JP7025729B2 - Resin composition for printed wiring boards, prepregs, resin sheets, laminated boards, metal foil-clad laminated boards, printed wiring boards, and multilayer printed wiring boards. - Google Patents

Description

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

In recent years, as semiconductor packages widely used in electronic devices, communication devices, personal computers, etc. have become more sophisticated and smaller, the high integration and high-density mounting of each component for semiconductor packages has accelerated in recent years. ing. Along with this, various characteristics required for printed wiring boards for semiconductor packages are becoming more and more severe. The characteristics required for such a printed wiring board include, for example, low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion factor, heat resistance, chemical resistance, high plating peel strength and the like. Can be mentioned. In addition to these, suppressing the warpage of printed wiring boards, especially multilayer coreless boards (achieving low warpage) has recently become an important issue, and various measures have been taken. There is.

One of the countermeasures is to reduce the thermal expansion of the insulating layer used for the printed wiring board. This is a method of suppressing warpage by making the thermal expansion rate of a printed wiring board close to the thermal expansion rate of a semiconductor element, and is currently being actively pursued (see, for example, Patent Documents 1 to 3).

As a method for suppressing the warp of the semiconductor plastic package, in addition to the low thermal expansion of the printed wiring board, the rigidity of the laminated board is increased (high rigidity) and the glass transition temperature of the laminated board is increased (high Tg). (See, for example, Patent Documents 4 and 5).

Japanese Unexamined Patent Publication No. 2013-216884 Japanese Patent No. 3173332 Japanese Unexamined Patent Publication No. 2009-035728 Japanese Unexamined Patent Publication No. 2013-001807 Japanese Unexamined Patent Publication No. 2011-178992

However, according to the detailed examination by the present inventors, even with the above-mentioned conventional technique, the warp of the printed wiring board, particularly the multilayer coreless substrate cannot be sufficiently reduced, and further improvement is desired. It is rare.

That is, in the present invention, there is no clear glass transition temperature (so-called Tg-less), and the warpage of the printed wiring board, particularly the multilayer coreless substrate, can be sufficiently reduced (low warpage is achieved). It is an object of the present invention to provide a resin composition for a board, and a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, a printed wiring board, and a multilayer printed wiring board using the resin composition for a printed wiring board. do.

As a result of diligent studies to solve the above problems, the present inventors have conventionally obtained a larger thermal storage elastic modulus in a cured prepreg with respect to the warp behavior of a printed wiring board for a semiconductor plastic package. And although it has been considered that a resin composition capable of achieving a higher elastic modulus maintenance rate is effective, it has been found that this is not always the case. Furthermore, as a result of diligent research, the present inventors have found that the above problems can be solved by using a cyanic acid ester compound and / or an epoxy compound in addition to the allylphenol compound and the maleimide compound, and the present invention has been developed. It came to be completed.

That is, the present invention is as follows.
[1]
Allylphenol compound (A) and
Maleimide compound (B) and
A resin composition for a printed wiring board containing a cyanic acid ester compound (C) and / or an epoxy compound (D).
The content of the allylphenol compound (A) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 10 to 50 parts by mass.
The content of the maleimide compound (B) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 40 to 80 parts by mass.
Resin composition for printed wiring boards.

[2]
The total content of the cyanic acid ester compound (C) and the epoxy compound (D) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 5 to 45 parts by mass.
The resin composition for a printed wiring board according to [1].

[3]
The content of the cyanic acid ester compound (C) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 0 to 25 parts by mass.
The resin composition for a printed wiring board according to [1] or [2].

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

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

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

[7]
The content of the filler (E) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 120 to 250 parts by mass.
The resin composition for a printed wiring board according to [5] or [6].

[8]
The allyl phenol compound (A) contains a compound represented by any of the following formulas (I) to (III).
The resin composition for a printed wiring board according to any one of [1] to [7].

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

[9]
The maleimide compound (B) is bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl). ) Containing at least one selected from the group consisting of methane and a maleimide compound represented by the following formula (1).
The resin composition for a printed wiring board according to any one of [1] to [8].

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

[10]
The cyanate ester compound (C) contains a compound represented by the following formulas (2) and / or (3).
The resin composition for a printed wiring board according to any one of [1] to [9].

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

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

[11]
The cured product obtained by thermally curing the prepreg containing the resin composition for a printed wiring board and the base material at 230 ° C. for 100 minutes is the following formulas (4) to (8);
E'(200 ° C) / E'(30 ° C) ≤ 0.90 ... (4)
E'(260 ° C) / E'(30 ° C) ≤ 0.85 ... (5)
E'(330 ° C) / E'(30 ° C) ≤ 0.80 ... (6)
E''max / E'(30 ° C) ≤ 3.0% ... (7)
E''min / E'(30 ° C) ≧ 0.5%… (8)
(In each formula, E'indicates the storage elastic modulus of the cured product at the temperature shown in parentheses, and E''max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C to 330 ° C. E''min indicates the minimum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C to 330 ° C.)
Satisfy the numerical range of physical property parameters related to mechanical properties represented by
The resin composition for a printed wiring board according to any one of [1] to [10].

[12]
With the base material
The resin composition for a printed wiring board according to any one of [1] to [11] impregnated or applied to the substrate, and the resin composition for a printed wiring board.
A prepreg with.

[13]
One or more of the base materials selected from the group consisting of E glass fiber, D glass fiber, S glass fiber, T glass fiber, Q glass fiber, L glass fiber, NE glass fiber, HME glass fiber, and organic fiber. It is composed of the fibers of
The prepreg according to [12].

[14]
With the support,
The resin composition for a printed wiring board according to any one of [1] to [11] laminated on one side or both sides of the support.
Resin sheet with.

[15]
It has at least one selected from the group consisting of the prepregs described in [12] and [13], and the resin sheet described in [14], in which at least one sheet is laminated.
Laminated board.

[16]
At least one selected from the group consisting of at least one laminated prepreg according to [12] and [13], and the resin sheet according to [14].
At least one kind of metal foil arranged on one side or both sides selected from the group consisting of the prepreg and the resin sheet, and
Metal leaf-clad laminate with.

[17]
Insulation layer and
A conductor layer formed on the surface of the insulating layer and
Have,
The insulating layer contains the resin composition for a printed wiring board according to any one of [1] to [11].
Printed wiring board.

