filler) is preferably 120 to 250 parts by mass, more preferably 150 to 230 parts by mass, and still more preferably 180 to 220 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 filler (E) is in the above range, the rigidity and warpage of the obtained cured product tend to be further increased.

[ silane coupling agent and wetting dispersant ]

The resin composition for a printed wiring board of the present embodiment may further contain a silane coupling agent and a wetting dispersant. The inclusion of the silane coupling agent and the wetting dispersant tends to further improve the dispersibility of the filler (E), the resin component, the filler (E), and the adhesive strength of the base material described later.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent used for surface treatment of a general inorganic substance, and examples thereof include aminosilane compounds such as γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane; epoxy silane compounds such as gamma-glycidoxypropyltrimethoxysilane; acrylic silane compounds such as gamma-acryloxypropyltrimethoxysilane; cationic silane compounds such as N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. The silane coupling agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for coating applications, and examples thereof include DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK Japan KK.

[ other resins, etc. ]

The resin composition for a printed wiring board of the present embodiment may further contain, as necessary, 1 or 2 or more selected from the group consisting of an allyl group-containing compound (hereinafter also referred to as "other allyl group-containing compound"), a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group, in addition to the above allyl phenol compound (a). By including such another resin or the like, the peel strength, flexural modulus, and the like of the copper foil of the obtained cured product tend to be further improved.

[ other allyl-containing compounds ]

The other allyl-containing compound is not particularly limited, and examples thereof include allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, and diallyl maleate.

The content of the other allyl-containing compound is preferably 0 to 50 parts by mass, more preferably 10 to 45 parts by mass, even more preferably 15 to 45 parts by mass, and even more preferably 20 to 35 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 other allyl group-containing compound is in the above range, the flexural strength, flexural modulus, heat resistance, and chemical resistance of the obtained cured product tend to be further improved.

[ phenol resin ]

As the phenol resin, any conventionally known phenol resin can be used as long as it has 2 or more hydroxyl groups in 1 molecule, and the type thereof is not particularly limited. Specific examples thereof include, but are not particularly limited to, 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 type phenol resin, glycidyl ester type phenol resin, aralkyl type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, multifunctional phenol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton-modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic type phenol resin, polyhydric alcohol type phenol resin, phosphorus-containing phenol resin, hydroxyl group-containing silicone resin, and the like. These phenol resin can be used alone in 1 or a combination of 2 or more. By including such a phenol resin, the cured product obtained tends to have more excellent adhesiveness, flexibility, and the like.

The content of the phenolic resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 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 phenol resin is in the above range, the obtained cured product tends to have further excellent adhesiveness, flexibility, and the like.

[ Oxetane resin ]

As the oxetane resin, a generally known one can be used, and the kind thereof is not particularly limited. Specific examples thereof include an alkyloxetane such as oxetane, 2-methyloxetane, 2-dimethyloxetane, 3-methyloxetane or 3, 3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3' -bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toyo Seiya Synthesis), OXT-121 (trade name manufactured by Toyo Seiya Synthesis), and the like. These oxetane resins can be used in 1 kind or in combination of 2 or more kinds. By containing such an oxetane resin, the resultant cured product tends to have more excellent 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 to 80 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. When the content of the oxetane resin is in the above range, the obtained cured product tends to have further excellent adhesion, flexibility, and the like.

[ benzoxazine compound ]

As the benzoxazine compound, a generally known compound can be used as long as it has 2 or more dihydrobenzoxazine rings in 1 molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A type benzoxazine BA-BXZ (trade name of Seikagaku corporation), bisphenol F type benzoxazine BF-BXZ (trade name of Seikagaku corporation), and bisphenol S type benzoxazine BS-BXZ (trade name of Seikagaku corporation). These benzoxazine compounds may be used in 1 kind or in a mixture of 2 or more kinds. By containing such a benzoxazine compound, the cured product obtained tends to be more excellent in flame retardancy, heat resistance, low water absorption, low dielectric constant, and the like.

The content of the benzoxazine compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 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 benzoxazine compound is in the above range, the heat resistance and the like of the obtained cured product tend to be further excellent.

[ Compound having polymerizable unsaturated group ]

As the compound having a polymerizable unsaturated group, a generally known compound can be used, and the kind thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl; (meth) acrylates of 1-or polyhydric alcohols such as methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.; epoxy (meth) acrylates such as bisphenol a type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; benzocyclobutene resin; (bis) maleimide resins, and the like. These compounds having a polymerizable unsaturated group may be used in 1 kind or in a mixture of 2 or more kinds. By including such a compound having a polymerizable unsaturated group, the resultant cured product tends to be more excellent in heat resistance, toughness, 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 3 to 80 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 compound having a polymerizable unsaturated group is in the above range, the resultant cured product tends to have further excellent heat resistance, toughness, and the like.

