JPWO2018124161A1 - Resin composition for printed wiring board, prepreg, resin sheet, laminated board, metal foil-clad laminated board, printed wiring board, and multilayer printed wiring board - Google Patents

Abstract

Resin composition for printed wiring board that does not have a clear glass transition temperature (Tg-less) and that can sufficiently reduce warpage of printed wiring boards, particularly multilayer coreless substrates (to achieve low warpage), and prepreg In order to provide a resin sheet, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board, the resin composition according to the present invention comprises an allylphenol compound (A), a maleimide compound (B), A cyanate ester compound (C) and / or an epoxy compound (D). Moreover, content of the allyl phenol compound (A) with respect to 100 mass parts of resin solid content in the resin composition for printed wiring boards is 10-50 mass parts, and resin solid content 100 in the resin composition for printed wiring boards Content of the maleimide compound (B) with respect to a mass part is 40-80 mass parts.

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 in size, higher integration and higher density mounting of each component for semiconductor packages has been accelerated in recent years. ing. As a result, various characteristics required for printed wiring boards for semiconductor packages have become increasingly severe. Properties 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 coefficient, 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, particularly multilayer coreless substrates (achieving low warpage) has become an important issue recently, and various countermeasures have been taken. Yes.

  One countermeasure is to reduce the thermal expansion of the insulating layer used in the printed wiring board. This is a technique for suppressing warpage by bringing the thermal expansion coefficient of a printed wiring board close to the thermal expansion coefficient of a semiconductor element, and is currently being actively worked on (see, for example, Patent Documents 1 to 3).

  In addition to lowering the thermal expansion of the printed wiring board, methods for suppressing the warpage of the semiconductor plastic package include increasing the rigidity of the laminated board (higher rigidity) and increasing the glass transition temperature of the laminated board (high Tg). (For example, see Patent Documents 4 and 5).

JP 2013-216684 A Japanese Patent No. 3173332 JP 2009-035728 A JP 2013-001807 A JP 2011-177892 A

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

  That is, the present invention does not have a clear glass transition temperature (so-called Tg-less), and can sufficiently reduce the warpage of a printed wiring board, particularly a multilayer coreless substrate (achieve low warpage). It is an object to provide a resin composition for a 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. To do.

  As a result of diligent studies to solve the above problems, the present inventors have heretofore been concerned about the warping behavior of a printed wiring board for a semiconductor plastic package. In addition, although it has been considered that a resin composition capable of realizing a higher elastic modulus maintenance factor has been 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-mentioned problems can be solved by using a cyanate ester compound and / or an epoxy compound in addition to the allylphenol compound and the maleimide compound. It came to be completed.

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

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

[3]
Content of the said cyanate ester compound (C) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 0-25 mass parts,
The resin composition for printed wiring boards according to [1] or [2].

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

[5]
Further containing a filler (E),
The resin composition for printed wiring boards 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,
[5] The resin composition for printed wiring boards according to [5].

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

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

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

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

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

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

(In formula (2), each 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 each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.)

[11]
Hardened | cured material obtained by thermosetting the prepreg containing the said resin composition for printed wiring boards and a base material on 230 degreeC and the conditions for 100 minutes is following formula (4)-(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 ′ represents the storage elastic modulus of the cured product at the temperature shown in parentheses, and E ″ max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C. E ″ min represents 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 the physical property parameters for mechanical properties expressed by
The resin composition for printed wiring boards according to any one of [1] to [10].

[12]
A substrate;
The resin composition for a printed wiring board according to any one of [1] to [11] impregnated or coated on the substrate;
Prepreg with

[13]
The substrate is one or more 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. Made up of fibers,
[12] The prepreg according to [12].

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

[15]
Having at least one selected from the group consisting of the prepreg according to [12] and [13] and the resin sheet according to [14], wherein at least one sheet is laminated;
Laminated board.

[16]
At least one selected from the group consisting of the prepreg according to [12] and [13] and the resin sheet according to [14], wherein at least one sheet is laminated;
A metal foil disposed on one or both sides of at least one selected from the group consisting of the prepreg and the resin sheet;
A metal foil-clad laminate.

[17]
An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The insulating layer includes 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 the prepreg according to [12] and [13] and the resin sheet according to [14], wherein at least one sheet is laminated; and Formed with at least one selected from the group consisting of the prepreg according to [12] and [13] and the resin sheet according to [14], wherein at least one sheet is laminated in one direction of the first insulating layer. A plurality of insulating layers comprising the second insulating layer formed;
A plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers, and a second conductor layer disposed on a surface of the outermost layer of the plurality of insulating layers;
A multilayer printed wiring board having:

  According to the present invention, there is no clear glass transition temperature (Tg-less), and a printed wiring board, particularly a printed wiring board that can sufficiently reduce warpage (achieve low warpage) of a multilayer coreless substrate. Resin composition, and prepreg, resin sheet, laminate, metal foil-clad laminate, printed wiring board, and multilayer printed wiring board using the resin composition for printed wiring board can be provided. .