[18]
A first insulating layer formed of at least one selected from the group consisting of at least one laminated prepreg according to [12] and [13], and the resin sheet according to [14], and Formed by at least one selected from the group consisting of the prepregs described in [12] and [13] and the resin sheet described in [14], in which at least one or more sheets of the first insulating layer are laminated in one side direction. A plurality of insulating layers composed of the second insulating layer formed on the resin,
A plurality of conductor layers composed of a first conductor layer arranged between each of the plurality of insulating layers and a second conductor layer arranged on the surface of the outermost layer of the plurality of insulating layers.
Multi-layer printed wiring board with.

According to the present invention, there is no clear glass transition temperature (Tg-less), and the warpage of the printed wiring board, particularly the multilayer coreless substrate, can be sufficiently reduced (low warpage is achieved). It is possible to provide a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, a printed wiring board, and a multilayer printed wiring board using the resin composition for printing and the resin composition for printed wiring boards. ..

It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate (however, the manufacturing method of a multilayer coreless substrate is not limited to this, and is the same in FIGS. 2 to 8 below). It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate. It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate. It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate. It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate. It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate. It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate. It is a process flow diagram which shows an example of the procedure for manufacturing a panel of a multilayer coreless substrate. It is a partial cross-sectional view which shows the structure of an example of a panel of a multilayer coreless substrate.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications may be made without departing from the gist thereof. It is possible. In the present embodiment, the "resin solid content" refers to a component of the resin composition for a printed wiring board excluding the solvent and the filler, unless otherwise specified, and is "100 parts by mass of the resin solid content". It means that the total of the components excluding the solvent and the filler in the resin composition for the printed wiring board is 100 parts by mass.

[Resin composition for printed wiring board]
The resin composition for a printed wiring board of the present embodiment contains an allylphenol compound (A), a maleimide compound (B), a cyanic acid 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, in a cured product obtained by curing a prepreg, a clear glass transition temperature does not exist (Tg-less), and the printed wiring board, In particular, there is a tendency that the warp of the multilayer coreless substrate can be sufficiently reduced (low warpage is achieved).

[Allylphenol compound (A)]
The allylphenol compound (A) is not particularly limited as long as it is a compound in which at least one allyl group and one or more hydroxyl groups are directly bonded to the aromatic ring, but for example, the hydrogen atom of the aromatic ring is substituted with the allyl group. The bisphenol that has been used can be mentioned. The bisphenol is not particularly limited, but for example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P. , Bisphenol PH, Bisphenol TMC, Bisphenol Z. Among these, bisphenol A is preferable, as the allylphenol compound (A), diallylbisphenol A is more preferable, and the compound represented by the following formula (I) or formula (II) is further 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 peel strength tend to be further improved.

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

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

Further, the allylphenol compound (A) may further have a reactive functional group other than the allyl group and the hydroxyl group. Further, the hydroxyl group directly bonded to the aromatic ring may be a compound modified to a reactive functional group other than the allyl group and the hydroxyl group. The reactive functional group other than the allyl group and the hydroxyl group is not particularly limited, and examples thereof include a cyanate group (cyanic acid ester group), an epoxy group, an amine group, an isocyanate group, a glycidyl group, and a phosphoric acid group. By having these, the bending strength, the bending elastic modulus, the thermal expansion coefficient, and the thermal conductivity tend to be further improved. As the allylphenol compound (A), one type may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, the reactive functional groups other than the allyl group and the hydroxyl group may be the same or different.

The number of allyl groups in one molecule of the allylphenol compound (A) is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2. Allylphenol compound (A) When the number of allyl groups in one molecule is within the above range, the bending strength, flexural modulus, and copper foil peel strength are further improved, the thermal expansion coefficient is low, and the thermal conductivity is increased. It tends to be excellent.

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

When the allyl phenol compound (A) has a reactive functional group other than the allyl group and the hydroxyl group described above, the number of reactive functional groups other than the allyl group and the hydroxyl group in one molecule of the allyl phenol compound (A) is preferable. It is 1 to 5, more preferably 2 to 4, and even more preferably 2. When the number of reactive functional groups other than the allyl group and the hydroxyl group in one molecule of the allylphenol compound (A) is within the above range, the bending strength, the bending elastic modulus, and the copper foil peel strength are further improved, and the thermal expansion coefficient is increased. Is low and tends to have excellent 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 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. It is 15 to 30 parts by mass. When the content of the allylphenol compound (A) is within the above range, the flexibility, bending strength, flexural modulus, thermal expansion rate, thermal conductivity, and copper foil peel strength of the obtained cured product are further improved. Tend to do.

[Maleimide compound (B)]
The maleimide compound (B) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule, and for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, and the like. 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 prepolymers of maleimide compounds and amine compounds. Among these, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, and At least one selected from the group consisting of the maleimide compound represented by the following formula (1) is preferable, and a resin composition having no clear glass transition temperature (Tg-less) can be easily obtained, and thus the following formula (1). The maleimide compound represented by is particularly preferable. By containing the above-mentioned maleimide compound (B), the thermal expansion rate of the obtained cured product tends to be further lowered, and the heat resistance and the glass transition temperature (Tg) tend to be further improved. The maleimide compound (B) may be used alone or in combination of two or more.

Here, in the formula (1), R ₅ independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Further, in the equation (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 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. It is ~ 65 parts by mass. When the content of the maleimide compound (B) is within the above range, the coefficient of thermal expansion of the obtained cured product tends to be further lowered, and the heat resistance tends to be further improved.

[Cyanic acid ester compound (C) and / or epoxy compound (D)]
The resin composition for a printed wiring board of this embodiment contains a cyanic acid 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 allylphenol compound (A) and the maleimide compound (B) described above, for example, in a cured product obtained by curing a prepreg, a clear glass is used. There is a tendency for the resin composition to have no transition temperature (Tg-less) and to sufficiently reduce the warpage of the printed wiring board, particularly the multilayer coreless substrate (achieve low warpage).

(Cyanic acid ester compound (C))
The cyanate ester compound (C) is not particularly limited, but for example, a naphthalal aralkyl type cyanate ester represented by the following formula (2), a novolak type cyanate ester represented by the following formula (3), and a biphenyl aralkyl type cyanide. Acid ester, bis (3,5-dimethyl4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,3,5- Tricianatobenzene, 1,3-disianatonaphthalene, 1,4-disyanatnaphthalene, 1,6-disianatonaphthalene, 1,8-disyanatnaphthalene, 2,6-disyanatnaphthalene, 2,7-disyanat Naphthalene, 1,3,6-trisianatonaphthalene, 4,4'-disyanatobiphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, 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 or in combination of two or more.

In the formula (2), R ⁶ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the equation (2), n ₂ represents an integer of 1 or more. The upper limit of n ₂ is usually 10, preferably 6.