[ curing accelerators ]

The resin composition for a printed wiring board of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperoxyphthalate, etc.; azo compounds such as azobisnitrile; tertiary amines such as N, N-dimethylbenzylamine, N-dimethylaniline, N-dimethyltoluidine, N-lutidine, 2-N-ethylanilinoethanol, tri-N-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol, and the like; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, and the like; the organic metal salts are dissolved in a hydroxyl group-containing compound such as phenol or bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; and organic tin compounds such as dioctyltin oxide, other alkyltin, and alkyltin oxide. Of these, triphenylimidazole is particularly preferable because it accelerates the curing reaction and tends to have an excellent thermal expansion coefficient.

[ solvent ]

The resin composition for a printed wiring board of the present embodiment may further contain a solvent. By including the solvent, the viscosity at the time of production of the resin composition for a printed wiring board is lowered, the handling property is further improved, and the impregnation property into a base material described later tends to be further improved.

The solvent is not particularly limited as long as it can dissolve a part or all of the resin components in the resin composition for a printed wiring board, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate, and the like. The solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

[ method for producing resin composition for printed Circuit Board ]

The method for producing the resin composition for a printed circuit board of the present embodiment is not particularly limited, and for example, a method in which the respective components are mixed in order in a solvent and sufficiently stirred may be mentioned. In this case, known processes such as stirring, mixing, and kneading may be performed to uniformly dissolve or disperse the respective components. Specifically, by performing the stirring dispersion treatment using a stirring tank equipped with a stirrer having an appropriate stirring ability, the dispersibility of the filler (E) in the resin composition for a printed wiring board can be improved. The stirring, mixing and kneading treatment can be suitably carried out by using a known apparatus such as a ball mill, a bead mill or the like for mixing, a revolution or rotation type mixing apparatus or the like.

In addition, an organic solvent may be used as necessary for the preparation of the resin composition for a printed circuit board of the present embodiment. The type of the organic solvent is not particularly limited as long as the resin in the resin composition for a printed wiring board can be dissolved. Specific examples thereof are as described above.

[ characteristics of resin composition for printed Circuit Board ]

In the resin composition for a printed wiring board of the present embodiment, a cured product obtained by heat-curing a prepreg containing the resin composition and a base material at 230 ℃ for 100 minutes preferably satisfies the numerical range of physical property parameters relating to mechanical properties shown in the following formulas (4) to (8), and more preferably satisfies the numerical range of physical property parameters relating to mechanical properties shown in 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)

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

Conventionally, regarding the warpage behavior of a printed circuit board, a resin composition that allows a cured product of a prepreg to achieve a higher storage modulus under heat and a higher retention rate of elastic modulus has been considered effective, but the present invention is not limited thereto, and the numerical value of the physical property parameter related to the mechanical properties of a cured product obtained by heat curing the prepreg at 230 ℃ for 100 minutes is within the ranges of the above-mentioned formulae (4) to (8), preferably formulae (4A) to (8A), whereby the glass transition temperature (Tg) can be sufficiently increased and the warpage amount of a laminate, a metal foil-clad laminate, a printed circuit board, and particularly a multilayered coreless substrate itself can be sufficiently reduced.

In other words, by setting the numerical values of the physical property parameters relating to the mechanical properties of the cured product obtained by heat curing the prepreg at 230 ℃ for 100 minutes to fall within the ranges of the above-described formulae (4) to (8), preferably formulae (4A) to (8A), it is possible to adequately reduce the warpage (achieve low warpage) of the printed wiring board (particularly, the multilayer coreless substrate) without having a clear glass transition temperature (no Tg). That is, it can be said that the expressions (7) and (8), preferably the expressions (7A) and (8A), which satisfy the loss modulus, have the same meaning as the absence of a clear glass transition temperature (no Tg), but if the cured product satisfies only the expressions (7) and (8), preferably the expressions (7A) and (8A), and does not satisfy the expressions (4) to (6), preferably the expressions (4A) to (6A), the loss modulus itself is small and the elongation is difficult, but when the cured product is formed into a printed wiring board, the elongation difficulty becomes troublesome and the low warpage is difficult to achieve. On the other hand, when the cured product satisfies not only the formulae (7) and (8), preferably the formulae (7A) and (8A), but also the formulae (4) to (8), preferably the formulae (4A) and (8A), there is a tendency that elongation is difficult due to the absence of Tg and low warpage of the printed wiring board is easily achieved.