It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate (however, the manufacturing method of a multilayer coreless board | substrate is not limited to this. It is the same in the following FIGS. 2-8). It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate. It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate. It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate. It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate. It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate. It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate. It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board | substrate. It is a fragmentary sectional view which shows the structure of an example of the panel of a multilayer coreless board | substrate.

  Hereinafter, although the form for implementing this invention (henceforth "this embodiment") is demonstrated in detail, this invention is not limited to this, In the range which does not deviate from the summary, various deformation | transformation is carried out. Is possible. In the present embodiment, “resin solid content” means a component excluding the solvent and filler in the resin composition for a printed wiring board unless otherwise specified, and “resin solid content 100 parts by mass”. The term “total” of the components excluding the solvent and the filler in the resin composition for printed wiring boards is 100 parts by mass.

[Resin composition for printed wiring board]
The resin composition for printed wiring boards of this embodiment contains an allylphenol compound (A), a maleimide compound (B), a cyanate ester compound (C) and / or an epoxy resin (D). When the resin composition for a printed wiring board contains such a composition, for example, in a cured product obtained by curing a prepreg, there is no clear glass transition temperature (Tg-less), and the printed wiring board, In particular, there is a tendency that warpage 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 hydroxyl group are directly bonded to the aromatic ring. For example, the hydrogen atom of the aromatic ring is substituted with an allyl group. Bisphenols produced. The bisphenol is not particularly limited. For example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P Bisphenol PH, bisphenol TMC, and bisphenol Z. Among these, bisphenol A is preferable, and as the allylphenol compound (A), diallyl bisphenol A is more preferable, and a compound represented by the following formula (I) or formula (II) is more preferable. By using such an allylphenol compound (A), bending strength, flexural modulus, thermal expansion coefficient, thermal conductivity, and copper foil peel strength tend to be further improved.

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

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

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

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

  When the allylphenol compound (A) has a hydroxyl group directly bonded to an aromatic ring, the number of the hydroxyl group in one molecule of the allylphenol compound (A) is preferably 1 to 5, more preferably 2 to 2. 4, more preferably 2. When the number 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. It tends to be excellent.

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

  Content of allylphenol compound (A) is 10-50 mass parts with respect to 100 mass parts of resin solid content in the resin composition for printed wiring boards, Preferably it is 10-35 mass parts, More preferably 15 to 30 parts by mass. When the content of the allylphenol compound (A) is within the above range, the flexibility, bending strength, bending elastic modulus, thermal expansion coefficient, thermal conductivity, and copper foil peel strength of the resulting cured product are further improved. Tend to.

[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. For example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-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 these, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and At least one selected from the group consisting of maleimide compounds represented by the following formula (1) is preferable, and from the viewpoint of easily obtaining a resin composition having no clear glass transition temperature (Tg-less), the following formula (1) Is particularly preferable. By including the maleimide compound (B) described above, the coefficient of thermal expansion of the obtained cured product is further lowered, and the heat resistance and the glass transition temperature (Tg) tend to be further improved. A maleimide compound (B) may be used individually by 1 type, and may use 2 or more types together.

Here, in formula (1), R ₅ each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Moreover, in Formula (1), n1 represents an integer greater than or equal to ₁ , Preferably it is an integer of 10 or less, More preferably, it is an integer of 7 or less.

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

[Cyanate ester compound (C) and / or epoxy compound (D)]
The resin composition for printed wiring boards of this embodiment contains a cyanate ester compound (C) and / or an epoxy compound (D). By using the cyanate ester compound (C) and / or the epoxy compound (D) together with the above-mentioned allylphenol compound (A) and maleimide compound (B), for example, in a cured product obtained by curing a prepreg, a clear glass There is a tendency that the resin composition has no transition temperature (Tg-less) and can sufficiently reduce the warpage of a printed wiring board, particularly a multilayer coreless substrate (achieve low warpage).

(Cyanate ester compound (C))
Although it does not specifically limit as cyanate ester compound (C), For example, the naphthol aralkyl type cyanate ester shown by following formula (2), the novolak type cyanate ester shown by following formula (3), biphenyl aralkyl type cyanide Acid ester, bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5- Tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanato Naphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4-cyanatofe Nyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2′-bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters It is done. These cyanate ester compounds (C) may be used alone or in combination of two or more.

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

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

  Among these, the cyanate ester compound (C) is composed of a naphthol aralkyl cyanate ester represented by the formula (2), a novolak cyanate ester represented by the formula (3), and a biphenyl aralkyl cyanate ester. It is preferable to include at least one selected from the group, and at least one selected from the group consisting of a naphthol aralkyl-type cyanate ester represented by the formula (2) and a novolac-type cyanate ester represented by the formula (3) It is more preferable to contain. By using such a cyanate ester compound (C), a cured product that is superior in flame retardancy, has higher curability, and has a lower thermal expansion coefficient tends to be obtained.