In the formula (3), R ⁷ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the equation (3), n ₃ represents an integer of 1 or more. The upper limit of n ₃ is usually 10, preferably 7.

Among these, the cyanic acid ester compound (C) is composed of a naphthol aralkyl-type cyanate ester represented by the formula (2), a novolak-type cyanate ester represented by the formula (3), and a biphenyl aralkyl-type cyanate ester. It is preferable to include one or more selected from the group, and one or more selected from the group consisting of the naphthol aralkyl type cyanate ester represented by the formula (2) and the novolak type cyanate ester represented by the formula (3). It is more preferable to include. By using such a cyanate ester compound (C), there is a tendency to obtain a cured product having better flame retardancy, higher curability, and a lower coefficient of thermal expansion.

The method for producing the cyanic acid ester compound (C) is not particularly limited, and a known method can be used as a method for synthesizing the cyanic acid ester compound. The known method is not particularly limited, but for example, a method of reacting a phenol resin and cyanogen halide in the presence of a basic compound in an inert organic solvent, a salt of the phenol resin and the basic compound, and water. Examples thereof include a method of forming the mixture in the contained solution and then allowing the obtained salt and cyanogen halide to undergo a two-phase interfacial reaction.

The phenol resin used as a raw material for these cyanate ester compounds (C) is not particularly limited, and for example, a naphthol aralkyl type phenol resin represented by the following formula (9), a novolak type phenol resin, and a biphenyl aralkyl type phenol resin can be used. Can be mentioned.

In formula (9), R ⁸ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Further, in the equation (9), n ₄ represents an integer of 1 or more. The upper limit 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 with cyanic acid. The naphthol aralkyl-type phenol resin is not particularly limited, and is, for example, naphthols such as α-naphthol and β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, and 1,4-. Examples thereof include those obtained by reaction with benzenes such as di (2-hydroxy-2-propyl) benzene. The naphthol aralkyl type cyanic acid ester can be selected from those obtained by condensing the naphthol aralkyl resin obtained as described above with cyanic acid.

The content of the cyanic acid ester compound (C) is preferably 0 to 25 parts by mass, and more preferably 0 to 20 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. be. 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 further improved.

(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, and for example, a bisphenol A type epoxy resin, a bisphenol E type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol. S-type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type Epoxy resin, 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, polyol type epoxy resin, isocyanurate ring-containing epoxy Examples thereof include resins and epoxies thereof. Further, as the epoxy compound (D), a non-halogenated epoxy compound (non-halogen-containing epoxy compound, halogen-free epoxy compound) is more preferable. When the allylphenol compound (A) has 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 with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. When the content of the epoxy compound (D) is within the above range, the flexibility of the obtained cured product, the copper foil peel strength, the chemical resistance, and the desmear resistance tend to be further improved.

As described above, the resin composition for the printed wiring board of the present embodiment contains the cyanate ester compound (C) and / or the epoxy compound (D), and the cyanate ester compound (C) and the epoxy compound ( When both of D) are contained, the total content of the cyanate ester compound (C) and the epoxy compound (D) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is preferably 5 to 45 mass by mass. It is a part, more preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass. When the total content of the cyanic acid ester compound (C) and the epoxy compound (D) is within the above range, the obtained cured product has flexibility, copper foil peel strength, heat resistance, chemical resistance, and desmear resistance. Tends to improve. Further, since the total content of the cyanate ester compound (C) and the epoxy compound (D) is within the above range, for example, in the cured product obtained by curing the prepreg, there is no clear glass transition temperature (Tg). There is a tendency for the resin composition to be able to further reduce the warpage (achieve low warpage) of the printed wiring board, particularly the multilayer coreless substrate.

[Filler (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 it is preferable that the filler (E) contains an inorganic filler, and the organic filler is used together with the inorganic filler. Is preferable. The inorganic filler is not particularly limited, but for example, silicas such as natural silica, molten silica, synthetic silica, amorphous silica, aerodil and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, etc. Metal oxides such as zirconium oxide; metal nitrides such as boron nitride, coagulated boron nitride, silicon nitride and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide and aluminum hydroxide heat-treated products (heating aluminum hydroxide) Metal hydrate such as treated and reduced part of crystalline water), boehmite, metal hydrate such as magnesium hydroxide; molybdenum compound such as molybdenum oxide and zinc molybdenum; zinc compound such as zinc borate and zinc tintate; alumina , Clay, kaolin, talc, fired clay, fired kaolin, fired talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20. , Glass short fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and 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 type powder, butadiene type powder, and acrylic type powder; core shell type rubber powder; silicone resin powder; silicone rubber powder; and silicone composite powder. Be done. As the filler (E), one type may be used alone, or two or more types may be used in combination.

Among these, at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride, which are inorganic fillers, may be contained. It is preferable to contain at least one selected from the group consisting of silica, alumina, and boramite. By using such a filler (E), the obtained cured product tends to have higher rigidity and lower warpage.

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

[Silane coupling agent and wet dispersant]
The resin composition for a printed wiring board of the present embodiment may further contain a silane coupling agent and a wet dispersant. By including the silane coupling agent and the wet dispersant, the dispersibility of the filler (E), the resin component, the filler (E), and the adhesive strength of the substrate described later tend to be further improved.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances, but for example, γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ. -Aminosilane-based compounds such as aminopropyltrimethoxysilane; epoxysilane-based compounds such as γ-glycidoxypropyltrimethoxysilane; acrylicsilane-based compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N-). Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane Hydrochloride and other cationic silane compounds; phenylsilane compounds and the like can be mentioned. The silane coupling agent may be used alone or in combination of two or more.

The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints, but for example, DISPERBYK-110, 111, 118, 180, 161 and BYK-W996 manufactured by Big Chemy Japan Co., Ltd. , W9010, W903 and the like.

[Other resins, etc.]
The resin composition for a printed wiring board of the present embodiment is, if necessary, an allyl group-containing compound (hereinafter, also referred to as “other allyl group-containing compound”) and a phenol resin other than the above-mentioned allylphenol compound (A). , Oxetane resin, benzoxazine compound, and one or more selected from the group consisting of a compound having a polymerizable unsaturated group. By including such other resins and the like, the copper foil peel strength, bending strength, bending elastic modulus and the like of the obtained cured product tend to be further improved.

[Other allyl group-containing compounds]
The other allyl group-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, diallyl maleate and the like. Can be mentioned.