The method for measuring the mechanical properties (storage modulus E' and loss modulus E ") of the cured product of the prepreg is not particularly limited, and can be measured, for example, by the following method. That is, copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of prepreg, and the pressure was set to 30kgf/cm²And was laminated at 230 ℃ for 100 minutes (thermosetting)Chemical reaction) to obtain a copper clad laminate having a predetermined insulating layer thickness. Next, the obtained copper clad laminate was cut into a size of 5.0mm × 20mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. The mechanical properties (storage modulus E' and loss modulus E ") were measured by the DMA method using this measurement sample according to JIS C6481 using a dynamic viscoelasticity analyzer (TA Instruments). In this case, an average value of n equal to 3 can be obtained.

[ use ]

The resin composition for a printed wiring board of the present embodiment can be suitably used as a prepreg, a resin sheet, an insulating layer, a laminate, a metal foil-clad laminate, a printed wiring board, or a multilayer printed wiring board. The prepreg, the resin sheet, the laminate, the metal foil-clad laminate, and the printed wiring board (including a multilayer printed wiring board) 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 prepreg production method may be carried out by a conventional method, and is not particularly limited. For example, the prepreg of the present embodiment can be produced by impregnating or applying the resin composition for a printed circuit board of the present embodiment to a base material, and then semi-curing (B-staging) the resin composition by heating the resin composition in a dryer at 100 to 200 ℃ for 1 to 30 minutes.

The content of the resin composition for a printed circuit board (including the filler (E)) of the prepreg according to the present embodiment is preferably 30 to 90 vol%, more preferably 35 to 85 vol%, and still more preferably 40 to 80 vol% based on the total amount of the prepreg. When the content of the resin composition is within the above range, moldability tends to be further improved.

The substrate is not particularly limited, and known substrates used for various printed wiring board materials can be appropriately selected and used according to the intended use and performance. Examples of the substrate include a glass substrate, an inorganic substrate other than glass, and an organic substrate, and among these, a glass substrate is particularly preferable from the viewpoint of high rigidity and dimensional stability under heating. Specific examples of the fibers constituting these substrates are not particularly limited, and examples of the glass substrate include fibers of 1 or more kinds of glass selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. As the inorganic substrate other than glass, inorganic fibers other than glass such as quartz can be cited. Further, examples of the organic substrate include wholly aromatic polyamides such as poly (p-phenylene terephthalamide) (Kevlar (registered trademark), manufactured by Du Pont), and copoly (p-phenylene 3, 4' -oxydiphenylene-p-phenylenediamine) (manufactured by Technora (registered trademark) and Teijin Techno Products limited); polyesters such as 2, 6-hydroxynaphthoic acid-p-hydroxybenzoic acid (Vectran (registered trademark), KURARAY co., LTD), and Zxion (registered trademark, KB SEIREN, LTD); and organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), available from Toyo Boseki Co., Ltd.) and polyimide. These substrates may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The shape of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. The weaving method of the woven fabric is not particularly limited, and for example, a plain weave, a basket weave, a twill weave, and the like are known, and can be appropriately selected from these known weaving methods according to the intended use and performance. Further, a glass woven fabric obtained by opening these fibers or surface-treated with a silane coupling agent or the like can be suitably used. The thickness and mass of the substrate are not particularly limited, and a substrate of about 0.01 to 0.3mm can be used as appropriate. Particularly, from the viewpoint of strength and water absorption, the substrate preferably has a thickness of 200 μm or less and a mass of 250g/m²The following glass woven fabric is more preferably a glass woven fabric formed of glass fibers of E glass, S glass, and T glass.

As described above, when the prepreg of the present embodiment is cured at 230 ℃ for 100 minutes to obtain a cured product satisfying the numerical ranges of physical property parameters relating to mechanical properties represented by the above-described formulae (4) to (8), preferably formulae (4A) to (8A), the prepreg, the metal foil-clad laminate, the printed wiring board, or the multilayer printed wiring board is preferred because there is no clear glass transition temperature (no Tg) and warpage can be sufficiently reduced (low warpage is achieved).

[ resin sheet ]

The resin sheet of the present embodiment includes a sheet base (support), and the resin composition for a printed circuit board laminated on one or both surfaces of the sheet base. The resin sheet is used as 1 means for forming a sheet, and can be produced by directly applying and drying a thermosetting resin (including the filler (E)) used for a prepreg or the like on a support such as a metal foil or a film.

The sheet base is not particularly limited, and known materials used for various printed circuit board materials can be used. Examples of the film include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, Polyethylene (PE) films, aluminum foils, copper foils, and gold foils. Among them, electrolytic copper foil and PET film are preferable.

Examples of the coating method include a method of coating a sheet base material with a bar coater, a die coater, a doctor blade, a Baker applicator, or the like for a solution in which the resin composition for a printed wiring board of the present embodiment is dissolved in a solvent.