  The method for producing these cyanate ester compounds (C) is not particularly limited, and a known method can be used as a method for synthesizing cyanate ester compounds. The known method is not particularly limited. For example, a method of reacting a phenol resin and cyanogen halide in an inert organic solvent in the presence of a basic compound, a salt of the phenol resin and the basic compound, water Examples thereof include a method of forming in a solution to be contained, and then causing 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 examples thereof include naphthol aralkyl type phenol resins, novolak type phenol resins, and biphenyl aralkyl type phenol resins represented by the following formula (9). Can be mentioned.

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

  The naphthol aralkyl type phenol resin represented by the formula (9) can be obtained by condensing a naphthol aralkyl resin and cyanic acid. Although it does not specifically limit as a naphthol aralkyl type phenol resin, For example, naphthols, such as alpha-naphthol and beta-naphthol, p-xylylene glycol, alpha, alpha'-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 cyanate ester can be selected from those obtained by condensing the naphthol aralkyl resin obtained as described above and 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 with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring boards. is there. 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. For example, 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 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 novolak type epoxy resin, naphthol aralkyl type epoxy resin Resins, dicyclopentadiene type epoxy resin, a polyol type epoxy resin, isocyanurate ring-containing epoxy resin, or these halides and the like. The epoxy compound (D) is more preferably a non-halogenated epoxy compound (a non-halogen-containing epoxy compound or a halogen-free epoxy compound). 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, 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 printed wiring boards. When content of an epoxy compound (D) exists in the said range, it exists in the tendency for the softness | flexibility of a hardened | cured material obtained, copper foil peel strength, chemical resistance, and desmear resistance to improve more.

  In addition, as mentioned above, the resin composition for printed wiring boards of this embodiment contains a cyanate ester compound (C) and / or an epoxy compound (D). 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 printed wiring boards is preferably 5 to 45 masses. Part, more preferably 5 to 40 parts by weight, and more preferably 10 to 30 parts by weight. When the total content of the cyanate ester compound (C) and the epoxy compound (D) is within the above range, flexibility of the obtained cured product, copper foil peel strength, heat resistance, chemical resistance, and desmear resistance Tend to improve more. Further, since the total content of the cyanate ester compound (C) and the epoxy compound (D) is within the above range, for example, in a cured product obtained by curing a prepreg, there is no clear glass transition temperature (Tg Less) and a printed wiring board, in particular, a multilayered coreless substrate, tends to be a resin composition that can further reduce warpage (achieve low warpage).

[Filler (E)]
It is preferable that the resin composition for printed wiring boards of this embodiment further contains a filler (E). Although it does not specifically limit as a filler (E), For example, an inorganic filler and an organic filler are mentioned, It is preferable to contain the inorganic filler among both, and an organic filler is used with an inorganic filler. Is preferred. Examples of the inorganic filler include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide, aluminum hydroxide heat-treated products (heating aluminum hydroxide) Treated and reduced in part of crystal water), metal hydrates such as 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 clay , Mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fiber (E glass, T glass, D glass, Including glass fine powders such as 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; It is done. A filler (E) may be used individually by 1 type, or may use 2 or more types together.

  Among these, the inorganic filler may contain 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. Preferably, it contains at least one selected from the group consisting of silica, alumina, and boehmite. By using such a filler (E), the resulting cured product tends to have higher rigidity and lower warpage.

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

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

  Although it will not specifically limit if it is a silane coupling agent generally used for the surface treatment of an inorganic substance as a silane coupling agent, For example, (gamma) -aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma Aminosilane compounds such as aminopropyltrimethoxysilane; Epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; Acrylic silane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N- Cationic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane compounds and the like. A silane coupling agent may be used individually by 1 type, or may use 2 or more types together.

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

[Other resins, etc.]
The resin composition for a printed wiring board according to the present embodiment includes an allyl group-containing compound (hereinafter, also referred to as “other allyl group-containing compound”), a phenol resin other than the above-described allylphenol compound (A), if necessary. , Oxetane resin, benzoxazine compound, and one or more selected from the group consisting of compounds having a polymerizable unsaturated group may be further contained. By including such other resins, etc., 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]
Examples of other allyl group-containing compounds include, but are not limited to, 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 printed wiring boards. More preferably, it is 15-45 mass parts, More preferably, it is 20-35 mass parts. When the content of the other allyl group-containing compound is within the above range, the bending strength, bending elastic modulus, heat resistance, and chemical resistance of the obtained cured product tend to be further improved.

[Phenolic resin]
As the phenol resin, generally known resins can be used as long as they are phenol resins having two or more hydroxy groups in one molecule, and the kind thereof is not particularly limited. Specific examples include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac type. Phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin Naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin Nord resins, alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a hydroxyl group-containing silicone resins and the like, but is not particularly limited. These phenol resins can be used individually by 1 type or in combination of 2 or more types. By including such a phenol resin, the cured product obtained 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 still more preferably with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring boards. 3 to 80 parts by mass. When the content of the phenol resin is within the above range, the obtained cured product tends to be more excellent in adhesiveness, flexibility, and the like.