The content of the other allyl group-containing compound is preferably 0 to 50 parts by mass, and more preferably 10 to 45 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. , More preferably 15 to 45 parts by mass, still more preferably 20 to 35 parts by mass. When the content of the other allyl group-containing compound is within the above range, the bending strength, flexural modulus, heat resistance, and chemical resistance of the obtained cured product tend to be further improved.

[Phenol resin]
As the phenol resin, a generally known phenol resin can be used as long as it is a phenol resin having two or more hydroxy groups in one molecule, and the type thereof 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 novolak type phenol resin, glycidyl ester type phenol resin, and aralkylnovolac type. Phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin , Naftor aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, hydroxyl-containing silicone resin, etc., but are particularly limited. It's not a thing. These phenol resins can be used alone or in combination of two or more. By containing such a phenol resin, the obtained cured product tends to be more excellent in adhesiveness and flexibility.

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

[Oxetane resin]
As the oxetane resin, generally known ones can be used, and the type thereof is not particularly limited. Specific examples thereof include alkyloxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3'. -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toa Synthetic), OXT-121 (manufactured by Toa Synthetic) Product name) and the like. These oxetane resins can be used alone or in combination of two or more. By including such an oxetane resin, the obtained cured product tends to be more excellent in adhesiveness and flexibility.

The content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring 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 further improved.

[Benzoxazine compound]
As the benzoxazine compound, a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type benzoxazine BA-BXZ (trade name manufactured by Konishi Chemicals), bisphenol F type benzoxazine BF-BXZ (trade name manufactured by Konishi Chemicals), and bisphenol S type benzoxazine BS-BXZ (trade name manufactured by Konishi Chemicals). First name) and so on. These benzoxazine compounds can be used alone or in admixture of two or more. By containing such a benzoxazine compound, the obtained cured product tends to be more excellent in flame retardancy, heat resistance, low water absorption, low dielectric 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 1 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. Is 3 to 80 parts by mass. When the content of the benzoxazine compound is within the above range, the heat resistance of the obtained cured product tends to be further improved.

[Compound having a polymerizable unsaturated group]
As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the type thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polypropylene glycol di ( (Meta) of monovalent or polyhydric alcohols such as trimethylolpropane di (meth) acrylate, trimethylol propanedi (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Examples thereof include acrylates; epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; benzocyclobutene resin; (bis) maleimide resin and the like. These compounds having a polymerizable unsaturated group can be used alone or in admixture of two or more. By containing such a compound having a polymerizable unsaturated group, the obtained cured product tends to be more excellent in heat resistance and toughness.

The content of the compound having a polymerizable unsaturated group is preferably 0 to 99 parts by mass, and more preferably 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board. Parts, more preferably 3 to 80 parts by mass. When the content of the compound having a polymerizable unsaturated group is within the above range, the obtained cured product tends to be more excellent in heat resistance and toughness.

[Curing accelerator]
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 is, for example, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate and the like. Organic peroxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylpyridine, 2-N-ethylanilino Tertiary amines such as ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenol, xylenol, cresol, resorcin, catechol Phenols such as: lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, organic metal salts such as acetylacetone iron; Those dissolved in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide and other organic tin compounds such as alkyl tin and alkyl tin oxide can be mentioned. .. Among these, triphenylimidazole is particularly preferable because it promotes the curing reaction and tends to have an excellent thermal expansion rate.

〔solvent〕
The resin composition for a printed wiring board of the present embodiment may further contain a solvent. By containing a solvent, the viscosity of the resin composition for a printed wiring board at the time of preparation is lowered, the handleability is further improved, and the impregnation property into a substrate, which will be 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 printed wiring boards, but for example, ketones such as acetone, methyl ethyl ketone and methyl cell solve; toluene, Examples include aromatic hydrocarbons such as xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and acetate thereof. As the solvent, one type may be used alone, or two or more types may be used in combination.

[Manufacturing method of resin composition for printed wiring board]
The method for producing the resin composition for a printed wiring board of the present embodiment is not particularly limited, and examples thereof include a method in which each component is sequentially mixed with a solvent and sufficiently stirred. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler (E) in the resin composition for a printed wiring board can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability. .. The above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or rotating type mixing apparatus.

Further, when preparing the resin composition for a printed wiring board of the present embodiment, an organic solvent can be used if necessary. 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 wiring board. Specific examples thereof are as described above.

[Characteristics of resin composition for printed wiring board]
The resin composition for a printed wiring board of the present embodiment is a cured product obtained by thermally curing a prepreg containing the prepreg containing the substrate at 230 ° C. for 100 minutes according to the following formulas (4) to (8). It is preferable that the numerical range of the physical property parameter relating to the represented mechanical property is satisfied, and it is more preferable that the numerical range of the physical property parameter relating to the mechanical property represented by the following formulas (4A) to (8A) is satisfied.

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

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

Conventionally, regarding the warp behavior of the printed wiring board, it has been considered that a resin composition capable of achieving a larger thermal storage elastic modulus and a higher elastic modulus maintenance rate is effective in the cured product of the prepreg. This is not always the case, and the numerical values of the physical property parameters related to the mechanical properties of the cured product obtained by thermally curing the prepreg at 230 ° C. and 100 minutes are the above formulas (4) to (8), preferably the formulas (4A) to. Within the range of (8A), the glass transition temperature (Tg) can be sufficiently increased, and the amount of warpage of the laminated board, the metal foil-covered laminated board, the printed wiring board, particularly the multilayer coreless substrate itself is sufficient. Can be reduced to.

In other words, the numerical values of the physical property parameters related to the mechanical properties of the cured product obtained by thermally curing the prepreg at 230 ° C. and 100 minutes are the above formulas (4) to (8), preferably the formulas (4A) to (8A). By being within the range of, preferably, there is no clear glass transition temperature (Tg-less), and the warp of the printed wiring board (particularly, the multilayer coreless substrate) is sufficiently reduced (low warpage is achieved). It becomes possible. That is, satisfying the formulas (7) and (8), preferably the formulas (7A) and (8A) relating to the loss elastic modulus can be said to be synonymous with the absence of a clear glass transition temperature (Tgless). If the object satisfies only the formulas (7) and (8) preferably only the formulas (7A) and (8A), and does not satisfy the formulas (4) to (6) preferably the formulas (4A) to (6A), the loss modulus Although the rate itself is small and difficult to stretch, when it is used as a printed wiring board, the difficulty in stretching is a disaster and it becomes difficult to achieve low warpage. On the other hand, the cured product satisfies not only the formulas (7) and (8) preferably the formulas (7A) and (8A) but also the formulas (4) to (8) preferably the formulas (4A) and (8A). Those are difficult to stretch due to Tg-less, and tend to easily achieve low warpage of the printed wiring board.