The resin sheet is preferably obtained by applying the resin composition for a printed wiring board to a sheet base and then semi-curing (B-staging). Specifically, for example, the following methods can be mentioned: and a method for producing a resin sheet, which comprises applying the resin composition for a printed wiring board to a sheet base material such as a copper foil, and then semi-curing the coated resin composition by a method of heating the coated resin composition in a dryer at 100 to 200 ℃ for 1 to 60 minutes. The amount of adhesion of the resin composition for a printed wiring board to the sheet base is preferably in the range of 1 to 300 μm in terms of the resin thickness of the resin sheet.

[ laminate and Metal foil-clad laminate ]

The laminate plate of the present embodiment has at least 1 or more sheets of the prepreg of the present embodiment and/or the resin sheet of the present embodiment stacked thereon. The metal foil-clad laminate of the present embodiment includes the laminate of the present embodiment (that is, at least 1 or more sheets of the prepreg of the present embodiment and/or the resin sheet of the present embodiment are laminated) and a metal foil (conductor layer) disposed on one surface or both surfaces of the laminate.

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

The method and conditions for forming the laminate or metal-clad laminate are not particularly limited, and the methods and conditions for forming the laminate and multilayer board for a printed wiring board can be generally applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used for molding the laminate sheet or the metal-clad laminate sheet. In addition, in the formation of the laminated plate or the metal-clad laminated plate (lamination formation), the temperature is usually 100 to 300 ℃, and the pressure is usually 2 to 100kgf/cm²And the heating time is within the range of 0.05-5 hours. Further, if necessary, post-curing may be performed at a temperature of 150 to 300 ℃. Particularly, when a multistage press is used, the temperature is preferably 200 to 250 ℃ and the pressure is preferably 10 to 40kgf/cm from the viewpoint of sufficiently promoting the curing of the prepreg and/or the resin sheet²The heating time is 80 to 130 minutes, more preferably 215 to 235 ℃, and the pressure is 25 to 35kgf/cm²And the heating time is 90 to 120 minutes. Further, a multilayer board can also be produced by laminating and molding the prepreg and/or the resin sheet and a wiring board for an inner layer separately produced.

[ printed circuit board ]

The printed wiring board of the present embodiment is a printed wiring board having an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer contains the resin composition for a printed wiring board. For example, the metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern thereon. Further, the metal foil-clad laminate using the resin composition for a printed wiring board of the present embodiment does not have a clear glass transition temperature (no Tg) and is likely to have a sufficiently reduced warpage (to achieve a low warpage), and therefore, can be effectively used as a printed wiring board particularly requiring such performance.

The printed wiring board of the present embodiment can be manufactured by the following method. First, the above-described metal foil-clad laminate (copper-clad laminate or the like) is prepared. The surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. The surface of the inner layer circuit of the inner layer substrate is subjected to surface treatment for improving the adhesive strength as required, and then a required number of the prepregs and/or resin sheets are stacked on the surface of the inner layer circuit, and further a metal foil for an outer layer circuit is stacked on the outer side thereof, and is subjected to heat and pressure to be integrally molded (stacked molding). In this way, a multilayer laminated board in which a base material and an insulating layer formed of a cured product of a thermosetting resin composition are formed between metal foils for an inner layer circuit and an outer layer circuit is manufactured. The method of lamination and the conditions for lamination are the same as those of the above-described laminate or metal foil-clad laminate. Next, after the multilayer laminated board is subjected to drilling for via holes and via holes, desmear treatment is performed to remove resin residues and desmear derived from the resin component contained in the cured product layer. Then, a metal coating film for conducting the metal foil for the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the hole, and the metal foil for the outer layer circuit is etched to form the outer layer circuit, thereby producing a printed wiring board.

For example, the prepreg (the base material and the resin composition for a printed wiring board impregnated therein) and the resin composition layer of the metal foil-clad laminate (the layer formed of the resin composition for a printed wiring board) constitute an insulating layer containing the resin composition for a printed wiring board.

In addition, in the case where a metal foil-clad laminate is not used, a printed wiring board can be produced by forming a conductor layer as a circuit on the prepreg or the object formed of the resin composition for a printed wiring board. In this case, the conductor layer may be formed by electroless plating.

Further, as shown in fig. 9, the printed wiring board of the present embodiment preferably includes a plurality of insulating layers and a plurality of conductive layers, the plurality of insulating layers including: at least 1 or more insulating layers (1) of at least 1 selected from the group consisting of the prepregs and the resin sheets and at least 1 or more insulating layers (2) of at least 1 selected from the group consisting of the prepregs and the resin sheets are laminated in one surface direction (the lower surface direction in the figure) of the insulating layer (1), wherein the plurality of conductive layers include: a 1 st conductor layer (3) disposed between the insulating layers (1, 2), and a 2 nd conductor layer (3) disposed on the outermost layer of the insulating layers (1, 2).