[Oxetane resin]
As the oxetane resin, generally known oxetane resins can be used, and the kind thereof is not particularly limited. Specific examples thereof include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 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 Toagosei), OXT-121 (produced by Toagosei) Product name). 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 still more preferably 3 with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring boards. ~ 80 parts by mass. When the content of the oxetane resin is within the above range, the obtained cured product tends to be more excellent in adhesion and flexibility.

[Benzoxazine compound]
As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A-type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F-type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S-type benzoxazine BS-BXZ (product manufactured by Konishi Chemical) Name). These benzoxazine compounds can be used alone or in combination. By including such a benzoxazine compound, the obtained cured product 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 still more preferably with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring boards. Is 3-80 parts by mass. When the content of the benzoxazine compound is within the above range, the resulting cured product tends to be more excellent in heat resistance and the like.

[Compound having a polymerizable unsaturated group]
As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the kind thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di ( Mono- or polyhydric alcohol (meth) such as (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylates; Epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; Benzocyclobutene resin; Scan) maleimide resins. These compounds having a polymerizable unsaturated group can be used alone or in combination. By including such a compound having a polymerizable unsaturated group, the resulting 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 with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring boards. Part, more preferably 3 to 80 parts by weight. When the content of the polymerizable unsaturated group-containing compound is within the above range, the cured product obtained tends to be more excellent in heat resistance, toughness, and the like.

[Curing accelerator]
The resin composition for printed wiring boards of this embodiment may further contain a curing accelerator. Although it does not specifically limit as a hardening accelerator, For example, imidazoles, such as a triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, etc. 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, cateco Phenols such as lead; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts Inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride; organic tin compounds such as dioctyl tin oxide, other alkyl tins, alkyl tin oxides, etc. It is done. Of these, triphenylimidazole is particularly preferable because it promotes the curing reaction and tends to have an excellent coefficient of thermal expansion.

〔solvent〕
The resin composition for printed wiring boards of this embodiment may further contain a solvent. By containing a solvent, the viscosity at the time of preparation of the resin composition for printed wiring boards is lowered, the handling property is further improved, and the impregnation property to a substrate 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 component in the resin composition for printed wiring boards. For example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; toluene, Aromatic hydrocarbons such as xylene; Amides such as dimethylformamide; Propylene glycol monomethyl ether and its acetate. A solvent may be used individually by 1 type, or may use 2 or more types together.

[Method for producing resin composition for printed wiring board]
Although the manufacturing method of the resin composition for printed wiring boards of this embodiment is not specifically limited, For example, the method of mix | blending each component with a solvent one by one and fully stirring is mentioned. At this time, in order to uniformly dissolve or disperse each component, known processes such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler (E) with respect to the resin composition for a printed wiring board can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. . The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill or a bead mill for mixing, or a revolving or rotating mixing device.

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

[Characteristics of resin composition for printed wiring board]
In the resin composition for a printed wiring board of the present embodiment, cured products obtained by thermally curing a prepreg containing the substrate and a base material under the conditions of 230 ° C. and 100 minutes are represented by the following formulas (4) to (8). It is preferable that the numerical value range of the physical property parameter related to the mechanical property is expressed, and it is more preferable that the numerical value range of the physical property parameter related to the mechanical property expressed 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 ° C.) ≧ 0.5% (8A)

  Here, in each formula, E ′ represents the storage elastic modulus of the cured product at the temperature indicated 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 loss elastic modulus of the cured product in a temperature range of 30 ° C. to 330 ° C. (E ″ indicates the loss elastic modulus of the cured product).

  Conventionally, regarding the warping behavior of a printed wiring board, in a cured product of a prepreg, it has been considered that a resin composition capable of realizing a larger storage modulus during heat and a higher elastic modulus retention rate is effective. The numerical value of the physical property parameter regarding the mechanical properties of the cured product obtained by thermally curing the prepreg at 230 ° C. and 100 minutes is not necessarily limited to the above formulas (4) to (8), preferably the formula (4A) to By being within the range of (8A), the glass transition temperature (Tg) can be sufficiently increased, and the amount of warping of the laminated board, the metal foil-clad laminated board, the printed wiring board, particularly the multilayer coreless board itself is sufficient. It becomes possible to reduce it.

  In other words, the numerical values of the physical property parameters relating to the mechanical properties of the cured product obtained by thermosetting 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, it is preferable that there is no clear glass transition temperature (Tg-less), and the warpage 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) relating to the loss elastic modulus, preferably the formulas (7A) and (8A) is synonymous with the absence of a clear glass transition temperature (Tg-less). If the product satisfies the formulas (7) and (8), preferably only the formulas (7A) and (8A), the formulas (4) to (6), preferably those that do not satisfy the formulas (4A) to (6A) Although the rate itself is small and difficult to stretch, when it is used as a printed wiring board, the difficulty of stretching is damaged, making it difficult to achieve low warpage. In contrast, the cured product satisfies not only formulas (7) and (8), preferably formulas (7A) and (8A), but also formulas (4) to (8), preferably formulas (4A) and (8A). Some are difficult to stretch due to the Tg-less, and tend to 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 prepreg is not particularly limited, and can be measured, for example, by the following method. That is, copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) is arranged on both upper and lower surfaces of one prepreg, and laminate molding (thermosetting) at a pressure of 30 kgf / cm ² and a temperature of 230 ° C. for 100 minutes ) To obtain a copper foil-clad laminate having 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 then the copper foil on the surface is removed by etching to obtain a measurement sample. 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 viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481. be able to. At this time, an average value of n = 3 may be obtained.