The method for measuring the mechanical properties (storage elastic modulus E'and loss elastic modulus E'') of the cured product of the prepreg is not particularly limited, and can be measured by, for example, the following method. That is, copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) is placed on both the upper and lower surfaces of one prepreg, 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 copper foil-clad laminate with a predetermined insulating layer thickness. Next, the obtained copper foil-clad laminate is cut into a size of 5.0 mm × 20 mm with a dicing saw, and the copper foil on the surface is removed by etching to obtain a sample for measurement. Using this measurement sample, the mechanical properties (storage elastic modulus E'and loss elastic modulus E'') are measured by the DMA method with a dynamic viscoelastic analyzer (manufactured by TA Instruments) in accordance with JIS C6481. be able to. At this time, the average value of n = 3 may 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 laminated board, a metal foil-clad laminated board, a printed wiring board, or a multilayer printed wiring board. Hereinafter, the prepreg, the resin sheet, the laminated board, the metal foil-covered laminated board, and the printed wiring board (including the multi-layer printed wiring board) will be described.

[Prepreg]
The prepreg of the present embodiment contains a base material and a resin composition for a printed wiring board impregnated or coated on the base material. The method for producing the prepreg can be carried out according to a conventional method, and is not particularly limited. For example, after impregnating or coating the substrate with the resin composition for a printed wiring board according to the present embodiment, it is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. ), The prepreg of the present embodiment can be produced.

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

The base material is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Examples of the base material include a glass base material, an inorganic base material other than glass, an organic base material, and the like, and among these, a glass base material is particularly preferable from the viewpoint of high rigidity and thermal dimensional stability. .. Specific examples of the fibers constituting these substrates are not particularly limited, and the glass substrate includes, for example, E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Examples include one or more glass fibers selected from the group. Inorganic base materials other than glass include inorganic fibers other than glass such as quartz. Furthermore, in the case of organic substrates, polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin Techno Products Limited) Total aromatic polyamides such as (manufactured by the company); polyesters such as 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB Salen); Examples thereof include organic fibers such as phenylene benzoxazole (Zylon (registered trademark), manufactured by Toyo Spinning Co., Ltd.) and polyimide. These base materials may be used alone or in combination of two or more.

The shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones according to the intended use and performance. .. Further, a glass woven fabric obtained by opening the fibers or surface-treating with a silane coupling agent or the like is preferably used. The thickness and mass of the base material are not particularly limited, but usually those having a thickness of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the base material is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less, and a glass woven fabric made of glass fibers of E glass, S glass, and T glass is preferable. More preferred.

Further, as described above, in the prepreg of the present embodiment, the cured product obtained by thermally curing the prepreg at 230 ° C. and 100 minutes is preferably the formulas (4) to (8), preferably the formulas (4A) to (4A). When the numerical range of the physical property parameters related to the mechanical properties represented by 8A) is satisfied, the laminated board, the metal foil-clad laminated board, the printed wiring board, or the multilayer printed wiring board does not have a clear glass transition temperature. It is preferable because it is (Tg-less) and tends to sufficiently reduce warpage (achieve low warpage).

[Resin sheet]
The resin sheet of the present embodiment has a sheet base material (support) and the resin composition for a printed wiring board laminated on one side or both sides of the sheet base material. The resin sheet is used as one means of thinning leaves. For example, a thermosetting resin (including a filler (E)) used for a prepreg or the like is directly applied to a support such as a metal foil or a film. It can be coated and dried to produce.

The sheet base material is not particularly limited, but known materials used for various printed wiring board materials can be used. Examples thereof include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, a polyethylene (PE) film, an aluminum foil, a copper foil, and a gold foil. Among them, electrolytic copper foil and PET film are preferable.

Examples of the coating method include a method in which a solution obtained by dissolving the resin composition for a printed wiring board of the present embodiment in a solvent is applied onto a sheet substrate with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Be done.

The resin sheet is preferably one in which the resin composition for a printed wiring board is applied to a sheet base material and then semi-cured (B-staged). Specifically, for example, the resin composition for a printed wiring board is applied to a sheet base material such as a copper foil, and then semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes. , A method of manufacturing a resin sheet and the like. The amount of the resin composition for a printed wiring board adhered to the sheet substrate is preferably in the range of 1 to 300 μm in terms of the resin thickness of the resin sheet.

[Laminated board and metal leaf-clad laminated board]
The laminated board of the present embodiment has at least one laminated plate of the prepreg of the present embodiment and / or the resin sheet of the present embodiment. Further, the metal leaf-clad laminate of the present embodiment includes the laminate of the present embodiment (that is, the prepreg of the present embodiment and / or the resin sheet of the present embodiment in which at least one is laminated) and the same. It has a metal foil (conductor layer) arranged on one side or both sides of the laminated plate.

The conductor layer can be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but a known copper foil such as a rolled copper foil or an 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 molding method of the laminated board or the metal foil-clad laminated board and the molding conditions thereof are not particularly limited, and general methods and conditions of the laminated board for printed wiring boards and the multilayer board can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous forming machine, an autoclave forming machine, or the like can be used at the time of forming a set laminated board or a metal leaf-clad laminated board. Further, in the molding of a laminated board or a metal leaf-clad laminated board (laminated molding), the temperature is generally in the range of 100 to 300 ° C., the pressure is 2 to 100 kgf / cm ² , and the heating time is generally in the range of 0.05 to 5 hours. Is. Further, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. In particular, when a multi-stage press machine is used, the temperature is preferably 200 ° C. to 250 ° C., the pressure is 10 to 40 kgf / cm ² , and the heating time is 80 minutes to 130 minutes from the viewpoint of sufficiently promoting the curing of the prepreg and / or the resin sheet. , The temperature is 215 ° C. to 235 ° C., the pressure is 25 to 35 kgf / cm ² , and the heating time is 90 minutes to 120 minutes. Further, it is also possible to form a multilayer board by laminating and molding the above-mentioned prepreg and / or resin sheet in combination with a wiring board for an inner layer separately prepared.

[Printed wiring board]
The printed wiring board of the present embodiment is a printed wiring board having an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the resin composition for a printed wiring board. For example, by forming a predetermined wiring pattern on the above-mentioned metal foil-clad laminate, it can be suitably used as a printed wiring board. The metal foil-clad laminate using the resin composition for the printed wiring board of the present embodiment does not have a clear glass transition temperature (Tg-less) and sufficiently reduces warpage (achieves low warpage). Since there is a tendency to be able to do so, it can be particularly effectively used as a printed wiring board that requires such performance.