According to the findings of the present inventors, it was confirmed that: a typical laminate sheet forms a multilayer printed circuit board by laminating at least 1 selected from the group consisting of prepregs and resin sheets in both-side directions of at least 1 selected from the group consisting of prepregs and resin sheets as a core substrate, for example, but at least 1 selected from the group consisting of prepregs and resin sheets of the present embodiment is particularly effective for a coreless multilayer printed circuit board (multilayer coreless substrate) produced by laminating at least 1 selected from the group consisting of prepregs and resin sheets in one-side directions of at least 1 selected from the group consisting of prepregs and resin sheets forming only one of the 1 st insulating layers (1) to form a 2 nd insulating layer (2).

In other words, when the prepreg, the resin sheet, and the resin composition for a printed wiring board according to the present embodiment are used for a printed wiring board, the amount of warpage can be effectively reduced, and the prepreg, the resin sheet, and the resin composition for a printed wiring board are particularly effective for a multilayer coreless substrate in a printed wiring board, although not particularly limited. That is, a normal printed circuit board is generally configured to be bilaterally symmetrical, and thus tends to be less likely to be warped, while a multilayer coreless substrate is easily configured to be bilaterally asymmetrical, and thus tends to be warped more easily than a normal printed circuit board. Therefore, the use of the prepreg, the resin sheet, and the resin composition for a printed circuit board according to the present embodiment can particularly effectively reduce the amount of warpage in a multilayer coreless substrate which tends to be easily warped in the past.

Fig. 9 shows a structure in which 2 insulating layers 2 are stacked on 1 insulating

layer

1, 2 insulating layers 2 (i.e., a structure in which a plurality of insulating layers are 3 layers), but the number of insulating layers 2 may be 1 or 2 or more. Therefore, the 1 st conductor layer (3) may be 1 layer or 2 or more layers.

As described above, with the printed wiring board of the present embodiment having the above-described configuration, the resin composition for a printed wiring board of the present embodiment can control the mechanical properties such as the storage modulus, loss modulus and the like in the hot state of the cured product obtained by curing the prepreg to a specific range suitable for low warpage, and thus does not have a clear glass transition temperature (no Tg) and can sufficiently reduce warpage (achieve low warpage) of the printed wiring board, particularly a multilayer coreless board, and therefore can be effectively used as a printed wiring board for semiconductor encapsulation and a multilayer coreless substrate in particular.

Examples

The present invention will be described more specifically below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[ Synthesis example 1] Synthesis of α -Naphthol aralkyl type cyanate ester Compound (SN495VCN)

In a reactor, 0.47 mol (in terms of OH group) of an α -naphthol aralkyl resin (SN495V, OH group equivalent: 236g/eq., manufactured by Nippon iron chemical Co., Ltd.; the number n of repeating units containing a naphthol aralkyl group is 1 to 5.) was dissolved in 500ml of chloroform, and 0.7 mol of triethylamine was added to the solution. While the temperature was maintained at-10 ℃ 300g of a chloroform solution of 0.93 mol of cyanogen chloride was added dropwise to the reactor over 1.5 hours, and after completion of the addition, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30g of chloroform was added dropwise to the reactor, and the reaction was terminated by stirring for 30 minutes. After removing by-produced hydrochloride of triethylamine by filtration from the reaction solution, the obtained filtrate was washed with 500ml of 0.1N hydrochloric acid, and washing with 500ml of water was repeated 4 times. It was dried over sodium sulfate and then at 75 deg.CEvaporating at 90 deg.C, and degassing under reduced pressure to obtain brown solid α -naphthol aralkyl type cyanate ester compound represented by the above formula (2) (R in the formula)⁶All are hydrogen atoms. ). The obtained alpha-naphthol aralkyl type cyanate ester compound was analyzed by infrared absorption spectroscopy, and the result was 2264cm^-1Absorption of cyanate ester groups was observed in the vicinity.