[Use]
The resin composition for printed wiring boards of this embodiment can be suitably used as a prepreg, resin sheet, insulating layer, laminated board, metal foil-clad laminated board, printed wiring board, or multilayer printed wiring board. Hereinafter, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, and a printed wiring board (including a multilayer printed wiring board) will be described.

[Prepreg]
The prepreg of this embodiment contains a base material and a resin composition for printed wiring boards impregnated or applied to the base material. The manufacturing method of a prepreg can be performed according to a conventional method, and is not specifically limited. For example, after impregnating or applying the resin composition for a printed wiring board in the present embodiment to a substrate, the substrate is semi-cured (B-staged) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. ), The prepreg of this embodiment can be manufactured.

  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 50%, based on the total amount of the prepreg. It is 85 volume%, More preferably, it is 40-80 volume%. When the content of the resin composition is within the above range, the moldability tends to be further improved.

  It does not specifically limit as a base material, The well-known thing used for various printed wiring board materials can be selected suitably according to the intended use and performance, and can be used. Examples of the substrate include a glass substrate, an inorganic substrate other than glass, an organic substrate, and the like. Among these, a glass substrate is particularly preferable from the viewpoint of high rigidity and heat dimensional stability. . Specific examples of the fibers constituting these base materials are not particularly limited. For glass base materials, for example, from E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. One or more glass fibers selected from the group consisting of: Moreover, in inorganic base materials other than glass, inorganic fibers other than glass, such as quartz, are mentioned. Furthermore, for organic substrates, polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), Teijin Techno Products Ltd. Wholly aromatic polyamides; polyesters such as 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB Selen); Examples thereof include organic fibers such as phenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide. These base materials may be used individually by 1 type, or may use 2 or more types together.

Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, a surfacing mat, etc. are mentioned. The weaving method of the woven fabric is not particularly limited, and for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones depending on the intended use and performance. . Moreover, the thing which spread-processed these, and the glass woven fabric surface-treated with the silane coupling agent etc. are used suitably. Although the thickness and mass of the substrate are not particularly limited, 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. More preferred.

  Moreover, as above-mentioned, as for the prepreg of this embodiment, the hardened | cured material obtained by thermosetting it on condition of 230 degreeC and 100 minutes is said Formula (4)-(8), Preferably Formula (4A)-( If the numerical value range of the physical property parameters related to the mechanical properties represented by 8A) is satisfied, the laminate, the metal foil-clad laminate, the printed wiring board, or the multilayer printed wiring board does not have a clear glass transition temperature. (Tg-less) and warp can be sufficiently reduced (low warpage can be achieved), which is preferable.

(Resin sheet)
The resin sheet of this embodiment has a sheet base material (support) and the above-mentioned resin composition for printed wiring boards laminated on one side or both sides of the sheet base material. The resin sheet is used as one means of thinning, for example, a thermosetting resin (including a filler (E)) used for a prepreg directly on a support such as a metal foil or a film. It can be produced by coating and drying.

  Although it does not specifically limit as a sheet | seat base material, The well-known thing 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 these, electrolytic copper foil and PET film are preferable.

  Examples of the application 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. It is done.

  The resin sheet is preferably one obtained by applying the resin composition for printed wiring board to a sheet base material and then semi-curing (B-stage). Specifically, for example, after the resin composition for a printed wiring board is applied to a sheet base material such as a copper foil, it is semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes. And a method for producing a resin sheet. The adhesion amount of the resin composition for printed wiring boards to the sheet substrate 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 laminated board of this embodiment has the prepreg of this embodiment and / or the resin sheet of this embodiment laminated at least one sheet. Further, the metal foil-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 laminated at least one sheet), It has metal foil (conductor layer) arranged on one side or both sides of the laminate.

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

The molding method and molding conditions of the laminate or metal foil-clad laminate are not particularly limited, and general techniques and conditions of a laminate for a printed wiring board and a multilayer board can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of forming a laminar laminate or a metal foil-clad laminate. Further, in forming a laminate or metal foil-clad laminate (lamination), the temperature is generally 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. It is. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. Particularly when a multi-stage press is used, a temperature of 200 ° C. to 250 ° C., a pressure of 10 to 40 kgf / cm ² , and a heating time of 80 minutes to 130 minutes are preferable from the viewpoint of sufficiently promoting the curing of the prepreg and / or resin sheet. More preferably, 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. Also, a multilayer board can be formed by laminating and molding the above-described prepreg and / or resin sheet and a separately prepared wiring board for an inner layer.