Specifically, the printed wiring board of the present embodiment can be manufactured by, for example, the following method. First, the above-mentioned metal foil-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 created. The inner layer circuit surface of this inner layer substrate is surface-treated to increase the adhesive strength as necessary, then the above-mentioned prepreg and / or resin sheet is laminated on the inner layer circuit surface in a required number, and the outer layer circuit is further outside. Metal leaf is laminated and heated and pressed for integral molding (laminated molding). In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. The method of laminating and molding and the molding conditions thereof are the same as those of the above-mentioned laminated board or metal leaf-clad laminated board. Next, after drilling holes for through holes and via holes in this multilayer laminated board, desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. .. After that, a plated metal film that conducts the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of this hole, and the metal foil for the outer layer circuit is further etched to form the outer layer circuit, and the printed wiring board is manufactured. Will be done.

For example, the above-mentioned prepreg (the base material and the above-mentioned resin composition for a printed wiring board attached thereto) and the resin composition layer of the metal foil-covered laminated board (the layer consisting of the above-mentioned resin composition for a printed wiring board) , The insulating layer containing the above-mentioned resin composition for a printed wiring board will be formed.

When the 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 to produce a printed wiring board. At this time, an electroless plating method can also be used to form the conductor layer.

Further, as shown in FIG. 9, the printed wiring board of the present embodiment is a first insulating layer formed of at least one selected from the group consisting of the above-mentioned prepreg and resin sheet in which at least one laminated sheet is laminated. It was formed of 1) and at least one selected from the group consisting of the above-mentioned prepreg and resin sheet laminated at least one sheet in one side direction (lower surface direction in the drawing) of the first insulating layer (1). A plurality of insulating layers composed of a second insulating layer (2), a first conductor layer (3) arranged between each of the plurality of insulating layers (1, 2), and a plurality of them. It is preferable to have a plurality of conductor layers composed of a second conductor layer (3) arranged on the outermost layer of the insulating layers (1, 2).

According to the findings of the present inventors, in a normal laminated board, for example, a group consisting of at least one kind of prepreg and another prepreg and a resin sheet selected from the group consisting of a prepreg and a resin sheet which are one core substrate in both sides. A multilayer printed wiring board is formed by laminating at least one selected from the above, and at least one selected from the group consisting of the prepreg and the resin sheet of the present embodiment is the first insulating layer. Selected from the group consisting of one prepreg and resin sheet forming (1) Select from the group consisting of another prepreg and resin sheet forming the second insulating layer (2) only in at least one one-sided direction. It has been confirmed that it is particularly effective for a coreless type multilayer printed wiring board (multilayer coreless substrate) manufactured by laminating at least one of these.

In other words, the prepreg, the resin sheet, and the resin composition for a printed wiring board of the present embodiment can effectively reduce the amount of warpage when used for a printed wiring board, and are not particularly limited. However, it is particularly effective for a multilayer coreless board among printed wiring boards. That is, while a normal printed wiring board generally has a double-sided symmetrical structure and tends to be difficult to warp, a multilayer coreless board tends to have a double-sided asymmetrical structure and is therefore more likely to warp than a normal printed wiring board. There is a tendency. Therefore, by using the prepreg, the resin sheet, and the resin composition for the printed wiring board of the present embodiment, it is possible to particularly effectively reduce the amount of warpage of the multilayer coreless substrate, which has tended to be easily warped in the past.

In FIG. 9, a configuration in which two second insulating layers (2) are laminated on one first insulating layer (1) (that is, a configuration in which a plurality of insulating layers are three layers) is provided. As shown, the second insulating layer (2) may be one or two or more. Therefore, the first conductor layer (3) may be one layer or two or more layers.

As described above, in the printed wiring board of the present embodiment having the above-described configuration, the resin composition for the printed wiring board of the above-described embodiment is, for example, a cured product obtained by curing a prepreg, and has a thermal storage elasticity and loss. By controlling mechanical properties such as elasticity to a specific range suitable for low warpage, there is no clear glass transition temperature (Tg-less), and warpage of printed wiring boards, especially multilayer coreless boards. Can be particularly effectively used as a printed wiring board for a semiconductor package and a multilayer coreless substrate, because the warpage is sufficiently reduced (low warpage is achieved).

Hereinafter, the present invention will be described in more detail 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, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd .: The number of repeating units n of naphthol aralkyl includes 1 to 5.) 0.47 mol (in terms of OH group) was dissolved in 500 ml of chloroform, and 0.7 mol of triethylamine was added to this solution. While maintaining the temperature at −10 ° C., 300 g of a 0.93 mol cyanogen chloride chloroform solution was added dropwise over 1.5 hours, and the mixture was stirred for 30 minutes after the addition was completed. After that, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was further added dropwise to the reactor, and the mixture was stirred for 30 minutes to complete the reaction. The by-produced triethylamine hydrochloride was filtered off from the reaction solution, the obtained filtrate was washed with 500 ml of 0.1N hydrochloric acid, and then washed with 500 ml of water was repeated 4 times. This is dried over sodium sulfate, evaporated at 75 ° C., and degassed under reduced pressure at 90 ° C. to obtain a brown solid α-naphthol aralkyl-type cyanate ester compound represented by the above formula (2) (in the formula). R ⁶ is all hydrogen atoms.) When the obtained α-naphthol aralkyl type cyanate ester compound was analyzed by infrared absorption spectrum, absorption of cyanate ester group was confirmed in the vicinity of 2264 cm ^-1 .

[ Reference Example 1]
Dialyl bisphenol A (DABPA, manufactured by Daiwa Kasei Kogyo Co., Ltd., hydroxyl group equivalent: 154 g / eq.), Which is an allyl phenol compound (A), 24.1 parts by mass, maleimide compound (B) (BMI-2300, Daiwa Kasei Kogyo Co., Ltd.) Maleimide Equivalent: 186 g / eq. Co., Ltd., 60.9 parts by mass, α-naphthol aralkyl type cyanate ester compound (SN495VCN, cyanate equivalent: 261 g / eq) of Synthesis Example 1 which is a cyanate ester compound (C). .) 5.0 parts by mass, epoxy compound (D) (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 328 g / eq.) 10.0 parts by mass, slurry silica as filler (E) ( SC-2050MB, 200 parts by mass of Admatex Co., Ltd. and 25 parts by mass of the same silicone composite powder (KMP-605M, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), silane coupling agent (KBM-403, Shin-Etsu Chemical Industry Co., Ltd.) ), And 0.5 parts by mass of triphenylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), which is a curing accelerator, were mixed and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and coated on an E-glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content for a printed wiring board of 73% by volume.