[ example 1]

Diallyl bisphenol A (DABPA, manufactured by Dasuka chemical industry Co., Ltd., hydroxyl equivalent: 154g/eq.)24.1 parts by mass as an allyl phenol compound (A), a maleimide compound (B) (BMI-2300, manufactured by Dasuka chemical industry Co., Ltd., maleimide equivalent: 186g/eq.)60.9 parts by mass, an α -naphthol aralkyl cyanate ester compound (SN495VCN, cyanate ester equivalent: 261g/eq.)5.0 parts by mass as a cyanate ester compound (C) in Synthesis example 1, an epoxy compound (D) (NC-FH 3000, manufactured by Nippon chemical industry Co., Ltd., epoxy equivalent: 328g/eq.)10.0 parts by mass, a slurry silica (SC-2050MB, manufactured by Admatech chemical Company Limited) 200 parts by mass as a filler (E) and an organosilicon compound powder (P-KMM 605) as a filler (E), Manufactured by shin-Etsu chemical 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 part by mass of triphenylimidazole (manufactured by imperial chemical Co., Ltd.) as a curing accelerator were mixed and diluted with methyl ethyl ketone to obtain a varnish. The varnish was impregnated into an E glass woven fabric and dried by heating at 160 ℃ for 3 minutes to obtain a prepreg containing 73 vol% of the resin composition for a printed wiring board.

[ example 2]

A prepreg containing 73 vol% of the resin composition for a printed wiring board was obtained in the same manner as in example 1, except that 19.9 parts by mass of the allyl phenol compound (A) (DABPA), 50.1 parts by mass of the maleimide compound (B) (BMI-2300), 10.0 parts by mass of the cyanate ester compound (C) (SN495VCN), and 20.0 parts by mass of the epoxy compound (D) (NC-3000 FH).

[ example 3 ]

A prepreg containing 73 vol% of the resin composition for a printed wiring board was obtained in the same manner as in example 1, except that the cyanate ester compound (C) (SN495VCN) and the epoxy compound (D) (NC-3000FH) were not used at 15.0 parts by mass.

[ example 4 ]

A prepreg containing 73 vol% of the resin composition for a printed wiring board was obtained in the same manner as in example 1, except that the cyanate ester compound (C) (SN495VCN) was changed to 15.0 parts by mass and the epoxy compound (D) (NC-3000FH) was not used.

[ comparative example 1]

A prepreg having a resin composition content of 73 vol% for a printed wiring board was obtained in the same manner as in example 1 except that 28.4 parts by mass of allyl phenol compound (A) (DABPA), 71.6 parts by mass of maleimide compound (B) (BMI-2300), and that cyanate ester compound (C) (SN495VCN) and epoxy compound (D) (NC-3000FH) were not used.

[ comparative example 2]

A prepreg containing 73 vol% of a resin composition for a printed wiring board was obtained in the same manner as in example 1, except that 60.0 parts by mass of allyl phenol compound (A) (DABPA), 32.1 parts by mass of maleimide compound (B) (BMI-2300), 2.6 parts by mass of cyanate ester compound (C) (SN495VCN), and 5.3 parts by mass of epoxy compound (D) (NC-3000 FH).

[ comparative example 3 ]

A prepreg containing 73 vol% of a resin composition for a printed wiring board was obtained in the same manner as in example 1, except that 12.7 parts by mass of the allyl phenol compound (A) (DABPA), 32.1 parts by mass of the maleimide compound (B) (BMI-2300), 50.0 parts by mass of the cyanate ester compound (C) (SN495VCN), and 5.2 parts by mass of the epoxy compound (D) (NC-3000 FH).

[ comparative example 4 ]

A prepreg containing 73 vol% of the resin composition for a printed wiring board was obtained in the same manner as in example 1, except that the allyl phenol compound (A) (DABPA) was 5.0 parts by mass, the maleimide compound (B) (BMI-2300) was 85.0 parts by mass, the cyanate ester compound (C) (SN495VCN) was 5.0 parts by mass, and the epoxy compound (D) (NC-3000FH) was 5.0 parts by mass.

[ evaluation of physical Properties measurement ]

Using the prepregs obtained in examples 1 to 4 and comparative examples 1 to 4, samples for physical property measurement evaluation were prepared according to the procedures shown in the following items, and the mechanical properties (storage modulus and loss modulus), physical property parameters related to the mechanical properties of formulae (4) to (8) and formulae (4A) to (8A), glass transition temperature (Tg), and warpage amount (3 types) were measured and evaluated. The results of the examples are shown together in table 1, and the results of the comparative examples are shown together in table 2.

[ mechanical characteristics ]

Copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 4, and the pressure was 30kgf/cm²Then, the laminate was laminated at 230 ℃ for 100 minutes (heat-curing) to obtain a copper clad laminate having an insulating layer thickness of 0.1 mm. The obtained copper clad laminate was cut to a size of 20mm × 5mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using the measurement sample, mechanical properties (storage modulus E' and loss modulus E ″) were measured by a DMA method according to JIS C6481 using a dynamic viscoelasticity analyzer (TA Instruments) (n is an average value of 3).