[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 printed wiring board. For example, it can be suitably used as a printed wiring board by forming a predetermined wiring pattern on the metal foil-clad laminate described above. And the metal foil tension laminated board using the resin composition for printed wiring boards of this embodiment does not have a clear glass transition temperature (Tg-less), and sufficiently reduces warpage (achieves low warpage). Therefore, it can be used particularly effectively as a printed wiring board that requires such performance.

  Specifically, the printed wiring board of this embodiment can be manufactured by the following method, for example. First, the metal foil-clad laminate (such as a copper-clad laminate) is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of the above-mentioned prepregs and / or resin sheets are stacked on the inner layer circuit surface, and the outer layer circuit is further outside. The metal foil is laminated and heated and pressed to perform integral molding (laminate molding). In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. The method of lamination molding and the molding conditions thereof are the same as those of the above-described laminate or metal foil-clad laminate. Next, after this multi-layer laminate is subjected to drilling for through holes and via holes, desmear treatment is performed to remove smears, which are resin residues derived from the resin component contained in the cured product layer. . After that, a plated metal film is formed on the wall surface of this hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and the outer layer circuit is formed by etching the metal foil for the outer layer circuit to produce a printed wiring board. Is done.

  For example, the above-mentioned prepreg (the substrate and the above-mentioned resin composition for a printed wiring board attached thereto), the resin composition layer of the metal foil-clad laminate (the layer comprising the above-mentioned resin composition for a printed wiring board) is provided. The insulating layer containing the above-described resin composition for printed wiring boards is constituted.

  When a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer that becomes a circuit on the prepreg or the resin composition for a printed wiring board. At this time, a method of electroless plating can be used for forming the conductor layer.

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

  According to the knowledge of the present inventors, in a normal laminated board, for example, a group consisting of another prepreg and a resin sheet in at least one double-sided direction selected from the group consisting of a prepreg and a resin sheet which are one core substrate. The multilayer printed wiring board is formed by laminating at least one selected from the above, but 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 another prepreg and resin sheet forming the second insulating layer (2) only in one direction of at least one selected from the group consisting of one prepreg and resin sheet forming (1) It is particularly effective for a coreless type multilayer printed wiring board (multilayer coreless substrate) manufactured by laminating at least one kind of There has been confirmed.

  In other words, the prepreg, resin sheet, and printed wiring board resin composition 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 in a multilayer coreless substrate among printed wiring boards. That is, a normal printed wiring board generally has a symmetrical structure on both sides, and thus tends to be warped. On the other hand, a multilayer coreless board tends to have a double-sided asymmetric structure, and thus is more likely to warp than a normal printed wiring board. There is a tendency. Therefore, by using the prepreg, resin sheet, and printed wiring board resin composition of the present embodiment, it is possible to particularly effectively reduce the amount of warping of the multilayer coreless substrate that has been prone to warping.

  In FIG. 9, a configuration in which two second insulating layers (2) are stacked on one first insulating layer (1) (that is, a configuration in which a plurality of insulating layers are three layers) is provided. Although shown, the number of 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 above-described resin composition for a printed wiring board of the present embodiment is, for example, a cured product obtained by curing a prepreg. The mechanical properties such as elastic modulus can be controlled within a specific range suitable for low warpage, so that there is no clear glass transition temperature (Tg-less) and warping of printed wiring boards, particularly multilayer coreless substrates. Can be sufficiently effectively used as a printed wiring board for a semiconductor package and a multilayer coreless substrate.

  Hereinafter, the present invention will be described more specifically 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 units.) 0.47 mol (OH group equivalent) 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 0.93 mol of cyanogen chloride in chloroform was added dropwise to the reactor over 1.5 hours, and the mixture was stirred for 30 minutes after completion of the addition. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was dropped into the reactor and stirred for 30 minutes to complete the reaction. After triethylamine hydrochloride formed as a by-product 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 four times. This was dried with sodium sulfate, evaporated at 75 ° C., and further degassed at 90 ° C. under reduced pressure to give an α-naphthol aralkyl type cyanate ester compound represented by the above formula (2) as a brown solid (in the formula: All of R ⁶ are hydrogen atoms). When the obtained α-naphthol aralkyl cyanate compound was analyzed by infrared absorption spectrum, absorption of a cyanate ester group was confirmed in the vicinity of 2264 cm ⁻¹ .

[Example 1]
Diallyl bisphenol A (DABPA, manufactured by Daiwa Kasei Kogyo Co., Ltd., hydroxyl group equivalent: 154 g / eq.) 24.1 parts by mass, maleimide compound (B) (BMI-2300, Daiwa Chemical Industries) Co., Ltd., maleimide equivalent: 186 g / eq.) 60.9 parts by mass, α-naphthol aralkyl-type cyanate ester compound (SN495VCN, cyanate equivalent: 261 g / eq) of 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, manufactured by Admatechs Co., Ltd.) 200 parts by mass and the silicone composite powder (KMP-605M) 25 parts by mass of Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), and triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 0.5 parts by mass was mixed and diluted with methyl ethyl ketone to obtain a varnish. This varnish was impregnated and applied to 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 printed wiring boards of 73% by volume.