[ Reference Example 2]
The allylphenol compound (A) (DABPA) was 19.9 parts by mass, the maleimide compound (B) (BMI-2300) was 50.1 parts by mass, and the cyanate ester compound (C) (SN495VCN) was used. The content of the resin composition for a printed wiring board was set to 10.0 parts by mass and the epoxy compound (D) (NC-3000FH) was set to 20.0 parts by mass by the same method as in Reference Example 1. 73% by weight prepreg was obtained.

[Reference Example 3 ]
Printed wiring by the same method as in Reference Example 1 except that the cyanic acid ester compound (C) (SN495VCN) was not used and the epoxy compound (D) (NC-3000FH) was 15.0 parts by volume. A prepreg having a resin composition content for plates of 73% by volume was obtained. In the following sentences and tables in the present specification , "Example 1", "Example 2", and "Example 3" are "Reference Example 1" and "Reference Example 2", respectively. , And "Reference Example 3 ".

[Example 4]
Printed wiring by the same method as in Example 1 except that the cyanic acid ester compound (C) (SN495VCN) was 15.0 parts by volume and the epoxy compound (D) (NC-3000FH) was not used. A prepreg having a resin composition content for plates of 73% by volume was obtained.

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

[Comparative Example 2]
The allylphenol compound (A) (DABPA) was 60.0 parts by mass, the maleimide compound (B) (BMI-2300) was 32.1 parts by mass, and the cyanate ester compound (C) (SN495VCN) was used. The content of the resin composition for a printed wiring board was set to 2.6 parts by mass and the epoxy compound (D) (NC-3000FH) was set to 5.3 parts by mass by the same method as in Example 1. 73% by weight prepreg was obtained.

[Comparative Example 3]
The allylphenol compound (A) (DABPA) was 12.7 parts by mass, the maleimide compound (B) (BMI-2300) was 32.1 parts by mass, and the cyanate ester compound (C) (SN495VCN) was used. The content of the resin composition for a printed wiring board was set to 50.0 parts by mass and the epoxy compound (D) (NC-3000FH) was set to 5.2 parts by mass by the same method as in Example 1. 73% by weight prepreg was obtained.

[Comparative Example 4]
The allylphenol compound (A) (DABPA) was 5.0 parts by mass, the maleimide compound (B) (BMI-2300) was 85.0 parts by mass, and the cyanate ester compound (C) (SN495VCN) was used. The content of the resin composition for a printed wiring board was set to 5.0 parts by mass and the epoxy compound (D) (NC-3000FH) was set to 5.0 parts by mass by the same method as in Example 1. 73% by weight prepreg was obtained.

[Measurement and evaluation of physical properties]
Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 4, a sample for physical property measurement and evaluation was prepared by the procedure shown in each of the following items, and the mechanical properties (storage elastic modulus and loss elastic modulus) were determined. Physical property parameters related to mechanical properties, glass transition temperature (Tg), and warpage amount (3 types) in the formulas (4) to (8) and formulas (4A) to (8A) were measured and evaluated. The results of the examples are summarized in Table 1, and the results of the comparative examples are summarized in Table 2.

[Mechanical characteristics]
Copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) was placed on both the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf / cm ² . , Lamination molding (thermosetting) was performed at a temperature of 230 ° C. for 100 minutes to obtain a copper foil-clad laminate having an insulating layer thickness of 0.1 mm. The obtained copper foil-clad laminate was cut into a size of 20 mm × 5 mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the mechanical properties (storage elastic modulus E'and loss elastic modulus E'') were measured by the DMA method with a dynamic viscoelastic analyzer (manufactured by TA Instruments) in accordance with JIS C6481. (Mean value of n = 3).

[Glass transition temperature (Tg)]
Copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) was placed on both the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf / cm ² . A copper foil-clad laminate having an insulating layer thickness of 0.1 mm was obtained by laminating and molding at a temperature of 230 ° C. for 100 minutes. The obtained copper foil-clad laminate was cut to a size of 12.7 × 2.5 mm with a dicing saw, and the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the glass transition temperature (Tg) was measured by the DMA method with a dynamic viscoelastic analyzer (manufactured by TA Instruments) in accordance with JIS C6481 (mean value of n = 3).

[Amount of warp: Bimetal method]
First, copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) was placed on both the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf /. A laminating mold was carried out at cm ² at a temperature of 220 ° C. for 120 minutes to obtain a copper foil-clad laminate. Next, the copper foil was removed from the obtained copper foil-clad laminate. Next, one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was further arranged on one side of the laminated plate from which the copper foil was removed, and the copper foil (3EC-VLP, Mitsui) was placed on both upper and lower surfaces thereof. Metal Mining Co., Ltd. (thickness 12 μm) was placed, and laminating molding was performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a copper foil-clad laminate again. Further, the copper foil was removed from the obtained copper foil-clad laminate to obtain a laminate. Then, a strip-shaped plate of 20 mm × 200 mm was cut out from the obtained laminated plate, and the maximum value of the amount of warpage at both ends in the long direction was measured with a metal scale with the surface of the second laminated prepreg facing up. , The average value was taken as the "warp amount" by the bimetal method.

[Amount of warpage: Multilayer coreless substrate]
First, as shown in FIG. 1, the carrier copper foil surfaces of the ultrathin copper foil (b1) with a carrier (MT18Ex, manufactured by Mitsui Metal Mining Co., Ltd., thickness 5 μm) are prepreged on both sides of the prepreg serving as the support (a). Arranged toward the side, the prepregs (c1) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were further arranged on the copper foil (d) (3EC-VLP, Mitsui Metal Mining Co., Ltd.). A copper foil-clad laminate shown in FIG. 2 was obtained by arranging a copper foil-clad laminate manufactured by Co., Ltd. and having a thickness of 12 μm) at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes.

Next, the copper foil (d) of the obtained copper foil-clad laminate shown in FIG. 2 was etched into a predetermined wiring pattern as shown in FIG. 3, for example, to form a conductor layer (d'). Next, as shown in FIG. 4, the prepregs (c2) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 are arranged on the laminated plate shown in FIG. 3 on which the conductor layer (d') is formed. Then, an ultrathin copper foil with a carrier (b2) (MT18Ex, manufactured by Mitsui Metal Mining Co., Ltd., thickness 5 μm) is further placed on it, and laminated molding is performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes. Then, the copper foil-clad laminate shown in FIG. 5 was obtained.