[ glass transition temperature (Tg) ]

Copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 4, and the pressure was 30kgf/cm²Then, the laminate was laminated at 230 ℃ for 100 minutes to obtain a copper clad laminate having an insulating layer thickness of 0.1 mm. The obtained copper clad laminate was cut to a size of 12.7 × 2.5mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. The dynamic viscoelasticity analyzer was used in accordance with JIS C6481 using the measurement sampleThe glass transition temperature (Tg) was measured by the DMA method (average value of n: 3) (TA Instruments).

[ amount of warp: bimetallic method (bimetallic method) ]

First, copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 4, and the pressure was 30kgf/cm²And laminated at 220 ℃ for 120 minutes to obtain a copper clad laminate. Next, the copper foil is removed from the obtained copper clad laminate. Next, 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 4 was further placed on one surface of the laminate from which the copper foil was removed, and the copper foil (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) was placed on both upper and lower surfaces thereof, and the resultant laminate was pressed at a pressure of 30kgf/cm²And then, the laminate was laminated at 220 ℃ for 120 minutes to obtain a copper clad laminate. Further, the copper foil is removed from the obtained copper clad laminate to obtain a laminate. Then, a 20mm × 200mm strip-shaped sheet was cut out from the obtained laminated sheet, the maximum value of the warpage amount at both ends in the longitudinal direction was measured with a metal ruler with the surface of the prepreg laminated on the 2 nd sheet as the upper side, and the average value thereof was defined as the "warpage amount" by the bimetallic strip method.

[ amount of warp: multilayer coreless substrate ]

First, as shown in FIG. 1, a carrier copper foil surface of an extra thin copper foil (b1) (MT18Ex, manufactured by Mitsui Metal mining Co., Ltd., thickness 5 μm) with a carrier was disposed on both surfaces of a prepreg as a support (a), prepregs (c1) obtained in examples 1 to 4 and comparative examples 1 to 4 were further disposed thereon, and a copper foil (d) (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) was disposed thereon, and the pressure was 30kgf/cm²Then, the laminate was laminated at 220 ℃ for 120 minutes to obtain a copper clad laminate shown in FIG. 2.

Next, the copper foil (d) of the obtained copper clad laminate shown in fig. 2 is etched in a predetermined wiring pattern as shown in fig. 3, for example, to form a conductor layer (d'). Next, on the laminate shown in FIG. 3 having the conductor layer (d') formed thereon, as shown in FIG. 4The prepregs (c2) obtained in examples 1 to 4 and comparative examples 1 to 4 were arranged in this manner, and an extra thin copper foil (b2) (MT18Ex, manufactured by Mitsui Metal mineral Co., Ltd., thickness 5 μm) with a carrier was further arranged thereon at a pressure of 30kgf/cm²Then, the laminate was laminated at 220 ℃ for 120 minutes to obtain a copper clad laminate shown in FIG. 5.

Next, in the copper clad laminate shown in fig. 5, the carrier copper foil of the extra thin copper foil with carrier (b1) disposed on the support (a) (the cured prepreg for a support) was peeled from the extra thin copper foil, whereby 2 sheets of the laminate were peeled from the support (a) and further the carrier copper foil was peeled from the extra thin copper foil with carrier (b2) on the upper portion of each laminate as shown in fig. 6. Next, the upper and lower extra thin copper foils of each of the obtained laminated sheets were processed by a laser processing machine, and as shown in fig. 7, predetermined through holes (v) were formed by electroless copper plating. Thereafter, as shown in FIG. 8, a conductor layer is formed by etching a predetermined wiring pattern, thereby obtaining a multilayer coreless substrate panel (size: 500 mm. times.400 mm). Then, the total warpage amounts of 8 portions of the obtained panel at the 4 corners and the 4-side center portion were measured with a metal ruler, and the average value thereof was defined as the "warpage amount" of the panel of the multilayer coreless substrate.

[ shrinkage ratio of substrate before and after reflow soldering ]

Copper foils (3EC-VLP, manufactured by Mitsui Metal mining Co., Ltd., thickness 12 μm) were placed on both upper and lower surfaces of 1 sheet of the prepreg obtained in examples 1 to 4 and comparative examples 1 to 4, and the pressure was 30kgf/cm²And laminated at 220 ℃ for 120 minutes to obtain a copper clad laminate. Next, the obtained copper clad laminate was drilled at 9 points uniformly in a grid pattern with a drill, and then the copper foil was removed.

Thereafter, first, the distance (distance a) between the holes of the laminated board from which the copper foil was removed was measured. Subsequently, the laminate was subjected to reflow treatment using an SALAMANDER reflow apparatus with a maximum temperature of 260 ℃. Thereafter, the distance (distance b) between the holes of the laminated plate was measured again. Then, the measured distance a and distance b are substituted into the following formula (I), and the dimensional change rate of the substrate in the reflow process is determined, and the value thereof is regarded as the substrate shrinkage rate before and after the reflow process.