[Example 2]
Allylphenol compound (A) (DABPA) was 19.9 parts by mass, maleimide compound (B) (BMI-2300) was 50.1 parts by mass, cyanate ester compound (C) (SN495VCN) Resin composition content for printed wiring boards in the same manner as in Example 1 except that 10.0 parts by mass and 20.0 parts by mass of epoxy compound (D) (NC-3000FH) were used. A 73% by volume prepreg was obtained.

Example 3
A printed wiring was produced in the same manner as in Example 1 except that the cyanate ester compound (C) (SN495VCN) was not used and that the epoxy compound (D) (NC-3000FH) was 15.0 parts by mass. A prepreg having a resin composition content for board of 73% by volume was obtained.

Example 4
According to the same method as in Example 1, except that the cyanate ester compound (C) (SN495VCN) was 15.0 parts by mass and the epoxy compound (D) (NC-3000FH) was not used, printed wiring A prepreg having a resin composition content for board of 73% by volume was obtained.

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

[Comparative Example 2]
Allylphenol compound (A) (DABPA) was 60.0 parts by mass, maleimide compound (B) (BMI-2300) was 32.1 parts by mass, cyanate ester compound (C) (SN495VCN) Resin composition content for printed wiring board by the same method as Example 1 except having set it as 2.6 mass parts and having set epoxy compound (D) (NC-3000FH) as 5.3 mass parts. A 73% by volume 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). Resin composition content for a printed wiring board in the same manner as in Example 1 except that it was 50.0 parts by mass and that the epoxy compound (D) (NC-3000FH) was 5.2 parts by mass. A 73% by volume prepreg was obtained.

[Comparative Example 4]
Allylphenol compound (A) (DABPA) was 5.0 parts by mass, maleimide compound (B) (BMI-2300) was 85.0 parts by mass, cyanate ester compound (C) (SN495VCN) Resin composition content for printed wiring board by the same method as in Example 1 except that 5.0 parts by mass and 5.0 parts by mass of epoxy compound (D) (NC-3000FH) were used. A 73% by volume prepreg was obtained.

(Measurement of physical properties)
Using the prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 4, samples for physical property measurement evaluation were prepared by the procedures shown in the following items, mechanical properties (storage elastic modulus and loss elastic modulus), The physical property parameters relating to mechanical properties, the glass transition temperature (Tg), and the warpage amount (three types) in the formulas (4) to (8) and the 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 properties)
Copper foils (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) are arranged on the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure is 30 kgf / cm ^2. Then, 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 measurement sample. Using this measurement sample, mechanical properties (storage elastic modulus E ′ and loss elastic modulus E ″) were measured by a DMA method using a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481. (Average value of n = 3).

[Glass transition temperature (Tg)]
Copper foils (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) are arranged on the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure is 30 kgf / cm ^2. Then, laminate molding 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 with a dicing saw into a size of 12.7 × 2.5 mm, and then the surface copper foil was removed by etching to obtain a measurement sample. Using this measurement sample, the glass transition temperature (Tg) was measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481 (average value of n = 3).

[Warpage amount: Bimetal method]
First, copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) is arranged on both upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and a pressure of 30 kgf / A laminate mold was performed at cm ² and 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 laminate from which the copper foil was removed, and the copper foil (3EC-VLP, Mitsui) was placed on both upper and lower sides. Metal Mining Co., Ltd. (thickness: 12 μm) was placed, laminate 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. Furthermore, the said copper foil was removed from the obtained copper foil tension laminated board, and the laminated board was obtained. Then, a 20 mm × 200 mm strip-shaped plate is cut out from the obtained laminated plate, and the maximum value of the warpage at both ends in the longitudinal direction is measured with a metal rule with the surface of the prepreg laminated on the second sheet facing up. The average value was defined as the “warp amount” by the bimetal method.

[Warpage amount: Multilayer coreless substrate]
First, as shown in FIG. 1, carrier copper foil surfaces of an ultrathin copper foil with carrier (b1) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 μm) are provided on both sides of the prepreg to be the support (a). The prepreg (c1) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 is further arranged thereon, and a copper foil (d) (3EC-VLP, Mitsui Mining & Mining ( Co., Ltd., thickness 12 μm) was placed, and laminate 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 shown in FIG.

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 laminate shown in FIG. 3 on which the conductor layer (d ′) is formed. Furthermore, an ultrathin copper foil with carrier (b2) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 μm) is further placed thereon, and laminated molding is performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes. And a 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) placed on the support (a) (cured support prepreg) are peeled off. Thus, as shown in FIG. 6, the two laminated plates were peeled from the support (a), and the carrier copper foil was further peeled from the ultrathin copper foil with carrier (b2) on the upper portion of each laminated plate. . Next, processing by a laser processing machine was performed on the upper and lower ultrathin copper foils of each obtained laminate, and a predetermined via (v) was formed by chemical copper plating as shown in FIG. 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 a total of eight locations of the four corners and the center of the four sides of the obtained panel was measured with a metal ruler, and the average value was defined as the “warpage amount” of the panel of the multilayer coreless substrate.