Next, in the copper foil-clad laminate shown in FIG. 5, the carrier copper foil and the ultrathin copper foil of the carrier-attached ultrathin copper foil (b1) arranged on the support (a) (cured support prepreg) are peeled off. As a result, as shown in FIG. 6, the two laminated plates were peeled off from the support (a), and further, the carrier copper foil was peeled off from the upper ultrathin copper foil with carrier (b2) in each of the laminated plates. .. Next, processing was performed on the upper and lower ultrathin copper foils of each of the obtained laminated plates by a laser processing machine, and as shown in FIG. 7, a predetermined via (v) was formed by chemical copper plating. Then, for example, as shown in FIG. 8, a conductor layer was formed by etching into a predetermined wiring pattern to obtain a panel (size: 500 mm × 400 mm) of a multilayer coreless substrate. Then, the amount of warpage at the four corners of the obtained panel and the central portion of the four sides was measured with a metal scale, and the average value was taken as the "warp amount" of the panel of the multilayer coreless substrate.

[Substrate shrinkage before and after reflow process]
Copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd., thickness 12 μm) was placed on both the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure was 30 kgf / cm ² . , A copper foil-clad laminate was obtained by laminating and molding at a temperature of 220 ° C. for 120 minutes. Next, the obtained copper foil-clad laminate was drilled evenly at 9 points in a grid pattern, and then the copper foil was removed.

Then, first, the distance between the holes in the laminated board from which the copper foil was removed was measured (distance a). Next, the laminated board was reflowed by a salamander reflow device with a maximum temperature of 260 ° C. After that, the distance between the holes in the laminated board was measured again (distance b). Then, the measured distance a and distance b were substituted into the following formula (I) to obtain the dimensional change rate of the substrate in the reflow process, and the value was taken as the substrate shrinkage rate before and after the reflow process.
((Distance a)-(Distance b)) / Distance a x 100 ... Equation (I)

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

Claims (17)

Allylphenol compound (A) and
Maleimide compound (B) and
A resin composition for a printed wiring board containing a cyanic acid ester compound (C), or a cyanic acid ester compound (C) and an epoxy compound (D).
The content of the allylphenol compound (A) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 10 to 50 parts by mass.
The content of the maleimide compound (B) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 40 to 70 parts by mass.
The content of the cyanic acid ester compound (C) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 14.2 to 25 parts by mass .
In the cured product of the resin composition for printed wiring board, there is no clear glass transition temperature, and the glass transition temperature is measured by the DMA method with a dynamic viscoelastic analyzer in accordance with JIS C6481. ,
Resin composition for printed wiring boards. The total content of the cyanic acid ester compound (C) and the epoxy compound (D) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 14.2 to 45 parts by mass.
The resin composition for a printed wiring board according to claim 1. The content of the epoxy compound (D) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 0 to 25 parts by mass.
The resin composition for a printed wiring board according to claim 1 or 2. Further containing the filler (E),
The resin composition for a printed wiring board according to any one of claims 1 to 3. The filler (E) is at least one selected from the group consisting of silica, alumina, and boehmite.
The resin composition for a printed wiring board according to claim 4. The content of the filler (E) with respect to 100 parts by mass of the resin solid content in the resin composition for a printed wiring board is 120 to 250 parts by mass.
The resin composition for a printed wiring board according to claim 4 or 5. The allyl phenol compound (A) contains a compound represented by any of the following formulas (I) to (III).
The resin composition for a printed wiring board according to any one of claims 1 to 6.

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

The maleimide compound (B) is bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl). ) Containing at least one selected from the group consisting of methane and a maleimide compound represented by the following formula (1).
The resin composition for a printed wiring board according to any one of claims 1 to 7.

(In formula (1), R ₅ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.) The cyanate ester compound (C) contains a compound represented by the following formulas (2) and / or (3).
The resin composition for a printed wiring board according to any one of claims 1 to 8.

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

(In formula (3), R ₇ independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.) The cured product obtained by thermally curing the prepreg containing the resin composition for a printed wiring board and the base material at 230 ° C. for 100 minutes is the following formulas (4) to (8);
E'(200 ° C) / E'(30 ° C) ≤ 0.90 ... (4)
E'(260 ° C) / E'(30 ° C) ≤ 0.85 ... (5)
E'(330 ° C) / E'(30 ° C) ≤ 0.80 ... (6)
E''max / E'(30 ° C) ≤ 3.0% ... (7)
E''min / E'(30 ° C) ≧ 0.5%… (8)
(In each formula, E'indicates the storage elastic modulus of the cured product at the temperature shown in parentheses, and E''max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C to 330 ° C. E''min indicates the minimum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C to 330 ° C.)
Satisfy the numerical range of physical property parameters related to mechanical properties represented by
The resin composition for a printed wiring board according to any one of claims 1 to 9. With the base material
The resin composition for a printed wiring board according to any one of claims 1 to 10 impregnated or applied to the substrate, and the resin composition for a printed wiring board.
A prepreg with. One or more of the base materials selected from the group consisting of E glass fiber, D glass fiber, S glass fiber, T glass fiber, Q glass fiber, L glass fiber, NE glass fiber, HME glass fiber, and organic fiber. It is composed of the fibers of
The prepreg according to claim 11. With the support,
The resin composition for a printed wiring board according to any one of claims 1 to 10, which is laminated on one side or both sides of the support.
Resin sheet with. It has at least one selected from the group consisting of the prepreg according to claim 11 and 12 in which at least one sheet is laminated, and the resin sheet according to claim 13.
Laminated board. At least one selected from the group consisting of the prepreg according to claim 11 and 12 and the resin sheet according to claim 13 in which at least one sheet is laminated.
At least one kind of metal foil arranged on one side or both sides selected from the group consisting of the prepreg and the resin sheet, and
Metal leaf-clad laminate with. Insulation layer and
A conductor layer formed on the surface of the insulating layer and
Have,
The insulating layer contains the resin composition for a printed wiring board according to any one of claims 1 to 10.
Printed wiring board. The first insulating layer formed of at least one selected from the group consisting of the prepreg according to claim 11 and 12 and the resin sheet according to claim 13 in which at least one sheet is laminated, and the first insulating layer. A second formed by at least one selected from the group consisting of the prepreg according to claims 11 and 12 and the resin sheet according to claim 13, wherein at least one insulating layer is laminated in one side direction. Insulation layer consisting of multiple insulation layers of
A plurality of conductor layers composed of a first conductor layer arranged between each of the plurality of insulating layers and a second conductor layer arranged on the surface of the outermost layer of the plurality of insulating layers.
Multi-layer printed wiring board with.

Images