((distance a) - (distance b))/distance a × 100 … formula (I)

[ Table 1]

[ Table 2]

Industrial applicability

The resin composition for a printed wiring board according to the present embodiment has industrial applicability as a material for a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, or a multilayer printed wiring board. The present application is based on Japanese patent application No. 2016-.

Claims

1. A resin composition for a printed circuit board, comprising:

an allylphenol compound (A),

Maleimide compound (B), and

a cyanate ester compound (C) and/or an epoxy compound (D),

the content of the allyl phenol compound (A) is 15-30 parts by mass relative to 100 parts by mass of resin solid content in the resin composition for the printed circuit board,

the content of the maleimide compound (B) is 45-80 parts by mass relative to 100 parts by mass of resin solid content in the resin composition for a printed circuit board,

the cured product of the resin composition does not have a clear glass transition temperature, which is measured by a DMA method using a dynamic viscoelasticity analyzer in accordance with JIS C6481.

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

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

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

5. The resin composition for a printed circuit board according to claim 1 or 2, further comprising a filler (E).

6. The resin composition for a printed circuit board according to claim 5, wherein the filler (E) is at least 1 selected from the group consisting of silica, alumina and boehmite.

7. The resin composition for a printed circuit board according to claim 5, wherein the content of the filler (E) is 120 to 250 parts by mass with respect to 100 parts by mass of a resin solid content in the resin composition for a printed circuit board.

8. The resin composition for a printed circuit board according to claim 6, wherein the content of the filler (E) is 120 to 250 parts by mass with respect to 100 parts by mass of a resin solid content in the resin composition for a printed circuit board.

9. The resin composition for a printed circuit board according to claim 1 or 2, wherein the allylphenol compound (A) comprises a compound represented by any one of the following formulas (I) to (III),

in the formula (I), R₁And R₂Each independently represents a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group,

10. the resin composition for a printed circuit board according to claim 1 or 2, wherein the maleimide compound (B) comprises at least 1 selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and a maleimide compound represented by the following formula (1),

in the formula (1), R₅Each independently represents a hydrogen atom or a methyl group, n₁Represents an integer of 1 or more.

11. The resin composition for a printed circuit board according to claim 1 or 2, wherein the cyanate ester compound (C) comprises a compound represented by the following formula (2) and/or (3),

in the formula (2), R₆Each independently represents a hydrogen atom or a methyl group, n₂Represents an integer of 1 or more and is,

in the formula (3), R₇Each independently represents a hydrogen atom or a methyl group, n₃Represents an integer of 1 or more.

12. The resin composition for a printed circuit board according to claim 1 or 2, wherein a cured product obtained by thermally curing a prepreg comprising the resin composition for a printed circuit board and a base material at 230 ℃ for 100 minutes satisfies a numerical range of physical property parameters relating to 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 modulus of the cured product at the temperature shown in parentheses, E ' max represents the maximum value of the loss modulus of the cured product in the temperature range of 30-330 ℃, and E ' min represents the minimum value of the loss modulus of the cured product in the temperature range of 30-330 ℃.

13. A prepreg, having:

a base material, and

the resin composition for a printed wiring board according to any one of claims 1 to 12 impregnated or coated on the base material.

14. The prepreg of claim 13, wherein the substrate is composed of 1 or more fibers selected from the group consisting of E glass fibers, D glass fibers, S glass fibers, T glass fibers, Q glass fibers, L glass fibers, NE glass fibers, HME glass fibers, and organic fibers.

15. A resin tablet having:

a support body, and

the resin composition for a printed wiring board according to any one of claims 1 to 12 laminated on one surface or both surfaces of the support.

16. A laminate panel having: at least 1 or more sheets of at least 1 selected from the group consisting of the prepregs according to claims 13 and 14 and the resin sheet according to claim 15 are laminated.

17. A metal-clad laminate comprising: stacking at least 1 or more sheets of at least 1 selected from the group consisting of the prepregs according to claims 13 and 14 and the resin sheet according to claim 15; and

18. A printed circuit board, having:

an insulating layer, and

a conductor layer formed on the surface of the insulating layer,

the insulating layer comprises the resin composition for a printed circuit board according to any one of claims 1 to 12.

19. A multilayer printed circuit board having: a plurality of insulating layers and a plurality of conductor layers,

the plurality of insulating layers includes: stacking at least 1 or more 1 st insulating layers formed of at least 1 selected from the group consisting of the prepregs according to claims 13 and 14 and the resin sheet according to claim 15; and at least 1 or more second insulating layers 2 each formed of at least 1 selected from the group consisting of the prepreg according to claims 13 and 14 and the resin sheet according to claim 15 are laminated in a single-side direction of the first insulating layer 1;