[Substrate shrinkage before and after reflow process]
Copper foils (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 μm) are arranged on the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the pressure is 30 kgf / cm ^2. Then, lamination molding was performed at a temperature of 220 ° C. for 120 minutes to obtain a copper foil-clad laminate. Next, the obtained copper foil-clad laminate was drilled at nine points uniformly in a grid pattern with a drill, and then the copper foil was removed.

Then, first, the distance between the holes in the laminate from which the copper foil was removed was measured (distance A). Next, the laminate was subjected to a reflow treatment at a maximum temperature of 260 ° C. using a salamander reflow apparatus. Thereafter, the distance between the holes in the laminate was measured again (distance b). Then, the measured distance A and distance B were substituted into the following formula (I) to determine the dimensional change rate of the substrate in the reflow process, and the value was used as the substrate shrinkage rate before and after the reflow process.
((Distance A)-(Distance B)) / Distance A x 100 ... Formula (I)

  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 laminated board, a metal foil-clad laminated board, a printed wiring board, or a multilayer printed wiring board. In addition, this application is based on the JP Patent application number 2016-255272 for which it applied on December 28, 2016, and uses the description here.

Claims (18)

An allylphenol compound (A);
A maleimide compound (B);
A resin composition for a printed wiring board containing a cyanate ester compound (C) and / or an epoxy compound (D),
Content of the said allylphenol compound (A) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 10-50 mass parts,
Content of the said maleimide compound (B) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 40-80 mass parts,
Resin composition for printed wiring boards. The total content of the cyanate ester compound (C) and the epoxy compound (D) with respect to 100 parts by mass of the resin solid content in the resin composition for printed wiring boards is 5 to 45 parts by mass,
The resin composition for printed wiring boards according to claim 1. Content of the said cyanate ester compound (C) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 0-25 mass parts,
The resin composition for printed wiring boards according to claim 1 or 2. Content of the said epoxy compound (D) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 0-25 mass parts,
The resin composition for printed wiring boards according to claim 1 or 2. Further containing a filler (E),
The resin composition for printed wiring boards of any one of Claims 1-4. The filler (E) is at least one selected from the group consisting of silica, alumina, and boehmite,
The resin composition for printed wiring boards according to claim 5. Content of the said filler (E) with respect to 100 mass parts of resin solid content in the said resin composition for printed wiring boards is 120-250 mass parts.
The resin composition for printed wiring boards according to claim 5 or 6. The allylphenol compound (A) includes a compound represented by any of the following formulas (I) to (III),
The resin composition for printed wiring boards of any one of Claims 1-7.

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

The maleimide compound (B) is bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) ) Including at least one selected from the group consisting of methane and a maleimide compound represented by the following formula (1):
The resin composition for printed wiring boards of any one of Claims 1-8.

(In Formula (1), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.) The cyanate ester compound (C) includes a compound represented by the following formula (2) and / or (3):
The resin composition for printed wiring boards of any one of Claims 1-9.

(In formula (2), each 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 each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.) Hardened | cured material obtained by thermosetting the prepreg containing the said resin composition for printed wiring boards and a base material on 230 degreeC and the conditions for 100 minutes is following formula (4)-(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 ′ represents the storage elastic modulus of the cured product at the temperature shown in parentheses, and E ″ max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C. E ″ min represents 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 the physical property parameters for mechanical properties expressed by
The resin composition for printed wiring boards of any one of Claims 1-10. A substrate;
The resin composition for a printed wiring board according to any one of claims 1 to 11, wherein the base material is impregnated or applied;
Prepreg with The substrate is one or more 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. Made up of fibers,
The prepreg according to claim 12. A support;
The resin composition for a printed wiring board according to any one of claims 1 to 11, which is laminated on one side or both sides of the support,
A resin sheet. At least one selected from the group consisting of the prepreg according to claim 12 and 13 and the resin sheet according to claim 14 laminated at least one sheet,
Laminated board. At least one selected from the group consisting of the prepreg according to claim 12 and 13 and the resin sheet according to claim 14 laminated at least one sheet,
A metal foil disposed on one or both sides of at least one selected from the group consisting of the prepreg and the resin sheet;
A metal foil-clad laminate. An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The said insulating layer contains the resin composition for printed wiring boards of any one of Claims 1-11,
Printed wiring board. A first insulating layer formed of at least one selected from the group consisting of at least one prepreg according to claim 12 and 13, and a resin sheet according to claim 14, and the first A prepreg according to claim 12 and 13 and at least one selected from the group consisting of a resin sheet according to claim 14 laminated at least one sheet in the direction of one side of one insulating layer. A plurality of insulating layers of insulating layers;
A plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers, and a second conductor layer disposed on a surface of the outermost layer of the plurality of insulating layers;
A multilayer printed wiring board having:

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